WO2024213626A1

WO2024213626A1 - Vinyl acetate having low deuterium content

Info

Publication number: WO2024213626A1
Application number: PCT/EP2024/059815
Authority: WO
Inventors: Thomas Weiss; Helmut Witteler; Stephan Hueffer; Juergen Tropsch; Christian Koenig; Marco Krueger; Ralf Widmaier
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2023-04-12
Filing date: 2024-04-11
Publication date: 2024-10-17
Anticipated expiration: 2025-10-12
Also published as: CN120936657A

Abstract

The present invention relates to processes for making vinyl acetate, based on methanol having a deuterium content below 90 ppm, comprising the step of reacting acetic acid with ethylene to give vinyl acetate, and to processes for making vinyl acetate, based on methanol having a deuterium content below 90 ppm, comprising the steps of reacting acetic anhydride with acetaldehyde to form ethyliden diacetate and reacting ethyliden diacetate to give vinyl acetate by thermal elimination of acetic acid, as well as to vinyl acetate having a deuterium content below 90 ppm, based on the total hydrogen content. The present invention further relates to a vinyl acetate having a natural abundance of carbon-14 from non-fossil resources, preferably from biomass, as well as to its use. The present invention also relates to a process for preparing alkoxylated compounds comprising ethylene oxide units and/or propylene oxide units, comprising the steps: (a) reacting hydrogen with carbon dioxide to form methanol, (b) converting the methanol from step (a) to ethene and/or propene, (c) reacting the ethene and/or propene from step (b) with oxygen or an oxidizing agent to form ethylene oxide and/or propylene oxide, and (d) reacting the ethylene oxide and/or propylene oxide with the at least one starter unit having Zerewitinoff active hydrogen atoms to form the alkoxylated compound, wherein the carbon dioxide in step (a) is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes; and the alkoxylated compounds obtainable by the process. The invention further relates to graft polymer based on ethylene oxide-comprising backbones being grafted with olefinically polymerizable monomers, preferably vinyl monomers, more preferably with a) vinyl esters or b) vinyllactams, wherein such graft polymer is at least partially based on hydrogen from non-fossil-based sources, wherein the molar share of deuterium is lower in such graft polymer than that in the identical chemical compound when derived solely from fossil-based sources.

Description

VINYL ACETATE HAVING LOW DEUTERIUM CONTENT

Description

The present invention relates to processes for making vinyl acetate, based on methanol having a deuterium content below 90 ppm, comprising the step of reacting acetic acid with ethylene to give vinyl acetate.

The present invention further relates to processes for making vinyl acetate, based on methanol having a deuterium content below 90 ppm, comprising the steps of reacting acetic anhydride with acetaldehyde to form ethyliden diacetate and reacting ethyliden diacetate to give vinyl acetate by thermal elimination of acetic acid.

The present invention further relates to vinyl acetate having a deuterium content below 90 ppm, based on the total hydrogen content.

The present invention further relates to processes for making vinyl acetate having a natural abundance of carbon-14 from non-fossil resources, preferably from biomass, the vinyl acetate obtained thereby as well as to its use.

In the chemical industry methanol serves as a raw material in the production of olefines, formaldehyde, acetaldehyde, acetic acid, methyl acetate, acetic anhydride and vinyl acetate. The conventional production method involves a catalytic process using fossil feedstock such as natural gas or coal.

Synthesis gas (syngas) for the production of methanol can be produced from many sources, including natural gas, coal, biomass, or virtually any hydrocarbon feedstock, by reaction with steam (steam reforming), carbon dioxide (dry reforming) or oxygen (partial oxidation).

Syngas is produced from solid feedstocks via coal gasification. Coal is reacted thereby in a mixture of partial oxidation with air or pure oxygen and gasification with water vapor to give a mixture of carbon monoxide and hydrogen. Via the Boudouard equilibrium carbon monoxide is in equilibrium with carbon and carbon dioxide.

Furthermore, the water gas shift reaction must be taken into account. n unV f- 0 "tj2 r v ;= vug + u2 ,

The exothermic reaction with oxygen provides the necessary energy to achieve the high reaction temperatures for the endothermic gasification reaction of carbon with water vapor.

In pricinple, beside coal, other solid feedstocks (wood, straw) can be used instead.

The most important gaseous educt for producing syngas is natural gas, which is reacted with water vapor via steam reforming. Natural gas provides the highest hydrogen to carbon monoxide ratio.

CH4 + H«> O — ‘r CO + 3 Hj ,

Also liquid educts, such as light naphtha cuts, can be reacted, after sulfur removal, with water vapor via steam reforming.

To produce methanol, the ratio of carbon monoxide to hydrogen in the synthesis gas is adjusted to meet the reaction equation

CO + 2 H₂ — > CH₃OH₅

Synthesis gas is mainly produced via steam reforming or partial oxidation of natural gas or via coal gasification. While natural gas is used for the methanol production in North America and in Europe, syngas production is based mainly on coal in China and South Africa. Depending on the carbon monoxide to hydrogen ratio, the product gases are named water gas (CO + H2), synthesis gas (CO + 2 H2) or spaltgas (CO + 3 H2). Spaltgas can be hydrogen depleted or carbon monoxide enriched, for example via the water gas shift reaction by adding carbon dioxide and removing water, and water gas can be hydrogen enriched or carbon monoxide depleted in order to obtain synthesis gas.

The synthesis of methanol from CO2 is less exothermic than that starting from synthesis gas, and it also involves as secondary reaction the reverse water-gas-shift (RWGS). To facilitate methanol synthesis, the CO in syngas is converted to CO2 through the water-gas shift (WGS) reaction AH298K = -49.5 kJ mol-1

AH298K = 41.2 kJ mol-1

The water-gas equilibrium mentioned above provides the basis to produce C02-neutral methanol if the CO2 comes from appropriate direct or indirect biogenic sources. According to the reverse water-gas-shift (RWGS) reaction, there is the opportunity of including biogenic CO2 directly to an adapted syngas - methanol -process. Syngas is then converted to methanol e.g. in the ranges of temperature of 250-300°C and pressure of 5 - 10 MPa, using CuO/ZnO/AhOs catalyst.

In that sense CO2 form different biogenic carbon sources could be included into the syngas to form methanol. The biogenic source of CO2 could be from fermentation processes of biomaterial, combustion processes of biomass or waste of biobased materials or form extractive processes of atmospheric CO2, for example by extractive regenerative process steps such as aminic CO2 scrubbing.

Of course, mixtures of CO2 from biogenic and fossil carbon source could be mixed to be used to produce methanol, too.

The natural isotopic abundance of ¹²C is about 98.9%, the natural isotopic abundance of ¹³C is about 1.1 %. The ¹³C/¹²C isotopic ratio of chemical compounds is given relative to an international standard, the Vienna-Pee-Dee-Belemnite-Standard (V-PDB). The ¹³C/¹²C isotopic ratio is given as 5¹³C value in the unit %o. The standard per definition has a 5¹³C value of 0 %o. Substances having a higher ¹³C content than the standard have positive, substances having a lower ¹³C content than the standard have negative %o values.

Fossil based methanol from fossil based synthesis gas has in general 5¹³C values ranging from -50 %o to - 25 %o, depending on the fossil feedstock. Methanol based on carbon dioxide captured from ambient air has in general 5¹³C values ranging from -10 %o to - 2.5 %o, corresponding the 5¹³C values of carbon dioxide captured from ambient air.

In preferred embodiments of the inventive process, the carbon dioxide provided in step (b) has a ¹³C-content corresponding to a 5¹³C value of > -20 %o. In particular, the carbon dioxide provided in step (b) has a ¹³C-content corresponding to a 5¹³C value of from -10 to -2.5 %o.

The invention also relates to methanol with a deuterium content below 90 ppm, based on the total hydrogen content. Preferably, the deuterium content is from 30 to 75 ppm, based on the total hydrogen content.

The methanol with a deuterium content below 90 ppm, preferably from 30 to 75 ppm, based on the total hydrogen content, can be used to prepare ethylene. In general, the obtained ethylene also has a low deuterium content of below 90 ppm, preferably from 30 to 75 ppm. If carbon dioxide is captured from ambient air, the ¹³C-content of the obtained ethylene also corresponds to a 5¹³C value of in general > -20 %o, more specifically to a 5¹³C value of from -10 to -2.5 %o.

In physical organic chemistry, a kinetic isotope effect is the change in the reaction rate of a chemical reaction when one of the atoms in the reactants is replaced by one of its isotopes. Formally, it is the ratio of rate constants ki. I kn for the reactions involving the light (ki.) and the heavy (kn) isotopically substituted reactants (isotopologues). This change in reaction rate is a quantum mechanical effect that primarily results from heavier isotopologues having lower vibrational frequencies compared to their lighter counterparts. In most cases, this implies a greater energetic input needed for heavier isotopologues to reach the transition state, and consequently a slower reaction rate.

Isotopic rate changes are most pronounced when the relative mass change is greatest, since the effect is related to vibrational frequencies of the affected bonds. For instance, changing a hydrogen atom (H) to its isotope deuterium (D) represents a 100 % increase in mass, whereas in replacing ¹²C with ¹³C, the mass increases by only 8 percent. The rate of a reaction involving a C-H bond is typically 6-10 times faster than the corresponding C-D bond, whereas a ¹²C reaction is only 4 percent faster than the corresponding ¹³C reaction.

A primary kinetic isotope effect may be found when a bond to the isotope atom is being formed or broken. A secondary kinetic isotope effect is observed when no bond to the isotope atom in the reactant is broken or formed. Secondary kinetic isotope effects tend to be much smaller than primary kinetic isotope effects; however, secondary deuterium isotope effects can be as large as 1.4 per deuterium atom.

Polyvinyl acetate (abbreviations PVAC, PVA) is a thermoplastic. Polyvinyl acetate is an amorphous, odourless and tasteless plastic with high light and weather resistance. It is combustible, but not easily flammable. The glass transition temperature of the homopolymer varies between 18 and 45 °C depending on the degree of polymerization. The electrical, mechanical and thermal properties are also largely dependent on the degree of polymerization. The minimum film forming temperature of homopolymer dispersions is about 15 to 18 °C. Polyvinyl acetate is processed in the form of solutions in organic solvents or as a dispersion.

PVA is used as a binder in paints and varnishes. The plastic is also used as an adhesive, for example as white glue (wood glue), wallpaper paste or parquet adhesive. The universal adhesive UHU, which is well known in Germany, is a forty percent solution of polyvinyl acetate in methyl acetate and acetone. Simple craft glue also often contains mainly polyvinyl acetate and is then called vinyl glue. Other applications include paper manufacturing and coating, textile impregnation, carpet backing or modification of plaster and concrete. In addition, PVA is often a component of chewing gum masses and is used for coating cheese or sausage.

Vinyl acetate is able to form copolymers with a variety of monomers such as ethylene, maleic anhydride, maleic esters, vinyl ethers and allyl ethers. From that copoymers especially the ethylene vinyl acetate copolymers (EVAC) are prepared in huge amounts to produce thermoplastic elastormers and thermoplastic materials. Depending on the ethylene : vinyl acetate ratio a broad variety off application can be addressed. Vinyl acetate contents of up to 7 % are almost exclusively used to improve the properties (especially to increase the elongation at break) of films. About half of EVAC production is made with a vinyl acetate content of less than 7 %. EVAC with a vinyl acetate content of 7 to 18 % is also often used as an exclusive material for special applications. Examples include cold-resistant pull-out spouts for canisters, films for agriculture and horticulture, shrink-wrap films (office supplies, solar panels), shower curtains, floor coverings, roofing membranes and electrical cables. The class of EV AC above with up to 28 % vinyl acetate is mainly used as a hot melt adhesive, which in turn is used for fibre bonding of very high quality tufted carpets and needle punched nonwovens, for perfect binding in book production and for manual use with hot melt glue guns. With vinyl acetate contents of more than 30% up to 90%, a rubber-like thermoplastic elastomer is produced. It is mainly used for shoe soles or as a polymer blend together with other elastomers.

Furthermore the vinyl acetate monomer (VAM) can be used to prepare watersoluble graft-poly- mers on polyether substrates. These graft-copolymers are used in laundry detergent compositions for antigraying, e.g. Sokalan HP22 (DE3711298; BASF SE).

Vinyl acetate is produced form precursor base stocks such as ethylene and acetic acid. These base stocks typically derive from fossil carbon base stocks, such as oil or natural gas. Since the carbon source leads to an unwanted CO2 balance there is need for production of vinyl acetate monomer (VAM) and polyvinyl acetate and copolymers in a way that does not use fossil carbon sources. Vinyl acetate can form polymers such a polyvinyl acetate which is able to be hydrolyzed to biodegradable polyvinyl alcohol and biodegradable acetic acid. The production of vinyl acetate monomer VAM from non-fossil, renewable hydrogen and carbon sources has not been described before.

It is an object of the present invention to provide an environmentally friendly process for producing methanol. It is a further object of the present invention to provide a methanol having a low deuterium content. The favorable kinetic isotope effect caused by the low deuterium content of the methanol may be cumulative, since it is also present in subsequent production steps further downstream in the value chain.

It is a further object of the present invention to provide an environmentally friendly process for producing vinyl acetate.

The object is solved by a process for making methanol having a deuterium content below 90 ppm, based on the total hydrogen content, comprising the steps:

(a) providing hydrogen with a deuterium content below 90 ppm by water electrolysis using electrical power that is generated at least in part from non-fossil, renewable resources;

(b) providing carbon dioxide;

(c) reacting hydrogen and carbon dioxide in the presence of a catalyst to form methanol.

The object is further solved by a process for making vinyl acetate, comprising the steps: (a) providing hydrogen with a deuterium content below 90 ppm, based on the total hydrogen content, by water electrolysis using electrical power that is generated at least in part from non-fossil, renewable resources;

(b) providing carbon dioxide;

(c) reacting hydrogen and carbon dioxide in the presence of a catalyst to form methanol with a deuterium content below 90 ppm, based on the total hydrogen content;

(d) reacting methanol from step (c) to form ethylene; and

(e) reacting methanol from step (c) with carbon monoxide to form acetic acid; and/or

(f1 ) reacting part of the ethylene from step (d) with oxygen and water to give acetaldehyde;

(f2) reacting acetaldehyde from step (f1 ) with oxygen to give acetic acid;

(g) reacting acetic acid from step (e) and/or step (f1 ) with ethylene from step (d) to give vinyl acetate.

The object is further solved by a process for making vinyl acetate, comprising the steps:

(a) providing hydrogen with a deuterium content below 90 ppm, based on the total hydrogen content, by water electrolysis using electrical power that is generated at least in part from non-fossil, renewable resources;

(b) providing carbon dioxide;

(d) reacting methanol from step (c) to form ethylene; and

(e) reacting ethylene from step (d) with oxygen and water to form acetaldehyde;

(f1 ) reacting part of the acetaldehyde from step (e) with oxygen to form acetic acid; and/or (f2) reacting methanol from step (c) with carbon monoxide to form acetic acid; and

(g1 ) reacting acetic acid from step (f1 ) and/or step (f2) with methanol from step (c) to form methyl acetate;

(g2) reacting methyl acetate from step (g1) with carbon monoxide to form acetic anhydride; and/or

(hi ) producing ketene from acetic acid from step (f1) and/or step (f2);

(h2) reacting ketene from step (hi ) with acetic acid from step (f1 ) and/or step (f2) to give acetic acid anhydride;

(i) reacting acetic anhydride form step (g2) and/or step (h2) with acetaldehyde from step (e) to form ethyliden diacetate;

(k) reacting ethyliden diacetate to give vinyl acetate by thermal elimination of acetic acid.

Fossil based methanol from synthesis gas has in general 5¹³C values ranging from -50 %o to - 25 %o, depending on the fossil feedstock. Methanol based on carbon dioxide captured from ambient air has in general 5¹³C values ranging from -10 %o to - 2.5 %o, corresponding to the 5¹³C values of carbon dioxide captured from ambient air. In preferred embodiments of the inventive process, the carbon dioxide provided in step (b) has a ¹³C-content corresponding to a 5¹³C value of > -20 %o. In particular, the carbon dioxide provided in step (b) has a ¹³C-content corresponding to a 5¹³C value of from -10 to -2.5 %o.

So if carbon dioxide is captured from ambient air, the ¹³C-content of the methanol corresponds to a 5¹³C value of in general > -20 %o, more specifically to a 5¹³C value of from -10 to -2.5 %o.

The deuterium content of hydrogen and chemical compounds containing hydrogen is given herein in atom-ppm based on the total hydrogen content (total atoms of protium ¹H and deuterium ²H).

Electrolysis of water is an environmentally friendly method for production of hydrogen because it uses renewable H2O and produces only pure oxygen as by-product. Additionally, water electrolysis utilizes direct current (DC) from sustainable energy resources, for example solar, wind, hydropower and biomass.

It is observed that by electrolysis of water, the deuterium atom content of the hydrogen is lower than in the hydrogen generated petrochemically, for example as contained in synthesis gas, in general below 90 ppm, preferably from 30 to 75 ppm. The deuterium atom content in electrolyti- cally produced hydrogen may be as low as 15 ppm. The deuterium is mainly present in the form of D-H rather than D2.

One suitable water electrolysis process is alkaline water electrolysis. Hydrogen production by alkaline water electrolysis is a well-established technology up to the megawatt range for a commercial level. In alkaline water electrolysis initially at the cathode side two water molecules of alkaline solution (KOH/NaOH) are reduced to one molecule of hydrogen (H2) and two hydroxyl ions (OH-). The produced H2 emanates from the cathode surface in gaseous form and the hydroxyl ions (OH-) migrate under the influence of the electrical field between anode and cathode through the porous diaphragm to the anode, where they are discharged to half a molecule of oxygen (O2) and one molecule of water (H2O). Alkaline electrolysis operates at lower temperatures such as 30-80°C with alkaline aqueous solution (KOH/NaOH) as the electrolyte, the concentration of the electrolyte being about 20% to 30 %. The diaphragm in the middle of the electrolysis cell separates the cathode and anode and also separates the produced gases from their respective electrodes, avoiding the mixing of the produced gases. However, alkaline electrolysis has negative aspects such as limited current densities (below 400 mA/cm²), low operating pressure and low energy efficiency.

In one preferred embodiment of the inventive process, hydrogen is provided by polymer electrolyte membrane water electrolysis. Variants of polymer electrolyte membrane water electrolysis are proton exchange membrane water electrolysis (PEMWE) and anion exchange membrane water electrolysis (AEMWE).

PEM water electrolysis was developed to overcome the drawbacks of alkaline water electrolysis. PEM water electrolysis technology is similar to the PEM fuel cell technology, where solid polysulfonated membranes (Nation®, fumapem®) are used as an electrolyte (proton conductor). These proton exchange membranes have many advantages such as low gas permeability, high proton conductivity (0.1 ± 0.02 S cm^-1), low thickness (20-300 pm), and allow high-pressure operation. In terms of sustainability and environmental impact, PEM water electrolysis is one of the most favorable methods for conversion of renewable energy to highly pure hydrogen. PEM water electrolysis has great advantages such as compact design, high current density (above 2 A cm^-2), high efficiency, fast response, operation at low temperatures (20-80°C) and production of ultrapure hydrogen. The state-of-the-art electrocatalysts for PEM water electrolysis are highly active noble metals such as Pt/Pd for the hydrogen evolution reaction (HER) at the cathode and lrO2/ uC>2 for the oxygen evolution reaction (OER) at the anode.

One of the largest advantages of PEM water electrolysis is its ability to operate at high current densities. This can result in reduced operational costs, especially for systems coupled with very dynamic energy sources such as wind and solar power, where sudden spikes in energy output would otherwise result in uncaptured energy. The polymer electrolyte allows the PEM water electrolyzer to operate with a very thin membrane (ca. 100-200 pm) while still allowing high operation pressure, resulting in low ohmic losses, primarily caused by the conduction of protons across the membrane (0.1 S/cm), and a compressed hydrogen output.

The PEM water electrolyzer utilizes a solid polymer electrolyte (SPE) to conduct protons from the anode to the cathode while insulating the electrodes electrically. Under standard conditions the enthalpy required for the formation of water is 285.9 kJ/mol. One portion of the required energy for a sustained electrolysis reaction is supplied by thermal energy and the remainder is supplied through electrical energy.

The half reaction taking place on the anode side of a PEM water electrolyzer is commonly referred to as the Oxygen Evolution Reaction (OER). Here the liquid water reactant is supplied to a catalyst where it is oxidized to oxygen, protons and electrons.

The half reaction taking place on the cathode side of a PEM water electrolyzer is commonly referred to as the Hydrogen Evolution Reaction (HER). Here the protons that have moved through the membrane are reduced to gaseous hydrogen.

PEMs can be made from either pure polymer membranes or from composite membranes, where other materials are embedded in a polymer matrix. One of the most common and commercially available PEM materials is the fluoropolymer PFSA, or Nation®, a DuPont product. While Nation® is an ionomer with a perfluorinated backbone like Teflon, there are many other structural motifs used to make ionomers for proton-exchange membranes. Many use polyaromatic polymers, while others use partially fluorinated polymers.

An overview over hydrogen production by PEM water electrolysis is given in S. Kumar and V. Himabindu, Material Science for Energy Technologies 2 (2019), pp. 4442 - 4454.

An overview over hydrogen production by anion exchange membrane water electrolysis is given in H. A. Miller et aL, Sustainable Energy Fuels, 2020, 4, pp. 2114 - 2133.

K. Harada et aL, International Journal of Hydrogen Energy 45 (2020), pp. 31389 - 31 395 report a deuterium depletion by a factor from 2 to 3 in polymer electrolyte membrane water electrolysis. The separation factor p

P = ([H]/[D])_gas I ([H]/[D])i_iquid where “gas” is the evolved gas and “liquid” is water before the electrolysis was found to be between 2 and 3 at current densities of from 1.0 to 2.0 A cm-², corresponding to a stoichiometric number A of between 4 and 9 at the given water mass flow in the anode. The stoichiometric number A is defined as follows:

A = V x p / (J/2F x 60 x MH2O) where V (mL min-¹) is the water mass flow in the anode, F is the Faraday constant, J is electrolysis current (A), p is the density of water (g mL-¹) and MH2O (g mol-¹) is the molar weight of water. A stoichiometric number A of 10 means that 10 times the amount of fresh water than can be theoretically consumed by electrolysis at the given electrolysis current is supplied to the anode.

H. Sato et aL, International Journal of Hydrogen Energy 46 (2021), pp. 33 689 - 33 695, report for anion exchange membrane water electrolysis that deuterium concentration in the evolving hydrogen gas is diluted by approximately 1/5 against the feed water, at A = 4.

Hence, deuterium in the evolving hydrogen gas can easily be depleted by a factor of from 2 to 5 with regard to feed water in polymer electrolyte membrane water electrolysis. Depending on the electrolysis conditions (water flow, current density), even higher depletion factors are possible. Since the average deuterium content of water is about 150 ppm, based on the total hydrogen content, hydrogen provided in step (a) of the inventive process may have a deuterium content of from 30 to 75 ppm, based on the total hydrogen content, or even lower.

The electrical power is generated at least in part from non-fossil, renewable resources. In other words, part of the electrical power can still be produced from fossil fuels, preferably from natural gas, since combustion of natural gas causes much lower carbon dioxide emission per Megajoule of electrical energy produced than combustion of coal. However, the portion of electrical energy produced from fossil fuels should be as low as possible, preferably < 50%, preferably < 30%, most preferably < 20%.

The electrical power from non-fossil resources used in water electrolysis according to the invention can be generated by nuclear energy. Nuclear energy is considered renewable by the European Commission, as long as certain preconditions (i. a. safe long-term storage of nuclear waste) are fulfilled.

The electrical power from non-fossil resources used in water electrolysis according to the invention is preferably generated from wind power, solar energy, biomass, hydropower and geothermal energy.

In one preferred embodiment of the inventive process, the electrical power used in water electrolysis is generated from hydropower. There are many forms of hydropower. Traditionally, hydroelectric power comes from constructing large hydroelectric dams and reservoirs. Small hydro systems are hydroelectric power installations that typically produce up to 50 MW of power. They are often used on small rivers or as a low-impact development on larger rivers. Run-of-the-river hydroelectricity plants derive energy from rivers without the creation of a large reservoir. The water is typically conveyed along the side of the river valley (using channels, pipes and/or tunnels) until it is high above the valley floor, whereupon it can be allowed to fall through a penstock to drive a turbine.

Wave power, which captures the energy of ocean surface waves, and tidal power, converting the energy of tides, are two forms of hydropower with future potential.

In one further preferred embodiment of the inventive process, the electrical power used in water electrolysis is generated from wind power. Wind power can be used to run wind turbines. Modern utility-scale wind turbines range from around 600 kW to 9 MW of rated power. The power available from the wind is a function of the cube of the wind speed, so as wind speed increases, power output increases up to the maximum output for the particular turbine. Areas where winds are stronger and more constant, such as offshore and high-altitude sites, are preferred locations for wind farms.

In one further preferred embodiment of the inventive process, the electrical power used in water electrolysis is generated from solar power, particularly preferred from photovoltaic systems. A photovoltaic system converts light into electrical direct current (DC) by taking advantage of the photoelectric effect. Concentrated solar power (CSP) systems use lenses or mirrors and tracking systems to focus a large area of sunlight into a small beam. CSP-Stirling has by far the highest efficiency among all solar energy technologies.

In one further preferred embodiment of the inventive process, the electrical power used in water electrolysis is generated from biomass. Biomass is biological material derived from living, or re- cently living organisms. It most often refers to plants or plant-derived materials which are specifically called lignocellulosic biomass. As an energy source, biomass can either be used directly via combustion to produce heat or electricity, or indirectly after converting it to various forms of biofuel. Conversion of biomass to biofuel can be achieved by different methods which are broadly classified into: thermal, chemical, and biochemical methods. Wood was the largest biomass energy source as of 2012; examples include forest residues - such as dead trees, branches and tree stumps -, yard clippings, wood chips and even municipal solid waste. Industrial biomass can be grown from numerous types of plants, including miscanthus, switchgrass, hemp, corn, poplar, willow, sorghum, sugarcane, bamboo, and a variety of tree species, ranging from eucalyptus to oil palm (palm oil).

Plant energy is produced by crops specifically grown for use as fuel that offer high biomass output per hectare with low input energy. The grain can be used for liquid transportation fuels while the straw can be burned to produce heat or electricity. Biomass can be converted to other usable forms of energy such as methane gas or transportation fuels such as ethanol and biodiesel. Rotting garbage, and agricultural and human waste, all release methane gas - also called landfill gas or biogas. Crops, such as corn and sugarcane, can be fermented to produce the transportation fuel, ethanol. Biodiesel, another transportation fuel, can be produced from left-over food products such as vegetable oils and animal fats.

In step (b) of the inventive process, carbon dioxide is provided. In preferred embodiments, the carbon dioxide that is provided in step (b) is captured from industrial flue gases or from ambient air. All available capture technologies may be used.

Capturing CO2 is most cost-effective at point sources, such as large carbon-based energy facilities, industries with major CO2 emissions (e.g. cement production, steelmaking), natural gas processing, synthetic fuel plants and fossil fuel-based hydrogen production plants. Extracting CO2 from air is possible, although the lower concentration of CO2 in air compared to combustion sources complicates the engineering and makes the process therefore more expensive.

In some preferred embodiments, the carbon dioxide that is provided in step (b) is captured from industrial flue gases.

In post combustion capture, the CO2 is removed after combustion of the fossil fuel — this is the scheme that would apply to fossil-fuel power plants. CO2 is captured from flue gases at power stations or other point sources. Absorption, or carbon scrubbing with amines is the dominant capture technology. It is the only carbon capture technology so far that has been used industrially.

CO2 adsorbs to a MOF (Metal-organic framework) through physisorption or chemisorption based on the porosity and selectivity of the MOF leaving behind a CO2 poor gas stream. The CO2 is then stripped off the MOF using temperature swing adsorption (TSA) or pressure swing adsorption (PSA) so the MOF can be reused. In some other preferred embodiments, the carbon dioxide that is provided in step (b) is captured from ambient air.

Direct air capture (DAC) is a process of capturing carbon dioxide (CO2) directly from the ambient air and generating a concentrated stream of CO2 for sequestration or utilization or production of carbon-neutral fuel. Carbon dioxide removal is achieved when ambient air makes contact with chemical media, typically an aqueous alkaline solvent or sorbents. These chemical media are subsequently stripped of CO2 through the application of energy (namely heat), resulting in a CO2 stream that can undergo dehydration and compression, while simultaneously regenerating the chemical media for reuse.

Dilute CO2 can be efficiently separated using an anionic exchange polymer resin called Marathon MSA, which absorbs air CO2 when dry, and releases it when exposed to moisture. A large part of the energy for the process is supplied by the latent heat of phase change of water. Other substances which can be used are metal-organic frameworks (or MOFs). Membrane separation of CO2 rely on semi-permeable membranes.

In step (c), hydrogen and carbon dioxide are reacted in the presence of a catalyst to form methanol.

An overview of suitable catalyst systems is given by Kristian Stangeland, Hailong Li & Zhixin Yu, Energy, Ecology and Environment volume 5, pages 272-285 (2020). Multi-component catalyst systems are required for this process. The interaction between components is essential for high activity and selectivity of CC>2-to-methanol catalysts. This has been demonstrated by numerous catalyst systems comprised of various metals (i.e., Cu, Pd, Ni) and metal oxides (i.e., ZnO, ZrC>2, ln₂O₃). These complex systems can contain a mixture of metallic, alloy, and metal oxide phases. The most promising catalyst systems for large-scale industrial processes are currently Cu-based and In-based catalysts due to their superior catalytic performance.

A process for the CC>2-to-methanol synthesis can be carried out, for example, by the method known from DE-A-4220 865, which produces methanol under the influence of silent electrical discharges.

Alternatively, methanol synthesis can also be carried out in a thermal reactor under pressure and elevated temperature and in the presence of a copper-based catalyst (DE 43 32 789 A1 ; DE 19739773 A1).

Typical catalysts are described, for example, in the publication by N.Kanoun et al. "Catalytic properties of Cu based catalysts containing Zr and/or V for methanol synthesis from a carbon dioxide and hydrogen mixture" in CATALYSIS LETTERS 15,(1992) 231-235. Potential catalysts like CuO/ZnO and Cu-ZnO-AhOs are also described by R. M. Navarro et al. “Methanol Synthesis from CO2: A Review of the Latest Developments in Heterogeneous Catalysis” Materials (2019), 12, 3902 and in “Catalytic carbon dioxide hydrogenation to methanol: A review of recent studies” in chemical engineering research and design 92 (2014) 2557-2567.

Recently a high selective catalysts ln2O3/ZrO2 has been described for industrial relevant conditions. A typical range of industrially relevant conditions for the hydrogenation of CO2 to methanol are T=200-300°C, p=10-50 MPa, and gas hourly space velocity (GHSV) of 16 000-48000 h’¹ (Angew. Chem. Int. Ed. 2016, 55, 6261 -6265).

Step (c) can be carried out in the presence of a copper-zinc-alumina catalyst. If copper-zinc-alu- mina catalysts are employed, the preferred temperature is in the range of from 150 to 300°C, preferably 175 to 300°C and the preferred pressure is in the range of from 10 to 150 bar (abs).

In general, ethylene is produced from methanol in a methanol to olefin-process (MTO-process). Since the process involves the cleavage of C-H bonds and C-D bonds, respectively, the related primary isotope effect will be pronounced. In the MTO process, a mixture of ethylene and propylene is produced from methanol on a highly selective silicon alumina phosphate zeolith-cata- lyst in fluid bed operation. The ratio propylene to ethylene can be adjusted by chosing appropriate process conditions, and may vary from 0.77 in the ethylene production mode and 1 .33 in the propylene production mode.

The overall kinetic isotope effect is cumulative, since it will also be present in all subsequent production steps downstream the value chain.

In environmentally friendly processes of the invention to produce vinyl acetate, vinyl acetate is produced from methanol obtained in step (c) by

(d) reacting methanol from step (c) to form ethylene; and

(f1 ) reacting part of the ethylene from step (d) with oxygen and water to give acetaldehyde; (f2) reacting acetaldehyde from step (f1) with oxygen to give acetic acid;

In step (d), ethylene is produced from methanol in a methanol to olefin-process (MTO-process) as described above.

Acetic acid can be produced by carbonylation of methanol in step (e). The process involves iodomethane as an intermediate, and occurs in three steps. A catalyst, metal carbonyl, is needed for the carbonylation (step 2).

Two related processes exist for the carbonylation of methanol: the rhodi um-catalyzed Monsanto process, and the iridium-catalyzed Cativa process.

The Monsanto process operates at a pressure of 30-60 atm and a temperature of 150-200°C and gives a selectivity greater than 99%. The catalytically active species is the anion cis- [Rh(CO)2l2]“. The first organometallic step is the oxidative addition of methyl iodide to cis- [Rh(CO)2l2]“ to form the hexacoordinate species [(CH3)Rh(CO)2l3]“. This anion rapidly transforms, via the migration of a methyl group to an adjacent carbonyl ligand, affording the pentacoordinate acetyl complex [(CH3CO)Rh(CO)l3]“. This five-coordinate complex then reacts with carbon monoxide to form the six-coordinate dicarbonyl complex, which undergoes reductive elimination to release acetyl iodide (CH3C(O)I). The catalytic cycle involves two non-organo- metallic steps: conversion of methanol to methyl iodide and the hydrolysis of the acetyl iodide to acetic acid and hydrogen iodide.

The Cativa process is a further method for the production of acetic acid by the carbonylation of methanol. The technology is similar to the Monsanto process. The process is based on an irid- ium-containing catalyst, such as the complex [I r(CO)2l2]“. The catalytic cycle for the Cativa process begins with the reaction of methyl iodide with the square planar active catalyst species to form the octahedral iridium(lll) species [lr(CO)2(CH3)l3]“. This oxidative addition reaction involves the formal insertion of the iridium(l) centre into the carbon-iodine bond of methyl iodide. After ligand exchange of iodide for carbon monoxide, the migratory insertion of carbon monoxide into the iridium-carbon bond results in the formation of a species with a bound acetyl ligand. The active catalyst species is regenerated by the reductive elimination of acetyl iodide. The acetyl iodide is hydrolysed to produce the acetic acid product, in the process generating hydroiodic acid which is in turn used to convert the starting material methanol to the methyl iodide used in the first step.

The Wacker process or the Wacker-Hoechst process refers to the oxidation of ethylene to acetaldehyde in the presence of palladi um(l I) chloride as the catalyst.

The net reaction can be described as follows:

[PdCI₄]² - + C₂H₄ + H₂O - CH3CHO + Pd + 2 HCI + 2 Cl-

This conversion is followed by reactions that regenerate the Pd(ll) catalyst: Pd + 2 CuCI₂ + 2 Cl - - [PdCI₄]^2- + 2 CuCI 2 CuCI + 1/2 O₂ + 2 HCI - 2 CuCI₂ + H₂O

Two routes are commercialized for the production of acetaldehyde: one-stage processes and two-stage processes. In the one-stage process, ethene and oxygen are passed co-currently in a reaction tower at about 130°C and 400 kPa. The catalyst is an aqueous solution of PdCh and CuCh. The acetaldehyde is purified by extractive distillation followed by fractional distillation. Extractive distillation with water removes the lights ends having lower boiling points than acetaldehyde (chloromethane, chloroethane, and carbon dioxide) at the top, while water and higher-boiling byproducts, such as acetic acid, crotonaldehyde or chlorinated acetaldehydes, are withdrawn together with acetaldehyde at the bottom.

In the two-stage process, reaction and oxidation are carried out separately in tubular reactors. Unlike the one-stage process, air can be used instead of oxygen. Ethylene is passed through the reactor along with catalyst at 105 - 110°C and 900 - 1000 kPa. Catalyst solution containing acetaldehyde is separated by flash distillation. The catalyst is oxidized in the oxidation reactor at 1000 kPa using air as oxidizing medium. Oxidized catalyst solution is separated and sent back to the reactor. Oxygen from air is used up completely and the exhaust air is circulated as inert gas. Acetaldehyde water vapor mixture is preconcentrated to 60 - 90% acetaldehyde by utilizing the heat of reaction and the discharged water is returned to the flash tower to maintain the catalyst concentration. A two-stage distillation of the crude acetaldehyde follows. In the first stage, low-boiling substances, such as chloromethane, chloroethane and carbon dioxide, are separated. In the second stage, water and higher-boiling by-products, such as chlorinated acetaldehydes and acetic acid, are removed and acetaldehyde is obtained in pure form overhead.

In both one- and two-stage processes the acetaldehyde yield is about 95%.

For further details, reference can be made to Marc Eckert, Gerald Fleischmann, Reinhard Jira, Hermann M. Bolt, Klaus Golka, Acetaldehyd, in Ullmann's Encyclopedia of Industrial Chemistry- 7th ed, Vol.1 , Kap. 4.3, p. 197.

Acetaldehyde can be oxidized with pure oxygen or with air in the presence of a redox catalyst to give acetic acid. The oxidation can be carried out in the presence of cobalt or manganese acetate in acetic acid as solvent at temperatures of 50 - 70°C in bubble columns (Hoechst process).

Most of the vinyl acetate is produced via the vapor-phase reaction of ethylene and acetic acid over a noble-metal catalyst, usually palladium. The reaction is typically carried out at 150 - 250°C, preferably 175 - 200°C and 5 - 9 bar pressure. The reaction is usually performed in the gas phase in a fixed bed tubular reactor using a supported catalyst. The amount of oxygen in the combined feed is within the range of 5 to 15 mol %. Preferably, the amount of acetic acid in the combined feed is within the range of 10 to 25 mol %. Preferably, the amount of ethylene in the combined feed is within the range of 65 to 80 mol %. Suitable catalysts include those known to the vinyl acetate industry. Preferably, the catalyst is a palladium-gold catalyst. Methods for preparing palladium-gold catalysts are known. For instance, U.S. Pat. No. 6,022,823 teaches how to prepare a palladium-gold catalyst which has high activity and selectivity. Preferably, the palladium-gold catalyst is supported on an inorganic oxide, such as alumina, silica, titania, and the like, and mixtures thereof. In further environmentally friendly processes of the invention, vinyl acetate is produced from methanol obtained in step (c) by

(d) reacting methanol from step (c) to form ethylene; and

(e) reacting ethylene from step (d) with oxygen and water to form acetaldehyde;

(f1 ) reacting part of the acetaldehyde from step (e) with oxygen to form acetic acid; and/or

(f2) reacting methanol from step (c) with carbon monoxide to form acetic acid; and

(hi) producing ketene from acetic acid from step (f1) and/or step (f2);

(h2) reacting ketene from step (hi) with acetic acid from step (f1) and/or step (f2) to give acetic acid anhydride;

This further route to vinyl acetate involves the reaction of acetaldehyde and acetic anhydride, in general in the presence of a ferric chloride catalyst, to give ethyliden diacetate (step (i)):

CH3CHO + (CH₃CO)₂O - (CH₃CO₂)2CHCH₃.

The reaction can be carried out in liquid phase at 120 - 140°C. Ethyliden diacetate can be converted to vinyl acetate by thermal elimination of acetic acid (step (k)):

(CH₃CO₂)₂CHCH₃ - CH₃CO₂CH=CH₂ + CH₃CO₂H.

For further details, reference is made to G. Roscher, "Vinyl Esters", in Ullmann's Encyclopedia of Chemical Technology, 2007 John Wiley & Sons, New York. doi:10.1002/14356007. a27_419.

Acetic acid can be reacted with methanol to give methyl acetate in step (g1).

For further details, reference can be made to Aslam, M., Torrence, G.P. and Zey, E.G. (2000), Esterification, in Kirk-Othmer Encyclopedia of Chemical Technology Vol.10, p.471 ; Le Berre, C., Serp, P., Kalck, P. and Torrence, G.P. (2014), Acetic Acid, in Ullmann's Encyclopedia of Industrial Chemistry, 7th ed, Kap.10.2.1 , p. 25.

Esters are most commonly prepared by the reaction of a carboxylic acid and an alcohol with the elimination of water. Esters are also formed by a number of other reactions utilizing acid anhydrides, acid chlorides, amides, nitriles, unsaturated hydrocarbons, ethers, aldehydes, ketones, alcohols, and esters (via ester interchange). In making acetate esters, the primary alcohols are esterified most rapidly and completely, ie, methanol gives the highest yield and the most rapid reaction. Most commercially available methyl acetate is a byproduct in the manufacture of acetic acid. Another method is the esterification of methanol and acetic acid with sulfuric acid as catalyst. The product ester is removed as the methanol/methyl acetate azeotrope

Acetic anhydride can be produced in step (g2) by carbonylation of methyl acetate:

CH3CO2CH3 + CO - (CH₃CO)₂O

This process is known as Tennessee Eastman acetic anhydride process and involves the conversion of methyl acetate to methyl iodide and an acetate salt. Carbonylation of the methyl iodide in turn affords acetyl iodide, which reacts with acetate salts or acetic acid to give the product. Rhodium chloride in the presence of lithium iodide is employed as catalyst. Because acetic anhydride is not stable in water, the conversion is conducted under anhydrous conditions.

For further details, reference can be made to Held, H., Rengstl, A. and Mayer, D. (2000), Acetic Anhydride and Mixed Fatty Acid Anhydrides, in Ullmann's Encyclopedia of Industrial Chemistry, 7th ed, Vol.1 , Kap.1 .3.3, p. 248 ff.

Acetic anhydride can also be prepared in step (h2) by the reaction of ketene with acetic acid, for example at 45 - 55°C and low pressure (0.05 - 0.2 bar). Ketene can be produced in step (hi) by the dehydration of acetic acid at 700 - 750°C.

For further details, reference can be made to Held, H., Rengstl, A. and Mayer, D. (2000), Acetic Anhydride and Mixed Fatty Acid Anhydrides, in Ullmann's Encyclopedia of Industrial Chemistry, 7th ed, VoL1 , Kap.1.3.1 , p. 245 ff.

Acetic anhydride can be also obtained directly by liquid-phase oxidation of acetaldehyde in step (f1). The peracetic acid formed from oxygen and acetaldehyde reacts under suitable conditions with a second molecule of acetaldehyde to form acetic anhydride and water. In practice, a 1 : 2 mixture of acetaldehyde and ethyl acetate is oxidized with the addition of 0.05 to 0.1 % cobalt acetate and copper acetate at 40°C; the ratio of Co:Cu is 1 :2. The ratio of acetic anhydride to acetic acid obtained is 56:44, whereas on oxidizing in the absence of ethyl acetate this ratio is only 20:80.

For further details, reference can be made to Held, H., Rengstl, A. and Mayer, D. (2000), Acetic Anhydride and Mixed Fatty Acid Anhydrides, in Ullmann's Encyclopedia of Industrial Chemistry, 7th ed, Vol.1 , Kap.1 .3.2, p. 244 ff.

The invention further concerns vinyl acetate with a deuterium content below 90 ppm, based on the total hydrogen content, obtainable by the processes as described herein. The vinyl acetate according has preferably a deuterium content of from 30 to 75 ppm, based on the total hydrogen content.

The vinyl acetate according can have a ¹³C-content corresponding to a 5¹³C value of from -10 to -2.5 %o, if the carbon dioxide of step (b) is captured from ambient air.

Vinyl acetate can be polymerized to polyvinyl acetate. Polyvinyl acetate is finally hydrolyzed to polyvinyl alcohol, which is biodegradable. Biodegradation of polyvinyl alcohol yields H2O and CO2, thereby closing the loop for a CC>2-neutral life cycle, if CO2 is taken from the atmosphere in step (b).

Poly(vinyl esters) are nontoxic but are degraded slowly in water, see Rinno, H. (2000), Polyvinyl esters), in Ullmann's Encyclopedia of Industrial Chemistry, 7th ed, Vol. 28, Kap.8, p. 477 ff.

Polyvinyl alcohol is recognised as one of the very few vinyl polymers soluble in water that is susceptible to ultimate biodegradation in the presence of suitably acclimated microorganisms. Polyvinyl alcohol is nontoxic but is expected to biodegrade within 90 d under aquatic conditions, see Dominic Byrne et aL, Biodegradability of polyvinyl alcohol based film used for liquid detergent capsules, Tenside Surf. Det. 58 (2021) 2; E. Chiellini et aL, Prog. Polym. Sci. 28 (2003), pp. 963-1014.

The present invention further relates to a process for preparing vinyl acetate having a natural abundance of carbon-14 from non-fossil resources, preferably from biomass, the vinyl acetate obtained thereby as well as to its use.

In the chemical industry, methanol serves as a raw material in the production of olefines, formaldehyde, acetaldehyde, acetic acid, methyl acetate, acetic anhydride and vinyl acetate. The conventional production method involves a catalytic process using fossil feedstock such as natural gas or coal.

Syngas is produced from solid feedstocks via coal gasification. Coal is reacted thereby in a mixture of partial oxidation with air or pure oxygen and gasification with water vapor to give a mixture of carbon monoxide and hydrogen.

Most of the vinyl acetate is produced via the vapor-phase reaction of ethylene and acetic acid over a noble-metal catalyst, usually palladium. Acetic acid can be produced by carbonylation of methanol by the Monsanto-process or the Cativa-process. Acetic acid can be alternatively produced by reacting ethylene with oxygen and water to give acetaldehyde, and further reaction of acetaldehyde with oxygen to give acetic acid.

Ethylene can be obtained by a methanol to olefin-process (MTO-process) from methanol.

Stephen M. Mudge, Juergen Tropsch, Thierry Beaudouin, Christophe Sene, and Horacio Hor- mazabal, J Surfact Deterg (2020) 23: 771-780, report on the determination of the bio-based carbon content of surfactants, following a call of the European Committee for Standardization (CEN) for the development of a European standard (EN 17035) to define bio-based surfactants and enable quantification of the bio-based carbon content of surfactants based on radiocarbon analyses. The analytical approach described in the reference was tested through directly contracted analyses and through a round robin procedure at commercial facilities in Europe.

According to the reference, there are two major analytical approaches that might be used to determine the quantity of bio-based carbon present within any sample:

Stable ¹³C isotope. The carbon isotope present within the surfactant molecule will reflect the initial carbon source and any transformations they may have undergone since formation. The 5¹³C for many crude oils is in the range of -23 to -28%o. This may be compared to -26 to -36%o for terrestrial plant matter and -20 to -26%o for unicellular algae. Since these ranges overlap, this may not be definitive in separating out the two sources.

Radiocarbon (¹⁴C). Along with the ¹³C stable isotope, a very small proportion of the carbon in a molecule will be of the naturally occurring radioactive form, ¹⁴C, also called radiocarbon. The 14C atoms are formed in the upper atmosphere due to interactions between cosmic rays and nitrogen atoms. The natural abundance of ¹⁴C in compounds is around 1 part per trillion (ppt; 10¹²). This radioactive carbon isotope decays with a half-life of 5730 years such that after six half-lives, it is functionally undetectable in a sample. Carbon compounds that are derived from fossil sources such as oil or gas will contain no radiocarbon, as it will have decayed away during the millions of years needed to make such reserves. This contrasts with recently grown plant-based materials that do contain measurable amounts of ¹⁴C. Radioactive carbon can be measured using gas proportional counting, liquid scintillation counting, and accelerator mass spectrometry (AMS). The latter approach is the most sensitive of the three.

It is an object of the present invention to provide an environmentally friendly process for producing vinyl acetate. It is a further object of the invention to provide vinyl acetate that can be used for determining the content of bio-based vinyl acetate or bio-based vinyl alcohol derived therefrom by hydrolysis in vinyl acetate or vinyl alcohol containing polymers and copolymers. It is a still further object of the present invention to provide vinyl acetate for determining the origin of decay products released during decomposition of vinyl acetate or vinyl alcohol containing polymers or copolymers. The object is solved by a process for making vinyl acetate from biomass, comprising the step of reacting (I) ethylene with (II) acetic acid to give vinyl acetate, wherein

(I) ethylene is provided, starting from biomass or ambient air, by a process comprising

(a) producing carbon oxides from biomass, or capturing carbon dioxide from ambient air, optionally followed by electrochemical reduction of carbon dioxide to carbon monoxide;

(b) electrochemical reduction of carbon oxides from step (a) to give ethylene; and/or

(c1 ) reacting hydrogen and carbon oxides from step (a) in the presence of a catalyst to give methanol,

(c2) reacting methanol from step (c1) to form ethylene; and/or

(d1) producing ethanol from biomass by fermentation, and

(d2) dehydrogenating ethanol from step (d1) to give ethylene; and/or

(e) directly producing ethylene from biomass by fermentation;

(II) acetic acid is provided, starting from biomass or carbon dioxide captured from ambient air, by a process comprising

(f) reacting methanol from step (c1) with carbon monoxide to give acetic acid; and/or

(g1 ) reacting part of the ethylene from steps (b), (c2), (d2) or (e) with oxygen and water to give acetaldehyde, and

(g2) reacting acetaldehyde from step (g1) with oxygen to give acetic acid; and/or

(h) oxidative fermentation of ethanol from step (d1) to give acetic acid; and/or

(i) producing acetic acid from biomass by biomass pyrolysis.

According to the invention, ethylene can be produced by one or more of steps (b), (c1)/(c2), (d1)/(d2) and (e). Acetic acid can be produced by one or more of steps (f), (g1)/(g2), (h) and (i).

In certain embodiments, ethylene is produced from one or more of steps (b), (c1)/(c2), (d1)/(d2) and (e), and acetic acid is produced form step (f). In one particular embodiment, the process comprises steps (c1), (c2) and (f). In another particular embodiment, the process comprises steps (c1), (c2), (g1) and (g2).

In certain other embodiments, ethylene is produced from one or more of steps (b), (c1)/(c2), (d1)/(d2) and (e), and acetic acid is produced form steps (g1)/((g2).

In certain other embodiments, ethylene is produced from one or more of steps (b), (c1)/(c2), (d1)/(d2) and (e), and acetic acid is produced form step (h).

In certain other embodiments, ethylene is produced from one or more of steps (b), (c1)/(c2), (d1)/(d2) and (e), and acetic acid is produced form step (i).

There are three naturally occurring isotopes of carbon on Earth: carbon-12 (¹²C), which makes up 99% of all carbon on Earth; carbon-13 (¹³C), which makes up 1 %; and carbon-14 (¹⁴C), which occurs in trace amounts, making up about 1 or 1.5 atoms per 10¹² atoms of carbon in the atmosphere. Carbon-12 and carbon-13 are both stable, while carbon-14 is unstable and has a half-life of 5700±30 years. Carbon-14 decays into nitrogen-14 (¹⁴N) through beta decay. The primary natural source of carbon-14 on Earth is cosmic ray action on nitrogen in the atmosphere, and it is therefore a cosmogenic nuclide.

The natural abundance of carbon-14 (14C) is approximately 1 ppt (parts per trillion; 10’¹²; 10’¹⁰ atom-%), in general 0.5 to 2.0 ppt, based on the total carbon content.

In step (a), carbon oxides are produced from biomass. A suitable biomass is lignocellulsoic biomass, for example lignocellulosic waste biomass.

CO2 or CO can be converted with hydrogen to methanol for further processing to ethylene. Alternatively, CO2 or CO can be converted to ethylene via electrified conversion processes, i.e., converted to C2 products electrochemically. CO2/CO electrolysis can be implemented via membrane electrode assembly technology. Biomass can be used as renewable carbon feedstock for electrochemical processes.

Ethylene production via biomass gasification and electrochemical CO reduction is described by Kluh et al. (2023), Assessment of electrified ethylene production via biomass gasification and electrochemical CO reduction, Front. Energy Res. 11 :1129076. doi: 10.3389/fenrg.2023.1129076, with further references:

The electrochemical reduction of CO2 (CO2R) can produce a wide range of products like ethylene, ethanol, acetic acid, propanol, methanol, or formic acid. The utilization of a two-step process from CO2 to C2 products via CO as intermediate is considered beneficial compared to direct CO2 conversion. Reduction of CO to C2 products (COR) can be combined with biomass gasification or biomass combustion.

In certain embodiments, carbon oxides are produced from biomass in step (a) via gasification of the biomass. In certain other embodiments, carbon oxides are produced from biomass in step (a) via combustion of the biomass.

The combination of biomass-based and electrified processes, termed Power-/Biomass-to-X (PBtX), has been widely investigated in recent years. Two main routes, both based on the electrochemical reduction of CO, utilize lignocellulosic waste biomass as feedstock, but differentiate in terms of the employed thermochemical treatment: gasification or combustion. In case of the gasification route, the biomass is dried and gasified in an oxygen and steam blown fluidized bed gasifier. The CO rich stream is sent to the electrochemical CO reduction. From the purge stream of the membrane separation, hydrogen is recovered via pressure swing adsorption (PSA). The leftover gas is used for heating the reformer. In case of the combustion-based route, biomass is combusted in a fluidized bed combined heat and power (CHP) plant producing heat and electricity for the operation of the processes. CO2 is separated from the flue gas with a monoethanolamine (MEA) wash. See Kluh et al. (2023), Front. Energy Res. 11 :1129076. The CO2 is further converted to CO in a CO2 electrolysis unit. The CO is then further processed in the electrochemical CO reduction unit.

During electrochemical reduction, the CO is converted in an electrochemical cell to ethylene, acetic acid, ethanol, oxygen, and hydrogen. Ethanol and acetic acid are separated from the electrolyte via rectification. Oxygen is easily separated from the liquid phase of the anode. Unreacted CO, H2, and ethylene from the cathode are separated via PSA. The unconverted CO together with traces of H2 and ethylene are recycled to the electrochemical cell.

Gasification of biomass can be carried out as described in by Kluh et al. (2023), Front. Energy Res. 11 :1129076. The gasification route consists of biomass drying and gasification, followed by COR and product separation. Biomass is dried before it can be further processed in gasification. The biomass dryer can be for instance a belt dryer operating at a temperature level of 120°C. The water content is reduced e. g. from 35 to 15 wt.%. The dried biomass is gasified in an oxygen blown fluidized bed gasifier. The gasifier can comprise two reactors. In the decomposition reactor (RYield), the biomass is broken down into its elements, while the subsequent reactor finds the chemical equilibrium.

The combustion-based route consists of biomass combustion with CO2 capture, conversion of CO2 by electrolysis, and electrochemical conversion of CO followed by product separation. The CO2 is separated from the flue gas of the biomass CHP plant. Post-combustion capture by absorption with MEA for CO2 separation can be used as an established technology for capturing CO2 from power plant flue gases.

In certain embodiments, carbon dioxide contained in the product gas obtained from biomass gasification or combustion is electrochemically reduced to carbon monoxide.

CO2 can be converted electrochemically to CO according Equation (1). On the cathode, carbon dioxide is reduced to carbon monoxide, while oxygen is formed on the anode. CO is separated from the product stream and the unreacted CO2, also containing some CO, can be recycled back to the electrolysis cell.

2 CO₂ - 2 CO + O₂ (1 )

Electrochemical reduction of the carbon dioxide contained in the gas stream provided in step (a) is carried out to obtain a gas stream containing carbon monoxide, optionally carbon dioxide and optionally hydrogen.

A large number of methods for the electrochemical production of CO from CO2 have been proposed. Most of these methods are at a very early stage of development. High-temperature electrolysis in solid oxide cells is a CO2 electrolysis technology that is approaching commercialization and for which long-term durability exceeding a year on stream has been demonstrated. A review of two alternative electrochemical technologies for CO production, low-temperature and molten carbonate electrolysis, is given in Reiner Kungas (2020), J. Electrochem. Soc. 167 044508, with further references:

Regardless of the choice of technology, an electrolysis cell always has at least three components: two electrodes in contact with an electrolyte. The electrolyte is either a liquid or a solid material that can conduct ions (e.g. protons, hydroxide ions, oxide ions, carbonate or bicarbonate ions), but that is impermeable to electrons. The ionic conductivity of the electrolyte depends strongly on temperature and the choice of the electrolyte material thereby determines the operating temperature of the cell. When an external voltage is applied between the two electrodes, electrochemical reactions start to occur. The electrode where the reduction of reactants (e.g. CO2 to CO) takes place is called the cathode. The electrode where the oxidation of reactants (e.g. OH- to O2 and H2O or O²- to O2) occurs is referred to as the anode.

In solid oxide electrolysis cells (SOECs), the electrolyte is a solid ceramic material. At temperatures above around 600 °C, electrolyte materials start to conduct oxide ions, but remain impermeable to gaseous oxygen and to electrons. As the ionic conductivity of electrolyte materials increases exponentially with temperature, the operating temperature of SOECs is typically chosen to be between 700 °C and 900 °C. Commonly used materials include stabilized zirconias, such as yttria-stabilized zirconia (YSZ, a solid solution of Y2O3 and Zr©2) and scandia-stabilized zirconia (ScSZ), as well as doped cerias, such as gadolinia-doped ceria (abbreviated either as GDC or CGO) or samaria-doped ceria (SDC or CSO).

CO2 is fed to the cathode side of the cell via gas channels, which help to distribute the gas across the cell. In the porous cathode (also referred to as the fuel electrode), carbon dioxide is reduced to carbon monoxide, following the reaction

CO₂ + 2e- -> CO + O²-

The electrons for the reaction are provided by an external power supply. The oxide ions (O²-) formed in the reaction are incorporated into the electrolyte and traverse through the electrode into the anode (also called the oxygen electrode), where the ions are oxidized into molecular oxygen according to the reaction

O²- -> ¹/₂ O₂ + 2 e-

The formed oxygen gas is led out of the cell via gas channels. It is important to note that as long as pure CO2 (or a mixture of CO and CO2) is fed to the fuel electrode, the formed product will be free of H2 and H2O.

Composites of metallic Ni and either CGO or YSZ are the most commonly used materials in SOEC fuel electrodes. Typical oxygen electrode materials for SOECs include doped perovskites of lanthanides and transition metals, such as Sr-doped LaMnOs (LSM), Sr-doped La(Fe,Co)C>3 (LSCF), Sr-doped SmCoOs (SSC) and many others.

In molten carbonate electrolysis cells (MCECs), the electrolyte is a carbonate melt. A combination of molten U2O/U2CO3 electrolyte, a titanium cathode and a graphite anode has been shown to give promising results. In this material system, carbonate ions are reduced to CO and oxide ions at the cathode (COs²' + 2 e- -> CO + 2 O²-), while oxide ions are oxidized to gaseous oxygen at the anode (O²- ->

O2 + 2 e-).

In effect, U2CO3 is electrochemically converted into U2O on the cathode, thereby increasing the U2O/U2CO3 ratio in the melt. As the oxide content in the electrolyte increases, new CO2 can chemically incorporated into the mixture. The ratio of Li2O/Li2CO3 in the electrolyte is thereby a function of both by the applied current density and the concentration of CO2 above the melt. A key advantage of MCECs is that the CO2 feed and the CO and O2 products do not mix, allowing pure gases to be extracted from the cell. Additionally, the method is only mildly affected by SO2- content in the feed gas, and can potentially use dilute and humid CO2 streams, suggesting that industrial flue gases may be used as feed.

In low-temperature electrolysis cells, CO2 reduction is carried out in aqueous solutions. The electrolytes can either be solid ion-selective membranes (e.g. Nation, Sustainion), aqueous solutions (e.g. KHCO3), or combinations thereof. Most of the low temperature electrolysis cells today operate in alkaline or pH-neutral conditions.

Most of the electrode development work on electrochemical CO2 reduction has been carried out using a cell configuration where both electrolyzer electrodes are immersed in electrolyte solutions (the anolyte and catholyte, respectively). Such an electrode configuration is referred to as the H-celL On the anode of such a cell, oxygen evolution proceeds according to either of the two reactions:

2 OH- -> ¹/₂ O₂ + H₂O + 2 e-

H₂O -> ¹/₂ O₂ + 2 H⁺ + 2 e-

On the cathode, CO2 is electrochemically reduced to CO:

CO₂ + H₂O + 2 e- -> CO + 2 OH-

Commonly, CO production is accompanied by hydrogen evolution, which in alkaline media proceeds via reaction

2 H₂O + 2 e- -> 2 OH- + H₂

The delivery of gas-phase CO2 to the cathode and the use of gas-diffusion electrodes present means of overcoming mass transport limitations in low-temperature electrolysis systems. In some designs, gas-diffusion electrodes are employed in both electrodes. I rC>2 is used almost exclusively as the catalyst material on the anode side of aqueous electrolysis cells. Cathode materials for the production of CO typically include Ag and Au, with catalyst supports shown to play an important role for activity, selectivity, and stability.

The electrical power necessary for the electrochemical reduction of CO2 to CO is generated at least in part from non-fossil, renewable resources. In other words, part of the electrical power can still be produced from fossil fuels, preferably from natural gas, since combustion of natural gas causes much lower carbon dioxide emission per Megajoule of electrical energy produced than combustion of coal. However, the portion of electrical energy produced from fossil fuels should be as low as possible, preferably < 50%, preferably < 30%, most preferably < 20%.

The electrical power from non-fossil resources used in carbon dioxide according to the invention can be generated by nuclear energy. Nuclear energy is considered renewable by the European Commission, as long as certain preconditions (i. a. safe long-term storage of nuclear waste) are fulfilled.

The electrical power from non-fossil resources used in carbon dioxide according to the invention is preferably generated from wind power, solar energy, biomass, hydropower and geothermal energy.

In some other preferred embodiments, the carbon dioxide that is provided in step (b) is captured from ambient air.

Carbon dioxide captured from ambient air can likewise be electrochemically reduced by the methods described above before being used in step (b) or in step (c1 ). In step (b), carbon monoxide is converted to C2 products in an electrochemical reactor. Besides ethylene, ethanol, acetic acid, oxygen and hydrogen can be formed as products, according to equation (2) to (5):

2 CO + 2 H₂O C2H4 + 2 O₂ (2)

2 CO + 3 H₂O - CH3CH2OH + 2 O₂ (3)

2 CO + 2 H₂O - CH3COOH + O₂ (4)

2 H₂O - 2 H₂ + O₂ (5)

The process is described by Kluh et al. (2023), Front. Energy Res. 11 :1129076, with further references.

In certain embodiments, a gas mixture containing carbon monoxide, hydrogen and carbon dioxide is reacted in step (c1 ) in the presence of a catalyst to give methanol.

The current world-scale technology for methanol synthesis is mostly based on the application of Cu/ZnO/AI2O3 (CZA) catalysts in either multi-tube reactors with boiling water as the cooling fluid, normally called isothermal reactors (e.g., the Lurgi process, the Linde process), or adiabatic reactors with intermediate cold syngas quenching, generally named quench reactors (e.g., ICI and the Casale process, the Haldor Topsoe process). Less common but also industrially applied are the adiabatic reactors with intermediate cooling (e.g., the Kellogg process, the Toyo process). Normally, temperatures between 200 and 300 ° C and pressures between 50 and 100 bar are applied. See Bozzano, G.; Manenti, F. Efficient methanol synthesis: Perspectives, technologies and optimization strategies. Prog. Energy Combust. Sci. 2016, 56, 71-105; and Ott, J.; Gronemann, V.; Pontzen, F.; Fiedler, E.; Grossmann, G.; Kersebohm, D.B.; Weiss, G.; Witte, C. Methanol. In Ullmann’s Encyclopedia of Industrial Chemistry; Wiley: New York, NY, USA, 2012.

In certain other embodiments, hydrogen and carbon dioxide are reacted in step (c1 ) in the presence of a catalyst to form methanol.

An overview of suitable catalyst systems is given by https://link.springer.com/arti- cle/10.1007/s40974-020-00156-4" \l "auth-Kristian-Stangeland, Hailong Li & Zhixin Yu, Energy, Ecology and Environment volume 5, pages 272-285 (2020). Multi-component catalyst systems are required for this process. The interaction between components is essential for high activity and selectivity of CO2-to-methanol catalysts. This has been demonstrated by numerous catalyst systems comprised of various metals (i.e., Cu, Pd, Ni) and metal oxides (i.e., ZnO, ZrO2, ln₂O₃). These complex systems can contain a mixture of metallic, alloy, and metal oxide phases. The most promising catalyst systems for large-scale industrial processes are currently Cu-based and In-based catalysts due to their superior catalytic performance.

A process for the CC>2-to-methanol synthesis can be carried out, for example, by the method known from DE-A-42 20 865, which produces methanol under the influence of silent electrical discharges. Alternatively, methanol synthesis can also be carried out in a thermal reactor under pressure and elevated temperature and in the presence of a copper-based catalyst, as described in DE 43 32 789 A1 and DE 19739773 A1 .

Recently a high selective catalysts ln2O3/ZrO2 was described for industrial relevant conditions. A typical range of industrially relevant conditions for the hydrogenation of CO2 to methanol are T = 200 - 300°C, p = 10 - 50 MPa, and gas hourly space velocity (GHSV) of 16 000 - 48000 h’¹ (Angew. Chem. Int. Ed. 2016, 55, 6261 -6265).

The reaction of hydrogen and carbon dioxide in step (c1) can be carried out in the presence of a copper-zinc-alumina catalyst. If copper-zinc-alumina catalysts are employed, the preferred temperature is in the range of from 150 to 300°C, preferably 175 to 300°C and the preferred pressure is in the range of from 10 to 150 bar (abs).

In step (c2), methanol from step (c1) is reacted to yield ethylene.

C2-C4-olefins can be manufactures by a methanol to olefin-process (MTO-process) from methanol. A preferred process for the manufacture of C2-C4-olefins from methanol and optionally ethanol comprises the steps:

A) feeding a methanol and optionally ethanol comprising feed stream A in a dimethyl ether fixed bed reactor and catalytic conversion of methanol to give dimethyl ether, wherein a product stream A1 comprising dimethyl ether, methanol, water vapor and optionally ethanol and ethylene is obtained;

B) mixing of the stream A1 with at last one hydrocarbon recycle stream R comprising C2-C6- hydrocarbons and catalytic conversion in an olefin fixed bed reactor to yield a raw product stream B comprising C2-C4-olefines, Cs-Ce-hydrocarbons und C7⁺-hydrocarbons;

C) cooling of the raw product stream B, wherein a hydrocarbon raw product stream C is obtained;

D) separating the hydrocarbon raw product stream C in a propylene containing value product stream, optionally an ethylene containing value product stream, a butene containing product stream, at least a Cs-Ce-hydrocarbon containing recycle stream and at least one Ce⁺-hydrocar- bons containing side product stream;

E) recycling of a part of the C2-C4-olefins and at least a part of the Cs-Ce-hydrocarbons as one or more hydrocarbon recycle streams R in step B);

F) recovering a propylene containing value product stream, an ethylene containing value product stream and optionally a butene containing value product stream;

G) discharging the Ce⁺-hydrocarbons containing side product stream.

In an alternative process, ethanol is produced from biomass by fermentation in step (d1 ), and ethanol is dehydrogenated to give ethylene in step (d2).

Ethylene production by bioethanol dehydration, using forest or agro-industrial waste is a sustainable alternative to oil-based one. Gasification of lignocellulosic biomass is a thermochemical route to produce bioethanol. Using chemical catalysts, the synthesis gas generates ethanol together with a mixture of alcohols. Another option to produce ethanol is the fermentation of the synthesis gas.

Bioconversion of wood waste to bio-ethylene is described in Mendieta, C. M., Cardozo, R. E., Felissia, F. E., Clauser, N. M., Vallejos, M. E., and Area, M. C. (2021 ). "Bioconversion of wood waste to bio-ethylene: A review," BioResources, 16(2), 4411-4437, with further references:

The ethylene production process consists of pretreatment, enzymatic hydrolysis, fermentation, recovery by distillation, and dehydration. The conditions and type of pretreatment depend exclusively on the chemical composition of the feedstock, which has a significant influence on the enzymatic hydrolysis and following processes.

Before the production of bioethanol, it is critical to pretreat the lignocellulosic biomass. An efficient pretreatment should apply to various substrates using cheap and easily recoverable reagents, with low energy consumption, and low investment and maintenance costs, among other features. The reactions must favor the formation of sugars, avoid their loss by degradation, and limit the production of inhibitory products. The pretreatment process extracts the lignin and hemicellulose in order to increase the porosity of the material to improve cellulose accessibility to the enzymatic attack. The pretreatment process should also limit the degradation of other carbohydrates and, in the saccharification stage, avoid the formation of inhibitor products.

The cellulose that is obtained from the pretreatment can be transformed into ethanol in two steps. Initially, cellulose is depolymerized to glucose by hydrolysis, and then these sugars are fermented into ethanol. The common pretreatment strategies are separate hydrolysis and fermentation (SHF) and simultaneous hydrolysis and fermentation (SSF). In the SHF process, cellulose hydrolysis and glucose fermentation are accomplished separately, which allows each stage to occur at its optimum conditions. On the other hand, the SSF process requires only one reactor for hydrolysis and fermentation. The SSF process is the most feasible and cost-effective alternative to produce bioethanol considering the low generation of inhibitory products and the utilization of only one fermenter in the whole process, which reduces the investment costs.

In the petrochemical industry, dehydration of ethanol to ethylene is a usual process. Nevertheless, for the ethylene process, ethanol purity must be higher than 95 wt%. Unlike ethanol, bioethanol comes from a fermentation broth that contains microorganisms, nutrients, and reaction by-products. The obtained bioethanol must be purified by removing contaminants and additional water. For this, several methods combine distillation, adsorption, extraction, among others, such as separation by membrane pervaporation, extractive distillation, or heteroazeotropic distillation, which have been exhaustively described in the literature. For ethylene production, in particular, Very High Gravity (VHG) fermentation emerges as an interesting option to explore and optimize when using SHF, since it can improve fermentation performance and purify ethanol simultaneously. Considering that this is a stage of great energy consumption, it is one of the steps that require optimization to contribute to the economic viability of bio-ethylene.

Ethylene is formed by the highly endothermic intramolecular dehydration of ethanol, which eliminates one oxygen atom and two hydrogen atoms. The formation of ethylene occurs at temperatures between 350 °C and 500 °C. At low temperatures, intermolecular dehydration also produces diethyl ether, which can be sequentially dehydrated to form ethylene. For the dehydration reaction, catalysts are necessary. Alumina or alumina in conjunction with metal oxides as promoters, silica, clay, several metal oxides, phosphorus oxides, phosphates, molybdates, sulfuric acid, and zeolites, among others, have been studied as catalysts. Industrially, phosphoric acid and alumina have been used on a small-scale and they have been used to increase the ethylene selectivity. Alumina is the most commonly used catalyst for the dehydration of bioethanol, as it can withstand temperatures above 450 °C, but it deactivates quickly at temperatures below 300 °C. Zeolites are used to carry out the reaction because they do not require high temperatures, but at low-temperatures coke formation can produce the catalyst deactivation.

The effluents contain a high amount of water from the dehydration reaction, as well as ethanol feedstock and heat-carrying fluid. Water can be separated in a quench tower, and the residual ethanol and water-soluble oxygenates can be re-heated and distilled. The residual ethanol and diethyl ether (low water solubility) can be recovered and recycled to the feedstock, while the C2H4O can be burned in the furnace. The gas from the top of the quench tower primarily contains ethylene (90% to 99.5%), hydrocarbons, H2, CO, CO2, and oxygenates. The ethylene can be washed with cool water in a second tower removes the oxygenates, and caustic washing can remove CO2 and acids.

In an alternative step (e), ethylene is directly produced from biomass by fermentation. Suitable fermentation processes are described in I. Pirkov, E. Albers, J. Norbeck, C. Larsson, Ethylene production by metabolic engineering of the yeast Saccharomyces cerevisiae, Metabolic Engineering, Volume 10, Issue 5, 2008, Pages 276-280; and Johansson, N., Quehl, P., Norbeck, J. et aL, Identification of factors for improved ethylene production via the ethylene forming enzyme in chemostat cultures of Saccharomyces cerevisiae. Microb Cell Fact 12, 89 (2013).

Acetic acid can be produced by carbonylation of methanol in step (f). The process involves iodomethane as an intermediate, and occurs in three steps. A catalyst, metal carbonyl, is needed for the carbonylation (step 2).

Acetic acid can alternatively be produced by

(g1 ) reacting part of the ethylene from steps (b), (c1 )/(c2), (d2) or (e) with oxygen and water to give acetaldehyde;

(g2) reacting acetaldehyde from step (g1 ) with oxygen to give acetic acid. The Wacker process or the Wacker-Hoechst process refers to the oxidation of ethylene to acetaldehyde in the presence of palladi um(l I) chloride as the catalyst.

The net reaction can be described as follows:

[PdCk]²’ + C₂H₄ + H₂O - CH3CHO + Pd + 2 HCI + 2 Cl-

This conversion is followed by reactions that regenerate the Pd(ll) catalyst: Pd + 2 CuCI₂ + 2 Cl - - [PdCk]²’ + 2 CuCI 2 CuCI + 1/2 O₂ + 2 HCI - 2 CuCI₂ + H₂O

Two routes are commercialized for the production of acetaldehyde: one-stage processes and two-stage processes.

In the one-stage process, ethene and oxygen are passed co-currently in a reaction tower at about 130°C and 400 kPa. The catalyst is an aqueous solution of PdCh and CuCh. The acetaldehyde is purified by extractive distillation followed by fractional distillation. Extractive distillation with water removes the lights ends having lower boiling points than acetaldehyde (chloromethane, chloroethane, and carbon dioxide) at the top, while water and higher-boiling byproducts, such as acetic acid, crotonaldehyde or chlorinated acetaldehydes, are withdrawn together with acetaldehyde at the bottom.

In both one- and two-stage processes the acetaldehyde yield is about 95%.

For further details, reference can be made to Marc Eckert, Gerald Fleischmann, Reinhard Jira, Hermann M. Bolt, Klaus Golka, Acetaldehyd, in Ullmann's Encyclopedia of Industrial Chemistry- 7th ed, Vol.1 , Kap. 4.3, p. 197. Acetaldehyde can be oxidized with pure oxygen or with air in the presence of a redox catalyst to give acetic acid in step (e2). The oxidation can be carried out in the presence of cobalt or manganese acetate in acetic acid as solvent at temperatures of 50 - 70°C in bubble columns (Hoechst process).

Acetic acid can also be produced in step (h) by oxidative fermentation of ethanol from step (d1). In a further alternative step (i), acetic acid can be produced from biomass by biomass pyrolysis.

Suitable processes for the production of acetic acid by biomass pyrolysis is described for instance in US2012/0172622 A1 . Methods for producing acetic acid include pyrolyzing biomass, in general a lignocellulosic material such as wood, corn stover, and/or switch grass, to provide a pyrolysis reactor effluent. The biomass subjected to pyrolysis in an oxygen depleted environment, for example using Rapid Thermal Processing (RTP), can be any plant material, or mixture of plant materials. The methods also comprise separating at least a portion of the pyrolysis reactor effluent in a first separation stage (e.g., a quenching tower that includes quench liquid recycle) to provide first stage overhead and first stage bottoms products. The methods further comprise recovering the acetic acid from the first stage overhead product or the first stage bottoms product. Recovery can involve various processing steps, some or all of which may enrich a recovered intermediate or end product (e.g., a purified acetic acid product) in acetic acid and deplete the recovered product in other compounds (e.g., water and other oxygenates) produced from pyrolysis.

According to the invention, vinyl acetate is made by reacting (I) ethylene with (II) acetic acid, both being produced starting form biomass or from CO2 captured from the atmosphere.

Most of the vinyl acetate is produced via the vapor-phase reaction of ethylene and acetic acid over a noble-metal catalyst, usually palladium. The reaction is typically carried out at 150 - 250°C, preferably 175 - 200°C and 5 - 9 bar pressure. The reaction is usually performed in the gas phase in a fixed bed tubular reactor using a supported catalyst. The amount of oxygen in the combined feed is within the range of 5 to 15 mol %. Preferably, the amount of acetic acid in the combined feed is within the range of 10 to 25 mol %. Preferably, the amount of ethylene in the combined feed is within the range of 65 to 80 mol %. Suitable catalysts include those known to the vinyl acetate industry. Preferably, the catalyst is a palladium-gold catalyst. Methods for preparing palladium-gold catalysts are known. For instance, U.S. Pat. No. 6,022,823 teaches how to prepare a palladium-gold catalyst which has high activity and selectivity. Preferably, the palladium-gold catalyst is supported on an inorganic oxide, such as alumina, silica, titania, and the like, and mixtures thereof.

The invention further concerns vinyl acetate with a natural abundance of carbon-14, obtainable by the processes as described herein. The vinyl acetate according can have a ¹³C-content corresponding to a 5¹³C value of from -10 to -2.5 %o, if the carbon dioxide of step (b) is captured from ambient air.

Vinyl acetate can be polymerized to polyvinyl acetate. Polyvinyl acetate is finally hydrolyzed to polyvinyl alcohol, which is biodegradable. Biodegradation of polyvinyl alcohol yields H2O and CO2, thereby closing the loop for a CC>2-neutral life cycle, if carbon oxides are prepared from biomass or CO2 is taken from the atmosphere in step (a).

Polyvinyl alcohol is recognised as one of the very few vinyl polymers soluble in water that is susceptible to ultimate biodegradation in the presence of suitably acclimated microorganisms. Polyvinyl alcohol is nontoxic but is expected to biodegrade within 90 d under aquatic conditions, see Dominic Byrne et aL, Biodegradability of polyvinyl alcohol based film used for liquid detergent capsules, Tenside Surf. Det. 58 (2021 ) 2; E. Chiellini et aL, Prog. Polym. Sci. 28 (2003), pp. 963-1014.

For the copolymerization of bio-based vinyl acetate several monomer are of relevance, mostly preferred monomers are selected from other vinyl ester, e.g. vinyl propionate and vinyl laurate, vinyl pivalate, vinyl ester of branched alkyl carbonic acids. Also of importance and preferred are maleic acid esters, fumaric esters, allyl ethers, vinyl ethers such as vinyl ethylether, vinyl chloride, cyclic vinyl amides such as vinyl pyrrolidone. It is known that also ethylene and styrene can be copolymerized. Acrylic acid esters and methacrylic esters such as methacryl methylester can also be copolymerized efficiently if a third monomer of the monomers mentioned above is present.

It is also known that vinyl acetate is grafted efficiently on polyethers such as polyethylene glycol and other polyalkylene glycols, e.g., polyethylene oxide -block-polypropylene oxide or even randomized copolymers of alkylene oxides. In that mode block copolymers of polyvinyl acetate with the mentioned poly ethers are available. These block copolymers of polyvinyl acetate are useful as amphiphilic surface-active polymers in laundry and as emulsifier for formulations with agricultural actives.

Grafting of vinyl acetate occurs also efficiently on polysaccharides and other suitable polyhydroxy polymers e.g., polyvinyl alcohol, resulting in the formation of biodegradable block-copolymers. Copolymers and terpolymers with combined vinyl acetate/vinyl alcohol monomer units are available through partial hydrolysis of the vinyl acetate copolymer.

The present invention also relates to polymers or copolymers of vinyl acetate as well as polymer dispersions comprising vinyl acetate, wherein the vinyl acetate has a natural abundance of car- bon-14. Polymer dispersions and specifically polymer emulsions comprising vinyl acetate are widely known and applied in many areas of application, as for example described in:

EP1924633 discloses a process and the dispersion consisting of vinyl acetate and 0.05-5.0% by weight of methacrylic acid, which is obtained by free-radically initiated emulsion polymerization. As protective colloid a water-soluble polymer and sodium dodecyl sulfate was used as the emulsifier. Target applications are film coatings in pharmacological and cosmetic applications, delayed release of active ingredients.

DE102004031970 describes a process and solution polymerization in methanol consisting of vinyl monomers such as vinyl acetate and ethylenically unsaturated polyethers such as allyl polyethers. Also claimed are the esters of polyethers corresponding to methacrylic acid with the end groups OH and OR, where R can be alkyl with C1-C40. Target application for the production of plasticized vinyl acetate solid resins.

JP2005089540 describes an emulsion process to produce a vinyl acetate polymer resin in the presence of polymerizable polyethylene glycol derivatives. The use of cellulose-based protective colloids is reported.

JP06093007 discloses a polyvinyl acetate-based emulsion produced by subjecting 50-100% by weight of vinyl acetate and 0-50% by weight of one or more comonomers (e.g. acrylic acid ester) to an emulsion polymerisation using a water-soluble modified starch as a protective colloid. Target application for producing films with good low temperature properties, high hardness. US4708999 describes a solution polymerization with vinyl acetate and C1 to C12 alkyl polyethylene glycol methacrylic acid ester (polyethylene glycol with 25 ethylene oxide) in methanol. The product is then subjected to methanolysis.

JP5915541 I discloses a copolymer of an oxyalkylene group-containing unsaturated monomer with vinyl acetate in a solution polymerization in alcohol. The copolymerization of vinyl acetate comprises an oxyalkylene group-containing unsaturated monomer (such as methacrylic acid). The number of oxyalkylene groups ranges from advantageously 1-50. The modified vinyl acetate resin, which is water-soluble even in the absence of alkali metal, is especially suitable for use in paste, adhesive or aqueous solution in paper processing or the like.

US3322703 relates to a copolymer consisting of vinyl acetate and an alkoxy polyalkylene glycol half ester of unsaturated dicarboxylic acids or/and vinyl acetate and an alkoxy polyalkylene glycol ester of unsaturated monocarboxylic acids and the method of preparation. Solution polymerization in methanol of vinyl acetate and methyoxpolyethylene glycol maleate was given as an example. A use is not claimed but described in the form of applications of gummed articles that can be moistened and form sticky films, for example for postage stamps.

A terpolymer consisting of vinyl alcohol, vinyl acetate and alkylpolyoxoethylene methacrylic acid ester is described in EP199358. The fabric protection includes at least 50% vinyl alcohol in the terpolymer. The use of the terpolymer as a barrier layer in thermoplastic processes for packaging articles.

PCT/EP2023/081697 describes aqueous polymer dispersions, which are suitable as opacifiers in liquid formulations, those aqueous polymer dispersions obtainable by radical emulsion polymerization in aqueous environment by polymerizing i) at least one vinyl ester, ii) least one (meth)acrylic acid ester, optionally further (meth)acrylic acid in minor amounts, the (meth)acrylic acid in the methacrylic acid ester being bonded via an ether-function to a polyalkylene oxide- derived-block-polymer of 2 to 40 alkylene oxides, and ill) optionally further polymerizable monomers, optionally in the presence of carboxyl-groups-containing compounds and non-carboxy- lated compounds, and c) at least one emulsifier selected from non-ionic and anionic surfactants. Such aqueous polymer dispersions were used preferably within cleaning compositions such as detergents, specifically as opacifiers.

The present invention also relates to the use of vinyl acetate having a natural abundance of car- bon-14 for determining the content of bio-based vinyl acetate or vinyl alcohol derived therefrom by hydrolysis in vinyl acetate or vinyl alcohol containing polymers and copolymers.

The present invention further relates to the use of vinyl acetate having a natural abundance of carbon-14 for determining the origin of decay products released during decomposition of vinyl acetate or vinyl alcohol containing polymers or copolymers.

Polymers and copolymers whose content of bio-based vinyl acetate or vinyl alcohol can be determined, or of which the origin of decay products released from the polymers and copolymers during decomposition can be determined include: polyvinyl acetate, polyvinyl alcohol, poly(vinyl acetate-co-vinyl alcohol); poly(vinyl acetate-co-vinyl alkyl ether), poly(vinyl acetate-co-allyl alkyl ether), poly(vinyl acetate-co-maleic acid derivatives), poly(vinyl acetate-co-acrylic acid derivatives), poly(vinyl acetate-co-methacrylic acid derivatives), poly(vinyl acetate-co-vinyl pyrrolidone) and their partially hydrolyzed derivatives (which are formally terpolymers);

- terpolymers of vinyl acetate, vinyl alcohol, and at least one further comonomer selected from vinyl laurate, vinyl versate, vinyl alkyl ethers, vinyl silyl ethers, vinyl pyrrolidone, vinyl caprolactone, maleic acid and maleic acid anhydrides and its derivative, e.g. methyl esters, Fumaric acid and fumaric acid derivatives, allyl alkyl ether, allyl alcohol esters, acrylic and methacrylic acid and derivatives thereof, e.g. amides and esters, keten derivatives such as cyclic ketene acetal monomers, and ethylene (the terpolymers can be obtained by the partial hydrolysis of the corresponding vinyl acetate copolymers); graft copolymers from vinyl acetate polymers, such as poly(vinyl acetate)-g-polyalkylene oxide, or poly(vinyl acetate)-g-polyglucane/polysaccharide derivative, and their derivatives obtained by hydrolysis or partial hydrolysis.

The carbon-14 carbon content in the (co)polymers or in the decay products can be determined using gas proportional counting, liquid scintillation counting, and accelerator mass spectrometry (AMS).

Alkoxylated compounds from ethylene oxide and propylene oxide

Alkoxylated compounds like polyalkylene glycols and compounds comprising alkylene glycol groups are used in various industrial fields and have high performance when used, for example, in home care products, cosmetic products, pharmaceutical products, food sector, building materials, lubricants like engine oils, bearing oils, gear oils, compressor oils, lubricating greases, heat transfer fluids, metalworking fluids and transmission fluids, antifoaming agents, softeners, rheology modifiers, emulsifiers, dispersing agents, thickeners, stabilizers, metal working fluids, agrochemicals like pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages and poly(urethane) applications.

A review concerning polyalkylene glycols is given in Chem. Rev. 2016, 116, 2170-2243. It is described therein that polyalkylene glycols are aliphatic polyethers which are generated by the ring-opening polymerization (ROP) of epoxide monomers, especially ethylene oxide (EO), propylene oxide (PO), and, to a lesser extent, butylene oxide (BO). The characteristic properties of polyether-based materials are due to their unique backbone, in particular its high flexibility leading to low glass transitions below -60 °C, and its hydrophilicity due to the C-O-C bond.

In the present application, the expressions “polyalkylene glycol” “polyethylene glycol”, “polypropylene glycol”, “polybutylene glycol” are used for the respective polymers or polymer blocks of any molecular weight.

The present invention further relates to a process for preparing alkoxylated compounds comprising i) 20 wt-% to <100 wt-% of ethylene oxide units and/or propylene oxide units, ii) 0 wt-% to 30 wt-% of at least one alkylene oxide unit different from ethylene oxide and propylene oxide units, iii) >0 wt-% to 80 wt-% of at least one starter unit having Zerewitinoff active hydrogen atoms, wherein the sum of the units mentioned under i), ii) and iii) is 100 wt-%, comprising the following steps:

(a*) reacting hydrogen with carbon dioxide to form methanol,

(b*) converting the methanol from step (a*) to ethene and/or propene,

(c*) reacting the ethene and/or propene from step (b*) with oxygen or an oxidizing agent to form ethylene oxide and/or propylene oxide, and

(d*) reacting the ethylene oxide and/or propylene oxide obtained in step (c*) and optionally the at least one alkylene oxide different from ethylene oxide and propylene oxide with the at least one starter unit having Zerewitinoff active hydrogen atoms in one or more steps to form the alkoxylated compound, wherein the carbon dioxide in step (a*) is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass.

The terms ethene and propene are the IUPAC names of compounds of the formulae CH2=CH2 and CH3CH=CH2, which are also known as ethylene and propylene.

The IUPAC name of the term ethylene oxide used in the present application is oxirane (C2H4O). Propylene oxide is in the meaning of the present application 1 ,2-propylene oxide. The IUPAC name of the term propylene oxide used in the present application is 2-methyloxirane (CsHeO). An alternative name is 1 ,2-epoxypropane.

An ethylene oxide unit is the reacted form of ethylene oxide in the alkoxylated compound, a propylene oxide unit is the reacted form of propylene oxide in the alkoxylated compound and an alkylene oxide unit is the reacted form of alkylene oxide in the alkoxylated compound.

The term “alkoxylated compound”, as used in the present application, covers alkoxylated compounds composed of at least one ethylene oxide unit and/or propylene oxide unit and at least one starter unit having Zerewitinoff active hydrogen atoms.

In accordance with REACH (Article 3(5)) (REACH Regulation (EC) No 1907/2006 of the European Parliament and of the Council of 18 December 2006), a polymer is defined as a substance meeting the following criteria:

(a) Over 50 percent of the weight for that substance consists of polymer molecules (see definition below); and,

(b) The amount of polymer molecules presenting the same molecular weight must be less than 50 weight percent of the substance.

In the context of this definition:

• A "polymer molecule" is a molecule that contains a sequence of at least 3 monomer units, which are covalently bound to at least one other monomer unit or other reactant.

• A "monomer unit" means the reacted form of a monomer substance in a polymer (for the identification of the monomeric unit(s) in the chemical structure of the polymer the mechanism of polymer formation may, for instance, be taken into consideration).

• A "sequence" is a continuous string of monomer units within the molecule that are covalently bonded to one another and are uninterrupted by units other than monomer units. This continuous string of monomer units can possibly follow any network within the polymer structure.

• "Other reactant" refers to a molecule that can be linked to one or more sequences of monomer units but which cannot be regarded as a monomer under the relevant reaction conditions used for the polymer formation process.

The term “polymer”, as used herein, includes both homopolymers and copolymers. The “polymers” are linear or branched.

The biodegradability of the alkoxylated compounds according to the present invention is determined based on the currently valid OECD guidelines.

The OECD in their guidelines distinguish 6 forms of biodegradation, as follows (OECD, 1981b, 1991 , 1992a, 1992b, 2001 , 2002, 2004a, 2008) (see https://www.ecetoc.org/technical-report- 123/measured-partitioning-property-data/biodegradation/definitions-according-to-oecd/). (i) Ultimate biodegradation (mineralisation): The level of degradation achieved when the test compound is totally utilised by micro-organisms resulting in the production of carbon dioxide, water, mineral salts and new microbial cellular constituents (biomass).

(ii) Primary biodegradation (biotransformation): The alteration in the chemical structure of a substance, brought about by biological action, resulting in the loss of a specific property of that substance.

(iii) Readily biodegradable: An arbitrary classification of chemicals which have passed certain specified screening tests for ultimate biodegradability; these tests are so stringent that it is assumed that such compounds will rapidly and completely biodegrade in aquatic environments under aerobic conditions.

(iv) Inherent biodegradable: A classification of chemicals for which there is unequivocal evidence of biodegradation (primary or ultimate) in any test of biodegradability.

(v) Half-life (t0.5): The time taken for 50% transformation of a test substance when the transformation can be described by first-order kinetics; it is independent of the initial concentration.

(vi) Disappearance time 50 (DT50): The time within which the initial concentration of the test substance is reduced by 50 percent.

The alkoxylated compounds according to the present invention are generally tested regarding their ready biodegradability according to OECD 301 B.

Test No. 301 : Ready Biodegradability (https://www.oecd-ilibrary.org/environment/test-no-301- ready-biodegradability_9789264070349-en)

This Test Guideline describes six methods that permit the screening of chemicals for ready biodegradability in an aerobic aqueous medium. The methods are: the DOC Die-Away (301 A), the CO2 Evolution (Modified Sturm Test) (301 B), the MITI (I) (Ministry of International Trade and Industry, Japan) (301 C), the Closed Bottle (301 D), the Modified OECD Screening (301 E) and the Manometric Respirometry (301 F).

A solution, or suspension, of the test substance, well determined/described, in a mineral medium is inoculated and incubated under aerobic conditions in the dark or in diffuse light. The running parallel blanks with inoculum but without test substance permits to determined the endogenous activity of the inoculum. A reference compound (aniline, sodium acetate or sodium benzoate) is run in parallel to check the operation of the procedures. Normally, the test lasts for 28 days. At least two flasks or vessels containing the test substance plus inoculum, and at least two flasks or vessels containing inoculum only should be used; single vessels are sufficient for the reference compound. In general, degradation is followed by the determination of parameters such as DOC, CO2 production and oxygen uptake. The pass levels for ready biodegradability are 70% removal of DOC and 60% of ThOD or ThCO2 production for respirometric methods. These pass values have to be reached in a 10-d window within the 28-d period of the test.

The ethylene glycol and propylene glycol part (i.e. the alkylene oxide units) in alkoxylated compounds has an important impact on the product carbon footprint of the alkoxylated compounds. The object is therefore achieved by ethylene glycol and/or propylene glycol based compounds (called alkoxylated compounds in the present invention, since beside ethylene glycol and propylene glycol one or more further alkylene glycols may be present), wherein the ethylene oxide and/or the propylene oxide employed in the synthesis of the alkoxylated compounds are prepared by the specific process of the present invention.

The process for preparing alkoxylated compounds, especially the precursors ethylene oxide and propylene oxide, is energy demanding and many of steps (a*) to (d*) of the process for preparing the alkoxylated compounds can be carried out by a number of alternative methods. The inventors found a process for the preparation of alkoxylated compounds, wherein each step is optimized or at least prepared for obtaining alkoxylated compounds having a low carbon footprint.

It was further found by the inventors that alkoxylated compounds having an especially low PCF are obtained when the hydrogen used in step (a*) for the preparation of methanol is obtained at least in part by water splitting, preferably electrolysis, based on electrical power generated at least in part from non-fossil resources.

Preferably, the hydrogen in step (a*) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy generated at least in part from non-fossil resources.

More preferably, in the process for preparing the alkoxylated compounds in step (a*) and in one or two further of steps (b*), (c*) and (d*) energy in form of heating energy and/or electrical power is used, and the energy used is generated at least in part from non-fossil resources. Most preferably, in all steps (a*) to (d*) energy in form of heating energy and/or electrical power is used, and the energy used in steps (a*) to (d*) is generated at least in part from non-fossil resources.

More preferably, in the process for preparing ethylene oxide or propylene oxide in step (a*) and in one or both further of steps (b*) and (c*) energy in form of heating energy and/or electrical power is used, and the energy used is generated at least in part from non-fossil resources. Most preferably, in all steps (a*) to (c*) energy in form of heating energy and/or electrical power is used, and the energy used in steps (a*) to (c*) is generated at least in part from non-fossil resources.

Most preferably, in all steps (a*) to (d*) energy in form of heating energy and/or electrical power is used, and the energy used in steps (a*) to (d*) is generated at least in part from non-fossil resources.

The term “at least in part from non-fossil resources” means that part of the energy can still be produced from fossil fuels, preferably from natural gas, since combustion of natural gas causes much lower carbon dioxide emission per Megajoule of energy produced than combustion of coal. However, the portion of energy produced from fossil fuels should be as low as possible, preferably < 50%, more preferably < 30%, most preferably < 20%, further most preferably < 10% of the energy in step (a*), preferably in step (a*) and in one or two further of steps (b*), (c*) and (d*), more preferably in all steps (a*) to (d*) is generated from fossil resources.

Further preferably, at least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90% and most preferably 100% of the total required energy input used in step (a*), preferably in step (a*) and in one or two further of steps (b*), (c*) and (d*), more preferably in all steps (a*) to (d*) is generated from non-fossil resources.

Most preferably, in the process for preparing the alkoxylated compounds the energy in step (a*), preferably in step (a*) and in one or two further of steps (b*), (c*) and (d*), more preferably in all steps (a*) to (d*) is generated exclusively from non-fossil resources.

Most preferably, in the process for preparing ethylene oxide or propylene oxide the energy in step (a*), preferably in step (a*) and in one or both further of steps (b*) and (c*), more preferably in all steps (a*) to (c*) is generated exclusively from non-fossil resources.

In a further preferred embodiment, at least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90% and most preferably 100% of the total required energy input used in the process of the present invention is generated from non-fossil resources.

Generally, the energy used in steps (a*), (b*), (c*) and (d*) is used in form of heating energy and/or electrical power.

The energy generated from non-fossil resources is preferably selected from the group consisting of solar energy (thermal, photovoltaic and concentrated), wind power, hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, heat captured by heat pumps, bioenergy (biofuel, biomass), the renewable part of waste, nuclear power and mixtures thereof.

The types of energy resources mentioned above are generally known by a person skilled in the art and detailed above.

Step (a*)

Step (a) concerns reacting hydrogen with carbon dioxide to form methanol. It is mandatory in the process of the present invention that the carbon dioxide in step (a*) is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass. By the inventive process alkoxylated compounds and ethylene oxide or propylene oxide, respectively, are provided having a low cradle to grave (i.e. including scope 3 downstream (for details: see above)) product carbon footprint (PCF) and the alkoxylated compounds generally having at the same time a good biodegradability.

The term “at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass” means that part of the carbon dioxide can still be obtained from other sources. For example, carbon dioxide is obtained technically by burning coke with excess air or as a by-product of lime burning and subsequent purification and natural gas sources (mineral water) are also used for extraction. However, the portion of carbon dioxide obtained from other sources than from capturing from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass should be as low as possible in the process of the present invention, preferably < 50%, preferably < 30%, most preferably < 20%, further most preferably < 10%. In one most preferred embodiment, the carbon dioxide is exclusively obtained from capturing from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass.

All available capture technologies may be used.

Further preferably, at least 50%, preferably at least 70%, more preferably at least 80%, further more preferably at least 90% and most preferably 100% of the total required carbon dioxide used in step (a*) in the process of the present invention is captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass.

Step (a*) generally corresponds to step (c) of the process for making vinyl acetate mentioned above. Therefore, the process conditions and descriptions mentioned for step (c) also apply to step (a*) as far as they are applicable to step (a*).

By performing step (a*), methanol is formed, CH3OH, by reacting carbon dioxide which is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from fermentation processes from waste or biomass with hydrogen.

Preparation (generation) of hydrogen:

The hydrogen in step (a*) may generally be obtained by any process known in the art. Hydrogen can be produced using a number of different processes. Thermochemical processes use heat and chemical reactions to release hydrogen from organic materials, such as fossil fuels and biomass, or from materials like water. Water (H2O) can also be split into hydrogen (H2) and oxygen (O2) using electrolysis or solar energy. Microorganisms such as bacteria and algae can produce hydrogen through biological processes. Said processes are known in the art (see for example https://en.wikipedia.org/wiki/Hydrogen_production and https://www.en- ergy.gov/eere/fuelcells/hydrogen-production-processes).

As of 2020, the majority of hydrogen (-95%) is produced from fossil fuels by steam reforming of natural gas and other light hydrocarbons, partial oxidation of heavier hydrocarbons, and coal gasification.

Preferably, the hydrogen in step (a*) is obtained using energy generated at least in part from non-fossil resources.

More preferably, the hydrogen in step (a*) is obtained at least in part by water splitting, preferably by electrolysis. Most preferably, the water splitting, preferably the electrolysis, using energy generated at least in part from non-fossil resources.

The term “at least in part from non-fossil resources” is detailed above.

The term “at least in part by water splitting” means that part of the hydrogen can still be produced by other processes, generally by steam reforming of natural gas and/or other light hydrocarbons, partial oxidation of heavier hydrocarbons, and coal gasification, preferably by steam reforming of natural gas and/or other light hydrocarbons. However, the portion of hydrogen in step (a*) produced by other methods than by water splitting should be as low as possible.

Preferably, in step (a*) of the process of the present invention < 50%, preferably < 30%, most preferably < 20%, further most preferably < 10% of the hydrogen is produced by other methods than by water splitting. In one embodiment, the hydrogen in step (a*) is produced exclusively by water splitting, preferably by electrolysis.

The hydrogen used in step (a*) in the process of the present invention, which is not obtained by water splitting, preferably by electrolysis, using energy generated at least in part from non-fossil resources, may generally be obtained by any process known in the art using any suitable energy, i.e. said hydrogen may be of any color mentioned above. In one embodiment, the hydrogen which is not obtained by water splitting, preferably by electrolysis, using energy generated at least in part from non-fossil resources is blue hydrogen obtained by steam methane reforming (SMR) with carbon capture and storage (CCS), i.e. a process used to produce hydrogen gas from natural gas while capturing and storing the resulting carbon dioxide emissions.

The hydrogen used in step (a*) in the process of the present invention, which is obtained by water splitting, preferably by electrolysis, but using energy generated from fossil resources, may generally obtained by using any energy generated from fossil resources known in the art. A preferred fossil resource is natural gas, since combustion of natural gas causes much lower carbon dioxide emission per Megajoule of energy produced than combustion of fer example coal. However, the portion of energy produced from fossil fuels should be as low as possible in the pro- cess of the present invention. Most preferably, in the case that the hydrogen in step (a*) is obtained by water splitting, preferably by electrolysis, the energy is fully generated from non-fossil resources.

Water splitting is an environmentally friendly method for production of hydrogen because it uses renewable H2O and produces only pure oxygen as by-product. The water splitting can generally performed by known processes like electrolysis; photocatalytic water splitting, also called photoelectrochemical (PEC) water splitting; chemically assisted electrolysis, e.g. carbon/hydrocarbon assisted water electrolysis (CAWE); radiolysis; ultrasound; thermolysis, especially via solar energy, e.g involving using solar concentrators to directly collect solar energy to heat water; pyrolysis on biomass; nuclear-assisted thermolysis, e.g in a high-temperature gas-cooled reactor (HTGR); thermochemical cycle combining solely heat sources (thermo) with chemical reactions to split water into its hydrogen and oxygen components, e.g the sulfur-iodine cycle (S-l cycle); ferrosilicon method; photobiological water splitting and mixtures thereof.

Generally, any water source can be used in the water splitting.

Preferably, the water splitting is performed by electrolysis and/or photocatalytic water splitting, more preferably by electrolysis.

In photocatalytic (photoelectrochemical (PEC)) hydrogen is produced from water using sunlight and one or more photocatalysts, in general specialized semiconductors called photoelectrochemical materials, which use light energy to directly dissociate water molecules into hydrogen and oxygen.

The photocatalysts (semiconductor materials) used in the photocatalytic (PEC) process are similar to those used in photovoltaic solar electricity generation, but for photocatalytic (PEC) applications the photocatalyst (semiconductor) is generally immersed in a water-based electrolyte, where sunlight energizes the water-splitting process.

PEC reactors can for example be constructed in panel form (similar to photovoltaic panels) as electrode systems or as slurry-based particle systems.

The most preferred water electrolysis generally utilizes as electrical power direct current (DC) at least in part from non-fossil energy resources.

Suitable water electrolysis processes are detailed above.

Most preferably, the hydrogen in step (a*) is obtained by water electrolysis, preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

Step (b*) In step (b*), methanol from step (a*) is converted to ethene and/or propene.

Preferably, the ethene and/or propene in step (b*) are obtained by a methanol-to-olefin process (MTO-process).

The methanol-to-olefin (MTO) process is a process in which olefins (especially ethene and propene) are produced from methanol.

The MTO process is generally known by a person skilled in the art.

Step (b*) generally corresponds to step (d) of the process for making vinyl acetate mentioned above. Therefore, the process conditions and descriptions mentioned for step (c) also apply to step (b*) as far as they are applicable to step (b*).

The ethene and/or propene in step (b*) are preferably obtained by a methanol-to-olefin process, preferably with a zeolite catalyst.

Step (c*)

In step (c*), ethene and/or propene from step (b*) is/are reacted with oxygen or an oxidizing agent to form ethylene oxide and/or propylene oxide.

Ethylene oxide:

Generally, ethylene oxide can be prepared by any process known in the art. Preferably, the ethylene oxide in step (c*) is obtained by oxidation of ethene (direct oxidation process).

The direct oxidation process is preferably performed in gas-phase, for example with oxygen or air, generally in the presence of a catalyst, preferably a silver catalyst, more preferably a silver catalyst supported on alumina.

The direct oxidation process of ethene is generally performed at a temperature of from 230 to 270°C. The pressure is preferably in the range of from 10 to 30 bar.

In a preferred embodiment, the direct oxidation process of ethene in step (c*) is performed by gas-phase selective ethene oxidation that is typically performed in fixed-bed tubular reactors with supported Ag/ AI2O3 catalysts at 230-270 °C and 10-30 bar.

Preferred catalysts for the process in direct oxidation process of ethene in step (c*) are silverbased catalysts like supported Re/Cs/Ag/AhOs catalysts that operate preferably in excess C2H4/O2; or alkaline-metal (Na, Cs)-promoted supported Ag/AhOs catalysts that operate preferably in excess O2/C2H4. Oxides of Mo and S have been found to also promote the supported Re/Cs/Ag/AhOs system for ethylene oxide (EO) formation. Therefore, the supported Re/Cs/Ag/AhOs system may additionally comprise oxides of Mo and/or S as promoters.

In addition, C2H4CI2 may also be added to deposit Cl on the catalyst, which acts as a promoter.

An example for a description can be found e.g. in “Ethylene Oxide” by Mia Monconduit and Karen Jobes, IHS Markit, Chemical Economics Handbook, 22 December 2020, p. 14 - 16.

Surprisingly, in the process according to the invention, a measurable increase in epoxide selectivity (correspondingly less by-products such as acetaldehyde and CO2 are formed and the catalyst runtime is longer), especially in the case of ethylene oxide, was found, compared with conventional processes using fossil-based raw materials.

Especially for the propylene oxide (see below) (HPPO process) it was found, that the reliability of the catalyst runtime is significantly improved. Higher run reliability has the advantage of improved planning-efficiency in industrial production practice, especially for a process with a relatively high frequency for catalyst regeneration-cycles such as HPPO.

Propylene oxide:

Generally, propylene oxide can be prepared by any process known in the art. Suitable processes for the preparation of propylene oxide are mentioned above. Preferably, propylene oxide in step (c*) is obtained by oxidation of propene with hydrogen peroxide as an oxidizing agent, generally in the presence of a catalyst, preferably a zeolite catalyst, more preferably in the presence of Titansilikalit-1 (TS-1 ) (HPPO process).

The HPPO process is generally carried out at temperatures below 90°C and pressures below 35 bar. The process may be carried out in single or multi reactors system, e.g. in a tubular reactor, e.g. in a fixed bed or trickle bed.

The HPPO process as well as other industrially relevant processes are for example described in M. Di Serio at aL, Ind. Eng. Chem. Res. 2013, 52, 1168-1178.

The hydrogen peroxide used as an oxidizing agent in the HPPO process which is preferably carried out for the preparation of propylene oxide according to the present invention may be obtained by any known process. Generally, the hydrogen peroxide is obtained by an anthraquinone process (NexantECA study publication by Jia Lin and Adam Chan, Propylene Oxide, TECH 2022-3, December 2022).

The anthraquinone process is based on the catalytic hydrogenation of anthraquinone to an- thrahydroquinone with hydrogen over a catalyst, e.g. a palladium catalyst. Subsequently, the anthraquinone is reformed in a re-oxidation with oxygen, for example pure oxygen or atmospheric oxygen, under elimination of hydrogen peroxide. Generally, the process steps in the anthraquinone process run under mild reaction conditions (generally a pressure below 1 MPa, i.e. 10 bar, generally a temperature below 100 °C) and preferably continuously.

Since the anthraquinone to anthrahydroquinone should not flocculate during the process, the solubility can be adapted via the alkyl substituents and the solvent composition. For this purpose alkylated derivatives such as 2-ethyl-, 2-tert-butyl- or 2-amyl anthraquinone are employed. To keep the anthraquinone in solution, often nonpolar substances such as C9-/C10-alkyl benzene mixtures are part of the of the working solution. Polar substances such as tris-(2- ethylhexyl)-phosphate, diisobutylcarbinol, tetra butylurea or urea or methyl cyclohexyl acetate take over this task for the hydroquinone.

The preparation of hydrogen peroxide is for example described in Anjali A. Ingle et aL, Environmental Science and Pollution Research (2022) 29:86468-86484 (anthraquinone process) , in Shu Hu et aL, ACS AppL Energy Mater. 2019, 2, 11 , 7972-7979 (electrochemical synthesis of hydrogen peroxide from oxygen and water) and in NexantECA study publication by Sandrine Romand, Hydrogen Peroxide, TECH 2019-8, September 2019.

In a preferred embodiment of the present invention, propylene oxide in step c) is obtained by oxidation of propene with hydrogen peroxide as an oxidizing agent, preferably in a HPPO process.

Preferably, the present invention therefore relates to a process for preparing propylene oxide comprising the following steps:

(a*) reacting hydrogen with carbon dioxide to form methanol,

(b*) converting the methanol from step (a*) to propene,

(c*) reacting the propene from step (b*) with an oxidizing agent to form propylene oxide, wherein the carbon dioxide in step (a*) is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass, and wherein the propylene oxide in step c) is therefore obtained by oxidation of propene with hydrogen peroxide as an oxidizing agent, preferably in a HPPO process, wherein the hydrogen peroxide is preferably obtained by an anthraquinone process.

As also mentioned above, the hydrogen in step (a*) of the process of the present invention is preferably obtained at least in part by water splitting, preferably by electrolysis. The by-product of the water splitting, preferably electrolysis is pure oxygen, which is usually released into the environment without further use. In one embodiment of the present invention, the oxygen in step (c*) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy generated at least in part from non-fossil resources.

The oxygen in step (c*) mentioned above is the oxygen which may be employed in the preparation of ethylene oxide, preferably by direct oxidation as well as the oxygen employed in the preparation of the oxidizing agent employed in the preparation of propylene oxide. The oxidizing agent is preferably hydrogen peroxide, more preferably hydrogen peroxide prepared by the anthraquinone process.

One carbon source for the production of ethylene oxide and propylene oxide, in step (a*) (production of methanol) is captured carbon dioxide. Therefore the by-product spectrum of methanol employed in the process for the preparation of ethylene oxide and propylene oxide according to the present invention is different from the by-product spectrum of methanol obtained by conventional processes (i.e. using synthesis gas “syngas,” which is a combination of varying amounts of H2, CO, and CO2 frequently derived from gasified coal or natural gas). E.g. conventionally obtained methanol generally comprises more methylformiate, acetone and higher alcohols (> C3) than methanol obtained by the process according to the present invention. The by-product spectrum of ethene and propene manufactured by cracking of fossil-based hydrocarbon raw materials such as naphtha or natural gas used in conventionally obtained ethylene oxide and propylene oxide is even more different than the ethylene oxide and propylene oxide obtained by the CO2 to olefins via Methanol-to-olefins pathway (CO2MTO) according to the present invention for example due to the highly undesired sulfur components present especially in naphtha.

The different by-product spectrum of methanol respectively ethene and propene is also reflected in the downstream products, e.g. in the ethylene oxide and propylene oxide and in the alkoxylated compounds obtained according to the invention.

Step (d*)

In step (d*), the ethylene oxide and/or propylene oxide obtained in step (c*) and optionally the at least one alkylene oxide different from ethylene oxide and propylene oxide is reacted with the at least one starter unit having Zerewitinoff active hydrogen atoms in one or more steps to form the alkoxylated compound.

The alkoxylated compound prepared in the process of the present invention comprises i) 20 wt-% to <100 wt-%, preferably 30 wt-% to <99.3 wt-% of ethylene oxide units and/or propylene oxide units, ii) 0 wt-% to 30 wt-%, preferably 0.5 wt-% to 20 wt -% of at least one alkylene oxide unit different from ethylene oxide and propylene oxide units, iii) >0 wt-% to 80 wt-%, preferably 0.2 wt-% to 70 wt -% of at least one starter unit having Zerewitinoff active hydrogen atoms, wherein the sum of the units mentioned under i), ii) and iii) is 100 wt-%. i) Ethylene oxide units and/or propylene oxide units:

The alkoxylated compound according to the present invention comprises ethylene oxide units (EO), propylene oxide units (PO) or both.

EO and PO can be present in various weight ratios. Typically, the alkoxylated compound has an EO:PO weight ratio of from 100:0 to 0:100, 90:10 to 10:90, 25:75 to 75:25, 25:75 to 85:15, 50:50 to 85:15, 55:45 to 80:20, or 60:40 to 75:25, or any range between the lowest and highest of these values. ii) At least one alkylene oxide unit different from ethylene oxide and propylene oxide units:

The alkoxylated compound according to the present invention may comprise at least one alkylene oxide unit different from ethylene oxide and propylene oxide units.

Examples of alkylene oxide units different from ethylene oxide and propylene oxide units are based on 1 ,2-butylene oxide, 2,3-butylene oxide, styrene oxide, 1 ,3-propylene oxide or tetrahydrofuran, preferably 1 ,2-butylene oxide or 2,3-butylene oxide, more preferably 1 ,2-butylene oxide (BuO).

Preferably, no alkylene oxide unit different from ethylene oxide and propylene oxide units is present, i.e. the alkoxylated compound prepared in the process of the present invention comprises 0 wt-% of alkylene oxide units different from ethylene oxide and propylene oxide units.

The alkylene oxide units may be present in the alkoxylated compound in form of exclusively one type of alkylene oxide units, i.e. exclusively ethylene oxide units or exclusively propylene oxide units, for example in the case of polymeric alkylene oxide units in the form of homopolymers, or in form of two or more different alkylene oxide units, e.g. ethylene oxide units and propylene oxide units in the ratios mentioned above, or ethylene oxide units and/or propylene oxide units and 1 ,2-butylene oxide units. For example in the case of polymeric alkylene oxide units in the form of random copolymers or block copolymers.

In certain embodiments, the polymer is EO capped. In other embodiments, the polymer is PO capped. Such capping may be referred to as a small block, e.g. a small block of EO which acts as the cap. If the polymer is capped, it may be referred to in the art as a block copolymer. In certain embodiments, the polymer is a block PAG. Such block PAGs can comprise blocks of all EO or PO, blocks of random EO/PO monomers with at least two blocks being of different EO/PO ratios, or a combination of all EO or PO blocks and random EO/PO blocks.

Preferred ethylene oxide units and/or propylene oxide units according to the present invention are characterized by the following formulae:

wherein n, m, n’ and m’ are each independently 1 to 500, preferably 1 to 100, more preferably 2 to 50; and the groups

n and in formula (Ic) are arranged in the form of two or more, preferably 2 or 3 blocks and/or randomly.

The total number average molecular weight of the ethylene oxide units is in the range of 88 to 22000 Da, preferably 88 to 4400 Da, more preferably 88 to 2200 Da and the total number average molecular weight of the propylene oxide units is in the range of 116 to 29000 Da, preferably 116 to 5800 Da, more preferably 116 to 2900 Da. The average molecular weight of the ethylene oxide units and/or propylene oxide units may be calculated based on its monomeric structure. iii) At least one starter unit having Zerewitinoff active hydrogen atoms

Zerewitinoff active hydrogen is reactive as determined by the Zerewitinoff method as described in the Analyst 1963, 88, 782-790. The quantitative determination of active hydrogens in a chemical substance by means of adding methylmagnesium iodide in pentyl ether to the solution of substrate and quantitatively measuring the volume of gaseous methane evolved is generally known as the Zerewitinoff determination.

Preferably, the starter units having Zerewitinoff active hydrogen atoms are selected from the group consisting of water, at least one of mono-, di- or polyfunctional alcohols, mono, di- or polyfunctional amines and mono-, di- or polyfunctional thio compounds. More preferred starter units are water, mono-, di- or polyfunctional alcohols and/or mono-, di- or polyfunctional amines.

The starter units preferably contain from 1 to 100, more preferably in the from 2 to 50, most preferably 2 or 8, further most preferably 2 or 3 Zerewitinoff active hydrogen atoms. In the case of polyethyleneimines as starter units, preferred polyethylene imine starter units having an amine number of 3 to 30 mmol/g, preferably 5 to 25 mmol/g, more preferably 10 to 22 mmol/g.

The amine number refers to the proportion of amine present in an element. The amine number is determined according to DIN 53176 (edition 2000-12).

Examples of suitable mono-, di- or polyfunctional alcohols include monools, diols, triols, tetrols or higher alcohols, which may also be referred to in the art as polyols. In certain embodiments, the alcohol is a monool. Examples of suitable monools include Ci- to C20 alcohols, for example n-butanol, iso-butanol, 2-ethyl hexanol, 2-propyl heptanol, butyl glycol, butyl diethyleneglycol, butyl triethyleneglycol, butyl propyleneglycol, butyl dipropyleneglycol, butyl tripropyleneglycol, methyl diglycol, methyl triglycol, methyldipropyleneglycol, methyldipropyleneglycol, methanol, ethanol, hexanol, iso-nonanol, decanol, 2-butyloctanol, oleyl alcohol, octadecanol (C18 alcohol) (e.g. stearyl alcohol), isononadecanol, C12 alcohol, C13 alcohol, C14 alcohol, C15 alcohol, C16 alcohol, C17 alcohol, 2-ethylhexanol, 2-propyl heptanol, 2-butyloctanol, 2-pentylnonanol, 2-hex- yldecanol, and mixtures of said alcohols like C13-C15 alcohol, C12-C18 alcohol, C16-C18 alcohol, or C12-C14 alcohol. In other embodiments, the alcohol is a diol. Examples of suitable diols include ethyleneglycol, 1 ,2-propylene glycol, 1 ,2-hexanediol, diethyleneglycol, triethyleneglycol, dipropyleneglycol, and tripropyleneglycol. In yet other embodiments, the alcohol is a polyol. Examples of suitable polyols include glycerol, trimethylolpropane, and pentaerithritol.

Various types of amines can be used to form the alkoxylated compound. Examples of suitable amines include monoamines, diamines, triamines or higher amines, which may also be referred to in the art as polyamines. Specific examples of suitable amines include alkanolamines, ethylene diamines, diethylene triamines, and polyethylenimines.

The term “polyethylenimine” in the context of the present invention does not only refer to poly- ethylenimine homopolymers but also to polyalkyleneimines containing NH-CH2-CH2-NH structural elements together with other alkylene diamine structural elements, for example NH-CH2- CH2-CH2-NH structural elements, NH-CH2-CH(CH3)-NH structural elements, NH-(CH2)4-NH structural elements, NH-(CH2)6-NH structural elements or (NH-(CH2)8-NH structural elements but the NH-CH2-CH2-NH structural elements being in the majority with respect to the molar share. Preferred polyethylenimines contain NH-CH2-CH2-NH structural elements being in the majority with respect to the molar share, for example amounting to 60 mol-% or more, more preferably amounting to at least 70 mol-%, referring to all alkyleneimine structural elements. In a special embodiment, polyethylenimine refers to those polyalkylene imines that bear one or zero alkyleneimine structural element per molecule that is different from NH-CH2-CH2-NH.

The “polyethylenimine” in the context of the present invention is linear or branched. The degree of the branching may be determined by a skilled person according to practical application by 13C NMR. Polyalkyleneimines, including polyethyleneimines, can be characterised by their degree of branching (DB). To define the degree of branching, reference is made to H. Frey et aL, Acata Polym. 1997, 48, 30. The degree of branching DB is defined therein as

DB (%) = (T+Z)/(T+Z+L) x 100, where

T is the average number of terminally bound monomeric units (primary amino groups), Z is the average number of branching monomeric units (tertiary amino groups),

L is the average number of linearly bound monomeric units (secondary amino groups). T, Z, and L can be determined via 13C-NMR in D2O.

The degree of branching DB of the polyalkyleneimines, especially polyethyleneimines, according to the present invention is preferably in the range of 55 to 95%, preferably in the range from 57 to 90% and more preferably in the range from 60 to 80%.

The polyalkyleneimine, preferably polyethyleneimine, employed in the reaction mixture may desirably have a weight average molecular weight (MW) or from 300 to 20,000, for instance from 300 to 15,000, suitably from 300 to 10,000, more suitably from 300 to 5000, preferably from 500 to 1500, more preferably from 500 to 1000 g/mol. The weight average molecular weight (Mw) can be determined by gel permeation chromatography (GPC), with hexafluoroisopropanol and 0,05w% ammoniumacetate as eluent and narrowly distributed polyethylene glycol standards as stationary phase.

Preparation:

There is no specific requirement on the process for obtaining the alkoxylated compounds of the present invention, and the preparation of the alkoxylated compounds of the present invention is generally known by a person skilled in the art.

The alkoxylation can generally be carried out in three ways: (i) anionic (base-initiated) polymerization, (ii) acid initiated polymerization, and (iii) by coordination polymerization.

The anionic polymerization of epoxides represents the “classical” technique for the synthesis of the respective polymers/compounds comprising ethylene oxide and/or propylene oxide units. The anionic polymerization is usually carried out by catalytic addition of ethylene oxide and/or propylene oxide and optionally at least one alkylene oxide different from ethylene oxide and propylene oxide, onto at least one starter unit having Zerewitinoff active hydrogen atoms.

As catalysts, metal compounds, preferably alkali metal (especially sodium, potassium, or cesium) compounds with high nucleophilicity can be employed. Examples are alkali metal hydroxides, alkali metal salts, alkali metal hydrides, or alkali metal amides. Potassium hydroxide having the greatest significance in practice (see for example US 6156720 A). A further suitable class of catalyst are multimetal cyanide compounds, preferably double metal cyanide compounds, especially zinc hexacyanometalates. These catalysts are frequently also referred to as DMC catalysts. The polyether alcohols prepared using multimetal cyanide compounds feature a very low content of unsaturated constituents. A further advantage in the use of multimetal cyanide compounds as catalysts consists in the distinctly increased space-time yield in the addition of the alkylene oxides. The alkoxylation in the presence of DMC catalysts is for example described in DD 203 735, DD 203 734, WO 97/29146, WO 98/03571 , WO 00/14143, WO 99/44739 and US 2008/0161509 A1.

Solvents employed for the anionic polymerization of epoxides are generally polar and aprotic; therefore, tetrahydrofuran (THF), dioxane, dimethyl sulfoxide (DMSO), and hexamethylphosphoramide (HMPA) are often used. Furthermore, polymerization in the bulk monomer is possible and is the preferred process.

Alkoxides with sodium, potassium, or cesium counterions in THF or other polar, aprotic solvents represent popular initiator systems.

The addition of complexing agents, such as crown ethers suitable for the respective cation can strongly accelerate the anionic polymerization of epoxides.

The temperatures during the alkoxylation are usually between 80 and 200°C, preferably 90 to 180°C.

The alkoxylated compounds of the present invention can be prepared either in a batchwise, semibatchwise or in a continuous process.

In a semibatch alkoxylation, for example, the catalyst and the at least one starter are initially charged while epoxide (ethylene or propylene oxide) is added during the reaction course. This particular synthesis strategy is due to the high reactivity of alkoxides and also to the high heat involved in alkoxylation reaction.

The polymerization rate of EO is considerably faster than that of PO, which plays an important role in the frequently used anionic copolymerization of EO and PO. Generally, the reactivity of alkylene oxides decreases with increasing length and bulkiness of the alkyl substituent at the epoxide moiety.

The alkoxylated polyethylenimines of the present invention can be obtained by alkoxylation of polyethylenimine via a process commonly known in the art. The alkoxylation of polyethyleneimines using ethylene oxide, propylene oxide and butylene oxide is for example described in Houben-Weyl, Methoden der organischen Chemie, 4. Ed., Vol.14/2, p.440 ff. (1963) and Vol. E 20, p.1367 f. (1987). The alkoxylated polyethylenimine of the present invention may be obtained as for example described in US5445765 and DE-A 2227546. In the case that the at least one starter unit is a mono-, di- or polyfunctional alcohol, the alcohol alkoxide components (alkoxlated alcohols) obtained can be converted into alkyl ether sulfate salts by sulfating them in a manner known per se using sulfuric acid or sulfuric acid derivatives to give acid alkyl ether sulfate salts (see for example US 2008/0207939 A1). Sulfation reactions of alcohols have already been described, for example in US 3,462,525, US 3,420,875 and US 3,524,864. Details on carrying out this reaction are also given in “Ullmann’s Encyclopedia of Industrial Chemistry”, 5th edition, Vol. A25 (1994), pages 779-783 and in the literature references given there.

If sulfuric acid itself is used for the esterification, expediently use is generally made of from 75 to 100% strength by weight, preferably from 85 to 98% strength by weight, acid (termed “concentrated sulfuric acid” or “monohydrate”. The esterification can be formed in a solvent or diluent if it is wanted for control of the reaction, for example heat development.

Generally, the alcoholic reactant is introduced first and the sulfation reagent is added gradually with continuous mixing. If complete esterification of the alcohol alkoxide component is desired, the sulfation reagent and the alcohol alkoxide component are generally used in a molar ratio of from 1 :1 to 1 :1 .5, preferably from 1 :1 to 1 :1 .2. Smaller amounts of sulfation reagent can be advantageous if mixtures of alcohol alkoxylates are used. The esterification is usually carried out at temperatures of from 25 to 85° C, preferably in the range from 45 to 75° C. If appropriate it can be expedient to carry out the esterification in a low-boiling, water-immiscible solvent and diluent at its boiling point, the water being formed in the esterification being distilled off azeotropi- cally.

Instead of sulfuric acid of the concentration stated above, for the sulfation of the inventive alcohol alkoxide component, use can also be made, for example, of sulfur trioxide, sulfur trioxide complexes, solutions of sulfur trioxide in sulfuric acid (“oleum”), chlorosulfonic acid, sulfuryl chloride or else sulfamic acid. The reaction conditions must then be modified appropriately as known by a person skilled in the art.

If sulfur trioxide is used as sulfation reagent, the reaction can also be carried out advantageously in a falling-film reactor in countercurrent or cocurrent flow, if appropriate also continuously. The batches, after the esterification, are neutralized by adding alkali and, if appropriate after removing excess alkali metal sulfate and any solvent present, are worked up.

If chlorosulfonic acid is used as sulfating reagent, the corresponding alcohol alkoxide component is charged into a stirred apparatus under inert conditions. Under vigorous stirring, a corresponding amount of chlorosulfonic acid is added dropwise. The molar ratio between alcohol component and chlorosulfonic acid is generally from 0.5:1 to 1 :0.5, preferably the ratio is from 0.75:1 to 1 :0.75. Very particularly preferably, the molar ratio of alcohol alkoxide component to chlorosulfonic acid is 1 :1 . After the HCI gas is removed, the reaction batch is adjusted to a slightly alkaline pH using sodium hydroxide solution. The alkoxylated compounds obtained in step (d*) are characterized by a low cradle to grave product carbon footprint (see the explanation above) compared with the same alkoxylated compounds obtained in conventional processes (i.e. without CO2 to olefins via Methanol-to-olefin pathway (CO2MTO), without carbon capturing etc.). The present invention therefore solves the dilemma mentioned above, and provides alkoxylated compounds having a low cradle to grave (i.e. including scope 3 downstream (see the explanation above)) product carbon footprint and generally at the same time a good biodegradability.

As discussed above, the different by-product spectrum of methanol, ethene and propene and of ethylene oxide and propylene oxide is also reflected in the downstream products, i.e. in the alkoxylated compounds obtained according to the invention.

It has surprisingly been found by the inventors of the present application that the high molecular by-products generated during the alkoxylation process are lower using ethylene oxide and/or propylene oxide according to the present invention compared to commonly prepared ethylene oxide and/or propylene oxide.

Reduction of these high molecular by-products is desired in the preparation of polyurethanes (from polyetherpolyols), as very high molecular weight by-product fractions are known to be potent surfactants to cause polyurethane foams collapsing or have negative influences on other applications, e.g. causes turbidity in blends or precipitation.

Preferably, the alkoxylated compounds according to the present invention satisfy the biodegradability requirements set forth in OECD 301 B (as mentioned above).

By the alkoxylated compounds and the process of the present invention both, a low cradle to grave product carbon footprint as well as generally a good biodegradability is achieved.

The alkoxylated compounds of the present invention comprising i) 20 wt-% to <100 wt-%, preferably 30 wt-% to 99.3 wt-% of ethylene oxide units and/or propylene oxide units, ii) 0 wt-% to 30 wt-%, preferably 0.5 wt-% to 20 wt-% of at least one alkylene oxide unit different from ethylene oxide and propylene oxide units, iii) >0 wt-% to 80 wt-%, 0.2 wt-% to 70 wt-% of at least one starter unit having Zerewitinoff active hydrogen atoms, wherein the sum of the units mentioned under i), ii) and iii) is 100 wt-%, wherein the ethylene oxide units and/or propylene oxide units, the alkylene oxide unit different from ethylene oxide and propylene oxide units and the starter unit having Zerewitinoff active hydrogen atoms are defined above.

In one embodiment, the alkoxylated compounds of the present invention comprising an EO:PO weight ratio of from 100:1 to 0:100, 90:10 to 10:90, 25:75 to 75:25, 25:75 to 85:15, 50:50 to 85:15, 55:45 to 80:20, or 60:40 to 75:25, or any range between the lowest and highest of these values.

The ethylene oxide units and/or propylene oxide units, the alkylene oxide unit different from ethylene oxide and propylene oxide units and the starter unit having Zerewitinoff active hydrogen atoms are defined above.

The inventive alkoxylated compounds generally having a number average molecular weight of 100 to 50000 Da, preferably 200 to 30000Da, more preferably 300 to 20000 Da, determined by GPC in THF with PEG standard.

The alkoxylated compounds of the present invention have a wide range of applications across various industries. Some of the applications are:

Lubricants: The alkoxylated compounds can be used as lubricants in various industries such as automotive, aerospace, and industrial machinery. They offer excellent lubrication properties, high thermal stability, and resistance to oxidation.

Personal care products: The alkoxylated compounds can be used in formulations of personal care products such as lotions, creams, and shampoos. They provide for example moisturizing and conditioning properties to the skin and hair.

Home care products: The alkoxylated products can be used as surfactants in laundry detergents, hard surface cleaner, and rinse aids. They provide excellent wetting, cleaning, and emulsifying properties

Pharmaceutical industry: The alkoxylated compounds can be used as excipients in the pharmaceutical industry to improve drug solubility, stability, and bioavailability. They are also used in formulations of ointments, creams, and gels.

Textile industry: The alkoxylated compounds can be used in the textile industry as softeners and anti-static agents. They can improve the texture and feel of fabrics and reduce static electricity.

Food industry: The alkoxylated compounds can be used in the food industry as emulsifiers, thickeners, and stabilizers. They can be used in the production of ice cream, dairy products, and baked goods.

Oil and gas industry: The alkoxylated compounds can be used as hydraulic fluids, oil breakers and heat transfer fluids in the oil and gas industry. They offer for example excellent lubrication properties and high thermal stability.

Agriculture/Agrochemicals: The alkoxylated compounds can be used as adjuvants in the agriculture industry for example to improve the effectiveness of herbicides and pesticides. Chemical industry: The alkoxylated compounds can be used as reaction media, surfactants, and dispersants in the chemical industry. They can be used in the production of polymers, resins, and coatings.

Building materials: The alkoxylated compounds can be used in the construction industry as additives in cement, concrete, and plaster to improve for example their workability, strength, and durability. Polyurethane production: The alkoxylated compounds can be used as starting materials for the production of fer example polyurethane foams, adhesives, and coatings. They can act as chain extenders and cross-linking agents in the polymerization process. Metalworking fluids: The alkoxylated compounds can be as coolants and lubricants in metalworking processes such as cutting, grinding, and drilling. They offer for example excellent thermal stability, low volatility, and high lubricity.

Electronics: The alkoxylated compounds can be used as heat transfer fluids in electronic cooling systems. They offer for example high thermal conductivity, low viscosity, and compatibility with various materials.

Fuel and energy: The alkoxylated compounds can be used as additives in fuels and lubricants, for example fuel performance packages, to improve their performance and reduce emissions. They can also be used as heat transfer fluids in solar and geothermal energy systems.

- Water treatment: The alkoxylated compounds can be used as flocculants and coagulants in water treatment processes. They can help removing suspended particles and impurities from water.

- Adhesives and sealants: The alkoxylated compounds can be used as binders and thickeners in the formulation of adhesives and sealants. They can provide improved adhesion, flexibility, and moisture resistance.

The present invention therefore further relates to the use of the inventive alkoxylated compounds in any one of the applications mentioned above.

Preferably, the present invention therefore further relates to the use of the alkoxylated compounds according to the present invention or obtained by a process according to the present invention in home care products, cosmetic products, pharmaceutical products, food sector, building materials, lubricants like engine oils, bearing oils, gear oils, compressor oils, lubricating greases, heat transfer fluids, metalworking fluids and transmission fluids, antifoaming agents, softeners, rheology modifiers, emulsifiers, dispersing agents, thickeners, stabilizers, metal working fluids, agrochemicals like pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages and poly(urethane) applications, and home care products, cosmetic products, pharmaceutical products, products in food sector, building materials, lubricants like engine oils, bearing oils, gear oils, compressor oils, lubricating greases, heat transfer fluids, metalworking fluids and transmission fluids, antifoaming agents, softeners, rheology modifiers, emulsifiers, dispersing agents, thickeners, stabilizers, metal working fluids, agrochemicals like pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages and poly(urethane) applications comprising at least one the alkoxylated compound according to the present invention or obtained by a process according to the present invention.

The starter units having Zerewitinoff active hydrogen atoms are preferably selected from the group consisting of at least one of mono-, di- or polyfunctional alcohols, mono-, di- or polyfunctional amines and mono-, di- or polyfunctional thio compounds. The present invention further relates to alkoxylated compounds obtainable by the process according to steps (a*) to (d*) according to the process of the present invention.

The alkoxylated compounds preferably satisfy the biodegradability requirements set forth in OECD 301 B.

Since it was found by an exact analysis of the different process steps for obtaining alkoxylated compounds that especially steps (a*), (b*) and (c*) are crucial for obtaining alkoxylated compounds having a low cradle to grave product carbon footprint, the present invention further relates to a process for preparing ethylene oxide or propylene oxide comprising the following steps:

(a*) reacting hydrogen with carbon dioxide to form methanol,

(b*) converting the methanol from step (a*) to ethene and/or propene,

(c*) reacting the ethene and/or propene from step (b*) with oxygen or an oxidizing agent to form ethylene oxide and/or propylene oxide, wherein the carbon dioxide in step (a*) is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass.

Steps (a*), (b*) and (c*) in the inventive process for preparing ethylene oxide or propylene oxide are the same as steps (a*), (b*) and (c*) in the inventive process for preparing the alkoxylated compounds, and the definitions of process steps (a*), (b*) and (c*) above and below apply to both processes.

The present invention therefore also relates to the following:

1 . Process for preparing alkoxylated compounds comprising i) 20 wt-% to <100 wt-% of ethylene oxide units and/or propylene oxide units, ii) 0 wt-% to 30 wt-% of at least one alkylene oxide unit different from ethylene oxide and propylene oxide units, iii) >0 wt-% to 80 wt-% of at least one starter unit having Zerewitinoff active hydrogen atoms, wherein the sum of the units mentioned under i), ii) and iii) is 100 wt-%, comprising the following steps:

(a*) reacting hydrogen with carbon dioxide to form methanol,

(b*) converting the methanol from step (a*) to ethene and/or propene,

2. The process according to embodiment 1 , wherein the hydrogen in step (a*) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy generated at least in part from non-fossil resources.

3. The process according to embodiment 1 or 2, wherein in all steps (a*) to (d*) energy in form of heating energy and/or electrical power is used, and the energy used in steps (a*) to (d*) is generated at least in part from non-fossil resources.

4. The process according to embodiment 2 or 3, wherein the energy generated from non-fossil resources is selected from the group consisting of solar energy (thermal, photovoltaic and concentrated), wind power, hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, heat captured by heat pumps, bioenergy (biofuel, biomass), the renewable part of waste, nuclear power and mixtures thereof.

5. The process according to any one of embodiments 2 to 4, wherein the hydrogen is obtained by water electrolysis, preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

6. The process according to any one of embodiments 1 to 5, wherein the ethene and/or propene in step (b*) are obtained by a methanol-to-olefin process, preferably with a zeolite catalyst.

7. The process according to any one of embodiments 1 to 6, wherein the ethylene oxide in step (c*) is obtained by epoxidation of ethene with oxygen, preferably in the presence of a silver-based catalyst.

8. The process according to any one of embodiments 1 to 7, wherein the propylene oxide in step (c*) is obtained by oxidation of propene with hydrogen peroxide as an oxidizing agent, preferably in the presence of a zeolite calalyst, more preferably in the presence of Titansilikalit-1 (TS-1 ).

9. The process according to any one of embodiments 1 to 8, wherein the oxygen in step (c*) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy generated at least in part from non-fossil resources.

10. The process according to any one of embodiments 1 to 9, wherein the starter units having Zerewitinoff active hydrogen atoms are selected from the group consisting of at least one of mono-, di- or polyfunctional alcohols, mono-, di- or polyfunctional amines and mono-, di- or polyfunctional thio compounds.

11 . Alkoxylated compounds obtainable by the process according to any one of embodiments 1 to 10.

12. Alkoxylated compounds according to embodiment 11 or obtainable by the process according to any one of numbers 1 to 10, wherein the alkoxylated compounds satisfying the biodegradability requirements set forth in OECD 301 B.

13. Process for preparing ethylene oxide or propylene oxide comprising the following steps: (a*) reacting hydrogen with carbon dioxide to form methanol,

(b*) converting the methanol from step (a*) to ethene and/or propene, (c*) reacting the ethene and/or propene from step (b*) with oxygen or an oxidizing agent to form ethylene oxide and/or propylene oxide, wherein the carbon dioxide in step (a*) is at least in part captured from industrial flue gases or from air or from ocean water or other natural waters or obtained from biological processes, for example from fermentation processes from waste or biomass.

14. Use of the alkoxylated compounds according to embodiment 11 or 12 or obtained by a process according to any one of numbers 1 to 10 in home care products, cosmetic products, pharmaceutical products, food sector, building materials, lubricants like engine oils, bearing oils, gear oils, compressor oils, lubricating greases, heat transfer fluids, metalworking fluids and transmission fluids, antifoaming agents, softeners, rheology modifiers, emulsifiers, dispersing agents, thickeners, stabilizers, metal working fluids, agrochemicals like pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages and poly(urethane) applications.

The invention is further illustrated by Examples 1 to 3 below.

Graft polymers based on non-fossil resources, process to produce, uses and compositions comprising them

The present invention further relates to graft polymers , having a low molar share of deuterium, a process for making such graft polymers based on non-fossil energy, the use of the molar share of deuterium in hydrogen and thus in such graft polymers based on hydrogen for tracing the origin, especially the energetic origin, of the hydrogen and thus of such graft polymers based on hydrogen, wherein the graft polymers are preferably graft polymers based ethylene oxide-comprising backbones being grafted with olefinically polymerizable monomers, preferably vinyl monomers, more preferably with a) vinyl esters and optionally further monomers, such further monomers preferably being selected from vinyllactams, more preferably vinylpyrrolidone, and olefinically unsaturated, radically polymerizable amine-containing monomers such as vinylamines, more preferably vinylimidaz- ole, and even more preferably such monomers being at least one vinyl ester, at least one lactam and optionally at least one vinylamine, and even more preferably such monomers being vinyl acetate, vinylpyrrolidone and vinylimidazole, or b) vinyllactams, more preferably vinylpyrrolidone, and olefinically unsaturated, radically polymerizable amine-containing monomers such as vinylamines, more preferably vinylimidazole; further encompassed is a process for tracing the origin, especially the energetic origin, of hydrogen and thus of such graft polymers based on hydrogen by determining the molar share of deuterium in hydrogen and said graft polymers based on hydrogen, wherein the graft polymers are preferably those as detailed before, applications of such graft polymers as detailed before and their uses and - further - products and formulations and compositions comprising any of such graft polymers or their mixtures, and - even further - the use of such graft polymers as liquid or solid CO2 absorbents in CO2 capturing processes.

The graft polymers of the inventions are known as such and widely used today or were just recently disclosed - as further detailed hereinafter - and thus are known to a person of skill in the art.

In modern processes, a significant amount of the hydrogen is provided by steam reforming, thus, from natural gas.

However, the petrochemical steam reforming process has its negative impacts with regard to its carbon footprint including the consumption of a lot of fossil-based natural resources and energy.

Nowadays it is important that the origin of the hydrogen and downstream compounds obtained by clean energy can be tracked in a reliable way. This is especially important to ensure that:

• Hydrogen and downstream compounds have been produced in accordance with sustainability criteria.

• Renewable attributes aren’t subject to double counting.

Hence, companies are placing increasing importance on sourcing green energy. Because of this, tracking systems have to be developed for the origin of the energy used in the preparation of hydrogen and downstream compounds.

US 2011/136097 relates to a method for determining origins of food products, more specifically for determining the geographic and/or biological origin of food products containing alcohols or sugars by using the specific isotope ratios of fer example sugars from different plants, which is influenced by climate conditions and the area of origin as isotopic “fingerprint” of the specific plants. However, the deuterium content taken advantage of in the present invention is not the natural “fingerprint”, but the finding that the deuterium content of hydrogen obtained by electrolysis of water is lower than the naturally occurring deuterium content of hydrogen. Further, not the geographic area of origin is determined, but the preparation process of the hydrogen.

US 6,495,609 concerns a method for recovering carbon dioxide from an ethylene oxide production process and using the recovered carbon dioxide as a carbon source for methanol synthesis. However, the hydrogen used in the process of US 6,495,609 is present in syngas, such as natural gas or refinery off-gas.

GB 2464 691 A relates to the manufacture of methanol from agricultural by-product cellulo- sic/lignitic material. In a first section of a synthesis factory, the cellulosic/lignitic by-product that remains after the cropping of agricultural products is converted to carbon dioxide by calorific oxidation. In another section of a synthesis factory, hydrogen gas is produced by electrolysis which is then reacted with carbon dioxide to make methanol.

WO 2016/149507 A1 relates to the oxidative coupling of methane for obtaining a high number of different products. Claim 217 for example discloses a method for producing oxalate compounds.

US 7,119,231 B2 relates to a process for preparing alkanolamines by reacting ammonia with alkylene oxide in a reaction space in the presence of a catalyst to give monoalkanolamine or dialkanolamine or trialkanolamine or a mixture of two or three of these compounds. There is no hint concerning the deuterium content of the hydrogen comprising compounds employed in US 7,119,231 B2 or concerning the use of non-fossil energies.

FR 2 851 564 A1 concerns a process for preparation of ethylene oxide and ethanolamines. As in FR 2 851 564 A1 does not contain any hint to the presence of deuterium in the hydrogencomprising compounds or the use of non-fossil energies.

US 2008/0283411 A1 relates to a method for converting a carbon source and a hydrogen source into hydrocarbons. It is mentioned that the method and the device are useful to produce a fossil fuel alternative energy source, store renewable energy, sequester carbon dioxide from the atmosphere, counteract global warming, and store carbon dioxide in a liquid fuel.

WO 2015/102985 A1 relates to a process for the preparation of ethanolamines comprising reacting a water-ammonia solution with ethylene oxide. However, there is no hint in WO 2015/102985 A1 concerning the preparation of hydrogen by electrolysis, the use of renewable energies and the presence of deuterium in the hydrogen-containing compounds disclosed in WO 2015/102985 A1.

It is therefore an object of the present invention to provide environmentally friendly graft polymers , having a low molar share of deuterium, wherein the graft polymers are preferably graft polymers based ethylene oxide-comprising backbones being grafted with vinylic monomers, preferably with a) vinyl esters and optionally further monomers, such further monomers preferably being at least one selected from vinyllactams and vinylamines such as more preferably vinylpyrrolidone and/or vinylimidazole, or b) vinyllactams and vinylamines such as more preferably vinylpyrrolidone and vinylimidazole; the object further encompasses an environmentally friendly process for making the same, that process using as little fossil-based energy as possible, ideally no fossil-based energy, thus such process therefore only adding as little as possible, ideally nothing, to CO2 emission; a further object is the use of the molar share of deuterium in hydrogen and thus in such graft polymers based on hydrogen for tracing the origin, especially the energetic origin, of the hydrogen and thus tracing of such graft polymers based on hydrogen.

Methods for determination of the molar share of deuterium in hydrogen and in downstream compounds based on hydrogen are known to a person skilled in the art and include mass spectrometry and NMR technologies.

Specifically, the object is achieved by the inventive graft polymers based ethylene oxide-com- prising backbones being grafted with vinylic monomers, preferably with a) vinyl esters and optionally further monomers, such further monomers preferably being at least one selected from vinyllactams and vinylamines such as more preferably vinylpyrrolidone and/or vinylimidazole, or b) vinyllactams and vinylamines such as more preferably vinylpyrrolidone and vinylimidazole, when using a process leading to non-fossil based ethylene oxide, which is then used to produce the inventive compounds using known means, wherein the molar share of deuterium is lower than in products made using ethylene oxide (EO) from fossil-based sources only. The deuterium content is preferably lower in the products using non-fossil-based-EO compared to products using only fossil-based-EO by at least 10, more preferably at least 20, even more preferably at least 30, even more preferably at least 50, such as more than 60, 70, 80 or even 90 percent, such percentage being based on the total hydrogen content of units stemming from EO having reacted to the compounds of the invention.

In a further embodiment of the present invention, the object is achieved by a process for making graft polymers based ethylene oxide-comprising backbones being grafted with vinylic monomers, preferably with a) vinyl esters and optionally further monomers, such further monomers preferably being at least one selected from vinyllactams and vinylamines such as more preferably vinylpyrrolidone and/or vinylimidazole, or b) vinyllactams and vinylamines such as more preferably vinylpyrrolidone and vinylimidazole, wherein said process comprises the following steps:

(a) providing hydrogen with a molar share of deuterium < 100 ppm, preferably in the range of from 10 to < 95 ppm, more preferably in the range of from 10 to < 90 ppm, most preferably in the range of from 10 to < 80 ppm, based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy,

(b) reacting the hydrogen from step (a) with carbon oxides, preferably carbon dioxide, to form methanol,

(c) converting the methanol from step (c) to ethylene and further to ethylene oxide, (d) converting the ethylene oxide from step (d) to a polymer or a mixture of polymers, such polymer(s) comprising ethylene oxide and optionally other monomers, such other monomers being selected from alkylene oxides other than ethylene oxide, in one or more steps using known methods such as alkoxylation reactions,

(e) reacting the polymer(s) from step (d) in a further reaction with at least one vinylic monomer, preferably with a) at least one vinyl ester and optionally at least one further monomer, such further monomer preferably being at least one monomer selected from vinyllactams and olefinically unsaturated, radically polymerizable amine-containing monomers, more preferably vinylpyrrolidone and/or vinylimidazole, or b) at least one vinyllactam, preferably vinylpyrrolidone, and optionally at least one vinylamine, preferably vinylimidazole, using a radical polymerization reaction using standard means, to obtain a graft polymer comprising less deuterium based on total hydrogen content compared to the chemical identical graft polymer obtained from fossil-based sources only.

It is nowadays further important that the origin of the hydrogen and downstream compounds obtained by clean energy can be tracked in a reliable way.

This is especially in order to ensure that:

• Hydrogen and the graft polymers resulting from such use of hydrogen have been produced in accordance with sustainability criteria.

• Renewable attributes aren’t subject to double counting.

As companies are placing an increasing importance on sourcing green energy, tracking systems have to be developed for the origin of the energy used in the preparation of hydrogen and downstream compounds.

The present invention provides for the possibility to track the inventive graft polymers back to non-fossil based ressources.

Hence, a method for tracing graft polymers back to its origin, especially also the energetic origin, and to non-fossil based ressources is also part of this invention by using the molar share of deuterium in hydrogen and thus in the inventive graft polymers based on such hydrogen.

Methods for determination of the molar share of deuterium in hydrogen and downstream compounds based on hydrogen are known to a person skilled in the art. A suitable method is described in the examples of the present application.

Depending on the further progress in science and technology and thus the development in more and more sophisticated measurement techniques, it is expected that the resolution of the measurement methods for determining the deuterium content over the total hydrogen-content will become more and more precise, so that in the future a even more precise determination will be possible and thus a distinction between tiny differences will become possible. The presently disclosed invention however will not change through this progress in science, but only the possibility to detect the invention will increase. A further environmental benefit of the environmentally friendly graft polymers according to the present invention is their use in carbon capturing processes, since the graft polymers according to the present invention are produced using as little fossil-based energy as possible, ideally no fossil-based energy, at least with respect to the content derived from EO, and do therefore only add as little as possible, ideally nothing, to CO2 emission.

The invention of course will be even more environmentally friendly if also for other ingredients, such as the other alkylene oxides and/or the monomers (i.e. vinylesters, vinyllactams, vinyla- mines), environmentally friendly processes will be employed. Thus, the invention encompasses also such even more environmentally friendly products, wherein the other alkylene oxides and/or the monomers employed are sourced from or made from renewable or even better non- fossil-based sources. Such sources are known already to date for at least some of those other ingredients.

A further embodiment of the present invention is the use of the graft polymers according to the present invention as liquid or solid CO2 absorbents in CO2 capturing processes.

A further embodiment of the present invention is the use of the graft polymers according to the present invention as in compositions, products or formulations, wherein such compositions, products or formulations are those as currently known for the use of the conventionally produced graft polymers of the same - besides the difference in deuterium content - chemically identical graft polymers.

The molar share of deuterium in hydrogen and downstream compounds based on hydrogen is given in the present application in ppm, based on the total hydrogen content, which is the mol-ppm content of deuterium, based on the total hydrogen content (in hydrogen or in the compounds discussed, respectively).

The deuterium content of hydrogen and downstream compounds based on hydrogen is given in the present application in atom-ppm based on the total molar hydrogen content (total atoms of protium ¹H and deuterium ²H). The terms “deuterium content” and “molar share of deuterium” are used synonymously throughout the application.

In physical organic chemistry, a kinetic isotope effect is the change in the reaction rate of a chemical reaction when one of the atoms in the reactants is replaced by one of its isotopes. Formally, it is the ratio of rate constants ki. I kn for the reactions involving the light (ki.) and the heavy (kn) isotopically substituted reactants (isotopologues). This change in reaction rate is a quantum mechanical effect that primarily results from heavier isotopologues having lower vibrational frequencies compared to their lighter counterparts. In most cases, this implies a greater energetic input needed for heavier isotopologues to reach the transition state, and consequently a slower reaction rate. Isotopic rate changes are most pronounced when the relative mass change is greatest, since the effect is related to vibrational frequencies of the affected bonds. For instance, changing a hydrogen atom (H) to its isotope deuterium (D) represents a 100 % increase in mass, whereas in replacing ¹²C with ¹³C, the mass increases by only 8 percent. The rate of a reaction involving a C-H bond is typically 6-10 times faster than the corresponding C-D bond, whereas a ¹²C reaction is only 4 percent faster than the corresponding ¹³C reaction.

Detailed process for making the inventive graft polymer comprising the various process steps as mentioned above:

Step (a)

Step (a) concerns the provision of hydrogen with a molar share of deuterium below 100 ppm, preferably below 90 ppm based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy.

The electrical power is generated at least in part from non-fossil resources.

The term “at least in part” means that part of the electrical power can still be produced from fossil fuels, preferably from natural gas, since combustion of natural gas causes much lower carbon dioxide emission per Megajoule of electrical energy produced than combustion of coal. However, the portion of electrical energy produced from fossil fuels should be as low as possible, preferably < 50%, preferably < 30%, most preferably < 20%, further most preferably < 10%. In one embodiment, the electrical power is generated exclusively from non-fossil resources. Various methods for certification and tracking of the “energy source mix” have been set up based on local legislations. Certificates such as “Non-Fossil Certificate Contracts” are common practice for tracking the ratio of non-fossil energy used in industrial processes and related products (https://www.ekoenergy.org/ecolabel/criteria/tracking/)

Preferably, the electrical power is generated at least in part from wind power, solar energy (thermal, photovoltaic and concentrated solar power), hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, ambient or industrial heat captured by heat pumps, bioenergy (biofuel, biomass), the renewable part of waste energy sources or nuclear energy (fission).

In a further embodiment, the electrical power is generated at least in part from renewable resources, preferably from wind power, solar energy (thermal, photovoltaic and concentrated solar power), hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, ambient heat captured by heat pumps, bioenergy (biofuel, biomass), or the renewable part of waste.

The types of electrical power resources mentioned above are generally known by a person skilled in the art.

In one preferred embodiment of the inventive process, the electrical power from nonfossil resources used in the electrolysis according to the invention can be generated at least in part by nuclear energy. The nuclear energy can be obtained by fission.

Fission occurs when a neutron enters a larger atomic nucleus, forcing it to excite and spilt into two smaller atoms — also known as fission products. Additional neutrons are also released that can initiate a chain reaction. When each atom splits, a tremendous amount of energy is released. Uranium and plutonium isotopes are most commonly used for fission reactions in nuclear power reactors because they are easy to initiate and control. The energy released by fission in these reactors heats water into steam. The steam is used to spin a turbine to produce carbon-free electricity.

In one preferred embodiment of the inventive process, the electrical power used in electrolysis is generated at least in part from wind power. Wind power can be used to run wind turbines. Modern utility-scale wind turbines range from around 600 kW to 9 MW of rated power. The power available from the wind is a function of the cube of the wind speed, so as wind speed increases, power output increases up to the maximum output for the particular turbine. Areas where winds are stronger and more constant, such as offshore and high-altitude sites, are preferred locations for wind farms.

In one further preferred embodiment of the inventive process, the electrical power used in electrolysis is generated at least in part from solar power, particularly preferred from photovoltaic systems. A photovoltaic system converts light into electrical direct current (DC) by taking advantage of the photoelectric effect. Concentrated solar power (CSP) systems use lenses or mirrors and tracking systems to focus a large area of sunlight into a small beam. CSP-Stirling currently has by far the highest efficiency among all solar energy technologies.

In one preferred embodiment of the inventive process, the electrical power used in electrolysis is generated at least in part from hydropower. There are many forms of hydropower. Traditionally, hydroelectric power comes from constructing large hydroelectric dams and reservoirs. Small hydro systems are hydroelectric power installations that typically produce up to 50 MW of power. They are often used on small rivers or as a low-impact development on larger rivers. Run-of-the-river hydroelectricity plants derive energy from rivers without the creation of a large reservoir. The water is typically conveyed along the side of the river valley (using channels, pipes and/or tunnels) until it is high above the valley floor, whereupon it can be allowed to fall through a penstock to drive a turbine.

In one further preferred embodiment of the inventive process, the electrical power used in electrolysis is generated at least in part from geothermal energy. Geothermal energy is the heat that comes from the sub-surface of the earth. It is contained in the rocks and fluids beneath the earth’s crust and can be found as far down to the earth’s hot molten rock, magma. To produce power from geothermal energy, wells are dug a mile deep into underground reservoirs to access the steam and hot water there, which can then be used to drive turbines connected to electricity generators. There are three types of geothermal power plants; dry steam, flash and binary. Dry steam is the oldest form of geothermal technology and takes steam out of the ground and uses it to directly drive a turbine. Flash plants use high-pressure hot water into cool, low-pressure water whilst binary plants pass hot water through a secondary liquid with a lower boiling point, which turns to vapor to drive the turbine.

In one further preferred embodiment of the inventive process, the electrical power used in electrolysis is generated at least in part from biomass. Biomass is biological material derived from living, or recently living organisms. It most often refers to plants or plant-derived materials which are specifically called lignocellulosic biomass. As an energy source, biomass can either be used directly via combustion to produce heat (e.g. heat from fermentation processes) or electricity, or indirectly after converting it to various forms of biofuel and gas. Conversion of biomass to biofuel can be achieved by different methods which are broadly classified into: thermal, chemical, and biochemical methods. Wood was the largest biomass energy source as of 2012; examples include forest residues - such as dead trees, branches and tree stumps -, yard clippings, wood chips and even municipal solid waste. Industrial biomass can be grown from numerous types of plants, including miscanthus, switchgrass, hemp, corn, poplar, willow, sorghum, sugarcane, bamboo, and a variety of tree species, ranging from eucalyptus to oil palm (palm oil).

Plant energy is produced by crops specifically grown for use as fuel that offer high biomass output per hectare with low input energy. The grain can be used for liquid transportation fuels while the straw can be burned to produce heat or electricity. Biomass can be converted to other usable forms of energy such as methane gas or transportation fuels such as ethanol and biodiesel. Rotting garbage, and agricultural and human waste, all release methane gas - also called landfill gas or biogas. Crops, such as corn and sugarcane, can be fermented to produce the transportation fuel, ethanol. Biodiesel, another transportation fuel, can be produced from left-over food products such as vegetable oils and animal fats. Biopower technologies convert renewable biomass fuels into heat and electricity using processes like those used with fossil fuels. There are three ways to harvest the energy stored in biomass to produce biopower: burning, bacterial decay, and conversion to a gas or liquid fuel. Biopower can offset the need for carbon fuels burned in power plants, thus lowering the carbon intensity of electricity generation. Unlike some forms of intermittent renewable energy, biopower can increase the flexibility of electricity generation and enhance the reliability of the electric grid.

The electrolysis in step (a) is generally an electrolysis of water.

According to the present invention, the electrolysis which is generally a water electrolysis utilizes as electrical power direct current (DC) at least in part from non-fossil energy resources.

It is now observed as a key observation of the present application that by the electrolysis of water, the deuterium atom content of the hydrogen is lower than in the hydrogen generated petro- chemically, for example as contained in fossil-based synthesis gas, i.e. < 100 ppm, preferably in the range of from 10 to < 95 ppm, more preferably in the range of from 10 to < 90 ppm, most preferably in the range of from 10 to < 80 ppm, based on the total hydrogen content. The deuterium atom content in electrolytically produced hydrogen may be as low as 10 ppm. The remaining deuterium is mainly present in the form of D-H rather than D2.

An overview of hydrogen production by alkaline water electrolysis powered by renewable energy is given in J. Brauns and T. Turek in Processes, 8(2) (2020), pp. 248. In one further embodiment of the inventive process, hydrogen is provided by polymer electrolyte membrane water electrolysis. Variants of polymer electrolyte membrane water electrolysis are proton exchange membrane water electrolysis (PEMWE, PEM water electrolysis) and anion exchange membrane water electrolysis (AEMWE, AEM water electrolysis).

PEM water electrolysis technology is similar to the PEM fuel cell technology, where solid polysulfonated membranes (Nation®, fumapem®) are used as an electrolyte (proton conductor). These proton exchange membranes have many advantages such as low gas permeability, high proton conductivity (0.1 ± 0.02 S cm^-1), low thickness (20-300 pm), and allow high-pressure operation. In terms of sustainability and environmental impact, PEM water electrolysis is one of the most favorable methods for conversion of renewable energy to highly pure hydrogen. PEM water electrolysis has great advantages such as compact design, high current density (above 2 A cm^-2), high efficiency, fast response, operation at low temperatures (20-90°C) and production of ultrapure hydrogen. The state-of-the-art electrocatalysts for PEM water electrolysis are highly active noble metals such as Pt/Pd for the hydrogen evolution reaction (HER) at the cathode and lrO2/ uC>2 for the oxygen evolution reaction (OER) at the anode.

PEMs can be made from either pure polymer membranes or from composite membranes, where other materials are embedded in a polymer matrix. One of the most common and commercially available PEM materials is the fluoropolymer PFSA (e.g. Nation®, a DuPont product). While Nation® is an ionomer with a perfluorinated backbone like Teflon, there are many other structural motifs used to make ionomers for proton-exchange membranes. Many use polyaromatic polymers, while others use partially fluorinated polymers.

A = V x p / (J/2F x 60 x M_H2O) where V (mL min-¹) is the water mass flow in the anode, F is the Faraday constant, J is electrolysis current (A), p is the density of water (g mL-¹) and MH2O (g mol-¹) is the molar weight of water. A stoichiometric number A of 10 means that 10 times the amount of fresh water than can be theoretically consumed by electrolysis at the given electrolysis current is supplied to the anode.

The AEM water electrolysis technology adopts low-cost catalytic materials, as in alkaline electrolysis, and a solid polymer electrolyte architecture, as in PEM electrolysis technology. AEM electrolysis technology operates in an alkaline environment (pH ~ 10), making it possible the use modest non-noble-metal electrocatalysts (i.e. platin group metal free catalysts = PGM free catalysts), whilst accommodating a zero-gap architecture. The membrane used in this type of electrolysis is a polymeric membrane, containing quaternary ammonium salts. It is relatively inexpensive and has low interaction with atmospheric CO2.

Catalysts:

As examples for hydrogen evolution reaction (HER) catalysts, catalysts based on Ni-Mo alloyed materials are suitable.

As examples for oxygen evolution reaction (OER) catalysts, high activity of transition metal mixed oxides are suitable. Specific examples are CuxCo3_xO4, NiCo2O4:Fe and Ni-Fe alloys on Ni foam supports, for example the PGM-free catalysts (Ni-Fe, Ni-Mo, Ni/(CeO2-La2O3)/C and CuxCo3_xO4).

Membranes and ionomers:

The chemical stability of AEMs under alkaline conditions has improved markedly due to the development of stabilized functional groups on the polymer backbone. This allows the use of such membranes in AEM electrolysis at higher temperatures for long periods. Suitable membranes and ionomers are known by a person skilled in the art and for example described in the review mentioned below. One example is the commercial membrane Tokuyama A201 .

Membrane electrode assembly preparation and cell performance:

The physical and electrochemical characterization of the membrane electrode assembly prepared by either the catalyst-coated substrate (CCS) or the catalyst-coated membrane (CCM) method suggests that the CCM is preferable because improvements in ionic conductivity far outweigh any improvements in electronic conductivity.

Liquid electrolyte: Pure water feeds generally result in poor current densities while 1 % K2CO3 or dilute KOH solutions give good results. A good electrolysis performance is achieved with a 1 % K2CO3 electrolyte. It is therefore preferable that the water electrolyte comprises 0.1 to 2 wt% K2CO3 or KOH.

Beside the alkaline water electrolysis, the AEM and PEM, a further commercially available electrolysis technology is the solid oxide electrolysis (SOE).

SOEC (solid oxide electrolysis cell) feeds water into the cathode and the water undergoes water reduction reaction (WRR), which converts water into hydrogen gas and oxide ions. This hydrogen gas is later brought to purification modules to separate hydrogen gas from the remaining water. Then, the oxide ions migrate from cathode to anode and they release electrons to external circuit to become oxygen gas via oxygen evolution reaction (OER). Typically, the operating temperatures for SOFCs are from 800 to 1 ,000 °C, because high temperatures are required to thermally activate the migration of oxide ions and to facilitate electrochemical reactions on both electrodes. As a result, the overall efficiency is improved. The SOEC is for example described in K. Kamlungsua et al., FUEL CELLS 20, 2020, No. 6, 644-649.

Preferably, the electrolysis in step (a) is a water electrolysis, more preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

In a further preferred embodiment, the electrolysis in step (a) is a solid oxide water electrolysis (SOE).

It is known in the art that deuterium in the evolving hydrogen gas can be depleted with regard to feed water in water electrolysis, e.g. polymer electrolyte membrane water electrolysis. The depletion factor is depending on the electrolysis conditions (water flow, current density). Since the average deuterium content (molar share of deuterium) of water is about 150 ppm, based on the total hydrogen content, hydrogen provided in step (a) of the inventive process has a molar share of deuterium (deuterium content) of < 100 ppm, preferably in the range of from 10 to < 95 ppm, more preferably in the range of from 10 to < 90 ppm, most preferably in the range of from 10 to < 80 ppm, based on the total hydrogen content, or even lower.

Generally, any water source can be used in the preferred water electrolysis in step (a). However, since the hydrogen prepared in step (a) has a molar share of deuterium (deuterium content) below < 100 ppm, preferably in the range of from 10 to < 95 ppm, more preferably in the range of from 10 to < 90 ppm, most preferably in the range of from 10 to < 80 ppm, based on the total hydrogen content, it is preferable to use water having a molar share of deuterium (deuterium content) below 160 ppm, based on the total hydrogen content.

Vienna Standard Mean Ocean Water (VSMOW) is an isotopic water standard defined in 1968 by the International Atomic Energy Agency. Despite the somewhat misleading phrase "ocean water", VSMOW refers to pure water (H2O) and does not include any salt or other substances usually found in seawater. VSMOW serves as a reference standard for comparing hydrogen and oxygen isotope ratios, mostly in water samples. Very pure, distilled VSMOW water is also used for making high accuracy measurement of water’s physical properties and for defining laboratory standards since it is considered to be representative of “average ocean water”, in effect representing the water content of Earth.

The isotopic composition of VSMOW water is specified as ratios of the molar abundance of the rare isotope in question divided by that of its most common isotope and is expressed as parts per million (ppm). For instance ¹⁶O (the most common isotope of oxygen with eight protons and eight neutrons) is roughly 2,632 times more prevalent in sea water than is ¹⁷O (with an additional neutron). The isotopic ratios of VSMOW water are defined as follows: ²H / ¹H = 155.76 ±0.1 ppm (a ratio of 1 part per approximately 6420 parts)

³H / ¹H = 1 .85 ±0.36 × 10’¹¹ ppm (a ratio of 1 part per approximately 5.41 × 10¹⁶ parts, ignored for physical properties-related work) is© 1 16Q = 2005.20 ±0.43 ppm (a ratio of 1 part per approximately 498.7 parts)

¹⁷O 1 ¹⁶O = 379.9 ±1 .6 ppm (a ratio of 1 part per approximately 2632 parts)

(see: https://en-academic.com/dic.nsf/enwiki/753132)

More preferably, the water in step (a) has an average deuterium content of 1 ppm (super light water to 156 ppm, based on the total hydrogen content, most preferably 2 ppm to 150 ppm, based on the total hydrogen content.

Processes for the depletion of deuterium in water are known by a person skilled in the art. However, said processes are generally energy consuming electrolysis processes as e.g. described in CN103848399A.

In the case that deuterium depleted water is used, it is therefore preferred to employ deuterium depleted water obtained from the following resources:

- A byproduct of “heavy water” (D2O) production (heavy water has applications in organic chemistry, drug development, and nuclear reactors); (deuterium content about 10-120 PPm)

- High mountain water; (deuterium content about 120-150 ppm)

- Surface river and lake water; (deuterium content about 130-150 ppm)

- Any water source with seasonally low deuterium content e.g. water collected at low temperature (cold winter water contains less deuterium than warm summer water); e.g. water obtained in winter time, e.g. from snow or ice; (deuterium content about 120-150 PPm)

- Pole water and antarctic glacier water (deuterium content about 90-150 ppm)

- Low salinity sea water e.g. close to river mouths, desalinated sea water or brackish water and waste water treatment effluent water; (deuterium content about 130 - 155 ppm)

Step (b)

Step (b) concerns reacting the hydrogen from step (a) with carbon oxides, preferably carbon dioxide to form methanol.

Suitable carbon oxides are carbon monoxide, carbon dioxide or mixtures of both, wherein carbon dioxide is preferred.

Process conditions for the hydrogenation of carbon monoxide or mixtures of carbon monoxide and carbon dioxide are known perse, for example a low-pressure synthesis, a medium-pressure-synthesis and a high-pressure synthesis. i) Low-pressure synthesis

The low-pressure synthesis is generally carried out at pressures between 50 and 100 bar. The temperature is generally 220 to 300°C. As a catalyst, generally a catalyst based on Cu, Zn and AI2O3 (e.g. CuO/ZnO/AhOs) is used. The low-pressure synthesis is the most preferred synthesis for the preparation of methanol from carbon monoxide or from mixtures of carbon monoxide and carbon dioxide. ii) Medium-pressure-synthesis

The medium-pressure-synthesis is generally carried out at pressures between 100 and 250 bar. The temperature is generally up to 300°C. As catalysts, generally a catalyst based on Zn/C^Os or Zn-Cu catalysts are used. iii) High-pressure synthesis The high-pressure-synthesis is generally carried out at pressures between 250 and 350 bar. The temperature is generally 320 to 380°C. As a catalysts, generally a catalyst based on zinc-chromium oxide is used. This process is less preferred for the production of methanol from carbon monoxide or from mixtures of carbon monoxide and carbon dioxide.

The current world energy system is still mainly based on the use of fossil fuels and, although the use of renewable energy sources has increased, it will continue in the medium and short term. The massive use of fossil fuels in industry and transport produce large amounts of CO2 emissions. Since it is an object of the present invention to provide environmentally friendly graft polymers and an environmentally friendly process for making the same, it is preferred that methanol is prepared by reacting the hydrogen from step (a) with carbon dioxide in step (c) according to the process of the present invention.

In preferred embodiments, the carbon dioxide that is provided in step (c) is captured from industrial flue gases or from ambient air. All available capture technologies may be used.

An overview of commercial CO2 capturing technologies is given in Koytsoumoa et aL, The Journal of Supercritical Fluids, Volume 132, February 2018, Pages 3-16.

Capturing CO2 is most cost-effective at point sources, such as large carbon-based energy facilities, industries with major CO2 emissions (e.g. cement production, ammonia synthesis, steelmaking), natural gas processing, synthetic fuel plants and fossil fuel-based hydrogen production plants. Extracting CO2 from air is possible, although the lower concentration of CO2 in air compared to combustion sources complicates the engineering and makes the process therefore more expensive.

The main industrial sources of CO2 are power plants based on burning of fossil fuels, oil refineries, biogas sweetening (e.g. fermentation) as well as the production of chemicals. Relevant chemical production processes are e.g. naphta cracking for C1-C4 olefins and Ce aromatics as well as downstream chemicals such as especially ammonia and other CC>2-intensive products). Furthermore industrial paper, food, cement, mineral and iron and steel production can be named as examples.

In post combustion capture, the CO2 is removed after combustion of the fossil fuel — this is the scheme that would apply to fossil-fuel power plants. CO2 is captured from flue gases at power stations or other point sources. Absorption, or carbon scrubbing with amines is the dominant capture technology. It is the only carbon capture technology so far that has been used industrially. Suitable post carbon capture methods are for example absorption (chemical, physical), adsorption (chemical, physical), membrane processes, biological and cryogenic processes.

Pre-conversion capture means capturing CO2 generated as an undesired co-product of an intermediate reaction of a conversion process. Some examples include the production of ammonia and coal gasification in power plants. In ammonia production, CO2 that is co-produced with hydrogen during steam reforming must be removed before the ammonia synthesis can take place - absorption in monoethanolamine (MEA) and/or diethanolamine (DEA) is commonly used for these purposes. Similarly, in an integrated gasification combined cycle (IGCC) power plant, CO2 must be separated from hydrogen. This is typically achieved using physical solvents such as selexol and rectisol. Note that, when applied in power plants, pre-conversion capture is also referred to as pre-combustion capture.

Oxy-fuel combustion technology involves the combustion of carbonaceous fuel in a stream of pure oxygen instead of air. Since the oxidant (O2) is free of other components in the air (such as nitrogen), the CO2 concentration in the flue gas will be very high, while the water vapor content can be easily removed.

CO2 adsorbs to a MOF (Metal-organic framework) through physisorption or chemisorption based on the porosity and selectivity of the MOF leaving behind a CO2 poor gas stream. The CO2 is then stripped off the MOF using temperature swing adsorption (TSA) or pressure swing adsorption (PSA) so the MOF can be reused.

Direct air capture (DAO) is a process of capturing carbon dioxide (CO2) directly from the ambient air and generating a concentrated stream of CO2 for sequestration or utilization or production of carbon-neutral fuel. Carbon dioxide removal is achieved when ambient air makes contact with chemical media, typically an aqueous alkaline solvent or sorbents. These chemical media are subsequently stripped of CO2 through the application of energy (namely heat), resulting in a CO2 stream that can undergo dehydration and compression, while simultaneously regenerating the chemical media for reuse.

In Chen, Lackner et aL, Angew. Chem. Int. Ed. 2020, 59, 6984 - 7006, “Sorbents for the Direct Capture of CO2 from Ambient Air” describes major types of sorbents designed to capture CO2 from ambient air categorized by the sorption mechanism: physisorption, chemisorption, and moisture-swing sorption.

In Kommalapati et aL, Energy TechnoL 2017, 5, 822 - 833, polyethylenimine applications in carbon dioxide capture and separation are described.

Dilute CO2 can be efficiently separated using an anionic exchange polymer resin called Marathon MSA, which absorbs air CO2 when dry, and releases it when exposed to moisture. A large part of the energy for the process is supplied by the latent heat of phase change of water. Other substances which can be used are metal-organic frameworks (or MOF's). Membrane separation of CO2 rely on semi-permeable membranes.

In a further embodiment, the present invention therefore relates to the use of the graft polymers according to the present invention as CO2 absorbents in CO2 capturing processes.

Suitable carbon capturing processes are mentioned above and known in the art.

In step (b) the carbon dioxide and hydrogen are reacted to form methanol.

Process conditions for the hydrogenation of carbon dioxide are known perse. Different process approaches are being developed for the synthesis of methanol by hydrogenation of CO2: (1 ) heterogeneous catalysis, (2), homogeneous catalysis, (3) electrochemical, and (4) photocatalysis (see R. Guil-Lopez, Materials 2019, 12, 3902; doi:10.3390/ma12233902). Preferably, the synthesis of methanol by hydrogenation of carbon dioxide is performed in the presence of a heterogeneous catalyst.

Generally, the methanol production is carried out in a synthesis converter, e.g. a fixed-bed, catalytic reactor.

The average temperature inside the reactor is generally in the range of 150 to 300oC. The average pressure inside the reactor is generally in the range of 50 to 150 bar (abs.).

An overview of suitable heterogeneous catalyst systems is given by Kristian Stangeland, Hai- long Li & Zhixin Yu, Energy, Ecology and Environment volume 5, pages 272-285 (2020). Multicomponent catalyst systems are required for this process. The interaction between components is essential for high activity and selectivity of CO2-to-methanol catalysts. This has been demonstrated by numerous catalyst systems comprised of various metals (i.e., Cu, Pd, Ni) and metal oxides (i.e.AhOs, ZnO, ZrC>2, ln₂O₃). These complex systems can contain a mixture of metallic, alloy, and metal oxide phases. The most promising catalyst systems for large-scale industrial processes are currently Cu-based and In-based catalysts due to their superior catalytic performance. A suitable catalyst is for example copper-zinc-alumina. By performing step (b), methanol is formed, by reacting carbon oxides, preferably carbon dioxide, with the hydrogen from step (a). The deuterium content is even lower than corresponding to the distribution obtained by classical petrochemical routes.

Step (c)

In step (c), methanol from step (b) is converted to ethylene and further to ethylene oxide.

Preferably, the ethylene oxide in step (c) is obtained by

(c1) a methanol-to-olefin process, wherein ethylene is obtained, followed by (c2) epoxidation of ethylene.

Step (c1)

In general, ethylene is produced from methanol in a methanol to olefin-process (MTO-process). The MTO process is an acid catalyzed reaction. Preferred catalysts are zeolithes like zeolithes containing silica and alumina (e.g. ZSM-5) and silicon alumina phosphate zeolith-catalysts (SAPO) (e.g. SAPO-34).

This reaction is generally carried out at temperatures of from 300-600 °C. The pressure is generally 0.1 -0.3 MPa.

The process is preferably carried out in a fluidized catalytic reactor.

The ratio propylene to ethylene can be adjusted by choosing appropriate process conditions, and may vary from 0.77 in the ethylene production mode and 1.33 in the propylene production mode.

Examples for commercial MTO technology licensors are UOP (e.g. UOP Advanced MTO process), Energy Technology Co. Ltd. (DMTO process) and Sinopec (SMTO process).

More detailed descriptions can be found e.g. in “Ethylene” by Adam Chan, Nexant, TECH 2018- 1 , July 2018, p. 100 - 109.

Step (c2)

In step (c2), the ethylene from step (c1) is converted to ethylene oxide.

The direct oxidation process is preferably performed in gas-phase, for example with oxygen or air, in the presence of a catalyst, preferably a silver catalyst, more preferably a silver catalyst supported on alumina. The step (c2) is generally performed at a temperature of from 230 to 270°C. The pressure is preferably in the range of from 10 to 30 bar.

In a preferred embodiment, step (c2) is performed by gas-phase selective ethylene oxidation (ethylene epoxidation) that is typically performed in fixed-bed tubular reactors with supported Ag/ AI2O3 catalysts at 230-270 °C and 10-30 bar.

Preferred catalysts for the process in step (c2) are silver-based catalysts like

- supported Re/Cs/Ag/AhOs catalysts that operate preferably in excess C2H4/O2; or

- alkaline-metal (Na, Cs)-promoted supported Ag/AhOs catalysts that operate preferably in excess O2/C2H4.

Oxides of Mo and S have been found to also promote the supported Re/Cs/Ag/AhOs system for EO formation. Therefore, the supported Re/Cs/Ag/AhOs system may additionally comprise oxides of Mo and/or S as promoters.

Step (d) of the process to produce polymers comprising ethylene oxide

In step (d), the ethylene oxide from step (c) is converted to a polymer or a mixture of polymers, such polymer(s) comprising ethylene oxide and optionally other monomers, such other monomers being selected from alkylene oxides other than ethylene oxide, in one or more steps using known methods such as alkoxylation reactions.

Such polymer is hereinafter also termed “polymer backbone” and “polymer backbone (A)”.

The resulting polymer comprises ethylene oxide and optionally further monomers. Thus, the polymer is either a homopolymer of ethylene oxide such as poly ethylene oxide and polyethylene glycol (the difference being only the end-groups; typically, it is “polyethylene glycol” as the end- groups as usually both hydroxy-groups), and co-polymers comprising ethylene oxide and at least one further monomer which can react with ethylene oxide.

Such copolymers include co-polymers of ethylene oxide with at least one other monomer, and can be obtained by polymerization of ethylene oxide and at least one alkylene oxide selected from the group of C3- to C -alkylene oxides, preferably C3- to Cs-alkylene oxides, such as 1 ,2-propylene oxide, 1 ,2-butylene oxide, 2,3-butylene oxide, 1 ,2-pentene oxide and/or 2,3-pen- tene oxide; and optionally at least one polyol selected from the group of C2- to Cs-polyols, preferably C2- to Ce-polyols. Such co-polymer may be any type of known copolymer, such as a block copolymer, an alternating copolymer or a statistical copolymer. Statistical copolymers are also known as random copolymers.

The term “block copolymer” as used herein means that the respective polymer comprises at least two, i.e., two or more, homopolymer subunits (blocks) linked by covalent bonds. Two block copolymers have two distinct blocks (homopolymer subunits), whereas triblock copolymers have, by consequence, three distinct blocks (homopolymer subunits), and so on. The number of individual blocks within such block copolymers is not limited, by consequence, an “n-block copolymer” comprises n distinct blocks (homopolymer subunits). Within the individual blocks (homopolymer subunits), the size/length of such a block may vary. The smallest length/size of a block is based on a minimum of two individual monomers. Various types of block copolymer backbones are commercially available, for example under the trademark series “Pluronic” (BASF SE, Ludwigshafen, Germany). Specific examples are Pluronic PE 6100, Pluronic PE 6800 or Pluronic PE 3100. When more than one alkylene oxide is polymerized to obtain the polymer backbone (A), the alkylene oxides are preferably selected from ethylene oxide, 1 ,2-propyl- ene oxide and/or 1 ,2-butylene oxide. In a preferred embodiment, ethylene oxide is polymerized with at least one alkylene oxide selected from 1 ,2-propylene oxide and/or 1 ,2-butylene oxide, preferably only 1 ,2-propylene oxide.

In order to obtain the polymer, at least one polyol or at least one polyamine 30 may optionally be polymerized with the at least one alkylene oxide.

When at least one polyol is polymerized to obtain the polymer, the polyol is a C2- to C14-polyol, preferably a C2- to C12-polyol, more preferably a preferably C2- to C8-polyoL The polyol may serve as a “core” molecule from which polymer chains extend. This means that the polyol is preferably present at the start of the polymerization reaction for obtaining the polymer. A polyol is an organic compound comprising multiple hydroxyl groups. The polyol is preferably an aliphatic or cycloaliphatic polyol, in particular an aliphatic polyol. The polyol is preferably selected from diols, which comprise two hydroxyl groups, and polyols comprising three to ten hydroxyl groups. Suitable aliphatic diols include aliphatic diols, i.e., glycols, such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1 ,3-propanediol, 1 ,3-butanediol, 2-methyl- 1 ,3-propanediol, triethylene glycol, and neopentyl glycol. A suitable cycloaliphatic diol is cyclohexanedimethanol. Suitable polyols comprising three to ten hydroxyl groups include aliphatic polyols and cycloaliphatic polyols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, glucose, fructose, sucrose and lactose, in particular glycerin. In one embodiment, the polymer backbone is obtained by polymerization of ethylene oxide and at least one alkylene oxide selected from 1 ,2-propylene oxide and/or 1 ,2-butylene oxide, preferably only 1 ,2-propylene oxide, and at least one polyol, in particular diethylene glycol and/or glycerin. When at least one polyamine is polymerized to obtain the polymer, the polyamine is a C2- to C14-polyamine, preferably a C2- to C12- polyamine, more preferably a preferably C2- to C8- polyamine. The polyamine may serve as a “core” molecule from which polymer chains extend. This means that the polyamine is preferably present at the start of the polymerization reaction for obtaining the polymer backbone.

A polyamine is an organic compound comprising multiple amino groups. The polyamine is preferably an aliphatic or cycloaliphatic polyamine, in particular an aliphatic polyamine. The polyamine is preferably selected from alkylene polyamines, such as ethylene diamine, propylene diamine, diethylene triamine and dipropylene triamine. In a preferred embodiment, the polymer backbone is obtained by polymerization of at least one alkylene oxide selected from the group of C2- to C10-alkylene oxides in the absence of a polyamine. In a more preferred embodiment, the polymer backbone is obtained by polymerization of at least one alkylene oxide selected from the group of C2- to C10-alkylene oxides in the absence of a polyol and in the absence of a polyamine.

The skilled person is well-aware of how to obtain different types of copolymers. A suitable discussion may be found, e.g., in EP 0 362 688 A2.

The polymer preferably has a number average molecular weight Mn of 500 to 12,000 g/mol, preferably at most 9,000 g/mol, more preferably at most 6,000 g/mol, even more preferably at most 3,800 g/mol or at most 3,500 g/mol, in particular at most 3,000 g/mol, such as at most 2,750 g/mol, at most 2,700 g/mol or at most 2,650 g/mol, and at least 1 ,000 g/mol, more preferably at least 1 ,500 g/mol. A low number average molecular weight Mn of the polymer backbone (A) increases the degree of biodegradability. The molecular weight may be determined as described below in the experimental part.

Polymers may be based on different amounts of hydrophilic ethylene glycol units (-C2H4-O) derived from ethylene oxide, which influences the overall properties of the graft polymer. The total EO content (%EO) describing the total amount of ethylene glycol units in the polymer backbone (A) is defined as: %EO = m(EO) I (m(total backbone)) wherein m(EO) is the total mass of the ethylene glycol units and m(total backbone) is the total mass of the polymer backbone (A). The polymer backbone can have low, medium or high total EO contents %EO, which has effects on the biodegradability as well as the performance in agrochemical compositions. The ranges are defined as follows: Low: 5 to 20 %EO Medium: 21 to 50 %EO High: 51 to 90 %EO In a preferred embodiment, the total EO content (%EO) is in the range of 10 to 80%, preferably at least 20%, and preferably at most 70%

In a further embodiment, the amount of ethylene oxide in the polymer backbone A is within 10 - 100 weight percent (in relation to the total molar amount of alkylene oxides in the polymer backbone (A)).

More preferably, the monomers in the polymer backbone stem from the use of ethylene oxide and optionally at least one further monomer selected from 1 ,2 propylene oxide (PO) and 1 ,2- butylene oxide, preferably only PO, with the amount of ethylene oxide in the polymer backbone A being within 10 to 100, preferably 10-90, more preferably at least thirty, even more preferably at least 50, even more preferably at least 70, most preferably at least 80 weight percent (in relation to the total amount of alkylene oxides in the polymer backbone (A)).

Thus, preferred polymer backbones (A) are selected from i) poly(ethylene oxide), and ii) polyalkylene oxide comprising only ethylene oxide (EO) and propylene-oxide (PO), preferably a EO/PO/EO triblock polymer, a PO/EO/PO triblock polymer or a random EO/PO copolymer, more preferably a EO/PO/EO triblock polymer or a PO/EO/PO triblock polymer, and most preferably a PO/EO/PO triblock polymer, with PO/EO/PO being overall preferred over - in descending order - random-EO/PO > 100%EO >EO/PO/EO.

The polymer backbone (A) may be optionally “capped” at one or both end groups, the capping is done in a further process step after polymerizing to obtain the polymer (i.e. the polymer backbone (A)) by C1-C25-alkyl groups using known techniques, preferably C1 to C4-groups.

In a preferred embodiment the polymer backbone (A) is not capped but bears hydroxy-groups at the chain ends.

Step (e)

In this step (e) the polymer(s) from step (d) are polymerized in a radical polymerization of at least one olefinic, radically polymerizable monomer, preferably a vinylic monomer, more preferably with a) at least one vinyl ester and optionally at least one further monomer, such further monomer preferably being at least one monomer selected from vinyllactams and olefinically unsaturated, radically polymerizable amine-containing monomers, more preferably vinylpyrrolidone and/or vinylimidazole, or b) at least one vinyllactam, preferably vinylpyrrolidone, and optionally at least one vinylamine, preferably vinylimidazole, using a radical polymerization reaction using standard means,

Embodiment E1 for graft polymer:

In Embodiment E1 , the graft polymer comprises polymeric sidechains (B) grafted onto the polymer backbone (A), wherein said polymeric sidechains (B) are obtainable by polymerization of monomers comprising at least one vinyl ester monomer (B1), and optionally at least one secondary monomer (B2), in the presence of the polymer backbone (A).

Preferably, the polymeric sidechains (B) are obtained by radical polymerization of monomers comprising at least one vinyl ester monomer (B1), and optionally at least one secondary monomer (B2), in the presence of the polymer backbone (A).

As vinyl ester monomer (B1), any vinyl ester as known to the skilled person may be employed, such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate or vinyl benzoate. Preferably, the vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, in particular vinyl acetate and vinyl laurate. In an especially preferred embodiment, the polymeric sidechains (B) are obtained by radical polymerization of vinyl acetate.

The secondary monomer (B2) is preferably selected from olefinically unsaturated nitrogen-con- taining monomers such as vinyl lactams and vinylimidazoles, in particular vinyl lactams; and vinyl ethers.

Suitable vinyl lactams include N-vinyl lactams, such as N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam, preferably N-vinylpyrrolidone and N-vinylcaprolactam, in particular preferably N-vinylpyrrolidone (NVP).

Suitable vinylimidazoles include 1-vinylimidazole and Ci-Cs-alkyl-substituted derivatives of 1-vi- nylimidazole including 2-methyl-1-vinylimidazole, preferably 1-vinylimidazole.

Suitable vinyl ethers include ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 4-hydroxy- butyl vinyl ether, cyclohexyl vinyl ether, 2-ethyl-hexyl vinyl ether, dodecyl vinyl ether, and octadecyl vinyl ether, in particular n-butyl vinyl ether, isobutyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether and 2-ethyl hexyl vinyl ether.

In case secondary monomer (B2) is used for obtaining the polymeric sidechains (B), the weight ratio of vinyl ester monomer (B1 ) to said secondary monomer (B2) is not especially limited.

However, the amount of vinyl ester monomer (B1) is usually not smaller than 1 wt.-%, relative to the total amount of monomers constituting the polymeric sidechains (B). In this case, the polymeric sidechains (B) are obtainable by polymerization, in particular radical polymerization, of 1 to 100 wt.-% of monomer (B1), which is most preferably vinyl acetate, and 0 to 99 wt.-% of at least one secondary monomer (B2).

In one embodiment, the polymeric sidechains (B) are obtained by polymerization, in particular by (free) radical polymerization of

10 to 100 wt.-%, preferably 25 to 100 wt.-%, more preferably 50 to 100 wt.-%, most preferably 75 to 100 wt.-%, relative to the total amount of monomers constituting the polymeric sidechains (B), of at least one vinyl ester monomer (B1), and optionally

0 to 90 wt.-%, preferably 0 to 75 wt.-%, more preferably 0 to 50 wt.-%, most preferably 0 to 25 wt.-%, relative to the total amount of monomers constituting the polymeric sidechains (B), of at least one secondary monomer (B2), in the presence of polymer backbone (A).

In a preferred embodiment, the polymeric sidechains (B) are obtained by polymerization, in particular by (free) radical polymerization of

65 to 100 wt.-%, preferably 70 to 100 wt.-%, more preferably 75 to 100 wt.-%, most preferably 80 to 100 wt.-%, relative to the total amount of monomers constituting the polymeric sidechains (B), of at least one vinyl ester monomer (B1), and optionally 0 to 35 wt.-%, preferably 0 to 30 wt.-%, more preferably 0 to 25 wt.-%, most preferably 0 to 20 wt.-%, relative to the total amount of monomers constituting the polymeric sidechains (B), of at least one secondary monomer (B2), in the presence of polymer backbone (A).

In a preferred embodiment, the polymeric sidechains (B) are obtained by polymerization of at least one vinyl ester monomer (B1 ), in particular vinyl acetate, in the presence of polymer backbone (A), in the absence of further monomers.

Alternative embodiment E2 for graft polymer:

In an alternative embodiment E2, no vinyl ester monomer is used, but only at least one vinyllac- tam and at least one olefinically unsaturated, radically polymerizable amine-containing monomer is employed for the radical polymerization in the presence of the polymer backbone.

The olefinically unsaturated amine-containing monomer is preferably 1-vinylimidazole or its derivative such as alkyl-substituted derivatives of 1-vinylimidazole such as 2-methyl-1-vinylimidaz- ole, more preferably being only 1-vinylimidazole.

The vinyllactame-monomer is preferably selected from N-vinyllactams, such as N-vinylpyrroli- done, N-vinylpiperidone, N-vinylcaprolactam, even more preferably N-vinylpyrrolidone, N-vinyl- caprolactam, and most preferably is N-vinylpyrrolidone.

Further monomers may be employed as optional monomers, such as any one or more of 1 -vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinyl pyridine-N-oxide, N-vinyl formamide (and its amine if hydrolyzed after polymerization), N-vinyl acetamide, N-vinyl-N-methyl acetamide, acrylamide, methyl acrylamide, N,N‘-di alkyl (meth) acrylamide, but such further monomers do not encompass vinyl ester monomers; preferably no further monomer is employed; at most such further monomer may be present as undesired impurity in very low amounts.

The inventive graft polymers of Embodiment E2 as detailed before in their composition, their preferred, more preferred etc., most preferred compositions contain the first and the second structural unit in the following amounts - each in weight percent being based on the total weight of the graft polymer: the amount of the polymer backbone (A) is from 70 to 95, preferably 73 to 90, more preferably 73 to 87, even more preferably 75 to 85, and most preferably 77 to 85, and the amount of polymeric side chains (B) is from 5 to 30, preferably 10 to 27, more preferably 13 to 27 even more preferably 15 to 25, most preferably 15 to 23, and the amount of vinyllactam (B1) is at least 4 and up to 29, and the amount of amine-monomer is at least 1 and up to 15,

- with the amount of amine-monomer (B2) in relation to vinyllactame being in all cases not more than 4-times, preferably not more than 3-times, more preferably not more than 2- times, even more preferably the same amount, and preferably at least 5%, more preferably at least 10%, even more preferably at least 25%, even more preferably at least 50, even more preferably at least 75% as/of the amount of vinyllactame, and the amount of further monomer(s) is from 0 to 5, preferably at most 2, more preferably 0, but in all cases at most 50% of the amount of vinyllactame, and not more than the amount of amine-monomer.

Hence, in a more preferred embodiment the following amounts are chosen - each in weight percent being based on the total weight of the graft polymer: the amount of the polymer backbone (A) is from 75 to 85, and most preferably 77 to 85, and the amount of polymeric side chains (B) is from 15 to 25, most preferably 15 to 23, and the amount of (B1) is at least 6 and up to 24, more preferably up to 20, even more preferably up to 15, even more preferably up to 12, and most preferably at least 7,5 and up to 10, and the amount of (B2) is at least 1 and up to 15, more preferably up to 13, even more preferably up to 12, even more preferably up to 11 , and most preferably at least 7,5 and up to 10, and more preferably with the amount of (B2) in relation to (B1) being the same amount however without exceeding the total upper or lower limit of (B).

In another embodiment the following amounts are chosen - each in weight percent being based on the total weight of the graft polymer: the amount of the polymer backbone (A) is from 75 to 85, and most preferably 77 to 85, and the amount of polymeric side chains (B) is from 15 to 25, most preferably 15 to 23, and the amount of (B1) is at least 6 and up to 24, more preferably up to 20, even more preferably up to 15, even more preferably up to 12, and most preferably at least 7,5 and up to 10, and the amount of (B2) is at least 1 and up to 15, more preferably up to 13, even more preferably up to 12, even more preferably up to 11 , and most preferably at least 7,5 and up to 10, and preferably the amount of (B2) in relation to (B1) in all cases being at most 75%, even more preferably at most 50%, and most preferably at most 25 %, as/of the amount of (B1).

In a preferred embodiment, the graft polymer as disclosed herein and specifically as detailed in the embodiments before wherein the

(A) the polymer backbone (A) is a tri-block polymer EO/PO/EO, the molecular weight of the polymer backbone (A) as Mn in g/mol is within 400 to 3000, with the relative amount of EO in the polymer backbone (A) being within 10 - 90, preferably 10 to 60, more preferably 15 to 50 weight percent in relation to the total molar amount of alkylene oxides in the polymer backbone

(A), and

(B) the polymeric side chains consist of the following monomers:

B1 is 1 -vinyl imidazole, and

B2 is a N-vinyllactame, preferably is N-vinylpyrrolidone.

It is to be understood that - in both Embodiments E1 and E2 - the amounts for polymer backbone and various monomer-types and that for the further monomers may be selected from the various detailed ranges given independently, i.e. lower and upper borders may be combined also from two different ranges given to result in a numerical range not specified explicitly herein in numbers, such combined range for e.g. backbone and various monomer-types or that for the further monomers however being explicitly intended to be encompassed by this present invention.

Also, broad ranges and very particularly preferred narrow ranges may be combined in one embodiment of this invention, with the selection of the ranges for one component being independent of that for the other component, in as far as the overall numbers add up to a “100%-poly- mer”: e.g. the most preferred range for polymer backbone (A) and monomers (B) may be chosen and combined with the broadest possible ranges given for the individual monomer-types, and any other possible combination.

Alternative embodiment E3 for graft polymer:

In this alternative embodiment the graft polymers as disclosed in W02023017061A1 are prepared using the monomers, backbones, reaction conditions etc. as detailed in that disclosures but with the use of the elements of the present invention, i.e. with the use of steps a) to d) of the present invention however otherwise following the selections of monomers, monomer ratios, ratios of backbone to monomers, reaction conditions, radical initiators and solvents as detailed in W02023017061A1.

Thus, this present invention enables to obtain and produce the polymers and their preferred versions as detailed in W02023017061 A1 but with a reduced amount of fossil-based hydrogencontent and thus an overall reduced carbon footprint.

In one general embodiment of the present invention applicable to E1 , E2 and E3, the polymeric sidechains (B) of the graft polymer according to the present invention are fully or at least partially hydrolyzed after the graft polymer as such is obtained. This means that the full or at least partial hydrolyzation of the polymeric sidechains (B) of the graft polymer is carried out after the polymerization process of the polymeric sidechains (B) is finished.

The hydrolysis can be carried out by any method known to a person skilled in the art. For example, the hydrolysis can be induced by addition of a suitable base, such as sodium hydroxide or potassium hydroxide.

Within this embodiment, it is preferred that the hydrolyzation of the polymeric sidechains (B) is only carried out partially, for example, to an extent that up to 20 wt.-%, 40 wt.-% or 60 wt.-% of the units derived from vinyl ester monomer (B1 ) are hydrolyzed, relative to the total weight of vinyl ester monomer (B1).

In a more preferred embodiment, the polymeric sidechains (B) are not hydrolyzed after polymerization.

As mentioned above, it is important that the origin of the hydrogen and downstream compounds obtained by clean energy can be tracked in a reliable way. Today, the majority of hydrogen is produced from fossil fuels by steam reforming of natural gas and other light hydrocarbons, partial oxidation of heavier hydrocarbons, and coal gasification.

However, up to now, there was no possibility to distinguish the hydrogen obtained by by steam reforming, partial oxidation and coal gasification, i.e. by fossil resources, from hydrogen obtained by electrolysis. As discussed above, hydrogen obtained by electrolysis is preferably obtained by using non-fossil energy sources. It is expected that the electrification (power generation) of fossil sources will be fully replaced by the generation of power by non-fossil resources in the near future.

The inventors therefore found a way for tracing the origin of hydrogen and downstream products of hydrogen, preferably the inventive graft polymers via the deuterium molar share of said compounds. These downstream products, i.e. graft polymers as detailed herein, based on hydrogen, such hydrogen obtained by electrolysis, and hydrogen itself can be distinguished by its deuterium molar share from the chemically in principle identical compounds prepared by processes based on fossil energy, i.e. made by petrochemical processes.

Furthermore by using carbon oxides such as carbon monoxide and preferably carbon dioxide together with hydrogen instead of petrochemical synthesis gas in the subsequent synthesis routes for graft polymers, the molar share of deuterium in these compounds was found to be uniquely low with excellent traceability.

The present invention therefore relates to the use of the molar share of deuterium in hydrogen and downstream compounds based on hydrogen for tracing the origin, especially the energetic origin, of the hydrogen and downstream compounds based on hydrogen, wherein the compounds are preferably graft polymers as detailed herein.

The present invention further relates to a process for tracing the origin, especially the energetic origin, of hydrogen and downstream compounds based on hydrogen by determining the molar share of deuterium in hydrogen and said downstream compounds based on hydrogen, wherein the compounds are graft polymers as detailed herein.

Tracing is in the meaning of the present invention synonymous with tracking.

The origin is in the meaning of the present invention the preparation method of the hydrogen employed, especially electrolysis and/or the energetic origin, i.e. non-fossil energy sources. As mentioned above, it is expected that the electrification (power generation) of fossil sources will be fully replaced by the generation of power by non-fossil resources in the near future. Hydrogen made by electrolysis is in this case hydrogen of non-fossil origin. Examples for non-fossil power sources are mentioned above. The inventive process for tracing the origin, especially the energetic origin, of hydrogen and downstream compounds mentioned above may be employed as a single tracing (tracking) method or in combination with further tracing (tracking) methods.

Inventive compounds accessible with the present invention encompasses any and all such graft polymers following the outline given herein, especially those as detailed in more specifics.

Such graft polymers are partially known to date from prior art, some of them being commercially available.

A graft polymer of vinylacetate grafted on a polyethyleneglycol (of a molecular weight of about 6000 g/mol) is commercially available from e.g. BASF.

Another such graft polymer is Kollicoat I R, which is a polymer obtained from polyethylene glycol (of a molecular weight of about 6000 g/mol) grafted with vinyl acetate, wherein the vinyl acetate is hydrolyzed after radical polymerization to obtain a “vinylalcohol-grafted” PEG.

Another polymer is a graft polymer of vinylcaprolactame and vinylacetate on polyethyleneglycol, being also available from BASF SE.

Further graft polymers are known from e.g. WO2021/160795, US 5,318,719 A, CN 102 030 871 , WO 03/042262, US 2019/0390142, WO 2007/138053, Y. Zhang et al. J. Coll. Inter. Sci 2005, 285, 80, W02020/005476, W02020/264077, W00018375, W02023017061 A1 , US2008/255326 - to mention only a few of the many disclosures.

All of the before mentioned and referenced graft polymers are encompassed by this present invention when produced using the present invention by replacing at least one element of the prior art process/starting material with an element of the present invention, e.g. replacing the standard fossil-based EO with the EO as producible or preferably produced with a process of this present invention.

The uses of and the products /formulations/compositions comprising such inventive graft polymers as disclosed and defined herein and with reference to prior art disclosures are the same as known in the art; such uses of and the products /formulations/compositions comprising such inventive graft polymers are especially those, respectively, being disclosed in any of the following disclosures - provided that the monomers used for grafting fit to the application (which is defined in such disclosures): e.g. US 2019/390142, W02020/264077, W02020/005476, W02023017061A1 , WO 03/042262, and generally also in pharmaceutical applications, in oilfied applications (as e.g. gas hydrate inhibitors), in detergents for primary washing, anti-greying, dye transfer inhibitions, in agrochemical formulations, printing, electronics etc.

In all of those disclosures of the state of the art and the known uses and applications, the graft polymers can be replaced partially or completely with inventive graft polymers when having the same or closely similar chemical structures but being produced using at least one element of the present invention, e.g. replacing the standard fossil-based EO with EO as producible or preferably produced with a process of this present invention. Uses, and Cleaning Compositions

The graft polymers of this invention as detailed herein before specifically and by reference to various prior art documents cited, may hereinafter also termed “inventive compound(s)” and “compound(s) of the invention”.

The terms ”at least one inventive compound” and “inventive compound(s)” encompasses one, two, three, four or more inventive compound(s) as a mixture.

The inventive compound(s) as directly obtained from the inventive process can be used advantageously in cleaning compositions.

They may be used as at least one inventive compound, or mixtures of more than one inventive compound.

Hence, another subject matter of the present invention is the use of the above-mentioned inventive compound(s) in cleaning compositions, specifically as prepared by the process defined herein.

The inventive compound(s) can be added to cleaning compositions. The inventive compound(s) are present in general in said formulations at a concentration of from about 0.1 % to about 50%, preferably from about 0,25% to 15%, more preferably from about 0.5% to about 10%, and even more preferably from about 0.5% to about 5%, and most preferably in amounts of up to 3%, each in weight % in relation to the total weight of such composition/product, optionally further comprising from about 1 % to about 70% by weight of a surfactant system, wherein - specifically - for a liquid hand dishwashing or spray detergent cleaning composition such composition comprising from 0.1 % to 50%, preferably from 1 % to 35%, more preferably from 3% to 30%, by weight of the total composition, of a surfactant system, and such surfactant system preferably comprising from 60% to 90%, more preferably from 70% to 80% by weight of the surfactant system of an anionic surfactant.

Hence, another subject matter of the present invention is the use of the inventive compound(s) obtained by a process of the invention as detailed before, in fabric and home care products, in particular cleaning compositions for improved oily and fatty stain removal, removal of solid dirt such as clay, prevention of greying of fabric surfaces, and/or anti-scale agents, wherein the cleaning composition is preferably a laundry detergent formulation and/or a dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.

Another subject-matter of the present invention is, therefore, also a cleaning composition, fabric and home care product, industrial and institutional cleaning product, preferably in laundry detergents, in cleaning compositions and/or in fabric and home care products, each comprising at least one inventive compound(s) obtained by a process of the invention. A further subject-matter of the present invention is a fabric and home care product, cleaning composition, industrial and institutional cleaning product, preferably a laundry detergent, a cleaning composition and/or a fabric and home care product, each containing at least one inventive compound obtained by a process of the invention.

In a preferred embodiment, it is a cleaning composition and/or fabric and home care product and/or industrial and institutional cleaning product, comprising at least one inventive compound obtained by a process of the invention. In particular, it is a cleaning composition for improved cleaning performance, especially improved primary washing, preferably a laundry detergent formulation and/or a manual dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.

In a preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition, preferably a liquid laundry detergent composition.

In another preferred embodiment, the cleaning composition of the present invention is a liquid or solid (e.g. powder or tab/unit dose) detergent composition for manual or automatic dish wash, preferably a liquid manual dish wash detergent composition. Such compositions are known to a person of skill in the art.

In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition that may be used for cleaning various surfaces such as hard wood, tile, ceramic, plastic, leather, metal, glass. One - preferred - example is a detergent formulation for washing dishes and cutlery, i.e. a “hand dish detergent”. Another example is a spray cleaner, which is typically to be sprayed on a hard surface and then wiped away thereby removing soil and grease etc.

In one embodiment of the present invention, the inventive compound(s) obtained by a process of the invention is a component of a cleaning compositions or fabric and home care product, preferably a laundry cleaning composition, a laundry care product or laundry treatment product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, that each additionally comprise at least one surfactant, preferably at least one anionic surfactant.

In one embodiment it is also preferred in the present invention that the cleaning composition comprises (besides at least one inventive compound obtained by a process of the invention) additionally at least one enzyme, preferably selected from one or more optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicoreductases, dispersins, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one enzyme being selected from lipases. Even more preferably, the cleaning compositions of the present invention comprising at least one inventive compound obtained by a process of the invention and optionally further comprising at least one surfactant or a surfactant system - as detailed before - are those for improved cleaning performance within laundry and manual dish wash applications, even more specifically, for improved cleaning performance (such actions as detailed before) such as those on fabrics and dishware, and may additionally comprise at least one enzyme selected from the list consisting of optionally further comprising at least one enzyme, preferably selected from one or more optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicoreductases, dispersins, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the foregoing types, more preferably at least one enzyme being selected from lipases.

In one embodiment, the inventive compound(s) obtained by a process of the invention may be utilized in cleaning compositions comprising a surfactant system comprising C10-C15 alkyl benzene sulfonates (LAS) as the primary surfactant and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

In a further embodiment the inventive compound(s) obtained by a process of the invention may be utilized in cleaning compositions or fabric and home care product, preferably a laundry cleaning composition, a laundry care product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, comprising C12-C18 alkyl ethoxylate surfactants with 5-10 ethoxy-units as the primary surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non-ionic surfactants, or mixtures thereof.

In a further embodiment, the inventive compound(s) obtained by a process of the invention may be utilized in the cleaning compositions or fabric and home care product, preferably a laundry cleaning composition, a laundry care product or laundry treatment product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, comprising C8-C18 linear or branched alkyl ethersulfates with 1-5 ethoxy-units as the primary surfactant and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

In one embodiment of the present invention, the inventive compound(s) obtained by a process of the invention is a component of a cleaning composition, such as preferably a laundry or a dish wash formulation, more preferably a liquid laundry or manual dish wash formulation, that each additionally comprise at least one surfactant, preferably at least one anionic surfactant. In a further embodiment, this invention also encompasses a composition comprising at least one inventive compound obtained by a process of the invention, further comprises an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2-phenoxy- ethanol, more preferably comprising said antimicrobial agent in an amount ranging from 2ppm to 5% by weight of the composition; even more preferably comprising 0.1 to 2% of phenoxyethanol.

In a further embodiment, this invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising inventive compound(s) obtained by a process of the invention in the amounts detailed before as described herein before, such composition further comprising 4,4’-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1 %, more preferably 0.01 to 0.6%, each by weight of the composition.

In a further embodiment, this invention also encompasses a composition, specifically a cleaning composition, more preferably a cleaning composition in liquid, solid or semi-solid form, preferably being a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation or solid automatic dish washing formulation, more preferably a laundry detergent formulation, comprising inventive compound(s) obtained by a process of the invention and in the amounts as detailed before, such composition being preferably a detergent composition, such composition further comprising an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2-phenoxy- ethanol, more preferably comprising said antimicrobial agent in an amount ranging from 2ppm to 5% by weight of the composition; even more preferably comprising 0.1 to 2% of phenoxyethanol.

In a further embodiment, this invention also encompasses a method of preserving an aqueous composition against microbial contamination or growth, such composition, specifically a cleaning composition, more preferably a cleaning composition in liquid, solid or semi-solid form, preferably being a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation or solid automatic dish washing formulation, more preferably a laundry detergent formulation, comprising inventive compound(s) obtained by a process of the invention and in the amounts detailed before, such composition being preferably a detergent composition, such method comprising adding at least one antimicrobial agent selected from the disclosed antimicrobial agents as disclosed hereinafter, such antimicrobial agent preferably being 2-phenoxyethanoL

In a further embodiment, this invention also encompasses a method of laundering fabric or of cleaning hard surfaces, which method comprises treating a fabric or a hard surface with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid sof- tener composition for use in laundry, such composition comprising inventive compound(s) obtained by a process of the invention in the amounts detailed before, such composition further comprising 4,4’-dichoro 2-hydroxydiphenylether.

As used herein the phrase "cleaning composition" as used for the inventive compositions and products includes compositions and formulations designed for cleaning soiled material. Such compositions include but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, dish washing compositions, hard surface cleaning compositions, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein. Such compositions may be used as a pre-laundering treatment, a post-laundering treatment, or may be added during the rinse or wash cycle of the laundering operation. The cleaning compositions may have a form selected from liquid, powder, single-phase or multi-phase unit dose, pouch, tablet, gel, paste, bar, or flake.

The cleaning compositions of the invention comprise a surfactant system in an amount sufficient to provide desired cleaning properties. In some embodiments, the cleaning composition comprises, by weight of the composition, from about 1 % to about 70% of a surfactant system. In other embodiments, the liquid cleaning composition comprises, by weight of the composition, from about 2% to about 60% of the surfactant system. In further embodiments, the cleaning composition comprises, by weight of the composition, from about 5% to about 30% of the surfactant system. In embodiments for a liquid hand dishwashing or spray detergent cleaning composition such composition comprises preferably from 60% to 90%, more preferably from 70% to 80% by weight of the surfactant system, more preferably of an anionic surfactant. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. Those of ordinary skill in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.

Even more preferably, the compositions or products of the present invention as detailed herein before comprising at least one inventive alkoxylated amino acid esters and/or their salts obtained by a process of the invention and in the amounts as specified in the previous paragraph, optionally further comprising at least one surfactant or a surfactant system in amounts from about 1 % to about 70% by weight of the composition or product, are preferably those for primary cleaning (i.e. removal of stains) and more preferably within laundry applications, and may additionally comprise at least one enzyme selected from lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases and peroxidases, more preferably at least two of the aforementioned types. The phrase "cleaning composition" as used herein includes compositions and formulations and products designed for cleaning soiled material. Such compositions, formulations and products include those designed for cleaning soiled material or soiled surfaces of any kind.

Compositions for “industrial and institutional cleaning” includes such cleaning compositions being designed for use in industrial and institutional cleaning, such as those for use of cleaning soiled material or surfaces of any kind, such as hard surface cleaners for surfaces of any kind, including tiles, carpets, PVC-surfaces, wooden surfaces, metal surfaces, lacquered surfaces.

“Compositions for Fabric and Home Care” include cleaning compositions including but not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, dish washing compositions, hard surface cleaning compositions, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein. Such compositions may be used as a pre-laun- dering treatment, a post-laundering treatment, or may be added during the rinse or wash cycle of the laundering operation, preferably during the wash cycle of the laundering or dish washing operation.

The cleaning compositions of the invention may be in any form, namely, in the form of a liquid; a solid such as a powder, granules, agglomerate, paste, tablet, pouches, bar, gel; an emulsion; types delivered in dual- or multi-compartment containers; single-phase or multi-phase unit dose; a spray or foam detergent; premoistened wipes (i.e., the cleaning composition in combination with a nonwoven material such as that discussed in US 6,121 ,165, Mackey, et al.); dry wipes (i.e., the cleaning composition in combination with a nonwoven materials, such as that discussed in US 5,980,931 , Fowler, et al.) activated with water by a user or consumer; and other homogeneous, non-homogeneous or single-phase or multiphase cleaning product forms.

The liquid cleaning compositions of the present invention preferably have a viscosity of from 50 to 10000 mPa*s; liquid manual dish wash cleaning compositions (also liquid manual “dish wash compositions”) have a viscosity of preferably from 100 to 10000 mPa*s, more preferably from 200 to 5000 mPa*s and most preferably from 500 to 3000 mPa*s at 20 1/s and 20°C; liquid laundry cleaning compositions have a viscosity of preferably from 50 to 3000 mPa*s, more preferably from 100 to 1500 mPa*s and most preferably from 200 to 1000 mPa*s at 20 1/s and 20°C.

The cleaning compositions and formulations of the invention may - and preferably do - contain adjunct cleaning additives (also abbreviated herein as “adjuncts”), such adjuncts being preferably in addition to a surfactant system as defined before. Suitable adjunct cleaning additives include builders, cobuilders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, and perfumes.

Liquid cleaning compositions additionally may comprise - and preferably do comprise at least one of - rheology control/modifying agents, emollients, humectants, skin rejuvenating actives, and solvents.

Solid compositions additionally may comprise - and preferably do comprise at least one of - fillers, bleaches, bleach activators and catalytic materials.

Suitable examples of such cleaning adjuncts and levels of use are found in WO 99/05242, U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.

Those of ordinary skill in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.

Hence, the cleaning compositions of the invention such as fabric and home care products, and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, preferably additionally comprise a surfactant system and, more preferably, also further adjuncts, as the one described above.

The surfactant system may be composed from one surfactant or from a combination of surfactants selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Those of ordinary skill in the art will understand that a surfactant system for detergents encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.

The cleaning compositions of the invention typically comprise a surfactant system in an amount sufficient to provide desired cleaning properties.

The liquid cleaning compositions of the present invention may have any suitable pH-value. Preferably the pH of the composition is adjusted to between 4 and 14. More preferably the composition has a pH of from 6 to 13, even more preferably from 6 to 10, most preferably from 7 to 9.

The pH of the composition can be adjusted using pH modifying ingredients known in the art and is measured as a 10% product concentration in demineralized water at 25°C. For example, NaOH may be used and the actual weight% of NaOH may be varied and trimmed up to the desired pH such as pH 8.0. In one embodiment of the present invention, a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine. The selection of the additional surfactants and further ingredients in these embodiments may be dependent upon the application and the desired benefit.

All such cleaning compositions, their ingredients including (adjunct) cleaning additives, their general compositions and more specific compositions are known, as for example illustrated in the publications 800542 and 800500 as published by Protegas, Liechtenstein, and also from WO 2022/136409 and WO 2022/136408, wherein in any of the before prior art documents the inventive compound, i.e. any of the graft polymers as detailed herein specifically or by reference to prior art disclosures, within the general compositions and also each individualized specific cleaning composition disclosed in the beforementioned publications may be replaced partially or completely by the respective inventive compound prepared using the present invention. In those beforementioned documents, also various types of formulations for cleaning compositions are disclosed; all such composition types - the general compositions and also each individualized specific cleaning composition - can be equally applied also to those cleaning compositions contemplated herein.

Hence, the present invention also encompasses any and all of such disclosed compositions of the before-mentioned prior art-disclosures but further comprising at least one of the inventive compounds in addition to or as a replacement for any already ins such prior art-composition contained compound of similar or - preferably - identical chemical nature and structure, or any such compound, which can be replaced by such inventive compound- such replacements in principle known to a person of skill in the art or readily obvious in view of the present invention. Typically the content of the inventive compound being present in said formulations is the same concentration as used in the referenced prior art document and the products and formulations therein; such concentration typically being from 0,05 to 20 wt.%, preferably up to 10 wt. %, more preferably 0.1 to 5 weight%, even more preferably at a concentration of 0.5 to 2 weight%.

General description of cleaning compositions, formulations and their ingredients

Cleaning compositions such as fabric and home care products and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, are known to a person skilled in the art. Any composition etc. known to a person skilled in the art, in connection with the respective use, can be employed within the context of the present invention by including at least one inventive compound, preferably at least one such inventive compound in amounts suitable for expressing a certain property within such a composition, especially when such a composition is used in its area of use.

Cleaning additives

The cleaning compositions and formulations of the invention may - and preferably do - contain adjunct cleaning additives (also abbreviated herein as “adjuncts”), such adjuncts being preferably in addition to a surfactant system as defined before. Suitable adjunct cleaning additives include builders, cobuilders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, and perfumes. All such adjuncts are detailed and exemplified further below in the following chapters.

Hence, the cleaning compositions of the invention such as fabric and home care products, and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, preferably additionally comprise a surfactant system and, more preferably, also further adjuncts, as the one described above and below in more detail.

The cleaning compositions of the invention preferably comprise a surfactant system in an amount sufficient to provide desired cleaning properties. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.

Laundry compositions

“Laundry composition” may be any composition, formulation or product which is intended for use in laundry including laundry care, laundry cleaning etc.; hence this term will be used in the following denoting any composition, formulation or product.

In laundry compositions, anionic surfactants contribute usually by far the largest share of surfactants within such formulation. Hence, preferably, the inventive cleaning compositions for use in laundry comprise at least one anionic surfactant and optionally further surfactants selected from any of the surfactant classes described herein, preferably from non-ionic surfactants and/or amphoteric surfactants and/or zwitterionic surfactants and/or cationic surfactants.

Cleaning compositions may - and preferably do - also contain anionic surfactants - which may be employed also in combinations of more than one other surfactant.

Nonlimiting examples of anionic surfactants - which may be employed also in combinations of more than one surfactant - useful herein include C9-C20 linear alkylbenzenesulfonates (LAS), C10-C20 primary, branched chain and random alkyl sulfates (AS); C10-C18 secondary (2,3) alkyl sulfates; C10-C18 alkyl alkoxy sulfates (AExS) wherein x is from 1 to 30; C10-C18 alkyl alkoxy carboxylates comprising 1 to 5 ethoxy units; mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonate (MES); and alpha-olefin sulfonate (AOS).

Preferred examples of suitable anionic surfactants are alkali metal and ammonium salts of C8- C12-alkyl sulfates, of C12-C18-fatty alcohol ether sulfates, of C12-C18-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated 04-012-alkylphenols (ethoxylation: 3 to 50 mol of ethylene oxide/mol), of C12-C18-alkylsulfonic acids, of 012-018 sulfo fatty acid alkyl esters, for example of 012-018 sulfo fatty acid methyl esters, of C10-C18-alkylarylsulfonic acids, preferably of n-C10-C18-alkylbenzene sulfonic acids, of 010-C18 alkyl alkoxy carboxylates and of soaps such as for example C8-C24-carboxylic acids. Preference is given to the alkali metal salts of the aforementioned compounds, particularly preferably the sodium salts.

In one embodiment of the present invention, anionic surfactants are selected from n-C10-C18- alkylbenzene sulfonic acids and from fatty alcohol polyether sulfates, which, within the context of the present invention, are in particular sulfuric acid half-esters of ethoxylated C12-C18-alka- nols (ethoxylation: 1 to 50 mol of ethylene oxide/mol), preferably of n-C12-C18-alkanols.

In one embodiment of the present invention, also alcohol polyether sulfates derived from branched (i.e., synthetic) C11-C18-alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol) may be employed.

Preferably, the alkoxylation group of both types of alkoxylated alkyl sulfates, based on C12- C18-fatty alcohols or based on branched (i.e., synthetic) C11-C18-alcohols, is an ethoxylation group and an average ethoxylation degree of any of the alkoxylated alkyl sulfates is 1 to 5, preferably 1 to 3.

Preferably, the laundry detergent formulation of the present invention comprises from at least 1 wt. % to 50 wt. %, preferably in the range from greater than or equal to about 2 wt. % to equal to or less than about 30 wt. %, more preferably in the range from greater than or equal to 3 wt. % to less than or equal to 25 wt. %, and most preferably in the range from greater than or equal to 5 wt. % to less than or equal to 25 wt. % of one or more anionic surfactants as described above, based on the particular overall composition, including other components and water and/or solvents. In a preferred embodiment of the present invention, anionic surfactants are selected from C10- C15 linear alkylbenzenesulfonates, C10-C18 alkylethersulfates with 1-5 ethoxy units and C10- C18 alkylsulfates.

Cleaning compositions may also contain non-ionic surfactants - which may be employed also in combinations of more than one other surfactant.

Non-limiting examples of non-ionic surfactants - which may be employed also in combinations of more than one other surfactant - include: C8-C18 alkyl ethoxylates, such as, NEODOL® non- ionic surfactants from Shell; ethylenoxide/propylenoxide block alkoxylates as PLURONIC® from BASF; C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x is from 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkylpolysaccharides as discussed in U.S. 4,565,647 Llenado, issued January 26, 1986; specifically alkylpolyglycosides as discussed in US 4,483,780 and US 4,483,779; polyhydroxy fatty acid amides as discussed in US 5,332,528; and ether capped poly(oxyalkylated) alcohol surfactants as discussed in US 6,482,994 and WO 01/42408.

Preferred examples of non-ionic surfactants are in particular alkoxylated alcohols and alkox- ylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, furthermore alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides). Examples of (additional) amphoteric surfactants are so-called amine oxides.

Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (A)

[ formula (A)] in which the variables are defined as follows:

R1 is selected from linear C1-C10-alkyl, preferably ethyl and particularly preferably methyl,

R2 is selected from C8-C22-alkyl, for example n-C8H 17, n-C10H21 , n-C12H25, n-C14H29, n- C16H33 or n-C18H37,

R3 is selected from C1-C10-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-bu- tyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl, m and n are in the range from zero to 300, where the sum of n and m is at least one. Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30.

Here, compounds of the general formula (A) may be block copolymers or random copolymers, preference being given to block copolymers.

Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (B)

[formula (B)] in which the variables are defined as follows:

R1 is identical or different and selected from linear C1-C4-alkyl, preferably identical in each case and ethyl and particularly preferably methyl,

R4 is selected from C6-C20-alkyl, in particular n-C8H17, n-C10H21 , n-C12H25, n-C14H29, n- C16H33, n-C18H37, a is a number in the range from zero to 6, preferably 1 to 6, b is a number in the range from zero to 20, preferably 4 to 20, d is a number in the range from 4 to 25.

Preferably, at least one of a and b is greater than zero.

Here, compounds of the general formula (B) may be block copolymers or random copolymers, preference being given to block copolymers.

Further suitable non-ionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable non-ionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Alkylphenol ethoxylates or alkyl polyglycosides or polyhydroxy fatty acid amides (glucamides) are likewise suitable. An overview of suitable further non-ionic surfactants can be found in EP A 0 851 023 and in DE-A 198 19 187. Mixtures of two or more different non-ionic surfactants may of course also be present.

In a preferred embodiment of the present invention, non-ionic surfactants are selected from C12/14 and C16/18 fatty alkoholalkoxylates, C13/15 oxoalkoholalkoxylates, C13-alkoholalkox- ylates, and 2-propylheptylalkoholalkoxylates, each of them with 3 - 15 ethoxy units, preferably 5-10 ethoxy units, or with 1-3 propoxy- and 2-15 ethoxy units.

Cleaning compositions may also contain amphoteric surfactants - which may be employed also in combinations of more than one other surfactant.

Non-limiting examples of amphoteric surfactants - which may be employed also in combinations of more than one other surfactant - include: water-soluble amine oxides containing one alkyl moiety of from about 8 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms. See WO 01/32816, US 4,681 ,704, and US 4,133,779. Suitable surfactants include thus so-called amine oxides, such as lauryl dimethyl amine oxide (“lauramine oxide”).

Preferred examples of amphoteric surfactants are amine oxides. Preferred amine oxides are alkyl dimethyl amine oxides or alkyl amido propyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides and especially coco dimethyl amino oxides. Amine oxides may have a linear or mid-branched alkyl moiety. Typical linear amine oxides include water-soluble amine oxides containing one R1 = C8-18 alkyl moiety and two R2 and R3 moieties selected from the group consisting of C1-C3 alkyl groups and C1-C3 hydroxyalkyl groups. Preferably, the amine oxide is characterized by the formula

R1-N(R2)(R3)-O wherein R1 is a C8-18 alkyl and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyL The linear amine oxide surfactants in particular may include linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides. Preferred amine oxides include linear C10, linear C10-C12, and linear C12-C14 alkyl dimethyl amine oxides. As used herein "midbranched" means that the amine oxide has one alkyl moiety having n1 carbon atoms with one alkyl branch on the alkyl moiety having n2 carbon atoms. The alkyl branch is located on the alpha carbon from the nitrogen on the alkyl moiety. This type of branching for the amine oxide is also known in the art as an internal amine oxide. The total sum of n1 and n2 is from 10 to 24 carbon atoms, preferably from 12 to 20, and more preferably from 10 to 16. The number of carbon atoms for the one alkyl moiety (n1) should be approximately the same number of carbon atoms as the one alkyl branch (n2) such that the one alkyl moiety and the one alkyl branch are symmetric. As used herein "symmetric" means that (n1-n2) is less than or equal to 5, preferably 4, most preferably from 0 to 4 carbon atoms in at least 50 wt. %, more preferably at least 75 wt. % to 100 wt. % of the mid-branched amine oxides for use herein. The amine oxide further comprises two moieties, independently selected from a C1-C3 alkyl, a C1-C3 hydroxyalkyl group, or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups. Preferably the two moieties are selected from a C1-C3 alkyl, more preferably both are selected as a C1 alkyl.

In a preferred embodiment of the present invention, amphoteric surfactants are selected from C8-C18 alkyl-dimethyl aminoxides and C8-C18 alkyl-di(hydroxyethyl)aminoxide.

Certain amphoteric surfactants can - besides their typical action as surfactant - promote corrosion inhibition, such as compounds having one or two carboxylic groups and one or more amine groups, and optionally further containing also amide-groups and/or hydroxy-groups; such compounds for example being N-(2-carboxyethyl)-N-dodecyl-beta-alaninate (also named N-lauryl- beta-iminodipropionate metal salt, cocoamphodiacetate di-metal salt, cocoamphoacetate metal salt (the metal typically being sodium). Hence, such amphoteric surfactants arte preferred when corrosion inhibition is of importance, such as in cleaning applications which typically have a high pH, e.g. automatic dish washing.

Cleaning compositions may also contain zwitterionic surfactants - which may be employed also in combinations of more than one other surfactant.

Suitable zwitterionic surfactants include betaines, such as alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines) as well as the phosphobetaines. Examples of suitable betaines and sulfobetaines are the following (designated in accordance with INCI): Almond amidopropyl of betaines, Apricotamidopropyl betaines, Avocadamidopropyl of betaines, Babassuamidopropyl of betaines, Behenamidopropyl betaines, Behenyl of betaines, Canol ami- dopropyl betaines, Capryl/Capramidopropyl betaines, Carnitine, Cetyl of betaines, Cocamido- ethyl of betaines, Cocamidopropyl betaines, Cocamidopropyl Hydroxysultaine, Coco betaines, Coco Hydroxysultaine, Coco/Oleam idopropyl betaines, Coco Sultaine, Decyl of betaines, Dihydroxyethyl Oleyl Glycinate, Di hydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl of PG-betaines, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow of betaines, Isostearamid-'opropyl betaines, Lauramidopropyl betaines, Lauryl of betaines, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl betaines, Minkamidopropyl of betaines, Myristamidopropyl betaines, Myristyl of betaines, Oleamidopropyl betaines, Oleamidopropyl Hydroxysultaine, Oleyl of betaines, Olivamidopropyl of betaines, Palmamidopropyl betaines, Palmitamidopropyl betaines, Palmitoyl Carnitine, Palm Kernelami- dopropyl betaines, Polytetrafluoroethylene Acetoxypropyl of betaines, Ricinoleam idopropyl betaines, Sesamidopropyl betaines, Soyamidopropyl betaines, Stearamidopropyl betaines, Stearyl of betaines, Tallowamidopropyl betaines, Tallowamidopropyl Hydroxysultaine, Tallow of betaines, Tallow Di hydroxyethyl of betaines, Undecylenamidopropyl betaines and Wheat Germamidopropyl betaines.

Preferred betaines are, for example, C12-C18-alkylbetaines and sulfobetaines. The zwitterionic surfactant preferably is a betaine surfactant, more preferable a Cocoamidopropylbetaine surfactant.

Non-limiting examples of cationic surfactants - which may be employed also in combinations of more than one other surfactant - include: the quaternary ammonium surfactants, which can have up to 26 carbon atoms include: alkoxylated quaternary ammonium (AQA) surfactants as discussed in US 6,136,769; dimethyl hydroxyethyl quaternary ammonium as discussed in US 6,004,922; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; cationic ester surfactants as discussed in US patents Nos. 4,228,042, 4,239,660 4,260,529 and US 6,022,844; and amino surfactants as discussed in US 6,221 ,825 and WO 00/47708, specifically amido propyldimethyl amine (APA).

Compositions according to the invention may comprise at least one builder. In the context of the present invention, no distinction will be made between builders and such components elsewhere called “co-builders”. Examples of builders are complexing agents, hereinafter also referred to as complexing agents, ion exchange compounds, and precipitating agents. Builders are selected from citrate, phosphates, silicates, carbonates, phosphonates, amino carboxylates and polycarboxylates.

In the context of the present invention, the term citrate includes the mono- and the dialkali metal salts and in particular the mono- and preferably the trisodium salt of citric acid, ammonium or substituted ammonium salts of citric acid as well as citric acid. Citrate can be used as the anhydrous compound or as the hydrate, for example as sodium citrate dihydrate. Quantities of citrate are calculated referring to anhydrous trisodium citrate.

The term phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogenphosphate, sodium pyrophosphate and polyphosphates such as sodium tripolyphosphate. Preferably, however, the composition according to the invention is free from phosphates and polyphosphates, with hydrogenphosphates being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate (“phosphate-free”). In connection with phosphates and polyphosphates, “free from” should be understood within the context of the present invention as meaning that the content of phosphate and polyphosphate is in total in the range from 10 ppm to 0.2% by weight of the respective composition, determined by gravimetry.

The term carbonates includes alkali metal carbonates and alkali metal hydrogen carbonates, preferred are the sodium salts. Particularly preferred is Na2CO3.

Examples of phosphonates are hydroxyalkanephosphonates and aminoalkanephosphonates. Among the hydroxyalkanephosphonates, the 1-hydroxyethane-1 ,1 -diphosphonate (HEDP) is of particular importance as builder. It is preferably used as sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Suitable aminoalkanephosphonates are preferably ethylene diamine-^,tetra-^,methylene-^,phosphonate (EDTMP), diethylenetriamine- penta-'methylene-'phosphonate (DTPMP), and also their higher homologues. They are preferably used in the form of the neutrally reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salts of DTPMP.

Examples of amino carboxylates and polycarboxylates are nitrilotriacetates, ethylene diamine tetraacetate, diethylene triamine pentaacetate, triethylene tetraamine hexaacetate, propylene diamines tetraacetic acid, ethanol-diglycines, methylglycine diacetate, and glutamine diacetate. The term amino carboxylates and polycarboxylates also include their respective non-substituted or substituted ammonium salts and the alkali metal salts such as the sodium salts, in particular of the respective fully neutralized compound.

Silicates in the context of the present invention include in particular sodium disilicate and sodium metasilicate, alumosilicates such as for example zeolites and sheet silicates, in particular those of the formula a-Na2Si2O5, p-Na2Si2O5, and 6-Na2Si2O5.

Compositions according to the invention may contain one or more builder selected from materials not being mentioned above. Examples of builders are a-hydroxypropionic acid and oxidized starch.

In one embodiment of the present invention, builder is selected from polycarboxylates. The term “polycarboxylates” includes non-polymeric polycarboxylates such as succinic acid, C2-C16-alkyl disuccinates, C2-C16-alkenyl disuccinates, ethylene diamine N,N’-disuccinic acid, tartaric acid diacetate, alkali metal malonates, tartaric acid monoacetate, propanetricarboxylic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid.

Oligomeric or polymeric polycarboxylates are for example polyaspartic acid or in particular alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers.

Suitable co-monomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. A suitable polymer is in particular polyacrylic acid, which preferably has a weight-average molecular weight Mw in the range from 2000 to 40 000 g/mol, preferably 2000 to 10 000 g/mol, in particular 3000 to 8000 g/mol. Further suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid. It is also possible to use copolymers of at least one monomer from the group consisting of mo- noethylenically unsaturated C3-C10-mono- or C4-C10-dicarboxylic acids or anhydrides thereof, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, with at least one hydrophil ically or hydrophobically modified co-monomer as listed below.

Suitable hydrophobic co-monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins with ten or more carbon atoms or mixtures thereof, such as, for example, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene, 1-eicosene, 1-do- cosene, 1 -tetracosene and 1 -hexacosene, C22-a-olefin, a mixture of C20-C24-a-olefins and polyisobutene having on average 12 to 100 carbon atoms per molecule.

Suitable hydrophilic co-monomers are monomers with sulfonate or phosphonate groups, and also non-ionic monomers with hydroxyl function or alkylene oxide groups. By way of example, mention may be made of: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, meth- oxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate. Polyalkylene glycols here can comprise 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.

Particularly preferred sulfonic-acid-group-containing monomers here are 1-acrylamido-1 -propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesul- fonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1- sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and salts of said acids, such as sodium, potassium or ammonium salts thereof.

Particularly preferred phosphonate-group-containing monomers are vinylphosphonic acid and its salts.

Moreover, amphoteric polymers can also be used as builders.

Compositions according to the invention can comprise, for example, in the range from in total 0.1 to 70% by weight, preferably 10 to 50% by weight, preferably up to 20% by weight, of builder(s), especially in the case of solid formulations. Liquid formulations according to the invention preferably comprise in the range of from 0.1 to 8% by weight of builder.

Formulations according to the invention can comprise one or more alkali carriers. Alkali carriers ensure, for example, a pH of at least 9 if an alkaline pH is desired. Of suitability are, for example, the alkali metal carbonates, the alkali metal hydrogen carbonates, and alkali metal metasilicates mentioned above, and, additionally, alkali metal hydroxides. A preferred alkali metal is in each case potassium, particular preference being given to sodium. In one embodiment of the present invention, a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine. In one embodiment of the present invention, the laundry formulation or composition according to the invention comprises additionally at least one enzyme.

Useful enzymes are, for example, one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types.

In one embodiment, the composition according to the present invention comprises additionally at least one enzyme.

Preferably, the at least one enzyme is a detergent enzyme.

In one embodiment, the enzyme is classified as an oxidoreductase (EC 1 ), a transferase (EC 2), a hydrolase (EC 3), a lyase (EC 4), an isomerase (EC 5), or a ligase (EC 6) (the EC-numbering is according to Enzyme Nomenclature, Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology including its supplements published 1993-1999). Preferably, the enzyme is a hydrolase (EC 3).

In a preferred embodiment, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, hemicellulases, phospholipases, esterases, pectinases, lactases, peroxidases, xylanases, cutinases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, nucleases, DNase, phosphodiesterases, phytases, carbohydrases, galactanases, xanthanases, xyloglucanases, oxidoreductase, perhydrolases, aminopeptidase, asparaginase, carbohydrase, carboxypeptidase, catalase, chitinase, cyclodextrin glycosyltransferase, alpha-galactosidase, beta-galactosidase, glucoamylase, alpha-glucosidase, beta-glucosidase, invertase, ribonuclease, transglutaminase, and dispersins, and combinations of at least two of the foregoing types. More preferably, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, DNases, dispersins, pectinases, oxidoreductases, and cutinases, and combinations of at least two of the foregoing types. Most preferably, the enzyme is a protease, preferably, a serine protease, more preferably, a subtilisin protease.

Such enzyme(s) can be incorporated into the composition at levels sufficient to provide an effective amount for achieving a beneficial effect, preferably for primary washing effects and/or secondary washing effects, like antigreying or antipilling effects (e.g., in case of cellulases). Preferably, the enzyme is present in the composition at levels from about 0.00001 % to about 5%, preferably from about 0.00001 % to about 2%, more preferably from about 0.0001 % to about 1 %, or even more preferably from about 0.001 % to about 0.5% enzyme protein by weight of the composition.

Preferably, the enzyme-containing composition further comprises an enzyme stabilizing system. Preferably, the enzyme-containing composition described herein comprises from about 0.001 % to about 10%, from about 0.005% to about 8%, or from about 0.01 % to about 6%, by weight of the composition, of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme.

Preferably, the enzyme stabilizing system comprises at least one compound selected from the group consisting of polyols (preferably, 1 ,3-propanediol, ethylene glycol, glycerol, 1 ,2-propane- diol, or sorbitol), salts (preferably, CaCI2, MgCI2, or NaCI), short chain (preferably, C1-C6) carboxylic acids (preferably, formic acid, formate (preferably, sodium formate), acetic acid, acetate, or lactate), borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts. Preferably, the enzyme stabilizing system comprises a combination of at least two of the compounds selected from the group consisting of salts, polyols, and short chain carboxylic acids and preferably one or more of the compounds selected from the group consisting of borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts. In particular, if proteases are present in the composition, protease inhibitors may be added, preferably selected from borate, boric acid, boronic acids (preferably, 4-FPBA), peptide aldehydes (preferably, peptide aldehydes like Z-VAL-H or Z-GAY- H), peptide acetals, and peptide aldehyde hydrosulfite adducts. Compositions according to the invention may comprise one or more bleaching agent (bleaches).

Preferred bleaches are selected from sodium perborate, anhydrous or, for example, as the monohydrate or as the tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as the monohydrate, and sodium persulfate, where the term “persulfate” in each case includes the salt of the peracid H2SO5 and also the peroxodisulfate.

In this connection, the alkali metal salts can in each case also be alkali metal hydrogen carbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulfate. However, the dialkali metal salts are preferred in each case.

Formulations according to the invention can comprise one or more bleach catalysts. Bleach catalysts can be selected from oxaziridinium-based bleach catalysts, bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.

Formulations according to the invention can comprise one or more bleach activators, for example tetraacetyl ethylene diamine, tetraacetylmethylene diamine, tetra^_,acetylglycoluril, tetraacetylhexylene diamine, acylated phenolsulfonates such as for example n-nonanoyl- or isononanoyloxybenzene sulfonates, N-methylmorpholinium-acetonitrile salts (“MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1 ,5-diacetyl-2,2-dioxohexahydro-1 ,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).

Formulations according to the invention can comprise one or more corrosion inhibitors. In the present case, this is to be understood as including those compounds which inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyro- gallol. In one embodiment of the present invention, formulations according to the invention comprise in total in the range from 0.1 to 1 .5% by weight of corrosion inhibitor.

Besides such “typical” corrosion inhibitors, also amphoteric surfactants can promote corrosion inhibition, such as compounds having one or two carboxylic groups and one or more amine groups, and optionally further containing also amide-groups and/or hydroxy-groups; such compounds for example being N-(2-carboxyethyl)-N-dodecyl-beta-alaninate (also named N-lauryl- beta-iminodipropionate metal salt, cocoamphodiacetate di-metal salt, cocoamphoacetate metal salt (the metal typically being sodium).

Formulations according to the invention may also comprise further cleaning polymers and/or soil release polymers.

The additional cleaning polymers may include, without limitation, “multifunctional polyethylene imines” (for example BASF’s Sokalan® HP20) and/or “multifunctional diamines” (for example BASF’s Sokalan® HP96). Such multifunctional polyethylene imines are typically ethoxylated polyethylene imines with a weight-average molecular weight Mw in the range from 3000 to 250000, preferably 5000 to 200000, more preferably 8000 to 100000, more preferably 8000 to 50000, more preferably 10000 to 30000, and most preferably 10000 to 20000 g/mol. Suitable multifunctional polyethylene imines have 80 wt. % to 99 wt. %, preferably 85 wt. % to 99 wt. %, more preferably 90 wt. % to 98 wt. %, most preferably 93 wt. % to 97 wt. % or 94 wt. % to 96 wt. % ethylene oxide side chains, based on the total weight of the materials. Ethoxylated polyethylene imines are typically based on a polyethylene imine core and a polyethylene oxide shell. Suitable polyethylene imine core molecules are polyethylene imines with a weight-average molecular weight Mw in the range of 500 to 5000 g/mol. Preferably employed is a molecular weight from 500 to 1000 g/mol, even more preferred is a Mw of 600 to 800 g/mol. The ethoxylated polymer then has on average 5 to 50, preferably 10 to 35 and even more preferably 20 to 35 ethylene oxide (EO) units per NH-functional group.

Suitable multifunctional diamines are typically ethoxylated C2 to C12 alkylene diamines, preferably hexamethylene diamine, which are further quaternized and optionally sulfated. Typical multifunctional diamines have a weight-average molecular weight Mw in the range from 2000 to 10000, more preferably 3000 to 8000, and most preferably 4000 to 6000 g/mol. In a preferred embodiment of the invention, ethoxylated hexamethylene diamine, furthermore quaternized and sulfated, may be employed, which contains on average 10 to 50, preferably 15 to 40 and even more preferably 20 to 30 ethylene oxide (EO) groups per NH-functional group, and which preferably bears two cationic ammonium groups and two anionic sulfate groups.

In a preferred embodiment of the present invention, the cleaning compositions may contain at least one multifunctional polyethylene imine and/or at least one multifunctional diamine to improve the cleaning performance, such as preferably improve the stain removal ability, especially the primary detergency of particulate stains on polyester fabrics of laundry detergents. The multifunctional polyethylene imines or multifunctional diamines or mixtures thereof according to the descriptions above may be added to the laundry detergents and cleaning compositions in amounts of generally from 0.05 to 15 wt. %, preferably from 0.1 to 10 wt. % and more preferably from 0.25 to 5 wt. % and even as low as up to 2 wt.%, based on the particular overall composition, including other components and water and/or solvents. Thus, one aspect of the present invention is a laundry detergent composition, in particular a liquid laundry detergent, comprising (i) at least one inventive compound and (ii) at least one compound selected from multifunctional polyethylene imines and multifunctional diamines and mixtures thereof.

In one embodiment of the present invention, the ratio of the at least one inventive compound and (ii) the at least one compound selected from multifunctional polyethylene imines and multifunctional diamines and mixtures thereof, is from 10:1 to 1 :10, preferably from 5:1 to 1 :5 and more preferably from 3:1 to 1 :3.

Cleaning compositions, fabric and home care products and specifically the laundry formulations comprising the inventive compound may also comprise at least one antimicrobial agent (named also “preservative”).

An antimicrobial agent is a chemical compound that kills microorganisms or inhibits their growth or reproduction. Microorganisms can be bacteria, yeasts or molds. A preservative is an antimicrobial agent which may be added to aqueous products and compositions to maintain the original performance, characteristics and integrity of the products and compositions by killing contaminating microorganisms or inhibiting their growth.

The composition/formulation may contain one or more antimicrobial agents and/or preservatives as listed in patent WO2021/115912 A1 (“Formulations comprising a hydrophobically modified polyethyleneimine and one or more enzymes”) on pages 35 to 39.

Especially of interest for the cleaning compositions and fabric and home care products and specifically in the laundry formulations are any of the following antimicrobial agents and/or preservatives:

4,4’-dichloro 2-hydroxydiphenyl ether (further names: 5-chloro-2-(4-chlorophenoxy) phenol, Di- closan, DCPP), Tinosan® HP 100 (commercial product of BASF SE containing 30% of the antimicrobial active 4,4’-dichoro 2-hydroxydiphenylether); 2-Phenoxyethanol (further names: Phenoxyethanol, Methylphenylglycol, Phenoxetyethanol, ethylene glycol phenyl ether, Ethylene glycol monophenyl ether, 2-(phenoxy) ethanol, 2-phenoxy-1 -ethanol); 2-bromo-2-nitropropane-1 ,3- diol (further names: 2-bromo-2-nitro-1 ,3-propanediol, Bronopol); Glutaraldehyde (further names: 1-5-pentandial, pentane-1 ,5-dial, glutaral, glutar-dialdehyde); Glyoxal (further names: ethandial, oxylaldehyde, 1 ,2-ethandial); 2-butyl-benzo[d]isothiazol-3-one (“BBIT”); 2-methyl-2H-isothiazol- 3-one (“MIT””); 2-octyl-2H-isothiazol-3-one (“OIT”); 5-Chloro-2-methyl-2H-isothiazol-3-one (“CIT” or “CMIT”); Mixture of 5-chloro-2-methyl-2H- isothiazol-3-one (“CMIT”) and 2-methyl-2H-isothia- zol-3-one (“MIT”) (Mixture of CMIT/MIT); 1 ,2-benzisothiazol-3(2H)-one (“BIT”); Hexa-2,4-dienoic acid (trivial name “sorbic acid”) and its salts, e.g., calcium sorb-ate, sodium sorbate; potassium (E,E)-hexa-2,4-dienoate (Potassium Sorbate); Lactic acid and its salts; L-(+)-lactic acid; especially sodium lactate; Benzoic acid and salts of benzoic acid, e.g., sodium benzoate, ammonium benzo-ate, calcium benzoate, magnesium benzoate, MEA-benzoate, potassium benzoate; Salicylic acid and its salts, e.g., calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate; Benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate; Didecyldimethylammonium chloride (“DDAC”); N-(3-aminopropyl)- N-dodecylpropane-1 ,3-diamine ("Diamine"); Peracetic acid; Hydrogen peroxide. At least one antimicrobial agent or preservative may be added to the inventive composition in a concentration of 0.001 to 10% relative to the total weight of the composition.

Preferably, the composition contains 2-phenoxyethanol in a concentration of 0.1 to 2% or 4,4’- dichloro 2-hydroxydiphenyl ether (DCPP) in a concentration of 0.005 to 0.6%.

The invention also encompasses a method of preserving an aqueous composition according to the invention against microbial contamination or growth, which method comprises addition of at least one antimicrobial agent or preservative, preferably 2-phenoxyethanol.

The invention also encompasses a method of providing an antimicrobial effect on textiles after treatment with a solid laundry detergent (e.g. powders, granulates, capsules, tablets, bars etc.), a liquid laundry detergent, a softener or an after-rinse containing 4,4’-dichloro 2-hydroxydiphe- nyl ether (DCPP).

Formulations according to the invention may also comprise water and/or additional organic solvents, e.g., ethanol or propylene glycol.

Further optional ingredients may be but are not limited to viscosity modifiers, cationic surfactants, foam boosting or foam reducing agents, perfumes, dyes, optical brighteners, and dye transfer inhibiting agents.

Dish wash compositions

Another aspect of the present invention is also a dish wash composition, comprising at least one inventive compound(s) as described above.

Thus, an aspect of the present invention is also the use of the inventive compound(s) as described above, in dish wash applications, such as manual or automated dish wash applications.

Dish wash compositions according to the invention can be in the form of a liquid, semi-liquid, cream, lotion, gel, or solid composition, solid embodiments encompassing, for example, powders and tablets. Liquid compositions are typically preferred for manual dish wash applications, whereas solid formulations and pouch formulations (where the pouches may contain also solids in addition to liquid ingredients) are typically preferred for automated dish washing compositions; however, in some areas of the world also liquid automated dish wash compositions are used and are thus of course also encompassed by the term “dish wash composition”.

The dish wash compositions are intended for direct or indirect application onto dishware and metal and glass surfaces, such as drinking and other glasses, beakers, dish and cooking ware like pots and pans, and cutlery such as forks, spoons, knives and the like.

The inventive method of cleaning dishware, metal and/or glass surfaces comprises the step of applying the dish wash cleaning composition, preferably in liquid form, onto the surface, either directly or by means of a cleaning implement, i.e., in neat form. The composition is applied directly onto the surface to be treated and/or onto a cleaning device or implement such as a dish cloth, a sponge or a dish brush and the like without undergoing major dilution (immediately) prior to the application. The cleaning device or implement is preferably wet before or after the composition is delivered to it. In the method of the invention, the composition can also be applied in diluted form.

Both neat and dilute application give rise to superior cleaning performance, i.e. the formulations of the invention containing at least one inventive compound(s)exhibit excellent degreasing properties. The effort of removing fat and/or oily soils from the dishware, metal and/or glass surfaces is decreased due to the presence of the inventive compound(s), even when the level of surfactant used is lower than in conventional compositions.

Preferably the composition is formulated to provide superior grease cleaning (degreasing) properties, long-lasting suds and/or improved viscosity control at decreased temperature exposures; preferably at least two, more preferably all three properties are present in the inventive dish wash composition. Optional - preferably present - further benefits of the inventive manual dish wash composition include soil removal, shine, and/or hand care; more preferably at least two and most preferably all three further benefits are present in the inventive dish wash composition.

In one embodiment of the present invention, the inventive compound(s) is one component of a manual dish wash formulation that additionally comprises at least one surfactant, preferably at least one anionic surfactant.

In another embodiment of the present invention, the inventive compound(s)is one component of a manual dish wash formulation that additionally comprises at least one anionic surfactant and at least one other surfactant, preferably selected from amphoteric surfactants and/or zwitterionic surfactants. In a preferred embodiment of the present invention, the manual dish wash formulations contain at least one amphoteric surfactant, preferably an amine oxide, or at least one zwitterionic surfactant, preferably a betaine, or mixtures thereof, to aid in the foaming, detergency, and/or mildness of the detergent composition.

Examples of suitable anionic surfactants are already mentioned above for laundry compositions. Preferred anionic surfactants for dish wash compositions are selected from C10-C15 linear alkylbenzenesulfonates, C10-C18 alkylethersulfates with 1-5 ethoxy units and C10-C18 alkylsulfates.

Preferably, the manual dish wash detergent formulation of the present invention comprises from at least 1 wt% to 50 wt%, preferably in the range from greater than or equal to about 3 wt% to equal to or less than about 35 wt%, more preferably in the range from greater than or equal to 5 wt% to less than or equal to 30 wt%, and most preferably in the range from greater than or equal to 5 wt% to less than or equal to 20 wt% of one or more anionic surfactants as described above, based on the particular overall composition, including other components and water and/or solvents.

Dish wash compositions according to the invention may comprise at least one amphoteric surfactant. Examples of suitable amphoteric surfactants for dish wash compositions are already mentioned above for laundry compositions.

Preferred amphoteric surfactants for dish wash compositions are selected from C8-C18 alkyldimethyl aminoxides and C8-C18 alkyl-di(hydroxyethyl)aminoxide.

The manual dish wash detergent composition of the invention preferably comprises from 1 wt% to 15 wt%, preferably from 2 wt% to 12 wt%, more preferably from 3 wt% to 10 wt% of the composition of an amphoteric surfactant, preferably an amine oxide surfactant. Preferably the composition of the invention comprises a mixture of the anionic surfactants and alkyl dimethyl amine oxides in a weight ratio of less than about 10:1 , more preferably less than about 8:1 , more preferably from about 5:1 to about 2:1 .

Addition of the amphoteric surfactant provides good foaming properties in the dish wash composition.

In this chapter on Dish Wash it needs to be emphasized again that certain amphoteric surfactants can - besides their typical action as surfactant - promote corrosion inhibition, such as compounds having one or two carboxylic groups and one or more amine groups, and optionally further containing also amide-groups and/or hydroxy-groups; such compounds for example being N-(2-carboxyethyl)-N-dodecyl-beta-alaninate (also named N-lauryl-beta-iminodipropionate metal salt, cocoamphodiacetate di-metal salt, cocoamphoacetate metal salt (the metal typically being sodium). Hence, such amphoteric surfactants are preferred when corrosion inhibition is of importance, such as in cleaning applications which typically have a high pH, e.g. automatic dish washing.

Dish wash compositions according to the invention may comprise at least one zwitterionic surfactant.

Examples of suitable zwitterionic surfactants for dish wash compositions are already mentioned above for laundry compositions.

Preferred zwitterionic surfactants for dish wash compositions are selected from betaine surfactants, more preferable from Cocoamidopropylbetaine surfactants.

In a preferred embodiment of the present invention, the zwitterionic surfactant is Cocamido- propylbetaine.

The manual dish wash detergent composition of the invention optionally comprises from 1 wt% to 15 wt%, preferably from 2 wt% to 12 wt%, more preferably from 3 wt% to 10 wt% of the composition of a zwitterionic surfactant, preferably a betaine surfactant.

Dish wash compositions according to the invention may comprise at least one cationic surfactant.

Examples of suitable cationic surfactants for dish wash compositions are already mentioned above for laundry compositions.

Cationic surfactants, when present in the composition, are present in an effective amount, more preferably from 0.1 wt% to 5 wt%, preferably 0.2 wt% to 2 wt% of the composition.

Dish wash compositions according to the invention may comprise at least one non-ionic surfactant. Examples of suitable non-ionic surfactants for dish wash compositions are already mentioned above for laundry compositions.

Preferred non-ionic surfactants are the condensation products of Guerbet alcohols with from 2 to 18 moles, preferably 2 to 15, more preferably 5-12 of ethylene oxide per mole of alcohol. Other preferred non-ionic surfactants for use herein include fatty alcohol polyglycol ethers, alkylpolyglucosides and fatty acid glucamides.

The manual hand dish detergent composition of the present invention may comprise from 0.1 wt% to 10 wt%, preferably from 0.3 wt% to 5 wt%, more preferably from 0.4 wt% to 2 wt% of the composition, of a linear or branched C10 alkoxylated non-ionic surfactant having an average degree of alkoxylation of from 2 to 6, preferably from 3 to 5. Preferably, the linear or branched C10 alkoxylated non-ionic surfactant is a branched C10 ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 2 to 6, preferably of from 3 to 5. Preferably, the composition comprises from 60 wt% to 100 wt%, preferably from 80 wt% to 100 wt%, more preferably 100 wt% of the total linear or branched C10 alkoxylated non-ionic surfactant of the branched C10 ethoxylated non-ionic surfactant. The linear or branched C10 alkoxylated non-ionic surfactant preferably is a 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5. A suitable 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of 4 is Lutensol® XP40, commercially available from BASF SE, Ludwigshafen, Germany. The use of a 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5 leads to improved foam levels and long-lasting suds.

Thus, one aspect of the present invention is a manual dish wash detergent composition, in particular a liquid manual dish wash detergent composition, comprising (i) at least one inventive compound, and (ii) at least one further 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5.

Dish wash compositions according to the invention may comprise at least one hydrotrope in an effective amount, to ensure the compatibility of the liquid manual dish wash detergent compositions with water.

Suitable hydrotropes for use herein include anionic hydrotropes, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium and ammonium toluene sulfonate, sodium, potassium, and ammonium cumene sulfonate, and mixtures thereof, and related compounds, as disclosed in U.S. Patent 3,915,903.

The liquid manual dish wash detergent compositions of the present invention typically comprise from 0.1 wt% to 15 wt% of the total liquid detergent composition of a hydrotrope, or mixtures thereof, preferably from 1 wt% to 10 wt%, most preferably from 2 wt% to 5 wt% of the total liquid manual dish wash composition.

Dish wash compositions according to the invention may comprise at least one organic solvent. Examples of organic solvents are C4-C14 ethers and diethers, glycols, alkoxylated glycols, C6- C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, amines, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.

When present, the liquid dish wash compositions will contain from 0.01 wt% to 20 wt%, preferably from 0.5 wt% to 15 wt%, more preferably from 1 wt% to 10 wt%, most preferably from 1 wt% to 5 wt% of the liquid detergent composition of a solvent. These solvents may be used in conjunction with an aqueous liquid carrier, such as water, or they may be used without any aqueous liquid carrier being present. At higher solvent systems, the absolute values of the viscosity may drop but there is a local maximum point in the viscosity profile.

The dish wash compositions herein may further comprise from 30 wt% to 90 wt% of an aqueous liquid carrier, comprising water, in which the other essential and optional ingredients are dissolved, dispersed or suspended. More preferably the compositions of the present invention comprise from 45 wt% to 85 wt%, even more preferably from 60 wt% to 80 wt% of the aqueous liquid carrier. The aqueous liquid carrier, however, may contain other materials which are liquid, or which dissolve in the liquid carrier, at room temperature (25 °C) and which may also serve some other function besides that of an inert filler.

Dish wash compositions according to the invention may comprise at least one electrolyte. Suitable electrolytes are preferably selected from inorganic salts, even more preferably selected from monovalent salts, most preferably sodium chloride.

The liquid manual dish wash compositions according to the invention may comprise from 0.1 wt% to 5 wt%, preferably from 0.2 wt% to 2 wt% of the composition of an electrolyte.

Manual dish wash formulations comprising the inventive compound(s) may also comprise at least one antimicrobial agent.

Examples of suitable antimicrobial agents for dish wash compositions are already mentioned above for laundry compositions.

The antimicrobial agent may be added to the inventive hand dish wash composition in a concentration of 0.0001 wt% to 10 wt% relative to the total weight of composition. Preferably, the formulation contains 2-phenoxyethanol in a concentration of 0.01 wt% to 5 wt%, more preferably 0.1 wt% to 2 wt% and/or 4,4’-dichloro 2-hydroxydiphenyl ether in a concentration of 0.001 wt% to 1 wt%, more preferably 0.002 wt% to 0.6 wt% (in all cases relative to the total weight of the composition).

Further additional ingredients are such as but not limited to conditioning polymers, cleaning polymers, surface modifying polymers, soil flocculating polymers, rheology modifying polymers, enzymes, structurants, builders, chelating agents, cyclic diamines, emollients, humectants, skin rejuvenating actives, carboxylic acids, scrubbing particles, bleach and bleach activators, perfumes, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, antibacterial agents, pH adjusters including NaOH and alkanolamines such as monoethanolamines and buffering means.

General cleaning compositions and formulations for Laundry and Dish Wash The disclosed liquid formulations in this chapter may and preferably do comprise 0 to 2 % 2- phenoxyethanol, preferably about 1 %, in addition to all other mentioned ingredients.

The disclosed liquid formulations in this chapter may and preferably do comprise 0-0,2% 4,4’- dichoro 2-hydroxydiphenylether, preferably about 0,15 %, in addition to all other mentioned ingredients.

The bleach-free solid laundry compositions may comprise 0-0,2% 4,4’-dichoro 2-hydroxydiphe- nylethe, preferably about 0,15 %, in addition to all other mentioned ingredients.

The disclosed formulations in this chapter may and preferably do comprise one or more enzymes selected from those disclosed herein above, more preferably a protease and/or an amylase, wherein even more preferably the protease is a protease with at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101 E (according to BPN’ numbering) and wherein the amylase is an amylase with at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881 A1 , such enzyme(s) preferably being present in the formulations at levels from about 0.00001 % to about 5%, preferably from about 0.00001 % to about 2%, more preferably from about 0.0001 % to about 1 %, or even more preferably from about 0.001 % to about 0.5% enzyme protein by weight of the composition.

The tables in this chapter show general cleaning compositions of certain types, which correspond to typical compositions correlating with typical washing conditions as typically employed in various regions and countries of the world. The at least one inventive compound may be added to such formulation(s) in suitable amounts as outlined herein.

When no inventive compound is added, a shown formulation is a “comparative formulation”; when the amount chosen is in the general range as disclosed herein and specifically within ranges disclosed herein as preferred amounts for the various ingredients and the inventive compound, the formulation is a formulation according to the invention. Ingredients (other than the inventive compound) listed with amounts including “zero%” in the mentioned range may be present but not necessarily have to be present, in both the inventive and the comparative formulations. Hence, each number encompassed by a given range is meant to be included in the formulations shown in this chapter, and all variations and permutations possible are likewise meant to be included.

In a preferred embodiment the inventive compound is used in a laundry detergent.

Liquid laundry detergents according to the present invention are preferably composed of: 0,1 - 5 % of at least one inventive compound 1 - 50% of surfactants

0,1 - 40 % of builders, cobuilders and/or chelating agents

0,1 - 50 % other adjuncts water to add up 100 %.

Preferred liquid laundry detergents according to the present invention are composed of: 0,5 - 2 % of at least one inventive compound

5 - 40 % of anionic surfactants selected from C10-C15- LAS and C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units

1 ,5 - 10 % of nonioic surfactants selected from C10-C18-alkyl ethoxylates containing 3 - 10 ethoxy-units

2 - 20 % of soluble organic builders/ cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxy-di- and hydroxytricaboxylic acids, aminopolycarboxylates and polycarboxylic acids

0,05 - 5 % of an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system

0,5 - 20 % of mono- or diols selected from ethanol, isopropanol, ethylenglycol, or propylengly- clol

0,1 - 20 % other adjuncts water to add up to 100%.

Solid laundry detergents (like e.g. powders, granules or tablets) according to the present invention are preferably composed of:

0,1 - 5 % of at least one inventive compound 1 - 50% of surfactants

0,1 - 90 % of builders, cobuilders and/or chelating agents

0-50% of fillers

0 - 40% of bleach actives

0,1 - 30 % of other adjuncts and/or water wherein the sum of the ingredients adds up 100 %.

Preferred solid laundry detergents according to the present invention are composed of: 0,5 - 2 % of at least one inventive compound

5 - 30 % of anionic surfactants selected from C10-C15- LAS, C10-C18 alkylsulfates and C10- C18 alkyl ethersulfates containing 1-5 ethoxy-units

1 ,5 - 7,5 % of non-ionic surfactants selected from C10-C18-alkyl ethoxylates containing 3 - 10 ethoxy-units

20 - 80 % of inorganic builders and fillers selected from sodium carbonate, sodium bicarbonate, zeolites, soluble silicates, sodium sulfate

0,5 - 15 % of cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hy- droxydi- and hydroxytricarboxylic acids, aminopolycarboxylates and polycarboxylic acids 0,1 - 5 % of an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system 0,5 - 30 % of bleach actives 0,1 - 20 % other adjuncts water to add up to 100%

In a preferred embodiment at least one compound according to the present invention is used in a manual dish wash detergent. Liquid manual dish wash detergents according to the present invention are composed of:

1 - 15 % of at least one inventive compound 1 - 90% of surfactants

0,1 - 50 % of other adjuncts water to add up 100 %.

Preferred liquid manual dish wash detergents according to the present invention are composed of:

1 ,5 - 10 % of at least one inventive compound

1 - 35 % of a surfactant system:

60% to 90%, more preferably from 70% to 80% by weight of the surfactant system of an anionic surfactant;

0.5% to 15% - by weight of the surfactant system - of a co-surfactant, preferably selected from the group consisting of an amphoteric surfactant, a zwitterionic surfactant, and mixtures thereof;

1 % to 10% - by weight of the surfactant system - of a non-ionic surfactant;

0 - 5 % of an enzyme, preferably also including an enzyme stabilizing system;

0,5 - 20 % of mono- or diols selected from ethanol, isopropanol, ethylene glycol, or propylene glycol;

0,1 - 20 % other adjuncts; water to add up to 100%.

Alternative preferred liquid manual dish wash detergents according to the present invention are composed of:

2 - 5 % of at least one inventive compound

5 - 80 % of anionic surfactants selected from C10-C15- LAS, C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units, and C10-C18 alkylsulfate

2 - 10 % of Cocamidopropylbetaine

0 - 10 % of Lauramine oxide

0 - 2 % of a non-ionic surfactant, preferably a C10-Guerbet alcohol alkoxylate

0 - 5 % of an enzyme, preferably Amylase, and preferably also an enzyme stabilizing system

0,1 - 20 % other adjuncts water to add up to 100%

It is clear that the total amount of all ingredients within the disclosed formulations have to add up to “100” percent by weight of the total formulation.

In the following tables: “Inventive Compound(s)” = at least one inventive compound as described in this present invention

General formula for laundry detergent compositions according to the invention: (numbers: wt.%)

Liquid laundry frame formulations according to the invention:

Liquid laundry frame formulations according to the invention - continued:

Laundry powder frame formulations according to the invention:

Laundry powder frame formulations according to the invention - continued:

Further typical liquid detergent formulations LD1 , LD2 and LD3 are shown in the following three tables: (numbers: wt.% active) Liquid detergent 1- LD1 “excellent” detergent

Liquid detergent 2- LD2 “medium” performance detergent

Liquid detergent 3- LD3 “medium” performance “biobased” detergent

All previous three tables on LD1 , LD2, LD3: *”graft polymer” = (poly ethylene glycol of Mn 6000 g/mol as graft base, grafted with 40 weigth % vinyl acetate (based on total polymer weight; produced following general disclosure of W02007138054A1)

Liquid manual dish wash frame formulations according to the invention:

It is preferred, that within the respective laundry detergent, cleaning composition and/or fabric and home care product, the at least one compound as described in this invention is present at a concentration of from about 0.1 % to about 20%, preferably from about 0.2% to 10%, more preferably from about 0.5% to about 5%, all in relation to the total weight of such composition or product in relation to the total weight of such composition or product, and all numbers in between, and including all ranges resulting from selecting any of the lower limits mentioned and including further 0.2, 0.3, 0.4, 1 , 1 ,5, 2, 2.5, 3, 3.5 and 4, and combing with any of the upper limits mentioned and including 19, 18, 17, 16, 14, 13, 12, 11 , 9, 8, 7, and 6.

The specific embodiments as described throughout this disclosure are encompassed by the present invention as part of this invention; the various further options being disclosed in this present specification as “optional”, “preferred”, “more preferred”, “even more preferred” or “most preferred” options of a specific embodiment may be individually and independently (unless such independent selection is not possible by virtue of the nature of that feature or if such independent selection is explicitly excluded) selected and then combined within any of the other embodiments (where other such options and preferences can be also selected individually and independently), with each and any and all such possible combinations being included as part of this invention as individual embodiments.

The present invention therefore also relates to the following:

1 . Graft polymer based on ethylene oxide-comprising backbones being grafted with olefinically polymerizable monomers, preferably vinyl monomers, more preferably with a) vinyl esters and optionally further monomers, such further monomers preferably being selected from vinyllactams, more preferably vinylpyrrolidone, and olefinically unsaturated, radically polymerizable amine-containing monomers such as vinylamines, more preferably vinylimidaz- ole, and even more preferably such monomers being at least one vinyl ester, at least one lactam and optionally at least one vinylamine, and even more preferably such monomers being vinyl acetate, vinylpyrrolidone and vinylimidazole, or b) vinyllactams, more preferably vinylpyrrolidone, and olefinically unsaturated, radically polymerizable amine-containing monomers such as vinylamines, more preferably vinylimidazole;

(such graft polymer as “compound”) wherein such compound is at least partially based on hydrogen from non-fossil-based sources, wherein the molar share of deuterium is lower in such compound than that in the identical chemical compound when derived solely from fossil-based sources, and wherein such compound may contain other monomers in the chains derived from alkylene oxides, preferably such alkylene oxides containing ethylene oxide, such other monomers being preferably selected from lactones and/or other alkylene oxides other than or besides ethylene oxide.

2. Process for making a graft polymer according to embodiment 1 , wherein said process comprises the following steps: providing hydrogen with a molar share of deuterium < 100 ppm, preferably in the range of from 10 to < 95 ppm, more preferably in the range of from 10 to < 90 ppm, most preferably in the range of from 10 to < 80 ppm, based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy,

(a) reacting the hydrogen from step (a) with carbon oxides, preferably carbon dioxide, to form methanol,

(b) converting the methanol from step (c) to ethylene and further to ethylene oxide,

(c) converting the ethylene oxide from step (d) to a polymer or a mixture of polymers, such polymer(s) comprising ethylene oxide and optionally other monomers, such other monomers being selected from alkylene oxides other than ethylene oxide, in one or more steps using known methods such as alkoxylation reactions,

(d) reacting the polymer(s) from step (d) in a further reaction with at least one vinylic monomer, preferably with a) at least one vinyl ester and optionally at least one further monomer, such further monomer preferably being at least one monomer selected from vinyllactams and olefinically unsaturated, radically polymerizable amine-containing monomers, more preferably vinylpyrrolidone and/or vinylimidazole, or b) at least one vinyllactam, preferably vinylpyrrolidone, and optionally at least one vinylamine, preferably vinylimidazole, using a radical polymerization reaction using standard means, to obtain a graft polymer comprising less deuterium based on total hydrogen content compared to the chemical identical graft polymer obtained from fossil-based sources only.

3. The process according to embodiment 2, wherein the electrical power is generated at least in part from wind power, solar energy (thermal, photovoltaic and concentrated), hydroelectricity (tidal power, wave power, hydroelectric dams, In-river-hydrokinetics), geothermal energy, ambient heat captured by heat pumps, bioenergy (biofuel, biomass), the renewable part of waste or nuclear power (fission).

4. The process according to embodiment 2 or 3, wherein step (a) is a water electrolysis, preferably PEM water electrolysis, alkaline water electrolysis, or AEM water electrolysis.

5. The process according to any one of embodiments 2 to 4, wherein carbon dioxide is employed in step (c), which is preferably captured from industrial flue gases or from ambient air.

6. The process according to any one of embodiments 2 to 5, wherein the ethylene oxide in step (d) is obtained by

(d1) a methanol-to-olefin process, preferably with a zeolite catalyst, wherein ethylene is obtained, followed by

(d2) epoxidation of ethylene, preferably with a silver-based catalyst.

7. The process according to any one of embodiments 2 to 6, wherein ammonia from step (b), ethylene oxide from step (d) and are reacted in one or more steps to a reaction product comprising monoethanolamine, diethanolamine and triethanolamine. 8. Use of the molar share of deuterium comprised in a compound according to embodiment

1 , or a compound obtainable by or preferably obtained by a process of any of embodiments 2 to 7, based on hydrogen for tracing the origin of preparation of such compounds based on hydrogen.

9. A process for tracing the origin of preparation of hydrogen comprised in a compound according to embodiment 1 , or a compound obtainable by or preferably obtained by a process of any of embodiments 2 to 7, by determining the molar share of deuterium in in hydrogen and said compound based on hydrogen.

10. Use of compound according to embodiment 1 , or a compound obtainable by or preferably obtained by a process of any of embodiments 2 to 7, preferably in a composition, that is more preferably a fabric and home care product, a cleaning composition, or an industrial and institutional cleaning product.

11 . The use according to embodiment 10, wherein the composition comprises at least one compound at a concentration of from about 0.1 % to about 20% in weight % in relation to the total weight of such composition or product.

12. The use according to embodiment 10 or 11 , wherein the composition is in liquid or semiliquid form.

13. The use according to any of embodiments 10 to 12, further fulfilling at least one of the following requirements: a. comprising at least one enzyme, b. comprising about 1 % to about 70% by weight of a surfactant system, c. comprising at least one further cleaning adjunct in effective amounts, preferably at least one compound selected from alkoxylated di-, oligo- and polyamines and alkoxylated polyethylene imine, alkoxylation being preferably using EO and/or propylene oxide, d. exhibiting an improved washing performance, preferably in primary cleaning, e. exhibiting dye transfer inhibition properties.

14. A composition being a laundry detergent, a cleaning composition or a fabric and home care product, containing at least one compound according to embodiment 1 , or a compound obtainable by or preferably obtained by a process of any of embodiments 2 to 7, comprising the at least one compound at a concentration of preferably from about 0.1 % to about 20% in weight % in relation to the total weight of such composition or product, and optionally further comprising at least one of a) to c) a. at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases and peroxidases, more preferably at least two of the aforementioned types, and in case an enzyme is comprised preferably also containing at least one enzyme-stabilizing system, b. about 1 % to about 70% by weight of a surfactant system, c. at least one further cleaning adjunct in effective amounts, preferably at least one compound selected from alkoxylated di-, oligo- and polyamines and alkoxylated polyethylene imine, alkoxylation being preferably using EO and/or propylene oxide, and optionally exhibiting an improved washing performance in primary cleaning (i.e. removal of stains) and/or dye transfer inhibiting properties.

15. The composition of embodiment 14 being in liquid or semi-liquid form, preferably being a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation or solid automatic dish washing formulation, more preferably a liquid laundry detergent formulation, optionally further comprising at least one antimicrobial agent, preferably 2-phenoxyethanol, in an amount ranging from 2 ppm to 5%, more preferably 0.1 to 2% by weight of the composition, and optionally comprising 4,4’-dichloro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each by weight of the composition.

16. A method of preserving a composition according to embodiment 14 or 15 against microbial contamination or growth, which method comprises addition of an antimicrobial agent selected from the group consisting of 2-phenoxyethanol to the composition which is an aqueous composition comprising water as solvent.

17. A method of laundering fabric or of cleaning hard surfaces, which method comprises treating a fabric or a hard surface with a composition according to embodiment 14 or 15, wherein the composition comprises 4,4’-dichloro 2-hydroxydiphenylether, preferably comprising 4,4’-dichloro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each by weight of the composition.

The invention is further illustrated by the working examples.

Examples

Preparation of Ethylene oxide, Propylene oxide and Alkoxylates - Experimental examples 1 - 3

Example 1 : Preparation of Ethylene oxide (EO)

Ethylene oxide has been prepared via direct oxidation of ethylene as described in US 5,739,075 Illustrative Embodiment 1 parts A, B and C for silver catalyst preparation (“Catalyst C” with PreDopants Nd, Co and Cs/Re/S) and part D for the microreactor test setup used for ethylene oxide synthesis. Ethylene raw material was continuously fed together with oxygen, nitrogen and CO2 into the microreactor in the composition, ratio and conditions as defined in the mentioned patent example and only the source of the ethylene feed material was varied using the following raw material grades: Table 1

All trial runs have been conducted with exactly the same silver catalyst batch. In order to simulate a regular industrial catalyst-lifetime longer than 1 full year, the catalyt was subjected to the accelerated aging conditions as described in US 5,739,075. Reproducibility was achieved by showing statistical relevancy of 3 conducted epoxidation runs each. The epoxide selectivity (to ethylene oxide) as molar amount of EO converted compared to the total molar amount of the raw material ethylene was measured over time. For comparison purposes the S40 selectivity (mol-% ethylene) was calculated as indicator for the epoxide selectivity at 40 mol-% oxygen conversion. Additionally, the concentration of two side products was analyzed in the product gas flow. With this experimental approach we can compare different ethylene feed qualities and their impact on the silver catalyst degradation performance.

In table 2 the epoxide selectivity S40 after runtimes of 21 , 56 and 105 days as well as the average content of the two side-products carbon dioxide (CO2) and acetaldehyde in the product gas are shown. All percent values are mol-% or mol-ppm based on raw material ethylene.

Table 2

For practical and economical reasons it is very important to achieve maximum catalyst lifetime. The examples show that the catalyst runtime is surprisingly higher and production of side-components is lower with an ethylene raw material feed based on the process of the invention. Example 2: Preparation of Propylene oxide (PO)

Propylene oxide has been prepared via the HPPO process as described in US 7,608,728 B2 example 4 including the catalyst preparation of example 3. The epoxidation tube reactor filled with the prepared Ti-MWW catalyst was continuously fed with propylene (propene), 40.2 wt% aqueous hydrogen peroxide and acetonitrile (solvent) in the composition, ratio and conditions as defined in the mentioned patent example and only the source of the propylene feed material was varied using the following raw material grades:

Table 3

All trial runs have been conducted with exactly the same Ti-MWW catalyst batch. The epoxide selectivity (to propylene oxide) as molar amount of PO converted compared to the total molar amount of raw material hydrogen peroxide (100% active) was measured after a runtime of 21 days respectively 504 hours. Reproducibility was achieved by showing statistical relevancy of 5 conducted epoxidation runs each. Furthermore side-products in the product stream were analyzed after the same runtime. Epoxide downstream products (Epoxide DP’s), meaning undesirable reaction products such as glycols and polyether polyols were checked as sum parameter and propylene glycol was analyzed separately. Side-product results are displayed as side-product selectivity in mol-% based on hydrogen peroxide, same as for the epoxide selectivity. With this experimental approach we can compare different propylene feed qualities and their impact on catalyst performance. Higher epoxide selectivities are equal to longer effective catalyst lifetimes and reduced number of regeneration cycles during HPPO production. Furthermore, sidecomponents are relevant to the total HPPO process yield respectively recycle efforts and waste generation. Table 4

The examples show that the PO selectivity is marginally higher and production of side-components is lower. However, especially the epoxidation reproducibility, clearly shown by a factor 3 lower standard deviation, is significantly higher with a propylene raw material feed based on the process of the invention. Higher run reproducibility has the advantage of improved planning-efficiency in industrial production practice, especially for a process with a relatively high frequency for catalyst regeneration-cycles such as HPPO. Example 3: Preparation of Alkoxylated compounds

The crude reaction products PO from example 2 were collected and subjected to purification by distillation resulting in the following two raw material product grades. Table 5

The propylene oxide raw materials shown in table 5 were used to prepare polyether polyols via DMC catalysis as described in US 5,777,177 table 1 and results are summarized in Table 6. Table 6

These examples show that the by-products generated during the alkoxylation process via DMC are lower using PO based on the process of the invention. The effect is more pronounced when less DMC catalyst is used. A lower degree of high molecular weight by-product could explain the reduction of unsaturation and a reduced polydispersity, as well as a reduction in viscosity. The reduction of these by-products is desired in PU foam applications, as such very high molecular weight fractions are known to be potent surfactants which cause collapsing polyurethane foam.

Regarding the preparation of specific alkoxylated compounds according to the present invention comprising ethylene oxide units and/or propylene oxide units and optionally at least one alkylene oxide unit different from ethylene oxide units and propylene oxide units, see experimental examples AO to A6, B1 to B11 , C1 to C8 and D1 to D3 below.

Alkoxylation examples

“Alkoxylated compounds (Alkoxylates) industrial production input ratios” almost quantitative conversion of EO, PO and higher epoxides is common industrial standard for alkoxylation technology. The experimental examples however, are mainly small lab-scale batch experiments. Therefore, the mentioned product yields <99% and thus product material losses are explained by remaining product sticking to comparably small lab equipment. Therefore, those yield losses mentioned in the following experimental examples are not relevant for the PCF calculations and have not been considered as such.

Alkoxylation experimental example AO: Synthesis of PEG 400 using KOH catalysis A mixture of 1322.4 g diethylene glycol and 5.7 g KOH solution 50% in water were given in a 6000 mL autoclave. The mixture was dried for 60 min at 110° under full vacuum. The reactor was pressurized with nitrogen to 2.5 bara and 3677.6 g of EO were added within 6 h at 158 °C. After post reaction of 3 h reaction at 154 °C the reaction mixture was cooled to 110 °C and all volatile components were removed under full vacuum. After cooling to 90 °C 5% Ambosol® MP 25 and 2% water were added for neutralization. The formed suspension was stirred for 3 h. Water was removed, and the product was filtered. The product was cooled to temperature and analyzed. 4900.2 g (98% yield) of a white solid was obtained.

Analytical values

Melting point: 6 °C

OH value: 281.7 mg KOH/g (DIN 53240-2; DIN= deutsche Industrienorm)

Biodegradability: >95 % CO2 formation relative to the theoretical value (28 d) (OECD 301 B; ISO 9439; 92/69/EEC, C.4-C) (activated sludge); Readily biodegradable.

Alkoxylation experimental example A1 : Synthesis of PEG 1500 using KOH catalysis

A mixture of 353.4 g diethylene glycol and 5 g KOH solution 50% in water were given in a 6000 mL autoclave. The mixture was dried for 60 min at 110° under full vacuum. The reactor was pressurized with nitrogen to 2.5 bara and 4646.6 g of EO were added within 6 h at 155 °C. After post reaction of 3 h reaction at 155 °C the reaction mixture was cooled to 110 °C and all volatile components were removed under full vacuum. After cooling to 90 °C 5% Ambosol® MP 25 and 2% water were added for neutralization. The formed suspension was stirred for 3 h. Water was removed, and the product was filtered. The product was cooled to temperature and analyzed.

4826.2 g (97% yield) of a white solid was obtained.

Analytical values

Melting point: 45 °C

OH value: 74.2 mg KOH/g (DIN 53240-2; DIN= deutsche Industrienorm)

Alkoxylation experimental example A2: Synthesis of PAG 2500 (-50% EO/50 % PO) using KOH catalysis

A mixture of 211.9 g diethylene glycol and 5 g KOH solution 50% in water were given in a 6000 mL autoclave. The mixture was dried for 60 min at 110° under full vacuum. The reactor was pressurized with nitrogen to 2.5 bara and a mixture of 2394.1 g of EO and 2394.1 g PO were added within 10 h at 125 °C. After post reaction of 5 h reaction at 125 °C the reaction mixture was cooled to 110 °C and all volatile components were removed under full vacuum. After cooling to 90 °C 5% Ambosol MP 25 and 2% water were added for neutralization. The formed suspension was stirred for 3 h. Water was removed, and the product was filtered. The product was cooled to temperature and analyzed. 4676 g (94% yield) of a colorless liquid was obtained. Analytical values

Viscosity: 225 mm2/s at 40 °C ASTM D445.

OH value: 45,3 mg KOH/g (DIN 53240-2; DIN= deutsche Industrienorm)

Biodegradability: 70 - 80 % CO2 formation relative to the theoretical value (28 d) (OECD 301 B; ISO 9439; 92/69/EEC, C.4-C) (activated sludge); Readily biodegradable.

Alkoxylation experimental example A3: Synthesis of PAG 2500 (-75% EO/25 % PO) using KOH catalysis

A mixture of 212.5 g diethylene glycol and 5 g KOH solution 50% in water were given in a 6000 mL autoclave. The mixture was dried for 60 min at 110° under full vacuum. The reactor was pressurized with nitrogen to 2.5 bara and a mixture of 3590.6 g of EO and 1196,7 g PO were added within 10 h at 125 °C. After post reaction of 5 h reaction at 125 °C the reaction mixture was cooled to 110 °C and all volatile components were removed under full vacuum. After cooling to 90 °C 5% Ambosol MP 25 and 2% water were added for neutralization. The formed suspension was stirred for 3 h. Water was removed, and the product was filtered. The product was cooled to temperature and analyzed. 4753 g (95% yield) of a colorless liquid was obtained.

Analytical values

Viscosity: 279 mm2/s at 40 °C ASTM D445.

OH value: 45.6 mg KOH/g (DIN 53240-2; DIN= deutsche Industrienorm)

Biodegradability: 70 - 80 % CO2 formation relative to the theoretical value (28 d) (OECD 301 B; ISO 9439; 92/69/EEC, C.4-C) (activated sludge) Readily biodegradable.

Alkoxylation experimental example A4: Synthesis of PPG 1500 using KOH catalysis

A mixture of 253.2 g mono propylene glycol and 5 g KOH solution 50% in water were given in a 6000 mL autoclave. The mixture was dried for 60 min at 110° under full vacuum. The reactor was pressurized with nitrogen to 1.5 bara and a mixture of 4746.8 g PO were added within 15 h at 120 °C. After post reaction of 5 h reaction at 120 °C the reaction mixture was cooled to 110 °C and all volatile components were removed under full vacuum. After cooling to 90 °C 5% Ambosol® and 2% water were added for neutralization. The formed suspension was stirred for 3 h. Water was removed, and the product was filtered. The product was cooled to temperature and analyzed. 4727 g (95% yield) of a colorless liquid was obtained.

Analytical values

Viscosity: 66 mm2/s at 40 °C ASTM D445

OH value: 75.1 mg KOH/g (DIN 53240-2 DIN= deutsche Industrienorm)

Biodegradability: 80 - 90 % (28 d) (OECD 301 B; ISO 9439; 92/69/EEC, C.4-C); Readily biodegradable (according to OECD criteria)

Alkoxylation experimental example A5: Synthesis of PPG 8000 using KOH catalysis

A mixture of 937 g PPG 1500 and 20 g KOH solution 50% in water were given in a 6000 mL autoclave. The mixture was dried for 60 min at 110° under full vacuum. The reactor was pressur- ized with nitrogen to 1 .5 bara and 4062.5 g PO were added within 14 h at 120 °C. After post reaction of 5 h reaction at 120 °C the reaction mixture was cooled to 110 °C and all volatile components were removed under full vacuum. After cooling to 90 °C 5% Ambosol® and 2% water were added for neutralization. The formed suspension was stirred for 3 h. Water was removed, and the product was filtered. The product was cooled to temperature and analyzed. 4634 g (93% yield) of a colorless liquid was obtained.

Analytical values

Viscosity: 243 mm2/s at 40 °C ASTM D445 Biodegradability: 29 % (28 d) (OECD 301 B; ISO 9439; 92/69/EEC, C.4-C); Moderately or partly biodegradable (according to OECD criteria)

Alkoxylation experimental example A6: Synthesis of PEG +20 BO +12 C12-Epoxide See EP 3 099 765 B1 page 19, Example 1 .

Alkoxylation experimental example B1 : Synthesis of C13C15 alcohol + 3 mol EO using KOH catalysis

2 mol C13C15 alcohol (418 g, 65% C13 alcohol, 35% C15 alcohol) and 2.1 g KOH (finely powdered) were mixed and dehydrated at 80°C and 40 mbar for 1 hour. The reaction product was introduced into an autoclave, the autoclave was rendered inert twice with nitrogen and then heated to 150°C. Over the course of 15 minutes, ethylene oxide was metered in to a maximum pressure of 1 bar. The system was maintained for 5 min at this pressure, then the pressure was increased to 3 bar by adding ethylene oxide over the course of 60 min, the system was held at this pressure for 5 hours, and finally the pressure was increased to 6 bar. During the last metered addition, ethylene oxide was added only until the desired amount of ethylene oxide (in total 6 mol, 264 g) was reached. The pressure was then maintained at 6 bar through the metered addition of nitrogen. After a reaction time of a further 10 hours, the system was left to cool to 80°C, and the reaction product was discharged. Volatile components were removed on a rotary evaporator at 30 mbar and 80°C.

Analytical value: cloud point accord, to EN1890, 5 g surfactant + 25 g diethylene glycol monobutylether solution (c=250g/L): 45°C

Alkoxylation experimental example B2: Synthesis of C13C15 alcohol + 7 mol EO using KOH catalysis

1 mol C13C15 alcohol (209 g, 65% C13 alcohol, 35% C15 alcohol) and 2.5 g KOH (finely powdered) were mixed and dehydrated at 80°C and 40 mbar for 1 hour. The reaction product was introduced into an autoclave, the autoclave was rendered inert twice with nitrogen and then heated to 150°C. Over the course of 15 minutes, ethylene oxide was metered in to a maximum pressure of 1 bar. The system was maintained for 5 min at this pressure, then the pressure was increased to 3 bar by adding ethylene oxide over the course of 60 min, the system was held at this pressure for 5 hours, and finally the pressure was increased to 6 bar. During the last metered addition, ethylene oxide was added only until the desired amount of ethylene oxide (in total 7 mol, 308 g) was reached. The pressure was then maintained at 6 bar through the metered addition of nitrogen. After a reaction time of a further 10 hours, the system was left to cool to 80°C, and the reaction product was discharged. Volatile components were removed on a rotary evaporator at 30 mbar and 80°C.

Analytical value: cloud point accord, to EN1890, 1 g surfactant + 100 g distilled water: 45°C

Alkoxylation experimental example B3: Synthesis of C12C18 alcohol + 7 mol EO using KOH catalysis

1 mol C12C18 alcohol (208 g, 55% C12 alcohol, 22% C14 alcohol, 11% C16 alcohol, 12% C18 alcohol) and 3.0 g KOH (finely powdered) were mixed and dehydrated at 80°C and 40 mbar for 1 hour. The reaction product was introduced into an autoclave, the autoclave was rendered inert twice with nitrogen and then heated to 150°C. Over the course of 15 minutes, ethylene oxide was metered in to a maximum pressure of 1 bar. The system was maintained for 5 min at this pressure, then the pressure was increased to 3 bar by adding ethylene oxide over the course of 60 min, the system was held at this pressure for 5 hours, and finally the pressure was increased to 6 bar. During the last metered addition, ethylene oxide was added only until the desired amount of ethylene oxide (in total 7 mol, 308 g) was reached. The pressure was then maintained at 6 bar through the metered addition of nitrogen. After a reaction time of a further 10 hours, the system was left to cool to 80°C, and the reaction product was discharged. Volatile components were removed on a rotary evaporator at 30 mbar and 80°C.

Analytical value: cloud point accord, to EN1890, 1 g surfactant + 100 g distilled water: 53°C

Alkoxylation experimental example B4: Synthesis of C16C18 alcohol + 25 mol EO using KOH catalysis

1 mol C16C18 alcohol (261 g, 30% C16 alcohol, 70% C18 alcohol) and 3.0 g KOH (finely powdered) were mixed and dehydrated at 80°C and 40 mbar for 1 hour. The reaction product was introduced into an autoclave, the autoclave was rendered inert twice with nitrogen and then heated to 150°C. Over the course of 15 minutes, ethylene oxide was metered in to a maximum pressure of 1 bar. The system was maintained for 5 min at this pressure, then the pressure was increased to 3 bar by adding ethylene oxide over the course of 60 min, the system was held at this pressure for 5 hours, and finally the pressure was increased to 6 bar. During the last metered addition, ethylene oxide was added only until the desired amount of ethylene oxide (in total 25 mol, 1101 g) was reached. The pressure was then maintained at 6 bar through the metered addition of nitrogen. After a reaction time of a further 10 hours, the system was left to cool to 80°C, and the reaction product was discharged. Volatile components were removed on a rotary evaporator at 30 mbar and 80°C. Analytical value: cloud point accord, to EN 1890, 1 g surfactant + 100 g NaCI solution (c=50g/L): 95°C

Alkoxylation experimental example B5: Synthesis of i-C13 alcohol + 9 mol EO using KOH catalysis

1 mol i-C13 alcohol (200 g) and 4.0 g KOH (finely powdered) were mixed and dehydrated at 80°C and 40 mbar for 1 hour. The reaction product was introduced into an autoclave, the autoclave was rendered inert twice with nitrogen and then heated to 150°C. Over the course of 15 minutes, ethylene oxide was metered in to a maximum pressure of 1 bar. The system was maintained for 5 min at this pressure, then the pressure was increased to 3 bar by adding ethylene oxide over the course of 60 min, the system was held at this pressure for 5 hours, and finally the pressure was increased to 6 bar. During the last metered addition, ethylene oxide was added only until the desired amount of ethylene oxide (in total 9 mol, 396 g) was reached. The pressure was then maintained at 6 bar through the metered addition of nitrogen. After a reaction time of a further 10 hours, the system was left to cool to 80°C, and the reaction product was discharged. Volatile components were removed on a rotary evaporator at 30 mbar and 80°C.

Analytical value: cloud point accord, to EN1890, 1 g surfactant + 100 g distilled water: 60°C

Alkoxylation experimental example B6: Synthesis of 2-propylheptanol + 8 mol EO using KOH catalysis

1 mol 2-Propylheptanol (158 g) and 3.0 g KOH (finely powdered) were mixed and dehydrated at 80°C and 40 mbar for 1 hour. The reaction product was introduced into an autoclave, the autoclave was rendered inert twice with nitrogen and then heated to 150°C. Over the course of 15 minutes, ethylene oxide was metered in to a maximum pressure of 1 bar. The system was maintained for 5 min at this pressure, then the pressure was increased to 3 bar by adding ethylene oxide over the course of 60 min, the system was held at this pressure for 5 hours, and finally the pressure was increased to 6 bar. During the last metered addition, ethylene oxide was added only until the desired amount of ethylene oxide (in total 8 mol, 352 g) was reached. The pressure was then maintained at 6 bar through the metered addition of nitrogen. After a reaction time of a further 10 hours, the system was left to cool to 80°C, and the reaction product was discharged. Volatile components were removed on a rotary evaporator at 30 mbar and 80°C.

Analytical value: cloud point accord, to EN1890, 1 g surfactant + 100 g distilled water: 56°C

Alkoxylation experimental example B7: Synthesis of 2-propylheptanol + 1.5 mol PO + 8 mol EO using KOH catalysis

158 g (1 mol) of 2-propylheptanol and 3.8 g KOH solution (c=400 g/L) were mixed in an autoclave and were dehydrated at a temperature of 100 °C and about 20 mbar for two hours. The system was then flushed three times with nitrogen and then heated to 130 °C. After the temperature had been reached, a total of 1.5 mol propylene oxide (87 g) were metered in at 140 °C with stirring. When the PO metered addition was complete, the mixture was stirred for a further 15 minutes at 130 °C, then heated to 150°C. Then the metered addition of a total of 8 mol ethylene oxide (352 g) was started. When the ethylene oxide metered addition was complete, the mixture was stirred for a further 1 h at 150 °C., and the reactor was flushed three times with nitrogen, then evacuated to degas to 20 mbar, then cooled to 80[deg.] C., and emptied. The reaction product was not filtered.

Alkoxylation experimental example B8: Synthesis of C12C14 alcohol + 2 mol EO + 4 mol PO using KOH catalysis

1.0 mol C12C14 alcohol (194 g, 70% C12 alcohol, 30% C14 alcohol) and 3.8 g KOH solution (c=400 g/L) were mixed in an autoclave and dehydrated at 80°C and 40 mbar for 1 hour. The autoclave was rendered inert twice with nitrogen and then heated to 150°C. The system was maintained for 5 min at this pressure, then the pressure was increased to 3 bar by adding ethylene oxide over the course of 60 min, the system was held at this pressure for 5 hours, and finally the pressure was increased to 6 bar. During the last metered addition, ethylene oxide was added only until the desired amount of ethylene oxide (in total 2 mol, 88 g) was reached. The temperature was then reduced to 130°C and propylene oxide was added under a maximum pressure of 6 bar until the desired amount was added (4 mol, 232 g). After a reaction time of a further 5 hours, the system was left to cool to 80°C, and the reaction product was discharged. Volatile components were removed on a rotary evaporator at 30 mbar and 80°C.

Analytical value: cloud point accord, to EN1890, 5 g surfactant + 25 g diethylene glycol monobutylether solution (c=250g/L): 30°C

Alkoxylation experimental example B9: Synthesis of EO/PO blockcopolymer with 20 mol EO and 30 mol PO using KOH catalysis

1 .0 mol PEG 600 (600 g) and 7.8 g KOH solution (c=400 g/L) were mixed in an autoclave and dehydrated at 80°C and 40 mbar for 1 hour. The autoclave was rendered inert twice with nitrogen and then heated to 150°C. The system was maintained for 5 min at this pressure, then the pressure was increased to 3 bar by adding ethylene oxide over the course of 60 min, the system was held at this pressure for 5 hours, and finally the pressure was increased to 6 bar. During the last metered addition, ethylene oxide was added only until the desired amount of ethylene oxide (in total 6.4 mol, 282 g) was reached. The temperature was then reduced to 130°C and propylene oxide was added under a maximum pressure of 6 bar until the desired amount was added (30 mol, 1740 g). After a reaction time of a further 5 hours, the system was left to cool to 80°C, and the reaction product was discharged. Volatile components were removed on a rotary evaporator at 30 mbar and 80°C. Analytical value: cloud point accord, to EN1890, 1 g surfactant + 100 g distilled water: 60°C

Alkoxylation experimental example B10: Synthesis of TEA + 15 mol EO + 42 mol PO using KOH catalysis

1 .0 mol triethanolamine (149 g) and 4,8 g KOH solution (c=400 g/L) were mixed in an autoclave and dehydrated at 80°C and 40 mbar for 1 hour. The autoclave was rendered inert twice with nitrogen and then heated to 150°C. The system was maintained for 5 min at this pressure, then the pressure was increased to 3 bar by adding ethylene oxide over the course of 60 min, the system was held at this pressure for 5 hours, and finally the pressure was increased to 6 bar. During the last metered addition, ethylene oxide was added only until the desired amount of ethylene oxide (in total 15 mol, 660 g) was reached. The temperature was then reduced to 130°C and propylene oxide was added under a maximum pressure of 6 bar until the desired amount was added (42 mol, 2436 g). After a reaction time of a further 5 hours, the system was left to cool to 80°C, and the reaction product was discharged. Volatile components were removed on a rotary evaporator at 30 mbar and 80°C.

Analytical value: cloud point accord, to EN1890, 1 g surfactant + 100 g distilled water: 35°C

Alkoxylation experimental example B11 : Synthesis of EO/PO blockcopolymer with 45 mol EO and 51 mol PO using KOH catalysis

0.5 mol PEG 1000 (500 g) and 10.6 g KOH solution (c=400 g/L) were mixed in an autoclave and dehydrated at 80°C and 40 mbar for 1 hour. The autoclave was rendered inert twice with nitrogen and then heated to 150°C. The system was maintained for 5 min at this pressure, then the pressure was increased to 3 bar by adding ethylene oxide over the course of 60 min, the system was held at this pressure for 5 hours, and finally the pressure was increased to 6 bar. During the last metered addition, ethylene oxide was added only until the desired amount of ethylene oxide (in total 11.15 mol, 506 g) was reached. The temperature was then reduced to 130°C and propylene oxide was added under a maximum pressure of 6 bar until the desired amount was added (25.5 mol, 1479 g). After a reaction time of a further 5 hours, the system was left to cool to 80°C, and the reaction product was discharged. Volatile components were removed on a rotary evaporator at 30 mbar and 80°C.

Analytical value: cloud point accord, to EN1890, 1 g surfactant + 100 g distilled water: 81 °C

Alkoxylation experimental example C1 : TEA +18 EO +42 PO (In analogy to WO 2020/043460) 74.6 g (0.50 mol) triethanolamine and 5.53 g 50% (wt%) KOH solution were mixed and then dehydrated in a 2.5 I autoclave at 100 °C and <10 mbar for two hours.

The autoclave was inerted by flushing three times with nitrogen and an initial pressure of 2 bar was set. The reactor was then heated to 120-130 °C, and 100 g and then within 45 minutes another 296 g of ethylene oxide (9 mol) were added and the reactor contents were stirred for 30 minutes. Propylene oxide was then dosed over 60 minutes, 1218g (21 moles). After the end of dosing, the reaction was allowed to react until the pressure was constant. Volatile components were removed at 90 °C and 20 mbar within two hours. 1660 g of a liquid polymer was obtained.

Alkoxylation experimental example C2: TEA +19.4 EO +15.9 PO (In analogy to WO 2020/043460)

118.5 g triethanolamine (0.794 mol) and 8 g 50% (wt%) KOH solution were mixed and then dehydrated in an autoclave at 100 °C and <10 mbar for two hours.

The autoclave was inerted by purging three times with nitrogen and an initial pressure of 2 bar was set. The reactor was then heated to 120-130 °C, and 152 g (2.62 mol) and then another 500 g (8.61 mol) of propylene oxide were added within 45 minutes and the reactor contents were stirred for 45 minutes. Subsequently, 677 g (15.37 mol) of ethylene oxide was dosed over 45 minutes. Finally, after a reaction time of 60 minutes, 232 g PO (3.99 mol) was dosed again. After the end of dosing, the reaction was allowed to react for another 90 minutes until the pressure was constant. Volatile components were removed at 90 °C and 20 mbar within two hours. 1676 g of a liquid polymer were obtained.

Alkoxylation experimental example C3: Alkoxylated polyamine condensate 1 See WO2023/061827, polymer A.8.7; page 39, table 3 and page 46, table 7

Alkoxylation experimental example C4: Alkoxylated polyethylenimine 1

See WO2023/061827, polymer A.15.10, page 39, table 3 and page 46, table 7

Alkoxylation experimental example C5: Alkoxylated polyamine condensate 2 Polymer A2.3 in the application EP22211163.5 (II.2 Synthesis of polymer (A2.2) and related polymers)

Synthesis of backbone (a1 .2)

Step (a.1.2) Conversion of MCDA ((a.2): MCDA, 4:1 molar mixture of 2,4-isomer and 2,6-iso- mer) with ethylene oxide, 0.4 to 1 mol per N-H group

A 5-liter steel autoclave was charged with 1 .6 kg (a.2) (12.5 mol, 50 mol N-H) in 160 g de-ion- ized water and then heated to 100 °C. An amount of 2.6 g of KOH was added. Then, 50 g of ethylene oxide were fed into the autoclave within 10 minutes. The start of an exothermic reaction was observed. Subsequently, 1 ,050 g of ethylene oxide (“EO”) were fed into the autoclave within 18 hours, 0.5 mol EO/N-H group. The reaction mixture was stirred at 100 °C for further 6 hours. After that, the mixture was removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 2.7 kg of intermediate ITM.2 were obtained as a yellow viscous liquid.

Analytics: total amine value: 510 mg KOH/g

OH value: 863 mg KOH/g Step (a2.2): ITM.2 : citric acid : sebacic acid: pentaerythrol : 1 : 0.1 : 0.9 : 0.1

A 500-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged ITM.2 (79.1 g, 0.45 mol), citric acid (17.2 g, 90 mmol) and sebacic acid (163.1 g, 808 mmol), 12.22 g pentaerythrol (90 mmol) and warmed to 60 °C. Then, the resulting liquid was stirred at 60 rpm under nitrogen atmosphere and heated to 120 °C over a period of 75 minutes. The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. The reaction mixture was then heated to 120 °C (inside temperature). Mild foaming was observed. Water distilled off and was collected. Stirring at 120°C was continued under nitrogen for 6.5 hours. Then, the reaction mixture was slowly cooled to ambient temperature. The resultant ester (a1 .2) was collected as a clear brown material.

GPC in HFIP: M_n 233 g/mol, M_w 4860 g/mol

Acid number: 207 mg KOH/g

OH value: 230 mg KOH/g

Ethoxylation:

A 2-liter steel autoclave was charged with 140 g backbone (a1 .2). An amount of 2.6 g of KOH (50%) was added and the mixture was heated to 130°C under stirring. Then, 50 g of ethylene oxide were fed into the autoclave within 15 minutes. The start of an exothermic reaction was observed. Subsequently, 456 g of ethylene oxide were fed into the autoclave within 8 hours, total amount of EO: 20 mol/OH or NH or COOH group. The reaction mixture was stirred at 130 °C for further 6 hours. After that, the mixture was removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 652 g of an ethoxylate was obtained as a brown liquid, total amine value: 27.0 mg KOH/g, OH value: 127.0 mg KOH/g.

End-cappings:

A 2-liter steel autoclave was charged with 400 g of the above ethoxylate and 1 .7 g of KOH (50%) and heated to 130°C under stirring with 100 rpm. Then, 55 g of propylene oxide were added within 60 minutes and stirred at 130°C under increased stirrer speed, 200 rpm, for another 6 hours. Then, the reaction mixture was slowly cooled down. The polymer was collected as a brown solid (455 g). Total amine value: 24 mg KOH/g, OH value: 122 mg KOH/g.

Alkoxylation experimental example C6: Alkoxylated polyethylenimine 2

See WO2018/146005, example B.1 D, page 15 (11.3.4 Synthesis of alkoxylated polyethylenimine (B.1 D))

Alkoxylation experimental example C7: Alkoxylated polyethylenimine 3 In analogy to example B.1 D in WO 2018/146005

A 500-I autoclave was charged with 15.0 kg of stagel-propoxylate 2 and 510 g KOH (48% aqueous solution). The water was removed at 20 mbar (2h, 130°C). Then, the autoclave was purged with nitrogen and subsequently heated to 172°C. 110 kg of ethylene oxide were (over a period of 2 h) added under stirring and allowed to react for 60 minutes until PO was dosed over a period of 90 minutes, 218 kg until pressure control signalized completion (13.4 h). The mixture so obtained was cooled to 120°C and the volatile ingredients were removed in vacuo. An amount of 344.5 kg of a faint yellowish liquid.

Alkoxylation experimental example C8: Grafted polyalkylenoxide 1

A 4-l-vessel with stirrer and three feeds was charged with 2,240 g of a di-block copolyether pol- yethylene/propylene glycol (weight ratio EO/PO: 1 ,5:1 , Mn: 4,100 g/mol) and heated to 90°C and purged with nitrogen. Solution of radical starter (81 g) was fed through feed 1 over a period of 7 hours. 15 minutes after the commencement of feed 1 , an amount of 746 g vinylacetate was fed continuously through feed 2 within 6 hours. After addition of feed 1 was completed, feed 3 (3 hours, 64 g solution of radical starter) commenced. After the addition of the radical starter had been completed the reaction mixture was stirred 100°C for another hour. Then, the pressure was set to 10 mbar, and volatile components were removed at 100°C and 10 mbar under stirring. The reaction mixture was then cooled to ambient temperature. Inventive graft copolymer was obtained as a white paste, 3029 g.

As radical starter, tert.-butyl-peroctoate was used as a 25 % by weight solution in tripropylene glycol (“solution of radical starter”).

Alkoxylation experimental example D1 : Rigid Polyol: Glycerol/Sucrose +PO using using KOH catalysis

See DE 10322784A1 , page 8, comparative example 1 (“Vergleichsbeispiel 1”)

Alkoxylation experimental example D2: Flexible Polyol: Glycerol+EO/PO heretic using DMC catalysis

See EP 1633799 B1 , page 8 [0070] (Polyolsynthese)

Alkoxylation experimental example D3: Molded Polyol: Glycerol+PO+EO block using KOH catalysis

See EP 102508, page 4 [10] (Polyether Polyol 1)

The following series of alkoxylate compounds have been considered based on the recipes shown in the “Alkoxylation experimental examples A0-A6, B1-B11 , C1-C8 and D1-3” section above. In Table 7 the effective total Starter-, EO- and “sum of PO and higher epoxides” contents as well as the carbon content and biodegradability of the alkoxylate compounds are shown. All analytical data is based on the experimental examples. Table 7:

1*) Calculated starter content in alkoxylated compound, mass ratio “starters and other materials” based on total alkoxylated compound product (in wt%); Starter content = 1 - EO content - PO+ content (Total = 100%)

2*) EO content in alkoxylated compound, mass ratio ethylene oxide based on total alkoxylated compound product (in wt%): For single-step alkoxylation this is directly the calculated total EO content of the batch in wt%; For multi-step alkoxylation recipes the mass-balance-effective total EO recipe amount for the final stage product must be calculated (wt% effective total EO based on final stage product); as an alternative, the EO content of alkoxylate product can also be measured analytically as described in Anal. Chem. 1968, 40, 11 , 1620-1627, Publication Date: September 1 , 1968

3*) PO+ content in alkoxylated compound, mass ratio “sum of proylene oxide and higher epoxides” based on total alkoxylated compound product (in wt%): For single-step alkoxylation this is directly the calculated total “sum of PO and higher epoxides” content of the batch in wt%; For multi-step alkoxylation recipes the mass-balance-effective total “sum of PO and higher epoxides” recipe amount for the final stage product must be calculated (wt% “effective total PO and higher epoxides” based on final stage product); as an alternative, the “sum of propylene oxide and higher epoxides” content of alkoxylate products can be measured analytically via as described in Anal. Chem. 1968, 40, 11 , 1620-1627, Publication Date: September 1 , 1968

4*) Carbon content in alkoxylated compound product, mass ratio carbon based on total product (in wt%): Calculated as effective mass-ratio carbon-content of the product via the weighted recipe amounts I molar masses I molar carbon-contents for all ingredients (this calculation is only exact for defined ingredients, in case of polymer ingredients the carbon content must be measured analytically); Analytical C-content determination via standard elemental analysis, e.g. C,H Analytik EMA 502 Analysator Fa. Velp. EMA 502 Elementaranalysator CHNS-0 (velp.com)

5*) Biodegradability of alkoxylated compound, determined via test protocol of OECD 301 B; ISO 9439; 92/69/EEC, C.4-C (28 days)

Example 4: Hydrogen Production

Experimental Setup and Method: Electrolysis cell design and Hydrogen production conditions

1 ) Polymer Electrolyte Membrane I Proton Exchange Membrane Electrolysis (PEM)

Electrolysis Cell

Water electrolysis was conducted with a circular commercial PEM electrolysis cell (model ZE 200, Sylatech Analysetechnik GmbH, 0.007 m² active area). The cell stack was sealed with O- rings and wrapped with heat insulation fabric for isothermal operating conditions. A Nation® 117 standard membrane (supplier DuPont, dry thickness 180 microns) was assembled by HIAT GmbH with catalytic active coating materials iridium (19 g/m²) and platinum (8 g/m²). Water distribution at the anode half-cell was realized with a titanium mesh. Before the polymer electrolyte membrane, a porous transport layer with sintered titanium fiber material is used for controlled flow while a porous graphite plate was situated on the cathode-side. Experimental Conditions

Water with controlled temperature was supplied at constant flow of 9.5 g/h to the anode compartment. The cell pressure on cathode and anode side was controlled with PC valves. Experimental conditions such as temperature and pressure settings see table. The evolved hydrogen and oxygen gas in the half-cells was separated in a two-step separator setup with an intermediate condenser cooled with 20°C cooling water. Water condensate flowed back to the separator tank. Anodic cell-water was re-cycled, whereas on the cathode the separated water was drained. Remaining gas moisture is separated by desiccant dryers, ensuring complete separation of moisture in the electrolysis gas flow. Small gas samples of the dehydrated cathodic hydrogen gas were taken from the continous flow with an auto-sampler at regular intervals to conduct hydrogen gas analytics described below.

2) Alkaline Electrolysis Cell (AEC)

Electrolysis Cell

Alkaline water electrolysis was conducted with a circular AEC electrolysis cell (model Electro MP Cell, supplier ElectroCell Europe A/S, 0.01 m² electrode area). As electrodes Nickel 2.4068 material was used and separated by a commercial standard Zirfon Perl UTP 500 membrane (open mesh polyphenylene sulfide fabric symmetrically coated with a mixture polymer / zirconium oxide; thickness 500 microns; 0.023 m² active area; supplier Agfa-Gevaert N.V.) in zerogap cell configuration.

Experimental Conditions

Alkaline water (32 wt% potassium hydroxide, technical standard grade) with controlled temperature was supplied at constant flow of 27.8 kg/h to the anode and cathode compartment. The cell pressure on cathode and anode side was equalized via PC valve control. Experimental conditions such as temperature and pressure settings see table. The evolved hydrogen and oxygen gas in the half-cells was separated in a two-step separator setup with an intermediate condenser cooled with 20°C cooling water. Water condensate flowed back to the separator tank. Anodic and cathodic cell-water was re-cycled. Remaining gas moisture is separated by desiccant dryers, ensuring complete separation of moisture in the electrolysis gas flow. Small gas samples of the dehydrated cathodic hydrogen gas were taken from the continous flow with an autosampler at regular intervals to conduct hydrogen gas analytics described below.

3) Anion Exchange Membrane I Alkaline Electrolyte Membrane Electrolysis (AEM)

Electrolysis Cell

The AEM experiments were executed in a commercial, fully automated 2.4 kW EL 4.0 cell supplied by Enapter GmbH, 10117 Berlin and a 1 wt% potassium hydroxide (standard grade) electrolyte solution.

Test station As recommended by the supplier the EL 4.0 electrolyzer is run with a 1 wt% potassium hydroxide (technical standard grade) solution, hydrogen production at operating conditions (experimental conditions such as temperature and pressure settings see table) was 480 l/h at approx. 400 ml water consumption. The evolved hydrogen gas was treated with desiccant dryers, ensuring complete separation of moisture in the electrolysis gas flow to yield < 0,03 wt% water in the hydrogen gas stream. Small gas samples of the dehydrated cathodic hydrogen gas were taken from the continous flow with an auto-sampler at regular intervals to conduct hydrogen gas analytics described below.

4) Solid Oxide Electrolysis Cell (SOE)

Solid Oxide cell stacks from Elcogen- Elco Stack (Elcogen OY, Vantaa 01510 Finland), were used and a E3000 unit was operated in reverse mode at 700°C and 35A electrolyzing current; Anode functional composition due to the supplier is NiO/YSZ. Cathode is of LSC type [La(Sr)CoO3]: The principle is also described in Novel high-performance solid oxide fuel cells with bulk ionic conductance dominated thin-film electrolytes - ScienceDirect; D. Stover et al, Journal of Power Sources; Volume 218, 15 November 2012, Pages 157-162.

The hydrogen stream was used with no further purification/dryer. Remaining gas moisture is separated by desiccant dryers, ensuring complete separation of moisture in the electrolysis gas flow. Small gas samples of the dehydrated cathodic hydrogen gas were taken from the continous flow with an auto-sampler at regular intervals to conduct hydrogen gas analytics described below.

The results of the hydrogen production are shown in table 8.

Experimental Results - Overview

Table 8

* Isar river surface water (Munich) collected in winter season January 2021.

Experimental Setup and Method: ”D content (Deuterium content) in samples'

The following method descriptions apply for determination of the molar share of deuterium based on the total hydrogen content (Deuterium content) of gas and liquid samples. The isotopic H/D-share analysis is based on mass spectroscopy. Two different methods are used: method A for gas samples and method B for liquid samples.

For determination of the “D content in gas and liquid samples” it is of crucial importance not to contaminate the samples e.g. with ambient humidity or other ambient components containing hydrogen or deuterium. Therefore gas-tight materials and sealings must be used with clean sample containers to avoid any cross-contamination. Therefore, before filling and sealing a sample container it must be flushed at least 20 times the sample container volume with the gas or liquid stream to be analyzed. The same is valid for the experimental setup of the gas sampler and mass spectrometer. Utmost care must be taken to avoid cross-contamination e.g. via condensation of humidity. The analytical setup from sampling to mass spectrometry is validated with known reference samples.

Method A) Gas samples

Total Deuterium from HD and D2 in hydrogen gas samples was determined via ultra-high resolution quadrapole mass spectrometry using a Hiden DLS-20 (Hiden Analytical Ltd., Warrington, Cheshire, UK) analyzer setup. The general method setup is described in C.C. Klepper, T.M. Biewer, U. Kruezi, S. Vartanian, D. Douai, D.L. Hillis, C. Marcus, Extending helium partial pressure measurement technology to JET DTE2 and ITER; Rev. Sci. Instrum., 87 (11) (2016); doi: 10.1063/1.4963713. For the hydrogen gas samples the threshold ionization mass spectrometry mode (TIMS) was used as described in S. Davies, J. A. Rees, D.L. Seymour; Threshold ionisation mass spectrometry (TIMS); A complementary quantitative technique to conventional mass resolved mass spectrometry; Vacuum, 101 (2014), pp. 416-422; doi: 10.1016/j. vacuum.2013.06.004. Sensitivity is +/-1 ppm.

Method B) Liquid samples

Analysis of liquid samples (ammonia, monoethanolamine (MEA) and polyethylenimine (PEI)) was executed via isotope ratio monitoring gas chromatography/mass spectrometry (I RMS). Therefore a DELTA V PLUS CF-IRMS mass spectrometer was used. This mass spectrometer with magnetic sector with continuous flux DELTA V PLUS CF-IRMS is used to measure the isotopic ratio of 2 H/1 H.

Measurement of D/H in a continuous He-flow mode needs the complete removal of low energy 4 He+ ions from the HD+ ion beam at m/z 3). The method is described in RAPID COMMUNICATIONS IN MASS SPECTROMETRY Rapid Commun. Mass Spectrom. 13, 1226-1230 (1999), W.A. Brandt et al. Sensitivity is within +/-3 ppm. Example 5: Production of ethylene oxide (EO)

Ethylene oxide is prepared with catalytic synthesis processes in industrial scale as described above.

By using non-fossil based energy for electrolytic hydrogen in the methanol synthesis at the root of this value chain, the only material hydrogen in the downstream resulting EO is actually originating from the electrolytic hydrogen with a low deuterium content.

In all of the large-scale commercial production processes in question using non-fossil hydrogen no significant additional amounts of hydrogen-species are introduced in the “input/output” process material balance. This is required in order to minimize output of undesired wastewater or other liquid and gaseous emission streams and to ensure high yields with purity according to the product specification.

If ambient air used for direct oxidation of ethylene in EO production the ambient moisture does not participate in the catalytic reaction and is therefore purged together with nitrogen and other inert gases. The EO product as such thus consists practically only of material hydrogen originating from the ethylene. Ethylene made via MTO or similar processes from methanol from hydrogen and carbon oxides has almost the same deuterium concentration as the hydrogen source.

In case water is used as processing aid for stripping/scrubbing/cleaning or quenching/condens- ing of process-internal streams in e.g. the methanol, and/or ethylene oxide synthesis steps this water is always run in an almost completely closed cycle with minimum purge ensuring insignificant cross-contamination with deuterium.

If hydrogen-species are introduced in the continuous industrial processes these feed streams are always minor compared to the output stream of the desired product, meaning at least 2 orders of magnitude smaller or in other words <1 % of the output stream. Therefore a worst-case factor 1 .01 calculative increase of the deuterium content was used for the ethylene (MTO based) process steps.

In table 9, the deuterium (D) content in hydrogen, based on fossil resources (FR’s) (comparative examples) and non-fossil resources (NFR’s) (inventive examples) is shown. The products from FR’s (comparative examples) are conventional petrochemical products from BASF SE. The deuterium contents of products from NFR’s are calculated as described above using the D content of hydrogen from examples I) to VI) (see table 1 ) as starting materials for both the ammonia and ethylene synthesis routes.

The examples based on NFR’s show a significantly lower D content and can be clearly distinguished from conventional products based on FR’s.

Using the EO of the invention as detailed herein and shown in this section before for the production of the polymers (polymer backbones (A)) and those in turn for producing the graft polymers is accomplished following the details given herein and/or the procedures given in the prior art documents being referenced in the description part of this disclosure.

When using the present invention to produce EO for the production of such polymer s for use as polymer backbones (A) and grafting those polymer backbones (A) with the monomers (B) to obtain the inventive graft polymers, the amount of hydrogen from non-fossil-based sources will increase in such graft polymer compared to graft polymers not using such EO of this invention. Obviously, the amount of hydrogen (and thus the content of deuterium) in such graft polymers depends on the actual structure of the graft polymer.

This amount can be defined as follows:

By defining the polymer structure of the polymer backbone (A) via defining the starting material and actually measuring the molecular weight Mn and thus defining the amount of hydrogen from EO in such polymer backbone, the polymer structure is defined and thus the amount of hydrogen in such structure can be calculated.

Thus, the amount of hydrogen and thus the amount of deuterium can be obtained and subsequently compared to a conventional graft polymer not being prepared using an element of the present invention. Obviously, when comparing such structure being obtained using the present invention (for introducing at least a part of the hydrogen in such structure) with the same chemical structure being derived from fossil-based sources only, the amount of deuterium in those non-fossil-based structure compared to the structure obtained using (to at least some extent) the present invention will be different.

As this difference will depend on the amount of hydrogen being introduced using the present invention (i.e. the amount of EO in the overall structure of the graft polymer and its molecular weight Mn, any precise number (a specific percentage of deuterium given in numerical numbers) will depend on the actual structure chosen (the amount of EO introduced relative to the total amount of hydrogen in the graft polymer).

Hence, no general defined numbers can be given; but it is clear that when the structure of the graft polymer (i.e. the structure of the polymer backbone, the amount of EO and the other monomers employed for preparation and the molecular weight of the polymer backbone; the amount and chemical structures of the monomers used for grafting; the radial initiator; the molecular weight of the graft polymer) is chosen and the molecular weights measured, then all the steps to obtain those structure of the graft polymer is defined and thus also the amount of hydrogen (via H2 and thus via EO) are defined, and then finally also that difference can be calculated and thus such defined non-fossil-based structure can be clearly distinguished from the chemically identical fossil-based structure.

As a result, the present invention can provide the inventive compounds (from at least partially non-fossil-based resources) having a deuterium-content which is lower than that of the same chemical structure but being derived from fossil-based resources only.

As this calculation is straight forward but depends on many parameters to be defined and measured, it is of no use to actually provide such example as in the end it only depends on the amount of hydrogen in such graft polymer which either stems from the inventive process steps or not, and thus there will be that difference between an inventive graft polymer and the very same graft polymer (i.e. the very same chemical structure in all of its aspects) but obtained from fossil sources.

Claims

Patent claims

1 . Process for making vinyl acetate, comprising the steps:

(b) providing carbon dioxide;

(d) reacting methanol from step (c) to form ethylene; and

(f2) reacting acetaldehyde from step (f1 ) with oxygen to give acetic acid;

(g) reacting acetic acid from step (e) and/or step (f1) with ethylene from step (d) to give vinyl acetate.

2. The process of claim 1 , wherein the electrical power is generated from wind power, solar energy, biomass, hydropower or geothermal energy.

3. The process according to claim 1 or 2, wherein the carbon dioxide that is provided in step (b) is captured from industrial flue gases or is captured form ambient air.

4. The process according to any one of claims 1 to 3, wherein the carbon dioxide provided in step (b) has a ¹³C-content corresponding to a 5¹³C value of from -10 to -2.5 %o.

5. Process for making vinyl acetate, comprising the steps:

(b) providing carbon dioxide;

(d) reacting methanol from step (c) to form ethylene; and

(e) reacting ethylene from step (d) with oxygen and water to form acetaldehyde;

(f2) reacting methanol from step (c) with carbon monoxide to form acetic acid; and (g1 ) reacting acetic acid from step (f1 ) and/or step (f2) with methanol from step (c) to form methyl acetate;

(g2) reacting methyl acetate from step (g1 ) with carbon monoxide to form acetic anhydride; and/or

(hi ) producing ketene from acetic acid from step (f1) and/or step (f2);

6. Vinyl acetate with a deuterium content below 90 ppm, based on the total hydrogen content, obtainable by the process according to any one of claims 1 to 5.

7. Vinyl acetate according to claim 6 having a ¹³C-content corresponding to a 5¹³C value of from -10 to -2.5 %o.

8. Process for making vinyl acetate from biomass, comprising the step of reacting (I) ethylene with (II) acetic acid to give vinyl acetate, wherein

(l) ethylene is provided, starting from biomass or ambient air, by a process comprising

(c2) reacting methanol from step (c1 ) to form ethylene; and/or

(d1 ) producing ethanol from biomass by fermentation,

(d2) dehydrogenating ethanol from step (d1 ) to give ethylene; and/or

(e) directly producing ethylene from biomass by fermentation;

(f) reacting methanol from step (c1 ) with carbon monoxide to give acetic acid; and/or

(g2) reacting acetaldehyde from step (g1 ) with oxygen to give acetic acid; and/or

(h) oxidative fermentation of ethanol from step (d1 ) to give acetic acid; and/or

(i) producing acetic acid from biomass by biomass pyrolysis.

9. The process of claim 8, wherein carbon oxides are produced in step (a) from biomass by gasification or combustion of the biomass, preferably of lignocellulosic biomass.

10. The process of claim 8 or 9, wherein in step (a) carbon dioxide is electrochemically reduced to carbon monoxide by carbon dioxide electrolysis.

11 . The process of any one of claims 8 to 10, wherein in step (c2) methanol is reacted to form ethylene in a methanol to olefin-process comprising the steps:

B) mixing of the stream A1 with at last one hydrocarbon recycle stream R comprising C2-C6-hydrocarbons and catalytic conversion in an olefin fixed bed reactor to yield a raw product stream B comprising C2-C4-olefines, Cs-Ce-hydrocarbons und C7⁺-hydrocarbons;

D) separating the hydrocarbon raw product stream C in a propylene containing value product stream, optionally an ethylene containing value product stream, a butene containing product stream, at least a Cs-Ce-hydrocarbon containing recycle stream and at least one Ce⁺-hydrocarbons containing side product stream;

G) discharging the Ce⁺-hydrocarbons containing side product stream.

12. The process of any one of claims 8 to 11 , wherein in step (d1 ) ethanol is produced by fermentation of lignocellulosic biomass.

13. The process of any one of claims 8 to 12, wherein ethylene is produced in step (b).

14. The process of any one of claims 8 to 13, wherein ethylene is produced in steps (c1 ) and

15. The process of any one of claims 8 to 14, wherein ethylene is produced in steps (d1 ) and (d2).

16. The process of any one of claims 8 to 15, wherein acetic acid is produced in step (f).

17. The process of any one of claims 8 to 16, wherein acetic acid is produced in steps (g1 ) and (g2).

18. The process of any one of claims 8 to 17, wherein acetic acid is produced in step (h).

19. The process of any one of claims 8 to 18, wherein acetic is produced in step (i).

20. Vinyl acetate having a natural abundance of carbon-14, obtainable by the process according to any one of claims 8 to 19.

21 . Polymers or copolymers of vinyl acetate and polymer dispersions comprising vinyl acetate, wherein the vinyl acetate has a natural abundance of carbon-14.

22. The use of vinyl acetate having a natural abundance of carbon-14 for determining the content of bio-based vinyl acetate or vinyl alcohol derived therefrom by hydrolysis in vinyl acetate or vinyl alcohol containing polymers or copolymers.

23. The of use of vinyl acetate having a natural abundance of carbon-14 for determining the origin of decay products released during decomposition of vinyl acetate or vinyl alcohol containing polymers or copolymers.

24. Process for preparing alkoxylated compounds comprising i) 20 wt-% to <100 wt-% of ethylene oxide units and/or propylene oxide units, ii) 0 wt-% to 30 wt-% of at least one alkylene oxide unit different from ethylene oxide and propylene oxide units, iii) >0 wt-% to 80 wt-% of at least one starter unit having Zerewitinoff active hydrogen atoms, wherein the sum of the units mentioned under i), ii) and iii) is 100 wt-%, comprising the following steps:

(a*) reacting hydrogen with carbon dioxide to form methanol,

(b*) converting the methanol from step (a*) to ethene and/or propene,

25. The process according to claim 24, wherein the propylene oxide in step (c*) is obtained by oxidation of propene with hydrogen peroxide as an oxidizing agent, preferably in the presence of a zeolite calalyst, more preferably in the presence of Titansilikalit-1 (TS-1 ).

26. The process according to claim 24 or 25, wherein the oxygen in step (c*) is obtained at least in part by water splitting, preferably by electrolysis, the water splitting, preferably the electrolysis, preferably using energy generated at least in part from non-fossil resources.

27. Alkoxylated compounds obtainable by the process according to any one of claims 24 to 26.

28. Process for preparing ethylene oxide or propylene oxide comprising the following steps: (a*) reacting hydrogen with carbon dioxide to form methanol,

29. Use of the alkoxylated compounds according to claim 27 or obtained by a process according to any one of claims 24 to 26 in home care products, cosmetic products, pharmaceutical products, food sector, building materials, lubricants like engine oils, bearing oils, gear oils, compressor oils, lubricating greases, heat transfer fluids, metalworking fluids and transmission fluids, antifoaming agents, softeners, rheology modifiers, emulsifiers, dispersing agents, thickeners, stabilizers, metal working fluids, agrochemicals like pesticides, textile and leather auxiliaries, bioprocessing, fuel performance packages and polyurethane) applications.

30. Graft polymer based on ethylene oxide-comprising backbones being grafted with olefini- cally polymerizable monomers, preferably vinyl monomers, more preferably with a) vinyl esters and optionally further monomers, such further monomers preferably being selected from vinyllactams, more preferably vinylpyrrolidone, and olefinically unsaturated, radically polymerizable amine-containing monomers such as vinylamines, more preferably vinylimidazole, and even more preferably such monomers being at least one vinyl ester, at least one lactam and optionally at least one vinylamine, and even more preferably such monomers being vinyl acetate, vinylpyrrolidone and vinylimidazole, or b) vinyllactams, more preferably vinylpyrrolidone, and olefinically unsaturated, radically polymerizable amine-containing monomers such as vinylamines, more preferably vinylim- idazole; wherein such graft polymer is at least partially based on hydrogen from non-fossil-based sources, wherein the molar share of deuterium is lower in such graft polymer than that in the identical chemical compound when derived solely from fossil-based sources, and wherein such graft polymer may contain other monomers in the chains derived from alkylene oxides, preferably such alkylene oxides containing ethylene oxide, such other monomers being preferably selected from lactones and/or other alkylene oxides other than or besides ethylene oxide.

31 . Process for making a graft polymer according to claim 30, wherein said process comprises the following steps: providing hydrogen with a molar share of deuterium < 100 ppm, preferably in the range of from 10 to < 95 ppm, more preferably in the range of from 10 to < 90 ppm, most preferably in the range of from 10 to < 80 ppm, based on the total hydrogen content, by electrolysis based on electrical power generated at least in part from non-fossil energy,

32. Use of the molar share of deuterium comprised in a compound according to claim 30, or a compound obtainable by or preferably obtained by a process of claim 31 , based on hydrogen for tracing the origin of preparation of such compounds based on hydrogen.

33. A process for tracing the origin of preparation of hydrogen comprised in a compound according to claim 30, or a compound obtainable by or preferably obtained by a process of claim 31 , by determining the molar share of deuterium in in hydrogen and said compound based on hydrogen.

34. Use of compound according to claim 30, or a compound obtainable by or preferably obtained by a process of claim 31 , preferably in a composition, that is more preferably a fabric and home care product, a cleaning composition, or an industrial and institutional cleaning product.

35. A composition being a laundry detergent, a cleaning composition or a fabric and home care product, containing at least one compound according to claim 30, or a compound obtainable by or preferably obtained by a process of claim 31 , comprising the at least one compound at a concentration of preferably from about 0.1 % to about 20% in weight % in relation to the total weight of such composition or product, and optionally further comprising at least one of a) to c) a. at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases and peroxidases, more preferably at least two of the aforementioned types, and in case an enzyme is comprised preferably also containing at least one enzyme-stabilizing system, b. about 1 % to about 70% by weight of a surfactant system, c. at least one further cleaning adjunct in effective amounts, preferably at least one compound selected from alkoxylated di-, oligo- and polyamines and alkoxylated polyethylene imine, alkoxylation being preferably using EO and/or propylene oxide, and optionally exhibiting an improved washing performance in primary cleaning (i.e. removal of stains) and/or dye transfer inhibiting properties.

36. A method of preserving a composition according to claim 35 against microbial contamination or growth, which method comprises addition of an antimicrobial agent selected from the group consisting of 2-phenoxyethanol to the composition which is an aqueous composition comprising water as solvent.

37. A method of laundering fabric or of cleaning hard surfaces, which method comprises treating a fabric or a hard surface with a composition according to 35, wherein the composition comprises 4,4’-dichloro 2-hydroxydiphenylether, preferably comprising 4,4’-dichloro 2-hy- droxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1 %, more preferably 0.01 to 0.6%, each by weight of the composition.