WO2025003331A1

WO2025003331A1 - Process to produce esteramines and their salts using orthoester as catalyst

Info

Publication number: WO2025003331A1
Application number: PCT/EP2024/068136
Authority: WO
Inventors: Sophia Ebert; Annalaura Del Regno
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2023-06-29
Filing date: 2024-06-27
Publication date: 2025-01-02
Anticipated expiration: 2025-12-29

Abstract

Process to produce Esteramines and their Salts using Orthoester as Catalyst, the esteramine, its salts, its uses, and compositions, specifically cleaning compositions, comprising such Esteramines and/or their Salts.

Description

Process to produce Esteramines and their Salts using Orthoester as Catalyst

Description

The use of orthoesters in the synthesis of amino acid esters is described in the literature; however, in all documents, the ortho esters are used in stoichiometric amounts referred to the amino acid. Additionally, the alkyl residual in the formed amino acid ester is identical in all of those documents to the alkyl residual in the used ortho ester.

For example, US7205433/WC2004018407 (priority date 23.08.2002) describes alanine methyl esters or ethyl esters as alkyl sulfonate salts, which are obtained from alanine, methanol or ethanol, alkylsulfonic acid and stoichiometric amounts of trimethyl or triethyl orthoesters.

WO 2005/110986 uses stoichiometric amounts of trimethyl orthoformiate to obtain allylglycine methyl-ester from allylglycine and methanol and hydrochloric acid.

The invention relates to a process for the synthesis of amino acid esters and its acid salts using at least one orthoester in sub-stoichiometric amounts, preferably in catalytic amounts. The invention also relates to amino acid esters and its salts obtainable by such process.

The esteramines and their salts obtainable or obtained by a process according to the present invention may be used in specific compositions, such as detergent, cleaning and/or fabric and home care compositions/formulations.

The esteramines and their salts obtainable or obtained by a process according to the present invention show good biodegradability properties when being employed, for example, within cleaning compositions.

Due to the climate change, one of the most important targets of the detergent and cleaning (D&C) industry today is to significantly lower the CO2 emission per wash, by improving e.g. cold water conditions by improving the cleaning efficiency at low temperatures of below 40, 30 or 20 or even colder, to lower the amounts of chemicals employed per wash, increasing the weight-efficiency of the cleaning technologies, introducing bio-derived components etc. Hence, one important target of the D&C industry is the need for biodegradable ingredients, to improve the sustainability of the cleaning formulations (and especially the laundry and dish wash formulations) and to avoid the accumulation of non-degradable compounds in the ecosystem. Hence, there is a need to provide compounds being bio-degradable and still having at least the same performance as already known but not bio-degradable compounds, such biodegradation as measured under defined conditions within 28 days as to be required by many users especially in the field of detergents, and as being a future requirement by applicable legislation in several countries and regions of the world.

Such reduction in CO2-emision or the desire to improve the "footprint” of any product is of high and even further rising interest in the industry and with the consumers, be it in terms of its origin like being from natural or renewable resources, or - all compared to previous products - its production in terms of production efficiency and thus reduced usage of energy, its efficiency in usage such as reduced amounts for the same performance or higher performance at the same amount levels used, its persistence in the natural environment upon and/or after its usage such as biodegradation.

Also, there is a need to improve the process to produce such esteramines and their salts with an improved process using less starting material, and with a reduced need for purification steps, to reduce the overall usage of compounds and energy and thus reduce also the carbon footprint of such process. As a result of these trends, there is a need for an improved process to prepare esteramines and their salts such as detailed in this present invention, providing at least comparable cleaning properties and a reduction in the CO2-foot- print not only by the properties of the compounds produced by also by the produces to produce such compounds. This goal was achieved by the present invention as described herein below and as reflected in the claims.

Definitions

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise”, and variations such as "comprises” and "comprising”, will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integer or step. When used herein the term "comprising” can be substituted with the term "containing” or "including” or sometimes when used herein with the term "having”.

When used herein, "consisting of" excludes any element, step, or ingredient not specified in the claim element. When used herein, "consisting essentially of" does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim.

In each instance herein any of the terms "comprising", "consisting essentially of" and "consisting of" may be replaced with either of the other two terms. "Comprising” may be replaced in a preferred embodiment with "consisting essentially of" and both may be replaced by "consisting of" in an even more preferred embodiment.

The compositions of the present disclosure can "comprise” (i.e. contain other ingredients), "consist essentially of” (comprise mainly or almost only the mentioned ingredients and other ingredients in only very minor amounts, mainly only as impurities), or "consist of' (i.e. contain only the mentioned ingredients and in addition may contain only impurities not avoidable in an technical environment, preferably only the ingredients) the components of the present disclosure.

Similarly, the terms "substantially free of... or" substantially free from .. or “ (contai ning/comprising) essentially no... may be used herein; this means that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, preferably, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included. The indicated material may be present, if at all, at a level of less than 1%, or even less than 0.1%, or even more less than 0.01%, or even 0%, by weight of the composition.

Specifically, the term "free of water" means that the composition contains no more than 5 wt.-% of water based on the total amount of solvent, in another embodiment no more than 1 wt.-% of water based on the total amount of solvent, in a further embodiment the solvent contains no water at all.

Generally, as used herein, the term "obtainable by” means that corresponding products do not necessarily have to be produced (i.e. obtained) by the corresponding method or process de-scribed in the respective specific context, but also products are comprised which exhibit all features of a product produced (obtained) by said corresponding method or process, wherein said products were actually not produced (obtained) by such method or process. However, the term "obtainable by” also comprises the more limiting term "obtained by”, i.e. products which were actually produced (obtained) by a method or process described in the respective specific context.

When used herein any definition requiring a compound or a substituent of a compound to consist of "at least [a number] of carbon atoms”, that number of carbon atoms refers to the total number of carbon atoms in said compound or substituent of a compound. For example for a substituent disclosed as "alkyl ether with at least 8 carbon atoms comprising alkylene oxide groups”, the total number of at least 8 carbon atoms needs to be the sum of the number of carbon atoms of the alkyl moiety and the number of carbon atoms of the alkylene oxide moieties.

All such terms not specifically defined have their ordinary meaning as known in the field of organic chemistry. The term "containing one hydroxy group” means that only one group -OH is present. Any functionalized group derived from a hydroxy group such as an ether group is not considered to be an -OH group.

The term "containing at least two hydroxy groups” means that two or more -OH groups are present. The term "hydroxy group” is equal to the term "hydroxyl group” or "-OH group”. Alcohols/compounds having only one hydroxy group, such as methanol or ethanol, do, by consequence, not fall under the definition of an alcohol containing at least two hydroxy groups according to compound (A) of the present invention. Any functionalized group derived from a hydroxy group such as an ether group is not considered to be an -OH group.

As used herein, the articles "a” and "an” when used in a claim or an embodiment, are understood to mean one or more of what is claimed or described. As used herein, the terms "include(s)” and "including” are meant to be nonlimiting, and thus encompass more than the specific item mentioned after those words.

The term "about” as used herein encompasses the exact number "X” mentioned as e.g. "about X%” etc., and small variations of X, including from minus 5 to plus 5 % deviation from X (with X for this calculation set to 100%), preferably from minus 2 to plus 2 %, more preferably from minus 1 to plus 1 %, even more preferably from minus 0,5 to plus 0,5 % and smaller variations. Of course if the value X given itself is already "100%” (such as for purity etc.) then the term "about” clearly can and thus does only mean deviations thereof which are smaller than "100”.

All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. Unless otherwise specified, all measurements herein are conducted at 20°C and under the atmospheric pressure. In all embodiments of the present disclosure, all percentages are by weight of the total composition, unless specifically stated otherwise. All ratios are weight ratios, unless specifically stated otherwise.

The phrase "fabric care composition” is meant to include compositions and formulations designed for treating fabric. 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, 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 and detailed herein below when describing the compositions. 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, and as further detailed herein below when describing the use and application of the inventive and compositions comprising such esteramine and its salts.

"Sulfonates” in this present invention are the anions derived from sulfonic acids, preferably alkane sulfonic acid and/or aryl sulfonic acid, more preferably alkane sulfonic acid, most preferably methane sulfonic acid; such acids are used to at least partially protonate the esteramines, thus forming the sulfonates of the esteramines.

Throughout this description, the term "inventive compound” may be used instead of the "inventive esteramine(s) and/or their salt(s)” and "esteramine(s) and/or their salt(s) of this (present) invention”, meaning those compounds being disclosed herein as invention, defined by their structure and/or their process to produce or obtainable by the process defined herein.

Detailed Description

The definitions and their preferences given within the “Definition”-section before are included as part of this invention as described herein below. 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” (or "preferably” etc.) 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 unless such independent selection is not possible by virtue of the nature of that feature or if such independent selection is explicitly excluded), with each and any and all such possible combinations being included as part of this invention as individual embodiments.

Process to produce Esteramines and their salts

It was surprisingly found, that the esterification of amino acids can be improved by use of sub-stoichiometric amounts and even catalytic amounts of ortho esters.

Further and unexpectedly, esteramines can be produced wherein the ester is derived from an another alcoholthan that present in the orthoester which is used as catalyst.

Thus, the present invention relates to an improved process of producing amino acid esters and their salts using sub- stoichiometric or even catalytic amounts of orthoesters.

Hence, the present invention relates to a process to produce esteramines or salts thereof using catalytic amounts of at least one orthoester, the process comprising the steps of a) reacting

I) at least one aminoacid selected from alpha-, beta-, gamma-, delta-, epsilon- etc. amino acids, such as alanine, glycine, leucine, isoleucine, valine, proline, phenylalanine, arginine, asparagine, aspartic acid, aspartate, glutamine, glutamate, histidine, lysine, threonine, tryptophan, tyrosine, cysteine, methionine, serine; alpha-amino acids with secondary or tertiary amino groups such as sarcosine, N, N-dimethylgly- cine; other amino acids such as 6-amino hexane acid, 4-amino butanoic acid, 3-amino propanoic acid, 12-amino dodecanoic acid, 11-aminoundecanoic acid; aminoacids formally derived from the hydrolysis of a-lactame (three ring atoms), p-lactame (four ring atoms), y-lactame (five ring atoms) and so on; such lactames preferably being p-propiolactame, g-butyrolactame, 5-valerolactame, g-valerolactame, e-capro- lactame, d-decalactame, g-decalactame, e-decalactame; preferably alanine, valine, beta-alanine, 6- amino hexane acid; with ii) at least one alcohol bearing at least one hydroxy group, being selected from mono-, di- and polyols, all of which may be optionally alkoxylated, wherein the alkoxy lation of the at least one hydroxy group takes place in a step before step a), with the alcohol being alkoylated with at least one alkylene oxide, preferably at least 1 and up to 200, preferably 1 to 100, more preferably up to 50 moles alkylene oxide per hydroxy group; in presence of ill) at least one acid (C), being selected from inorganic and organic acids, wherein said organic or inorganic acid has preferably a pKa value in the range of from -3 and up to +5, more preferably from -2,5 to 1 ,5, preferably at least one organic acid, such as sulfonic acids, more preferably alkane sulfonic acid and/or aryl sulfonic acid, more preferably alkane sulfonic acid, most preferably methane sulfonic acid; and iv) in the presence of at least one ortho ester, such as triethyl orthoformiate, trimethyl orthoformiate, triethyl orthoacetate, trimethyl orthoacetate, and the like; wherein the ortho ester is used in sub-stoichiometric amounts, preferably catalytic amounts (referred to the amounts of the amino acid) and wherein the alcohol used for the esterification is different from the alcohol-residual in the ortho ester; to produce an amino acid ester salt; b) optionally remove water and/or excess alcohol during and/or after the reaction to obtain the purified aminoester salt; c) optionally neutralize the obtained amino acid ester salt with at least one base to obtain the free amino acid ester.

Further process steps can be included in the inventive process:

The reaction mixture may be inertized before and/or during the reaction, preferably prior to the addition of the acid C. Inertization can be achieved by a steam of gas such as nitrogen or argon, and/or by adding an oxygen-scavenging compound.

Such oxygen-scavengers are known. Advantageous is the use of small amounts of inorganic salts with reducing properties towards oxygen, such as a hypophosporous compound, such as hypophosphorous acid or any of their salts, especially any alkali or ammonium or earth alkali salts, more preferably the acid, which can be added to the reaction mixture prior to adding the sulfuric acid.

As one of the effect, this addition of the oxygen-scavenging compound leads to an improved colour of the resulting product, i.e. meaning a reduced coloring, when compared to omitting such addition.

The reaction is performed the reaction is performed at a temperature of from 50 to 200°C, preferably 70- 180°C, more preferably 80°C- 160°C, most preferably 120°C - 150°C, such as 60, 65, 75, 85, 90, 95, 100, 110, 115, 120, 125, 130, 135, 140, 145, 155, 165, 170, 190 °C;

- for a period of from 1 to 30, preferably from 2, , more preferably from 3 hours, even more preferably at least 5 hours, and preferably up to 48, more preferably up to 20, even more preferably up to 15 hours, such as preferably 3 to 24 , more preferably 5 to 24 , most preferably 10 - 24 hour(s); and at from 0,001 to 10 bar pressure, such as from 0,001 , more preferably from 0,005, even more preferably from 0, 1, and preferably up to 8, more preferably up to 5, even more preferably up to 4 bar, such as 1 to 10, more preferably 1 to 5, even more preferably 1 to 4 bar, or such as 1 to 1000 mbar, more preferably 100 to 500 mbar.

Preferably, the temperature, the duration and the pressure are both as defined individually before, preferably the preferred ranges of all three parameters, more preferably the more preferred ranges and so on of all three parameters are selected.

In one embodiment of the present invention, the temperature is kept constant for the duration of the reaction. In another embodiment, the temperature is varied within the temperature range during the duration of the reaction.

In one embodiment of the present invention the reaction with acid C is carried out under atmospheric pressure. In another embodiment the reaction with acid C is carried out in a closed vessel under a pressure of from 0,001 to 1 bar. In another embodiment the reaction with acid C is carried out in a closed vessel under pressure of more than 1 to 10 bar.

In one embodiment a protective atmosphere of an inert gas such as nitrogen gas or argon gas is used to carry out the reaction. In another embodiment inertization is carried out by adding an oxygen-scavenging agent, preferably small amounts of inorganic salts with reducing properties towards oxygen, such as a hypophosporous compound, such as hypo- phosphorous acid or any of their salts, especially any alkali or ammonium or earth alkali salts, more preferably the acid is a hypophosphorous compound, more preferably hypophosphorous acid.

In another embodiment inertization is carried out by adding an oxygen-scavenging agent as defined before and with the use of a protective atmosphere of an inert gas as defined before.

It is clear that the temperature, pressure and duration can be chosen independently from the disclosed values and ranges and combined with each other. Similarly to this, also the way inertization is achieved can be chosen and combined with the temperatures, durations and pressures chosen, all as defined before.

During or following the reaction, preferably at least during the reaction, water and/or excess alcohol can be removed. Removal of water and alcohol can be carried out by all techniques known in the art, for example by application of a stream of gas and/or applying a distillation method, preferably a distillation, more preferably a distillation method under reduced pressure and/or at elevated temperature, preferably both, a preferred method being the use of an apparatus such as a Dean-Stark-trap.

In another embodiment, water and/or alcohol is removed using a stream of gas, such as using gas such as inert gas as nitrogen or argon, preferably nitrogen, or steam made from water, preferably using inert gas, more preferably nitrogen.

In a more preferred embodiment, water and/or alcohol is removed by application of a vacuum and/or increasing the temperature, most preferably using an apparatus such as a Dean-Stark-trap.

The optional removal of water and/or excess of alcohol is more preferably carried out applying a vacuum in the range of from 0.1 mbar to 800 mbar, preferably of from 1 mbar to 500 mbar and more preferably of from 10 mbar to 100 mbar, and using elevated temperatures.

In a preferred embodiment, during the reaction a steam of inert gas, such as nitrogen or argon, preferably nitrogen, is passed through the reaction mixture. This helps to keep the reaction mixture inert, but also supports the removal of forming water from the chemical reaction, and thus to control the amount of water present.

The molar ratio of amino acid to hydroxyl group of the (optionally alkoxylated) alcohol is

(0.8*n) : 1 to (1*n) : 1.5, with the number of hydroxy-groups of the (optionally alkoxylated) alcohol being n.

In one embodiment, the process is carried out with the molar ratio of the acid C to the amino acid being in the range of from 0.8 : 1 to 1.2 : 1.

Suitable solvents for the reaction may be toluene, xylene, heptanol, cyclohexene, and the like, preferably the reaction is carried out without solvent.

In a preferred embodiment, the reaction is performed with the minimum practically possible of water being present, preferably substantially free of water, and most preferably free from water during the start and the most part of the reaction, more preferably from start to essentially complete reaction

Obviously, such amino acids are known, and can be prepared usually from natural sources. Others can be produced starting from natural sources by modifying them to obtain aminoacids as starting material in the present invention. If such modification does result in the addition of carbon-atoms, e.g. by chemical addition reactions, and if such addition reactions use non-fossil carbon atoms, then aminoacids contain only non-fossil based carbon. Hence, it is preferred, that only naturally occurring aminoacids and/or nature-derived aminoacids (not being made with the addition of non-fossil carbon in building blocks to obtain such nature-derived aminoacids) are employed in this invention. Even more preferably, only naturally occurring aminoacids are employed. The same applies for the lactams: whenever a lactam is accessible from natural sources, such natural or nature-derived lactam is preferably; more preferable are of course naturally occurring lactams, to increase the overall content in non-fossil-based carbon content.

The at least one alcohol bearing at least one hydroxy group, being selected from mono-, di- and polyols, all of which may be optionally alkoxylated, wherein the al koxy lation of the at least one hydroxy group takes place in a step before step a), with the alcohol being alkoylated with at least one alkylene oxide, preferably at least 1 and up to 200, preferably 1 to 100, more preferably up to 50 moles alkylene oxide per hydroxy group, and in one embodiment even more preferably up to 20, such as up to 15 or even up to 10 moles alkylene oxide per hydroxy group;

Alcohols containing one hydroxy-group are well-known in the art. Similarly, alcohols containing at least two hydroxy groups according to compound (A) are known to a person skilled in the art. As mentioned above, the respective alcohol may contain one, two, three, four, five or even more hydroxy groups within the respective molecule/compound. The respective alcohol may contain linear, branched and/or cyclic alkyl fragments. Beyond that, the respective alcohol may also contain aromatic fragments as well as combinations of alkyl and aromatic fragments ("aralkyl” fragments). Furthermore, the respective alcohol may also contain alkyl ether fragments. Examples of alcohols according to compound (A) are glycerol, pentaerythritol, sorbitol, 1 ,1 , 1 -trimethylolpropane (TMP), erythritol or alkoxylated alcohols, such as polyethylene glycol.

Many alcohols according to compound (A) of the present invention are commercially available, for example, under the tradename "Pluronic(s)” or “Pluriol” (for example as polyethylene glycol block (co)polymers) from BASF SE.

The alcohol (A) for the inventive esteramine and the inventive process as described herein is selected from (Aa) mono-alcohols such as C1- to C36-alkanols, selected from the groups non-alkoxylated linear C2- to C36-alco- hols, such as mixture of such alcohols selected from C6- to C22-fatty alcohols, preferably C8- to C22-fatty alcohols, more preferably C12- and C14-fatty alcohols, most preferably C16- and C18-fatty alcohols; non- alkoxylated branched C3- to C36-alcohols such as 2-ethylhexanol, 2-propylheptanol, isotridecanol, isonona- nol, C9-C17 oxoalcohols; alkoxylated linear C2- to C36-alcohols such as alkoxylated mixture of C6- to C22-fatty alcohols, preferably alkoxylated mixtures of C8- to C22-fatty alcohols, more preferably alkoxylated mixtures of C12- and C14-fatty alcohols, most preferably alkoxylated mixtures of C16- and C18-fatty alcohols; alkoxylated branched C3- to C36-alcohols such as alkoxylated 2-ethylhexanol, alkoxylated 2-propylheptanol, alkoxylated isotridecanol, alkoxylated isononanol, alkoxylated C9-C17 oxoalcohols;

(Ab) di-alcohols such als alkane diols, poly alkoxy I ated C2-C6-alkandiols bearing at least two hydroxy groups, (Ac) oligo-alcohols such as sugar alcohols, polyalkoxylated sugar alcohols, C3-C6-alkantriols , polyalkoxylated C3- C6-alkantriols, bearing at least three hydroxy groups,

(Ad) polyols such as C5-C6-alkane polyols , polyalkoxylated C5-C6-alkane polyols, polyetherols such as polyglycerol or di- or tri-pentaerythritol, alkoxylated polyetherols such as alkoxylated polyglycerol, alkoxylated di- or tri-pen- taerythritol,

(Ae) phenoxyalkanols such as phenoxyethanol; with the alcohol(s) selected from the groups of mono-alcohols and alkoxylated di-, oligo-alcohols and alkoxylated polyols being preferred, and the alcohols selected from the group(s) mono-alcohols and alkoxylated di-alcohols being even more preferred.

In one embodiment of the present invention, at least one linear or branched C2- to C36-alcohol containing at least one hydroxy group is used.

In a preferred embodiment thereof at least one Cs- to C22-fatty alcohol containing at least one hydroxy group is used. In a more preferred embodiment thereof a mixture of Ci6- and C -fatty alcohols each containing at least one hydroxy group is used.

In another more preferred embodiment thereof a mixture of C - and C22-fatty alcohols each containing at least one hydroxy group is used.

In another more preferred embodiment thereof at least one branched C9- to C17 alcohol is used.

In a further more preferred embodiment thereof linear or branched Cs- to Gw-mono-alcohols containing at least one hydroxy group are used.

In a further even more preferred embodiment thereof 2-propyl heptanol or 2-ethy lhexanol are used.

In another even more preferred embodiment thereof 2-ethy lhexanol is used.

In a further preferred embodiment of the present invention, at least one phenoxyalkanol is used. In another more preferred embodiment phenoxyethanol is used.

Obviously, such alcohols are known, many of them from natural sources. Others can be produced starting from natural sources by modifying them. If such modification does result in the addition of carbon-atoms, e.g. by chemical addition reactions, and if such addition reactions use non-fossil carbon atoms, then alcohols contain only non-fossil based carbon. Hence, it is preferred, that only naturally occurring alcohol and/or nature-derived alcohols (not being made with the addition of non-fossil carbon in building blocks to obtain such nature-derive alcohols) are employed in this invention. Even more preferably, only naturally occurring alcohols are employed.

In a more preferred embodiment, the alcohol (A) employed for the inventive esteramine and the inventive process is an alkoxylated alcohol. Such alkoxylated alcohol is typically and thus preferably obtained by alkoxylating at least one hydroxy group of the alcohol as defined herein before with one or more alkylene oxides to produce alkylene oxychains comprising one or more moieties stemming from alkylene oxides selected from C2 to C22-alkylene oxides, preferably C2-C4-alkylene oxides, whereas the moieties stemming from the alkylene oxide(s) may be arranged in random, block or multiblock-order or combinations thereof, preferably as block.

In one embodiment of the present invention, alkyl alcohols alkoxylated with only a single alkylene oxide are used. In a further embodiment, alkyl alcohols alkoxylated with a first alkylene oxide followed by alkoxyl ation with a second alkylene oxide, thereby forming a block structure of different alkylene oxide blocks, are used.

Within the context of the present invention, it is also preferred that in case compound (A) comprises an alkoxylated alcohol comprises the alkoxylated fragment being based on at least one C2-C22 alkylene oxide, preferably C2-C4- alkylene oxides, more preferably ethylene oxide and/or propylene oxide, most preferably the respective alcohol comprises at least one block based on ethylene oxide and/or propylene oxide, and even more preferably contains only one block consisting of ethylene oxide or consisting of two blocks with the first block - preferably the "inner block” directly linked to the hydroxy-group of the alcohol - consisting of ethylene oxide and a second block - preferably being the "outer block linked to the ethylene oxide-block - consisting of propylene oxide.

More preferably, the EO-block comprises 3 to 10 EO-derived moieties and the PO-block comprises 1 to 10 PO-de- rived moieties.

Most preferably, only ethylene oxide is employed.

The al koxy lation of the alcohol can be achieved by either carrying out the alkoxy I ation reaction with only one alkylene oxide or with more than one alkylene oxide. If more than one alkylene oxide is used, the resulting alkylether alcohols comprises either randomly distributed alkylene oxide units or a block of one alkylene oxide followed by a block of another alkylene oxide or a block of one alkylene oxide followed by another block which comprises two or more alkylene oxides arranged in random order or a block comprising two or more alkylene oxides is followed by another block which comprises two or more alkylene oxides with each such block being different in their relative amount of alkylene oxides, their arrangement of alkylene oxides and/or the identity of the alkylene oxides such that the two blocks linked to each other differ in their chemical composition and/or arrangement; any such combination of arrangements is in principle possible, and as such is encompassed by this present invention.

It is clear that when switching from one block to the next there might be - depending on how the al koxy I ation reaction is performed - there might be a relatively small "region” in between the blocks which do not have a sharp "border” between the block which is identical on every molecule of the alkoxylated monoalkohol, such that there might be some "dirty” structures which means that some very small amounts (such as a single or perhaps two or three) alkylene oxides of the first type employed might be inserted only after one or more of the second alkylene oxide have reacted; this depends mainly on the conversion rate achieved for the first alkylation reaction at the time point when the second alkylene oxide is added, i.e. if at that time of adding the second alkylene oxide still some unreacted amounts of the first alkylene oxide are present.

Similarly, it is clear that due to the statistical reaction of the al koxy lation polymerization the block lengths might differ slightly from individual compound to the next, and thus the "the alkoxylated monoalkohol” in fact is a mixture of compounds having slightly differing chain lengths and block lengths.

This alkoxylation reaction may be undertaken generally in the presence of a catalyst at a reaction temperature from about 70 to about 200°C, in another embodiment from about 80 to about 160°C. This reaction may be affected at a pressure of up to about 10 bar, in another embodiment at a pressure of up to about 8 bar.

Examples of suitable catalysts comprise basic catalysts such as alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal alkoxides, in particular sodium and potassium Ci-C4-alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, alkali metal and alkaline earth metal hydrides such as sodium hydride and calcium hydride, and alkali metal carbonates such as sodium carbonate and potassium carbonate. In one embodiment, alkali metal hydroxides are used. In another embodiment, potassium hydroxide and sodium hydroxide are used. Typical use amounts for the base are from 0.01 to 10% by weight, in particular from 0.05 to 2% by weight, based on the total amount of alcohol and C2- to C22 alkylene oxide, preferably C2-C4-alkylene oxides.

It is noted that the alkylene oxide used to prepare the alkoxylated alcohol(s) may be derived from a fossil or non-fos- sil carbon source or even a mixture thereof. Preferably, the amount of non-fossil carbon atoms in the alkylene oxide employed is at least 10%, at least 20%, at least 40%, at least 70%, at least 95% and most preferably up top 100% based on non-fossil derived carbon atoms; the same applies to the total inventive compound as such. The skilled person is well-aware of commercial alkylene oxide products made of non-fossil carbon sources (these products are often sold as being "sustainable”, "renewable” or "bio-based”). For example, Croda International, Snaith, UK, sells ethylene oxide and related products based on bio-ethanol as "ECO”-Range. Additionally, methods to prepare biobased propylene oxide are also known (see Abraham, D. S., "Production of propylene oxide from propylene glycol" Master's Thesis University of Missouri-Columbia (2007) (75 pages)).

The acid (C) for the inventive esteramine and their salts and the inventive process is selected from i) sulfonic acids, such as alkyl sulfonic acids such as methane sulfonic acid, ethylsulfonic acid, propylsulfonic acid, camphorsulfonic acid; alkylaryl sulfonic acids and specifically alkylbenzene sulfonic acids, such as toluene sulfonic acid (including the mixture of isomers thereof), p-toluene sulfonic acid, o-toluene sulfonic acid, m-toluene sulfonic acid, xylene sulfonic acid (mixture of isomers), 2, 6-dimethylbenzene sulfonic acid, 2, 5-dimethylbenzene sulfonic acid, 2, 4-dimethylbenzene sulfonic acid, 4-dodecylbenzene sulfonic acid, iso-propyl benzene sulfonic acid, ethylbenzene sulfonic acid, and naphthalene sulfonic acid, and

II) inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid.

The acids employed preferably are concentrated such that the amount of water introduced into the reaction is minimized or are employed as solids. As such, also gases such as hydrogenchloride may be employed as this can be introduced as gas.

In one embodiment for the inventive esteramine and the inventive process, the acid is preferably selected from group I), more preferably para-toluene sulfonic acid and/or methane sulfonic acid, most preferably methane sulfonic acid.

In case the amount of water introduced into the reaction via the acid, water can be removed using known means such as distillative procedures and equipment (such as a Dean-Stark-trap and the like) before the orthoester is introduced.

The esteramine is obtained as a at least partially protonated salt in cationic form.

In a preferred embodiment, methane sulfonic acid is used as concentrated methane sulfonic acid. In another preferred embodiment, methane sulfonic acid is used as about 70wt.-% methane sulfonic acid solution in water or as "pure” acid, e.g. typically close to 100wt.% purity (equal to "about 100 wt.%”); any concentration in between however can also be employed. In a further preferred embodiment methane sulfonic acid is used as about 70 wt.-% methane sulfonic acid-solution in water. However, in the most preferred embodiment, the sulfonic acid such as the methane sulfonic acid is introduced as solid, even more preferably as dried solid (to reduce the amount of water introduced into the reaction).

In one embodiment of the present invention the total amount of acid (C) is added at the beginning of the reaction . In another embodiment the acid is added dropwise for a certain period during the reaction, provided that during the reaction the acid (C) is always present.

The present invention can also provide inventive amino acid esters and their salts starting from natural amino acids and/or natural alcohols, and thus enables providing products with high content of bio-derived material. As the alkylene oxide(s) can be also derived from non-fossil sources, the inventive compound can be obtained containing only carbon-atoms from non-fossil sources. Such products are being highly sought after by consumers and industries.

Uses

Another subject matter of the present invention is the use of the above-mentioned esteramines and their salts as disclosed via their structure or via the process to produce in cleaning compositions.

The esteramines and their salts can be added to cleaning compositions.

The esteramines and/or their salts are present in said formulations at a concentration of 0.1 to 5 weight%, preferably at a concentration of 0.5 to 2 weight%.

The inventive esteramines and their salts can also be added to a cleaning composition comprising from about 1% to about 70% by weight of a surfactant system. The inventive esteramines and/or their salts may be present in a cleaning composition at a concentration of from about 0.1% to about 5% by weight of the composition, or at a concentration of from about 0.5% to about 2% by weight of the composition. Hence, another subject matter of the present invention is the use of the esteramines and their salts of this invention and/or obtained by or obtainable by a process of the invention and/or 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 esteramine or salt thereof as defined above or obtained by or obtainable by a process of the invention and/or as detailed herein.

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 esteramine or salt thereof of the invention and/or as described above.

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 esteramine or salt thereof as defined above. 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/un it 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.

In one embodiment of the present invention, the inventive esteramine or its salt 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 esteramine or salt thereof as described above) 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 esteramine or salt 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, disperses, 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 esteramine or salt thereof 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 esteramine or its salt 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 esteramine or its salt 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 esteramine or salt thereof 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 esteramine or salt thereof as described herein before, further comprises an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2-phenoxyethanol, 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 an esteramine or its salt 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 an esteramine or its salt as described herein before 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-phenoxyethanol, 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 an esteramine or its salt as described herein before 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 softener composition for use in laundry, such composition comprising an esteramine or its salt 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. 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 esteramine and/or its salt obtained or obtainable by the inventive process as detailed herein 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-laundering 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.

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.

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-homogene- ous 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-re- deposition 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, properfumes, and perfumes. All such adjuncts are in principle known as detailed and exemplified further as describe below.

Liquid cleaning compositions additionally may comprise - and preferably do comprise at least one of - rheology con- trol/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.

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.

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 and below in more detail.

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 preferably 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. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.

The liquid formulations of this invention may and preferably do comprise 0 to 2 % 2-phenoxyethanol, preferably about 1 %, in addition to all other mentioned ingredients. The liquid formulations 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-hydroxydiphenylethe, preferably about 0,15 %, in addition to all other mentioned ingredients.

The formulations of the invention 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.

It is preferred, that within the respective laundry detergent, cleaning composition and/or fabric and home care product, the at least one esteramine and/or salt thereof as described in this invention is present at a concentration of from about 0.1% to about 20%, preferably from about 0.2% to 5%, 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.

All such cleaning compositions, their ingredients including (adjunct) cleaning additives, their general compositions and more specific compositions are known, as for example illustrated in WO 2022/136409 and WO 2022/136408, wherein in any of the before prior art documents the esteramines and their salts within the general compositions and also each individualized specific cleaning composition disclosed in the beforementioned publications may be replaced partially or completely by the esteramines and/or their salts of this 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 compositions disclosed in any of the beforementioned prior art-disclosures, preferably those in the previous paragraph, but further comprising at least one of the inventive esteramines and/or their salts in addition to or as a replacement for any already ins such prior art-composition contained esteramine or esteramine saltor any such compound, which can be replaced by such inventive esteramine or salts - such replacements known to a person of skill in the art - , with the content of the inventive esteramine or its salt being present in said formulations at a concentration of generally 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%, 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. Experimental Section

Methods

¹H NMR measured in MeOD with Bruker Avance 400 MHz spectrometer. pH is measured in 10 % aqueous solution.

Hydroxyl values are measured according to DIN 53240-1.

Molecular weight of polyalkylene oxides (e.g. polyethylene glycol) is calculated from the measured hydroxyl values by following formula:

Molecular weight [g/mol] = 1000 1 (hydroxyl value [mgKOH/g] / 56.11) x hydroxyl groups per molecule

(E = inventive example; CE = Comparative Example)

2-EH: 2-ethyl hexanol 2-PH: 2-propylheptanol

Lutensol XP30: 2-propylheptanol, ethoxylated in average with 3 EO/OH

Example 1 : L-valine-2-propylheptylether ester as methane sulfonic acid salt, catalyzed with 0.02 Eq triethylor- thoformiate

In a 4-neck vessel with thermometer, Dean-Stark trap with reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 237.5 g 2-propylheptanol, 0.9 g hypophosphorous acid (50 % in water), 117.1 g L-valine and 2.9 g triethylor- thoformiate were placed. 99.0 g methane sulfonic acid were added within 15 minutes. The temperature raised from room temperature to 47°C during the addition. The reaction mixture was heated to 135°C bath temperature under a constant stream of nitrogen bubbling through the reaction mixture. Water was distilled off from the reaction mixture with the Dean-Stark trap. The mixture was stirred for 3.5 hours, and a sample was analyzed by 1 H-NMR in MeOD (results s. table). The mixture was stirred for additional 5 hours, and a sample was taken for 1 H-NMR in MeOD (results s. table). Conversion to ester was concluded by integral of multiplett from 4.1 to 4.2 ppm in 1 H-NMR in MeOD for esterified CH2-OH groups.

The other examples are synthesized in similar manner using the ingredients and conditions as listed in the table before, with the results also given in that table.

Claims

Claim 1

Process to produce an esteramine or salt thereof using catalytic amounts of at least one orthoester, the process comprising the steps of a) reaction of

I) at least one aminoacid selected from alpha-, beta-, gamma-, delta-, epsilon- etc. amino acids,, such as alanine, glycine, leucine, isoleucine, valine, proline, phenylalanine, arginine, asparagine, aspartic acid, aspartate, glutamine, glutamate, histidine, lysine, threonine, tryptophan, tyrosine, cysteine, methionine, serine; alpha-amino acids with secondary or tertiary amino groups such as sarcosine, N, N-dimethylgly- cine; other amino acids such as 6-amino hexane acid, 4-amino butanoic acid, 3-amino propanoic acid, 12-amino dodecanoic acid, 11-aminoundecanoic acid; aminoacids formally derived from the hydrolysis of a-lactame (three ring atoms), p-lactame (four ring atoms), y-lactame (five ring atoms) and so on; such lactames preferably being p-propiolactame, g-butyrolactame, 5-valerolactame, g-valerolactame, e-capro- lactame, d-decalactame, g-decalactame, e-decalactame; preferably alanine, valine, beta-alanine, 6- amino hexane acid; with ii) at least one alcohol (A) bearing at least one hydroxy group, being selected from mono-, di- and polyols, all of which may be optionally alkoxylated, wherein the alkoxylation of the at least one hydroxy group takes place in a step before step a), with the alcohol being alkoy lated with at least one alkylene oxide, preferably at least 1 and up to 200, preferably 1 to 100, more preferably up to 50 moles alkylene oxide per hydroxy group; in presence of ill) at least one acid (C), being selected from inorganic and organic acids, wherein said organic or inorganic acid has preferably a pKa value in the range of from -3 and up to +5, more preferably from -2,5 to 1 ,5, preferably at least one organic acid, such as sulfonic acids, more preferably alkane sulfonic acid and/or aryl sulfonic acid; and iv) in the presence of at least one ortho ester, such as triethyl orthoformiate, trimethyl orthoformiate, triethyl orthoacetate, trimethyl orthoacetate, and the like; whereas the ortho ester is used in sub-stoichiometric amounts, preferably catalytic amounts (referred to the amino acid) and whereas the alcohol used for the esterification is different from the alcohol-residual in the ortho ester; to produce an amino acid ester salt; b) optional neutralization of the obtained amino acid ester salt with at least one base to obtain the free amino acid ester.

Claim 2

Process according to Claim 1, wherein the alcohol (A) is selected from

(Aa) mono-alcohols such as C1- to C36-alkanols, selected from the groups non-alkoxylated linear C2- to C36-alco- hols, such as mixture of such alcohols selected from C6- to C22-fatty alcohols, preferably C8- to C22-fatty alcohols, more preferably C12- and C14-fatty alcohols, most preferably C16- and C18-fatty alcohols; non- alkoxylated branched C3- to C36-alcohols such as 2-ethylhexanol, 2-propylheptanol, isotridecanol, isonona- nol, C9-C17 oxoalcohols; alkoxy I ated linear C2- to C36-alcohols such as alkoxy lated mixture of C6- to C22-fatty alcohols, preferably alkoxylated mixtures of C8- to C22-fatty alcohols, more preferably alkoxylated mixtures of C12- and C14-fatty alcohols, most preferably alkoxylated mixtures of C16- and C18-fatty alcohols; alkoxylated branched C3- to C36-alcohols such as alkoxylated 2-ethylhexanol, alkoxylated 2-propylheptanol, alkoxylated isotridecanol, alkoxylated isononanol, alkoxylated C9-C17 oxoalcohols;

(Ab) di-alcohols such als alkane diols, polyalkoxylated C2-C6-alkandiols bearing at least two hydroxy groups, (Ac) oligo-alcohols such as polyalkoxylated C3-C6-alkantriols, bearing at least three hydroxy groups, (Ad) polyols such as sugar alcohols, polyalkoxylated C5-C6-alkane polyols, glycerols such as diglycerol, triglycerol polyglycerol, dipentaerythritol, tripentaerythritol; and/or

Claim 3

Process according to any of the previous claims, wherein the alcohol (A) employed is an alkoxylated alcohol which is obtained by alkoxylating at least one hydroxy group of the alcohol according to Claim 2 with one or more alkylene oxides to produce alkylene oxy-chains comprising one or more moieties stemming from alkylene oxides selected from C2 to C22-alkylene oxides, preferably C2-C4-alkylene oxides, whereas the moieties stemming from the alkylene oxide(s) may be arranged in random, block or multiblock-order or combinations thereof, preferably as block, more preferably contains only one block consisting of ethylene oxide or consisting of two blocks with the first block - preferably the "inner block” directly linked to the hydroxy-group of the alcohol - consisting of ethylene oxide and a second block - preferably being the "outer block linked to the ethylene oxide-block - consisting of propylene oxide, such diblock even more preferably consisting of 3 to 10 EO-derived moieties and the PO-block consisting of 1 to 10 PO-de- rived moieties.

Claim 4

Process according to any of the previous claims, wherein the acid (C) is selected from i) alkyl sulfonic acids, such as methane sulfonic acid, ethylsulfonic acid, propylsulfonic acid, camphorsulfonic acid; alkylaryl sulfonic acids and specifically alkylbenzene sulfonic acids, such as toluene sulfonic acid (including the mixture of isomers thereof), p-toluene sulfonic acid, o-toluene sulfonic acid, m-toluene sulfonic acid, xylene sulfonic acid (mixture of isomers), 2, 6-dimethylbenzene sulfonic acid, 2, 5-dimethylbenzene sulfonic acid, 2, 4-dimethylbenzene sulfonic acid, 4-dodecylbenzene sulfonic acid, iso-propyl benzene sulfonic acid, ethylbenzene sulfonic acid, and naphthalene sulfonic acid, preferably para-toluene sulfonic acid and methane sulfonic acid, more preferably methane sulfonic acid; ii) inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid; preferably selected from group i).

Claim 5

Process according to any of the previous claims, wherein the acid (C) is chosen such that the esteramine is obtained as salt in cationic form, preferably the acid chosen is methane sulfonic acid and the esteramine obtained is a salt in cationic form.

Claim 6

Process according to any of the previous claims, wherein the molar ratio of amino acid to hydroxyl group of the (optionally alkoxylated) alcohol is (0.8*n) : 1 to (1*n) : 1 .5, with the number of hydroxy-groups of the (optionally alkoxylated) alcohol being n. Claim 7

Process according to any of the previous claims, wherein the process is carried out with the molar ratio of the acid ( C ) to the amino acid is in the range of from 0.8 : 1 to 1 : 1 .2.

Claim 8

Process according to any of the previous claims, wherein in the process the reaction is performed at a temperature of from 50 to 200°C, preferably 70- 180°C, more preferably 80°C- 160°C, most preferably 120°C - 150°C, such as 60, 65, 75, 85, 90, 95, 100, 110, 115, 120, 125, 130, 135, 140, 145, 155, 165, 170, 190 °C; for a period of from 1 to 30, preferably from 2, more preferably from 3 hours, even more preferably at least 5 hours, and preferably up to 48, more preferably up to 20, even more preferably up to 15 hours, such as preferably 3 to 24 , more preferably 5 to 24 , most preferably 10 - 24 hour(s); and at from 0,001 to 10 bar pressure, such as from 0,001 , more preferably from 0,005, even more preferably from 0,1 , and preferably up to 8, more preferably up to 5, even more preferably up to 4 bar, such as 1 to 10, more preferably 1 to 5, even more preferably 1 to 4 bar, or such as 1 to 1000 mbar, more preferably 100 to 500 mbar.

Claim 9

Process according to any of the previous claims, wherein in the process the solvents for the reaction are selected from water, toluene, xylene, heptanol, cyclohexene, and the like, preferably only being water.

Claim 10

Process according to any of the previous claims, wherein during or following the reaction, preferably at least during the reaction, water and/or excess alcohol are removed, such removal preferably being carried out by application of a stream of gas such as using gas such as inert gas as nitrogen or argon, preferably nitrogen, or steam made from water, preferably using inert gas, more preferably nitrogen, and/or applying a distillation method, preferably a distillation, more preferably a distillation method under reduced pressure and/or at elevated temperature, preferably both, a more preferred method being the use of an apparatus such as a Dean-Stark-trap, most preferably using a Dean- Stark-trap, such removal more preferably carried out applying a vacuum in the range of from 0.1 mbar to 800 mbar, preferably of from 1 mbar to 500 mbar and more preferably of from 10 mbar to 100 mbar, and using elevated temperatures.

Claim 11

Process according to any of the previous claims, wherein the amount of orthoester in the resulting product is 10% relative to the esteramine salt obtained by such process.

Claim 12

Use of an esteramine or a salt thereof obtained or obtainable by a process according to any of Claims 1 to 11 in a composition, that is a fabric and home care product, a cleaning composition, or an industrial and institutional cleaning product, preferably being in liquid or semi-liquid form, more preferably in liquid form.

Claim 13

The use according to Claim 12, wherein the composition comprises at least one esteramine and/ or at least one salt thereof at a concentration of from about 0.1 % to about 5% in weight % in relation to the total weight of such composition or product, preferably the composition 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, and d. exhibiting an improved washing performance, preferably in primary cleaning.

Claim 14

A composition being a cleaning composition or a fabric and home care product, preferably a cleaning composition, more preferably a laundry detergent or a dish wash detergent, containing at least one esteramine and/or a salt thereof obtained by or obtainable by the process according to any of Claims 1 to 11, comprising the at least one esteramine and/or the at least one salt thereof at a concentration of preferably from about 0.1% to about 5% 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, b. about 1 % to about 70% by weight of a surfactant system, c. at least one further cleaning adjunct in effective amounts, and optionally exhibiting an improved washing performance in primary cleaning, preferably being in liquid or semi-liquid form, more preferably being a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation, even more preferably a liquid laundry detergent formulation or a liquid hand dish wash detergent formulation, optionally further comprising at least one antimicrobial agent, preferably 2-phenoxyethanol, in an amount ranging from 2ppm 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.