WO2024115420A1

WO2024115420A1 - Detergent compositions

Info

Publication number: WO2024115420A1
Application number: PCT/EP2023/083236
Authority: WO
Inventors: James Hanley Clark; Craig Jonathon FAIRGRIEVE; Thomas James FARMER; David Stephen Grainger; Kirsten HAWKINS; Sean Philip Nigel Rouse
Original assignee: Unilever Global IP Ltd; Unilever IP Holdings BV; Conopco Inc
Current assignee: Unilever Global IP Ltd; Unilever IP Holdings BV; Conopco Inc
Priority date: 2022-11-28
Filing date: 2023-11-27
Publication date: 2024-06-06
Anticipated expiration: 2025-05-28

Abstract

The invention relates to a home or personal care detergent composition comprising: from 0.5 to 50 wt.% of a furan-based surfactant having the following structure: (I) wherein X is a connecting linker moiety; wherein M is a monovalent cation; wherein R is a C₈ to C₁₈ carbon chain which is linear or branched, and saturated or unsaturated; and, wherein R₁ is a C₁ to C₁₂ alkyl chain; the invention further relates to the use of said furan-based surfactant in a laundry process to improve soil removal from fabrics.

Description

DETERGENT COMPOSITIONS

Field of the Invention

The invention relates to the field of detergent compositions. The compositions are particularly useful for the washing of the items in the home, including dishes, cutlery and other cooking and eating utensils, for in particularly for the laundering of clothes. The compositions of the invention are particularly useful in the field of home care, for example in laundry compositions and hand dish wash compositions.

Background of the Invention

Consumer detergent products, particularly those relating to home care purposes, such as laundry and hand dish wash compositions need to address a range of cleaning challenges. There are usually a number of different soil/stain types that need to be addressed by any home care detergent product. Furthermore, these products also need to be able to work under a broad range of conditions (e.g. temperature, water hardness etc..).

Typical stains can include fatty and oily stains amongst others. Standard workhorse surfactants (typically anionic and nonionics which form the basis of most home care detergent products) are very useful at general cleaning of oily substrates. They are designed to be effective on hydrophobic stains such as fats and oils because they are designed to go to hydrophobic/hydrophilic interfaces.

Of particular use are surfactants that can clean fatty oily soils at low temperatures. Low temperature cleaning is an important aspect of meeting the environmental pressures of the future. Fats and oils are prone to solidifying at lower temperatures and this makes their removal much more difficult. In that respect, one of the most widely used and most weight effective materials Linear Alkylbenzene Sulphonate (or LAS) is the best current high volume commercial material available.

However, there is a need for non-petrochemical surfactants that have excellent cleaning performance on fatty and oily soils, that are easily soluble, have improved calcium tolerance and are dispersible even at low temperatures.

WO2020/229158 discloses furan-based surfactants comprising a beta sulphonate head group, a furan and a C10-20 hydrophobic group which is either attached directly to the furan or by way of a linker. WO2020/229158 discloses multiple linker groups (including ester and amide groups), solely in combination with a furan head group and a beta sulphonate.

We have surprisingly found that some specific furan-based surfactants can perfume similarly to LAS.

We have further surprisingly found that some specific furan-based surfactants can perform in a superior manner to those disclosed in WO2020/229158, particularly in relation to solubility and calcium tolerance. of the Invention

The invention relates in a first aspect to a detergent composition comprising: from 0.5 to 50 wt.%, preferably from 0.75 to 40 wt.%, more preferably from 1 to 30 wt.% of a furan-based surfactant having the following structure:

wherein X is COO or CONH; wherein M is a monovalent cation; preferably Na⁺, K⁺, NH₄ ⁺ wherein R is a Cs to C carbon chain which is linear or branched, and saturated or unsaturated.

Preferably the furan-based surfactant has the following structure:

Preferably the R group is a C12 to C carbon chain. Preferably the R group is a saturated alkyl chain.

Preferably the the furan-based surfactant is selected from:

Preferably the R group is a linear carbon chain.

Preferably the composition additionally comprises a fragrance, preferably from 0.0001 to 5 wt.% of a fragrance. Preferably the detergent composition comprises one or more additional surfactants selected from anionic and nonionic surfactants, wherein if present, then the anionic surfactant is present at a level of from 1 to 80 wt.%, preferably from 2 to 50 wt.%, more preferably from 3 to 30 wt.% and is preferably selected from linear alkyl benzenesulphonate, secondary alkane sulphonate, laureth ether sulphate, lauryl sulphate, anionic alkyl polyglycosides, isethionates, alpha olefin sulphonate, internal olefin sulphonate, methyl ester sulphonate, oleyl sulphate, oleyl ether sulphate and rhamnolipids, most preferably selected from linear alkyl benzenesulphonate, secondary alkane sulphonate, laureth ether sulphate, lauryl sulphate, methyl ester sulphonate, oleyl sulphate, oleyl ether sulphate and rhamnolipids; wherein if present, then the nonionic surfactant is present at a level of from 1 to 80 wt.%, preferably from 2 to 50 wt.%, more preferably from 3 to 30 wt.% and is preferably selected from an alcohol ethoxylate, an alcohol propoxylate, a methyl ester ethoxylate, and an alkyl poly glycoside.

Preferably the composition is a home care detergent composition, more preferably a hand dish wash detergent composition or a laundry detergent composition, most preferably a laundry detergent composition. Preferably the home care detergent composition, more preferably the laundry detergent composition is in the form of a liquid, solid, powder, pastille, bead or paste, preferably a liquid, solid or powder, more preferably a liquid.

If the composition is a home care composition, then preferably the composition additionally comprises an enzyme, preferably the detergent composition comprises from 0.05 to 5 wt.%, more preferably from 0.1 to 4 wt.%, more preferably from 0.5 to 3 wt.% of an enzyme, wherein the enzyme is preferably selected from one or more of a protease, amylase, mannanase, cellulase, lipase, pectate lyase, laccase, phosphodiesterase and mixtures thereof.

If the composition is a home care composition, then preferably the composition additionally comprises from 0.5 to 15 wt.%, more preferably from 0.75 to 15 wt.%, even more preferably from 1 to 12 wt.%, most preferably from 1.5 to 10 wt.% of cleaning boosters selected from antiredeposition polymers, soil release polymers, alkoxylated polycarboxylic acid esters and mixtures thereof, more preferably selected from antiredeposition polymers, and soil release polymers. Preferably the antiredeposition polymers are alkoxylated polyamines; and/or wherein the soil release polymer is a polyester soil release polymer.

If the composition is a home care composition, preferably a laundry composition, then preferably the composition additionally comprises from 0.05 to 8 wt.%, preferably from 0.1 to 5 wt.%, more preferably from 0.5 to 2 wt.% of a sequestrant, preferably the sequestrant is preferably selected from HEDP, DTPMP, EDTA, MGDA, GLDA or citric acid.

In a second aspect, the invention relates to the use of a furan-based surfactant as defined in the first aspect in a laundry process to improve soil removal from fabrics.

Detailed Description of the Invention

Furan based surfactant

The detergent composition comprises from 0.5 to 50 wt.%, preferably from 0.75 to 40 wt.%, more preferably from 1 to 30 wt.%of a furan-based surfactant having the following structure:

Preferably the furan-based surfactant has the following structure:

wherein X is COO or CONH; wherein M is a monovalent cation; preferably Na⁺, K⁺, NH₄ ⁺ wherein R is a Cs to C carbon chain which is linear or branched, and saturated or unsaturated. Preferably the R group is a C12 to C carbon chain.

Preferably the R group is a saturated alkyl chain.

Preferred furan-based surfactants are selected from:

The R group can be linear or branched, preferably it is linear.

While the carbon chain, R, of the furan-based surfactant may be linear or branched, preferably the carbon chain of the furan-based surfactant is linear. The linker group ‘X’ is COO or CONH giving an ester or an amide linkage between the furan group and the carbon chain R. Most preferably X is COO to give an ester linkage.

M is a monovalent cation; preferably Na⁺, K⁺, NF , more preferably Na⁺.

The furan ring creates a naturally occurring aromatic structure in the surfactant headgroup. The furan ring group can be achieved through dehydration of sugars from biomass.

All the structures have a pendant methyl attached to the furan ring. In our naming convention, we specify that the methyl group is attached to the 5-position of the furan ring (the 1 -position being the oxygen in the furan ring). The carbon chain is attached via the 2-position of the furan ring.

Applicants, without wishing to be bound by theory, believe that the pendant methyl attached to the ring in the 5-position is critical. Even if the longer alkyl hydrophobe is linear, this pendant methyl on the ring in the 5-position can disrupt the linear packing. It increases the overall hydrophobicity of the molecule without running into issues such as poor solubility or high Krafft point. We believe that this non-linearity is also important for performance on oily soils at low temperatures. This is because i) the surfactant is still fully soluble at low temperatures and ii) the nonlinearity of the hydrophobic part of the surfactant can also disrupt the packing in the fatty soil.

The furan-based surfactants can be made by any suitable process, particularly suitable processes are exemplified in the examples.

Home or Personal Care

The home or personal care detergent composition is suitable for uses in home care or in personal care, for example hand dish wash or laundry for home care, or washing the hands, body, face or hair for personal care. Preferably the composition is a home care detergent composition, preferably a hand dish wash detergent composition or a laundry detergent composition, more preferably a laundry detergent composition.

Preferably the home care detergent composition, preferably a laundry detergent composition, is in the form of a liquid, solid, powder, pastille, bead or paste, more preferably a liquid, solid or powder, more preferably a liquid. It may be preferred that the composition is a liquid detergent composition, preferably a nonaqueous liquid detergent composition.

Preferably the home or personal care detergent composition as herein described, additionally comprises a fragrance, preferably from 0.0001 to 5 wt.% of a fragrance. As used herein the terms fragrance and perfume are used interchangeably.

The composition preferably comprises a perfume. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.

Preferably the perfume comprises at least one note (compound) from: alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamal; linalool; pentanoic acid, 2-methyl-, ethyl ester; octanal; benzyl acetate; 1 ,6-octadien-3-ol, 3,7-dimethyl-, 3-acetate; cyclohexanol, 2-(1 , 1- dimethylethyl)-, 1 -acetate; delta-damascone; beta-ionone; verdyl acetate; dodecanal; hexyl cinnamic aldehyde; cyclopentadecanolide; benzeneacetic acid, 2-phenylethyl ester; amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl anthranilate; alpha-irone; betaphenyl ethyl benzoate; alpa-santalol; cedrol; cedryl acetate; cedry formate; cyclohexyl salicyate; gamma-dodecalactone; and, beta phenylethyl phenyl acetate.

Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavour Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavour Chemicals by S. Arctander 1969, Montclair, N.J. (USA).

Additional Surfactants

The home or personal care detergent composition may additionally comprise one or more additional surfactants selected from anionic and nonionic surfactants. If present, then the anionic surfactant is present at a level of from 1 to 80 wt.%, preferably from 2 to 50 wt.%, more preferably from 3 to 30 wt.% and is preferably selected from linear alkyl benzenesulphonate, secondary alkane sulphonate, laureth ether sulphate, lauryl sulphate, anionic alkyl polyglycosides, isethionates, alpha olefin sulphonate, internal olefin sulphonate, methyl ester sulphonate, oleyl sulphate, oleyl ether sulphate and rhamnolipids, most preferably selected from linear alkyl benzenesulphonate, secondary alkane sulphonate, laureth ether sulphate, lauryl sulphate, methyl ester sulphonate, oleyl sulphate, oleyl ether sulphate and rhamnolipids;

If present, then the nonionic surfactant is present at a level of from 1 to 80 wt.%, preferably from 2 to 50 wt.%, more preferably from 3 to 30 wt.% and is preferably selected from an alcohol ethoxylate, an alcohol propoxylate, a methyl ester ethoxylate, and an alkyl poly glycoside. Most preferred nonionic surfactants are preferably selected from alcohol ethoxylates having from C12-C15 with a mole average of from 5 to 9 ethoxylates and/or alcohol ethoxylates having from C16-C18 with a mole average of from 5 to 14 ethoxylates.

For home care compositions especially, it is preferred that the composition additionally comprises an enzyme, preferably comprising from 0.05 to 5 wt.%, more preferably from 0.1 to 4 wt.%, more preferably from 0.5 to 3 wt.% of an enzyme, wherein the enzyme is preferably selected from one or more of a protease, amylase, mannanase, cellulase, lipase, pectate lyase, laccase, phosphodiesterase and mixtures thereof.

Cleaning Boosters

For home care compositions especially, it is preferred that the composition additionally comprises from 0.5 to 15 wt.%, more preferably from 0.75 to 15 wt.%, even more preferably from 1 to 12 wt.%, most preferably from 1.5 to 10 wt.% of cleaning boosters selected from antiredeposition polymers; soil release polymers; alkoxylated polycarboxylic acid esters, and mixtures thereof. More preferably selected from antiredeposition polymers, and/or soil release polymers.

Preferred antiredeposition polymers include alkoxylated polyamines.

A preferred alkoxylated polyamine comprises an alkoxylated polyethylenimine, and/or alkoxylated polypropylenimine. The polyamine may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both. Where a nitrogen atom is alkoxylated, a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25. A preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30 preferably from 15 to 25, where a nitrogen atom is ethoxylated.

Soil release polymer

Preferably the soil release polymer is a polyester soil release polymer.

Preferred soil release polymers include those described in WO 2014/029479 and WO 2016/005338.

Preferably the polyester based soil release polymer is a polyester according to the following formula (I)

wherein

R¹ and R² independently of one another are X-(OC2H4)n-(OC3H6)m wherein X is C1.4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OCsHe) groups are arranged blockwise and the block consisting of the -(OCsHe) groups is bound to a COO group or are HO-(C₃H6), and preferably are independently of one another X-(OC2H4)n- (OC₃H₆)m, n is based on a molar average number of from 12 to 120 and preferably of from 40 to 50, m is based on a molar average number of from 1 to 10 and preferably of from 1 to 7, and a is based on a molar average number of from 4 to 9. Preferably the polyester provided as an active blend comprising:

A) from 45 to 55 % by weight of the active blend of one or more polyesters according to the following formula (I)

wherein

R¹ and R² independently of one another are X-(OC2H4)n-(OC3H6)m wherein X is C1.4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OCsHe) groups are arranged blockwise and the block consisting of the -(OCsHe) groups is bound to a COO group or are HO^CsHe), and preferably are independently of one another X-(OC2H4)n- (OC₃H₆)m, n is based on a molar average number of from 12 to 120 and preferably of from 40 to 50, m is based on a molar average number of from 1 to 10 and preferably of from 1 to 7, and a is based on a molar average number of from 4 to 9 and

B) from 10 to 30 % by weight of the active blend of one or more alcohols selected from the group consisting of ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,2- butylene glycol, 1 ,3-butylene glycol, 1 ,4-butylene glycol and butyl glycol and

C) from 24 to 42 % by weight of the active blend of water.

ic acid esters

Alkoxylated polycarboxylic acid esters are obtainable by first reacting an aromatic polycarboxylic acid containing at least three carboxylic acid units or anhydrides derived therefrom, preferably an aromatic polycarboxylic acid containing three or four carboxylic acid units or anhydrides derived therefrom, more preferably an aromatic polycarboxylic acid containing three carboxylic acid units or anhydrides derived therefrom, even more preferably trimellitic acid or trimellitic acid anhydride, most preferably trimellitic acid anhydride, with an alcohol alkoxylate and in a second step reacting the resulting product with an alcohol or a mixture of alcohols, preferably with C16/C18 alcohol.

For home care compositions especially, it is preferred that the composition additionally comprises from 0.05 to 8 wt.%, preferably from 0.1 to 5 wt.%, more preferably from 0.5 to 2 wt.% of a sequestrant, preferably the sequestrant is preferably selected from HEDP, DTPMP, EDTA, MGDA, GLDA or citric acid.

Further Ingredients

The formulation may contain further ingredients.

Builders or Complexing Agents

The detergent formulation in the form of a non-liquid, preferably powder, preferably comprises a builder or a complexing agent. This may be present at levels of from 5 to 75 wt.%, preferably from 8 to 65 wt.%, more preferably from 10 to 60 wt.% of the detergent composition.

Such materials may include: calcium sequestrant materials; precipitating materials; calcium ionexchange materials; and mixtures thereof.

Preferred examples of such materials include carbonates, layered silicates, polycarboxylates (e.g. EDTA, NTA), citrates (e.g. trisodium citrate), silicates (e.g. sodium silicate) and zeolites.

Preferred builders or complexing agents are carbonates, for example sodium carbonate.

The detergent formulation in the form of a non-liquid, preferably powder, preferably comprises less than 20 wt.%, more preferably less than 15 wt.%, most preferably less than 10 wt.% of zeolite (an aluminosilicate material).

Most preferably the detergent formulation comprises less than 1 wt.% of phosphate.

The detergent formulation in the form of a non-liquid, preferably powder can preferably be not built i.e., contain less than 1 wt.% of builder.

If the detergent composition is an aqueous liquid laundry detergent it is preferred that mono propylene glycol or glycerol is present at a level from 1 to 30 wt.%, most preferably 2 to 18 wt.%. Fluorescent

The composition preferably comprises a fluorescent agent (optical brightener).

Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.

The total amount of the fluorescent agent or agents used in the composition is generally from 0.0001 to 0.5 wt.%, preferably 0.005 to 2 wt.%, more preferably 0.01 to 0.1 wt.%.

Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.

Preferred fluorescers are fluorescers with CAS-No 3426-43-5; CAS-No 35632-99-6; CAS-No 24565-13-7; CAS-No 12224-16-7; CAS-No 13863-31-5; CAS-No 4193-55-9; CAS-No 16090- 02-1; CAS-No 133-66-4; CAS-No 68444-86-0; CAS-No 27344-41-8.

Most preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1 ,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5-triazin-2- yl)]amino}stilbene-2-2' disulphonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1 , 3, 5-triazi n-2- yl)]amino} stilbene-2-2' disulphonate, and disodium 4,4'-bis(2-sulphostyryl)biphenyl.

It is advantageous to have shading dye present in the formulation, especially if the composition is a laundry composition.

Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zurich, 2003) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003).

Dyes for use in laundry detergents preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700nm) of greater than 5000 L mol^-1 cm^-1, preferably greater than 10000 L mol^-1 cm^-1. Preferred dye chromophores are azo, azine, anthraquinone, phthalocyanine and triphenylmethane. Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged. Azine dyes preferably carry a net anionic or cationic charge.

Blue or violet Shading dyes are most preferred. Shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. In this regard the dye gives a blue or violet colour to a white cloth with a hue angle of 240 to 345, more preferably 260 to 320, most preferably 270 to 300. The white cloth used in this test is bleached nonmercerised woven cotton sheeting.

A mixture of shading dyes may be used.

The shading dye is preferably present is present in the composition in range from 0.0001 to 0.1 wt %. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class. As stated above the shading dye is preferably a blue or violet shading dye.

The composition may comprise one or more further polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.

Where alkyl groups are sufficiently long to form branched or cyclic chains, the alkyl groups encompass branched, cyclic and linear alkyl chains. The alkyl groups are preferably linear or branched, most preferably linear.

The detergent compositions optionally include one or more laundry adjunct ingredients.

To prevent oxidation of the formulation an anti-oxidant may be present in the formulation.

The term "adjunct ingredient" includes: perfumes, dispersing agents, stabilizers, pH control agents, metal ion control agents, colorants, brighteners, dyes, odour control agent, properfumes, cyclodextrin, solvents, soil release polymers, preservatives, antimicrobial agents, chlorine scavengers, anti-shrinkage agents, fabric crisping agents, spotting agents, antioxidants, anti-corrosion agents, bodying agents, drape and form control agents, smoothness agents, static control agents, wrinkle control agents, sanitization agents, disinfecting agents, germ control agents, mould control agents, mildew control agents, antiviral agents, antimicrobials, drying agents, stain resistance agents, soil release agents, malodour control agents, fabric refreshing agents, chlorine bleach odour control agents, dye fixatives, dye transfer inhibitors, shading dyes, colour maintenance agents, colour restoration, rejuvenation agents, anti-fading agents, whiteness enhancers, anti-abrasion agents, wear resistance agents, fabric integrity agents, anti-wear agents, and rinse aids, UV protection agents, sun fade inhibitors, insect repellents, anti-allergenic agents, enzymes, flame retardants, water proofing agents, fabric comfort agents, water conditioning agents, shrinkage resistance agents, stretch resistance agents, and combinations thereof. If present, such adjuncts can be used at a level of from 0.1% to 5% by weight of the composition. The invention will be further described with the following non-limiting examples.

Synthesis of various furan-based surfactants

5-methyl-furan-2-ester/amide intermediates

N-Dodecyl-5 methylfuran-2-carboxamide

5-methyl-2-furoic acid (1 g, 7.93 mmol) was dissolved in dichloromethane (30mL) and stirred at 0 °C for 5 minutes. Then EDC«HCI (2.63 g, 13.80 mmol) and DMAP (0.96 g, 7.93 mmol) were added the solution was stirred for ca. 30 minutes before addition of dodecylamine (1.46 g, 7.14 mmol). The mixture was stirred for 2 hours at 0 °C followed by a 12 hour stir at room temperature. The reaction mixture was then washed with 2 M hydrochloric acid solution (20 mL), water, 1 M NaOH (20 mL) and brine (20 mL). The organic solvent was dried over magnesium sulfate. The organic solvent was removed in vacuo to yield a white solid. (1.8 g, 6.13 mmol, 85%).

¹H NMR (400 MHz, Chloroform-D) 56.98 (1 H, d, J = 3.1 Hz, H₃), 6.23 (1H, br s, H₄), 6.07 (1H, d, J = 2.4 Hz, H₂), 3.39 (2H, q, J = 6.9 Hz, H₅), 2.33 (3H, s, Hi), 1.57 (2H, s, H₆), 1.25 (18H, s, H7-15), 0.87 (3H, t, J = 5.8 Hz, HI₆).

5-methyl-N,N-dioctylfuran-2-carboxamide synthesis

5-methyl-2-furoic acid (1 g, 7.93 mmol) was dissolved in dichloromethane (30mL) and stirred at 0 °C for 5 minutes. Then EDC«HCI (2.63 g, 13.80 mmol) and DMAP (0.96 g, 7.93 mmol) were added the solution was stirred for ca. 30 minutes before addition of dioctylamine (2.3 mL, 7.93 mmol). The mixture was stirred for 2 hours at 0 °C followed by a 12 hour stir at room temperature. The reaction mixture was then washed with 2 M hydrochloric acid solution (20 mL), water, 1 M NaOH (20 mL) and brine (20 mL). The organic solvent was dried over magnesium sulfate. The organic solvent was removed in vacuo to yield a white solid (2.13 g, 6.12 mmol, 77%).

¹H NMR (400 MHz, DMSO-D₆) 5 6.81 (1 H, d, J = 3.3 Hz, H₂), 6.21 (1 H, d, J = 3.3 Hz, H₃), 2.30 (3H, s, Hi), 1.53 (4H, br s, H_{4 a}nd i₂), 1.25 (22H, s, H₅-i₀ and HI₃-I₈), 0.85 (6H, t, J = 6.5 Hz, Hu and 19).

Tetradecan-2-yl-5-methylfuran-2-carboxylate

5-methyl-2-furoic acid (1 g, 7.93 mmol) was dissolved in dichloromethane (30mL) and stirred at 0 °C for 5 minutes. Then EDC«HCI (2.63 g, 13.80 mmol) and DMAP (0.96 g, 7.93 mmol) were added the solution was stirred for ca. 30 minutes before addition of 2-tetradecanol (1.90 g, 7.14 mmol). The mixture was stirred for 2 hours at 0 °C followed by a 12 hour stir at room temperature. The reaction mixture was then washed with 2 M hydrochloric acid solution (20 mL), water, 1 M NaOH (20 mL) and brine (20 mL). The organic solvent was dried over magnesium sulfate. The organic solvent was removed in vacuo to yield a white solid. (2.82 g, 8.75 mmol, 100% - impurities present).

¹H NMR (400 MHz, Chloroform-D) 5 7.02 (1 H, d, J = 3.6 Hz, H₂), 6.07 (1 H, d, J = 3.4 Hz, H₃), 5.17 - 4.98 (1 H, m, H₄), 1.72 - 1.61 (m, 1 H) (2H, m, HI₆), 1.59 - 1.47 (2H, m, H₆), 1.36 - 1.18 (H21 , m, H₅and 7-1₅), 0.85 (3H, t, J = 6.6 Hz, H17).

N-(2-hexyldecyl)-5-methylfuran-2-carboxamide

5-methyl-2-furoic acid (1 g, 7.93 mmol) was dissolved in dichloromethane (30mL) and stirred at 0 °C for 5 minutes. Then EDC«HCI (2.63 g, 13.80 mmol) and DMAP (0.96 g, 7.93 mmol) were added the solution was stirred for ca. 30 minutes before addition of 2-hexadecan-1 -amine (2.33 mL, 7.93 mmol). The mixture was stirred for 2 hours at 0 °C followed by a 12 hour stir at room temperature. The reaction mixture was then washed with 2 M hydrochloric acid solution (20 mL), water, 1 M NaOH (20 mL) and brine (20 mL). The organic solvent was dried over magnesium sulfate. The organic solvent was removed in vacuo to yield a brown oil (2.34g, 6.71 mmol, 84%).

¹H NMR (400 MHz, DMSO-D₆) 5 8.07 (1 H, t, J = 6.0 Hz, H₅), 6.94 (1 H, d, J = 3.3 Hz, H₂), 6.21 (1 H, d, J = 3.5 Hz, H₃), 3.08 (2H, t, J = 6.4 Hz, H₆), 2.31 (3H, s, Hi), 1.55 (1 H,br s J = 7.9 Hz, H₇), 1.38 - 1.02 (24 H, m, H₈-i₄ and H16-20), 0.84 (6H, t, J = 4.8 Hz, Hi_{5 a}nd 2i).

N-(2-butyloctyl)-5-methylfuran-2-carboxamide

5-methyl-2-furoic acid (1 g, 7.93 mmol) was dissolved in dichloromethane (30mL) and stirred at 0 °C for 5 minutes. Then EDC«HCI (2.63 g, 13.80 mmol) and DMAP (0.96 g, 7.93 mmol) were added the solution was stirred for ca. 30 minutes before addition of 2-Butyl-n-octan-1-amine (1/83 mL, 7.93 mmol). The mixture was stirred for 2 hours at 0 °C followed by a 12 hour stir at room temperature. The reaction mixture was then washed with 2 M hydrochloric acid solution (20 mL), water, 1 M NaOH (20 mL) and brine (20 mL). The organic solvent was dried over magnesium sulfate. The organic solvent was removed in vacuo to yield a white solid. (942 mg, 3.21 mmol, 40%).

¹H NMR (400 MHz, Chloroform-D) 5 6.97 (1 H, d, J = 3.5 Hz, H₂), 6.23 (1 H, t, J = 6.1 Hz, H₃), 6.07 (1 H, d, J = 3.7 Hz, H₅), 3.33 (2H, t, J = 6.1 Hz, H₆), 2.33 (3H, s, Hi), 1.57 (1 H, t, J = 5.9 Hz, H₇), 1.45 - 1.12 (16H, m, H 8-12 and 14- i₆), 0.99 - 0.75 (6H, m, H 1₃ and 1₇). (2-butyl -octyl )-5-methy I -2-f uroate

2-butyloctanol (9.30 g, 0.05 mol) and methyl 5-methylfuran-2-furoate (7.00 g, 0.05 mol) were heated for 30 minutes at 70°C with stirring under a nitrogen headspace purge exhausting via a condenser configured for distillation. Sodium methoxide (0.14 g, 5 mol %) was added and the temperature increased to 75°C for 4 h. The reaction was cooled to 60°C and lactic acid (0.23 g) added. The crude product was dissolved in ethyl acetate and the precipitated catalyst residue was filtered off. The clear ethyl acetate solution was dried (Na2SO4) and after filtration the solvent was evaporated to yield (2-butyl-octyl)-5-methyl-2-furoate as an amber oil (13.66 g, 93%).

N-tetradecyl-5-methyl-2-furamide

Tetradecylamine (4.82 g, 0.0226 mol) and methyl 5-methylfuran-2-furoate (2.80 g, 0.02 mol) were heated for 30 minutes at 75°C with stirring under a nitrogen headspace purge exhausting via a condenser configured for distillation. Sodium methoxide (0.05 g, 5 mol %) was added and heating was continued at 75°C for 6 h before cooling to ambient. The crude product was dissolved in a mixture of ethyl acetate and washed with 2.5 M HCI (3 x 100 ml) and brine (4 x 100 ml). The organic layer was separated, and the solvent evaporated to yield the crude product (6.50 g), which tic indicated to contain tetradecylamine hydrochloride by-product. The crude product was purified by dry flash chromatography (eluent ethyl acetate:methanol, 10:1) to yield N-tetradecyl- 5-methyl-2-furamide as a pale cream wax (4.43 g, 69%). tetradecyl-5-methyl-2-furoate

Tetradecanol (4.29 g, 0.02 mol) and methyl 5-methylfuran-2-furoate (2.80 g, 0.02 mol) were heated for 30 minutes at 105°C with stirring under a nitrogen headspace purge exhausting via a condenser configured for distillation. The mixture was then cooled to 90°C and stirred for 1 h before cooling to 60°C and adding sodium methoxide (0.05 g, 5 mol %). The reaction was then heated at 80°C for 4 h before cooling to ambient. Further methyl 5-methylfuran-2-carboxylate (0.16 g, 0.0011 mol) was charged, and reaction was continued at 80°C under nitrogen for 3 h. The reaction was cooled to 60°C and lactic acid (0.09 g) added to neutralise the catalyst. The crude product was dissolved in heptane and washed with brine (50 ml), with ethyl acetate added to prevent gelling. After a second brine wash (50 ml) the organic layer was evaporated to yield tetradecyl-5-methyl-2-furoate as a pale brown wax (5.98 g, 93%). hexadecyl-5-methyl-2-furoate

Hexadecanol (4.85 g, 0.02 mol) was heated for 30 minutes at 100°C with stirring under a nitrogen headspace purge exhausting via a condenser configured for distillation. After cooling to 70°C, methyl 5-methylfuran-2-furoate (2.80 g, 0.02 mol) was added, and the mixture stirred for 30 minutes. Sodium methoxide (0.05 g, 5 mol %) was charged and the temperature increased to 80°C for 4.5 h. The reaction was cooled to 70°C and lactic acid (0.09 g) added. The crude product was dissolved in ethyl acetate and the precipitated catalyst residue was filtered off. The solvent was evaporated to yield hexadecyl-5-methyl-2-furoate as a pale brown wax (6.69 g, 95%).

Direct ring-sulfonation to 5-methyl-furan-2-ester/amide intermediates

The furan ester/amide intermediates were sulfonated as described hereinafter.

N-dodecyl-4-methylsulfonate-5-methyl-2-furamide

N-dodecyl-5-methyl-2-furamide (1.47 g, 0.005 mol), DMF-SO3 (0.77 g, 0.005 mol) and anhydrous acetonitrile (15 ml) were heated under reflux at 85°C for 26 h. The reaction was cooled to room temperature and neutralised to pH 7 by addition of Na₂CO3 (0.32 g, 0.003 mol) in water (10 ml). After filtration (to remove humins) the clear filtrate was carefully evaporated to dryness by azeotroping with fresh acetonitrile to prevent excessive foaming. The resultant amber foam was further dried in vacuo over P2O5. The dried foam (2.12 g) was triturated with hot heptane; the resulting powdery solid filtered off and the heptane evaporated to yield unreacted starting material (0.10 g). The powdery solid (1.93 g) was triturated with hot acetonitrile; the residual powdery solid filtered off and the acetonitrile evaporated to yield further starting material (0.03 g). The powdery solid (1.86 g) was triturated with hot methanol and the resulting insoluble inorganic solids filtered off (0.04 g). The methanol solution was evaporated to dryness yielding the desired product as a cream powder (1.49 g, 75%).

¹H NMR (400 MHz, DMSO-D₆) 6 8.17 (1 H, t, J = 5.4 Hz, H₃), 6.98 (1 H, s, H₂), 3.14 (2H dd, J = 12.6, 6.0 Hz, H₅), 2.39 (1H, S, HI), 1.53 - 1.34 (2H, m, H₄), 1.37 - 1.14 (18H, m, H₆-I₄), 0.85 (3H, t, J = 6.2 Hz, H15).

Direct ring-sulfonation of 5-methyl-N,N-dioctylfuran-2-carboxamide

To DMF-SO3 complex (262 mg, 2.14 mmol) under nitrogen was added dry acetonitrile (27 mL) followed by the 5-methyl-N,N-dioctylfuran-2-carboxamide (500 mg, 1.43 mmol) dissolved in a small quantity of dry acetonitrile (3 mL). The mixture was then refluxed under nitrogen for 48 h at 85°C. The solution was cooled and then an aqueous solution of Na₂CO3 (195 mg, 1.85 mmol in 27.5 mL DI water) was added to bring the pH to 7. This was stirred for 1 hour. After 1 h the aqueous solution was then washed with heptane (50 mL) then ethyl acetate (3x 50 mL). The organic solvent was removed in vacuo to yield the desired product. (534 mg, 1.18 mmol, 82%).

¹H NMR (400 MHz, DMSO-D₆) bppm: 6.72 (1H, s, H₂), 2.39 (3H, s, Hi), 1.25 (24H, s, H_4.9and H12-17), 0.85 (6H, t, J = 6.7 Hz, Hindis). tetradecane-2-yl-4-methylsulfonate-5-methyl-2-furoate

To DMF-SO3 complex (1.99 mg, 13 mmol) under nitrogen was added dry acetonitrile (27mL) followed by the tetradecane-2-yl-5-methyl-2-furoate (2.8 mg, 8.69 mmol) dissolved in a small quantity of dry acetonitrile (3 mL). The mixture was then refluxed under nitrogen for 48 h at 85°C. The solution was cooled and then an aqueous solution of Na2CC>3 (707 mg, 6.73 mmol in 112 mL DI water) was added to bring the pH to 7. This was stirred for 1 hour. After 1 h the aqueous solution was then washed with heptane (50 mL) then ethyl acetate (3x 50 mL). the organic solvent was removed in vacuo to yield the desired product. (1.78 g, 4.19 mmol, 48%, solvent still present in NMR). ¹H NMR (400 MHz, DMSO-D₆) 5 6.97 (1 H, s, H₂), 5.17 - 4.98 (1 H, m, H₃), 1.65 - 1.48 (m, 2 H₅), 1.36 - 1.18 (H 23, m, H₄and ₆-i₅), 0.85 (3H, t, J = 6.6 Hz, HI₆).

Direct ring-sulfonation of N-(2-hexyldecyl)-5-methylfuran-2-carboxamide

To DMF-SO3 complex (328 mg, 2.14 mmol) under nitrogen was added dry acetonitrile (27 mL) followed by the N-(2-hexyldecyl)-5-methylfuran-2-carboxamide (500 mg, 1.43 mmol) dissolved in a small quantity of dry acetonitrile (3 mL). The mixture was then refluxed under nitrogen for 48 h at 85°C. The solution was cooled and then an aqueous solution of Na₂CO3 (195 mg, 1.85 mmol in 27.5 mL DI water) was added to bring the pH to 7. This was stirred for 1 hour. After 1 h the aqueous solution was then washed with heptane (50 mL) then ethyl acetate (3x 50 mL). The organic solvent was removed in vacuo to yield the desired product. (399 mg, 0.88 mmol, 61%).

¹H NMR (400 MHz, DMSO-D₆) 6 8.07 (1 H, t, J = 5.8 Hz, H₃), 6.99 (1 H, s, H₂), 3.03 (2H, t, J =

6.2 Hz, H₄), 2.36 (1 H, s, Hi), 0.81 (1 H, br s, H₅), 1.19 (24H, s, H₆-i₂ and HI₄.I₈), 0.81 (6H, t, J =

5.2 Hz, Hi₃and 19). Direct ring-sulfonation of N-(2-butyloctyl)-5-methylfuran-2-carboxamide

To DMF-SO3 complex (737 mg, 4.82 mmol) under nitrogen was added dry acetonitrile (47 mL) followed by the N-(2-butyloctyl)-5-methylfuran-2-carboxamide (909 mg, 3.21 mmol) dissolved in a small quantity of dry acetonitrile (3 mL). The mixture was then refluxed under nitrogen for 48 h at 85°C. The solution was cooled and then an aqueous solution of Na₂CO3 (434 mg, 4.14 mmol in 69 mL DI water) was added to bring the pH to 7. This was stirred for 1 hour. After 1 h the aqueous solution was then washed with heptane (50 mL) then ethyl acetate (3x 50 mL). The organic solvent was removed in vacuo to yield the desired product. (580 mg, 1.46 mmol, 45%).

¹H NMR (400 MHz, DMSO-D₆) 6 8.15 (1 H, t, J = 5.7 Hz, H₃), 7.04 (1 H, s, H₂), 3.07 (2H, t, J = 6.4 Hz, H₄), 2.40 (3H, br s, Hi), 1.53 (1 H, s, H₅), 1.42-1.10 (16 H, br s, H₆-i₂and Hu-is), 0.83 (6H, m, Hi₃and H19).

(2-butyl-octyl)-4-methylsulfonate-5-methyl-2-furoate

(2-Butyl-octyl)-5-methyl-2-furoate (8.82 g, 0.03 mol), DMF-SO3 (4.59 g, 0.03 mol) and anhydrous acetonitrile (40 ml) were heated under reflux at 85°C for 24 h. The reaction was cooled to room temperature and neutralised to pH 7 by addition of Na2CO3 (1.89 g, 0.018 mol) in water (20 ml). After stirring for 1 h the reaction was filtered to separate off a precipitate (0.46 g). The clear filtrate was carefully evaporated to dryness by azeotroping with fresh acetonitrile to prevent excessive foaming. The resultant amber gum (14.87 g) was triturated with heptane but the resulting semi-solid could not be filtered. The contaminated filter papers and filter funnel were washed through with methanol and the solvent evaporated to yield an amber gum (2.63 g, 85:15 mixture of product: starting material). The semi-solid that had been collected and the heptane were recombined and water (100 ml) and NaCI (5 g) added, forming a clear heptane layer (A), an emulsified interfacial layer (B), and a hazy aqueous layer (C). The clear heptane layer (A) was evaporated to dryness yielding an oil (0.59 g, starting material) and the interfacial layer (B) was separated by addition of further NaCI, with evaporation of the heptane yielding an amber gum (1.81 g, 60:40 mixture of product: starting material). The hazy aqueous layer (C) was separated off and extracted with ethyl acetate (150 ml); evaporation of the solvent gave an amber gum (5.65 g). The gum was washed with hot heptane, with successive solvent additions decanted off and combined. Removal of the heptane gave 0.13 g of starting material. The residue was dried to remove traces of heptane, yielding the target sulfonated product as a brittle, slightly sticky pale orange foam (4.52 g, 38%).

¹H NMR (400 MHz, DMSO-D₆) 5 7.00 (1 H, s, H₂), 4.11 (2H, d, J = 5.6 Hz, H₃), 2.43 (3H, s, Hi), 1.79 - 1.60 (1H, m, H₄), 1.42 - 1.14 (16H, m, H_5-9 and Hn-n), 0.85 (6H, q, J = 6.8 Hz, H and ).

Sulfonated 5-methyl N-tetradecylfuran-2-carboxamide

5-Methyl N-tetradecylfuran-2-carboxamide (1.61 g, 0.005 mol), DMF-SO₃ (0.77 g, 0.005 mol) and anhydrous acetonitrile (25 ml) were heated under reflux at 85°C for 24 h. The reaction was cooled to room temperature and neutralised to pH 7 by addition of Na₂CO₃ (0.34 g, 0.003 mol) in water (10 ml). After stirring for 1 h the reaction was filtered to separate off a precipitate (0.01 g, sodium sulfate). The clear filtrate was carefully evaporated to dryness by azeotroping with fresh acetonitrile to prevent excessive foaming. The resultant amber solid (1.80 g) was triturated with hot heptane; the resulting powdery solid filtered off and the heptane evaporated to yield unreacted starting material (0.14 g). The powdery solid (1.51 g) was triturated with hot methanol and the insoluble inorganic solids filtered off (0.05 g, sodium sulfate and sodium carbonate). The clear filtrate was evaporated to dryness yielding the desired product as a cream powder (1.28 g, 60%).

¹H NMR (400 MHz, DMSO-D₆) 5 8.17 (1 H, t, J = 5.4 Hz, H₃), 6.98 (1 H, s, H₂), 3.14 (2H, m, H₄), 2.39 (3H, s, Hi), 1.53 - 1.34 (2H, m, H₅), 1.37 - 1.14 (22H, m, H₆-I₆), 0.85 (3H, t, J = 6.2 Hz, H17). Sulfonated tetradecyl 5-methylfuran-2-carboxylate

Tetradecyl 5-methylfuran-2-carboxylate (1.61 g, 0.005 mol), DMF-SO3 (0.77 g, 0.005 mol) and anhydrous acetonitrile (15 ml) were heated under reflux at 85°C for 26 h. The reaction was cooled to room temperature and neutralised to pH 7 by addition of Na₂CO3 (0.37 g, 0.0035 mol) in water (20 ml). After stirring for 1 h the reaction was filtered to separate off a precipitate (0.35 g, unreacted starting material). The clear filtrate was carefully evaporated to dryness by azeotroping with fresh acetonitrile to prevent excessive foaming. The resultant amber foam (1.73 g) was triturated with hot heptane, the resulting powdery solid filtered off and the heptane evaporated to yield further unreacted starting material (0.26 g). The powdery solid (1.40 g) was triturated with methanol and the insoluble inorganic solids filtered off (0.23 g, sodium sulfate). The clear filtrate was evaporated to dryness yielding the desired product as a pale orange powder (1.07 g, 50%).

¹H NMR (400 MHz, DMSO-D₆) 5 6.98 (1 H, s, H₂), 4.15 (2H, t, J = 6.6 Hz, H₃), 2.39 (3H, s, Hi), 1.59 (2H, q, J = 6.8 Hz, H₄), 1.37 - 1.08 (22H, m, H₄), 0.81 (3H, t, J = 6.7 Hz, HI₆). hexadecyl-4-methylsulfonate-5-methyl-2-furoate

Hexadecyl-5-methyl-2-furoate (6.13 g, 0.0175 mol), DMF-SO3 (2.68 g, 0.0175 mol) and anhydrous acetonitrile (15 ml) were heated under reflux at 85°C for 25 h. The reaction was cooled to room temperature and neutralised to pH 7 by addition of Na2CO3 (1.08 g, 0.010 mol) in water (20 ml). After stirring for 1 h the reaction was filtered to separate off a precipitate (5.88 g). The clear filtrate was carefully evaporated to dryness by azeotroping with fresh acetonitrile to prevent excessive foaming, yielding a sticky orange solid (1.85 g). Both the precipitate and the evaporation residue were triturated with hot heptane; the heptane extracts were combined and evaporated to give a wax (1.38 g, starting material). The solid (1.26 g) from the heptane trituration of the evaporation residue was triturated with hot methanol and after filtration and evaporation yielded impure sulfonated product (1.08 g, -70% purity). The solid residue (4.70 g) from the heptane trituration of the precipitate was triturated with hot methanol and the resulting solid filtered off (0.33 g, inorganic salts). The clear filtrate was evaporated to dryness yielding impure sulfonated product as a pale brown powder (3.75 g), which was washed with hot heptane to remove free hexadecanol (0.18 g) and then hot acetonitrile to remove sulfonated methyl 5-methylfuran-2-carboxylate (0.26 g). The residual solid was dried in vacuo to give the target sulfonated product as a beige powder (2.90 g, 37%).

Further furan-based surfactants such as:

can be made in a similar fashion to the materials described above. For example, 5-methyl-2- furoic acid is dissolved in dichloromethane (30mL) and stirred at 0 °C for 5 minutes. Then EDC«HCI and DMAP are added and the solution was stirred for ca. 30 minutes before addition of the required amount of 2-octyldecanol, hexadecyl amine or dodecanol. The mixture then stirred for 2 hours at 0 °C followed by a 12 hour stir at room temperature. The reaction mixture is then washed with 2 M hydrochloric acid solution (20 mL), water, 1 M NaOH (20 mL) and brine (20 mL). The organic solvent is dried over magnesium sulfate. The organic solvent is removed in vacuo to yield the product. The product(s) are then sulfated as described above to yield the furan-based surfactants.

Example 2 - Cleaning Studies

The following furan-based surfactants were made as per the methods outlined in example 1.

For the purposes of this work, the comparative control will be a commercial grade of LAS.

CMC measurement

For the individual surfactants, 2g/l samples of each surfactant were prepared in 0.1 M NaCI. These were then serially diluted (1/2) using a Hamilton Liquid handler across a 96 well plate giving a concentration range of 2-0.000977g/l. The surface tension was measured using a Kibron Delta 8 surface tensiometer, 4 repeats were carried out for each sample and averaged to generate the results below (see columns 2 and 3 of table 1).

Then the CMC and the surface tension of each surfactant was measured in a 3:1 blend by weight with Neodol 25-7 (ex Shell: a C12-15 alcohol ethoxylate nonionic surfactant with an average 7EO groups) in water (24FH water hardness) and these results are shown in columns 4 and 5 of table 1.

From the results shown in table 1, both as individual surfactants and in mixtures with nonionic, the furan-based surfactants of the invention perform extremely well and are comparable to the high-performing benchmark, the ubiquitous commercial anionic surfactant LAS.

Table 1 - Comparing CMC and Surface Tension of the Furan-based surfactants versus LAS Interfacial tension measurement

These have been measured on the Kruss DVT50 tensiometer. Total surfactant concentration used in each case was 0.5g/L and the water hardness was chosen to be 12FH. Each surfactant was measured as 3:1 mixture (by weight) with Neodol 25-7 (ex Shell: a C12-15 alcohol ethoxylate nonionic surfactant with an average 7EO groups). The interfacial tension measurements given are those measured at a flow rate of 0.0099 ml/min with pure olive oil used as the oil phase. The results are shown in table 2.

Table 2 - Comparing Interfacial Tension of the Furan-based surfactants versus LAS

Again, it can be seen that the furan-based surfactants of the invention perform extremely well and compare well to the high performing benchmark anionic surfactant LAS.

Cleaning Studies

Wash studies were completed using a small scale multi-pot Linitester. Each pot was filled with 100ml of a 0.4gpL surfactant solution. Two types of stained fabric swatches were sourced from Warwick Equest

Knitted cotton fabric that had been stained with Yellow Curry, Tomato & Sunflower Oil, Economy Chocolate Ice Cream and Chilli Con Carne

Knitted polyester fabric that had been stained with Lard & Violet Dye, Red Pepper Oil and Cooking Oil & Violet Dye

One cotton and one polyester stained fabric swatch was added to each Linitest pot along with 50 ball bearings to simulate agitation.

The surfactant solution used was a 3:1 blend of the test surfactant in combination with the Nonionic alcohol ethoxylate Neodol 25-7 (total surfactant = 0.4gpL i.e. 0.04g of surfactant in each pot containing 100ml of 12FH water)

The fabrics were washed for 30 min @ 100 rpm at 30°C (i.e. at a temperature just above ambient so it could be controlled). 50 stainless steel balls were added for agitation.

After wash cycles, fabrics were squeezed dry and returned to wash pot with 100 ml clean 12 FH water for a 5 min rinse cycle @ 30°C at 100 rpm.

Following rinse cycle fabrics were squeezed out and lay on drying rack in the dark overnight to minimise UV bleaching of stains.

Delta E measurements were taken before washing and after drying for 24hrs.

Delta (delta E) figures were calculated as follows:

Delta (DeltaE) = Beforewash DeltaE - Afterwash DeltaE The results for the stained fabrics are shown in table 3 (stained knitted cotton) and table 4 (stained knitted polyester).

Table 3 - Comparing cleaning results for Furan-based surfactants versus LAS on Knitted Cotton (All given as Delta (DeltaE))

Table 4 - Comparing cleaning results for Furan-based surfactants versus LAS on Knitted Polyester (All given as Delta (DeltaE))

Example 3 - solubility and calcium tolerance

Furans 1 and 5 (as according to example 2) were synthesized and compared with surfactants made according to WO2020/229158.

The following comparative structures were produced according to the methods disclosed in WO2020/229158 for use in this example.

Furans 2 and 5 and comparative samples B, C and D were gently stirred for 1 hour into demineralised water at room temperature at a concentration of 50g/l. The samples were then left to stand and assessed visually after 5 mins. For some of the samples a non-ionic surfactant with a C12-15 alkyl chain and an average of 7EO groups (Neodol 25-7, ex: Shell) was also added (at a 3:1 weight ratio of test surfactants to non-ionic surfactant). This was done with the aim of further improving surfactant solubility.

Table 5 - comparing solubility in demineralised water at 50g/l for the different surfactants and mixtures thereof:

It can clearly be seen that the direct attachment of the sulphonate group to the Furan ring in combination with a direct attachment of a methyl group is superior over the beta sulphonate structure with regards to solubility in water at room temperature. Furthermore, the addition of non-ionic surfactant to the mixture does not improve the situation, clearly demonstrating the strong solubility benefit of furan structures made according to the invention. Further experiments were undertaken to assess the appearance as a function of temperature. All samples were heated to the selected temperatures and held there for 30 minutes. The results recorded were as follows: Table 6 - solubility in demineralised water as a function of temperature

As can be seen in table 6, the solubility of structures made according to the invention is superior at lower temperatures than all of the comparative structures.

A further experiment was undertaken to assess the calcium tolerance by including in 24° FH water at 0.5g/l. The results recorded were as follows:

Table 7 -

It can clearly be seen that the direct attachment of the sulphonate group to the furan ring in combination with a direct attachment of a methyl group is superior over the beta sulphonate structure with regards to calcium tolerance in 24°FH water at room temperature.

Example formulations

The furan surfactants are easily incorporated in the following exemplar detergent compositions.

Low Foam Laundry Liquid

High Foam Laundry Liquid

Sulphate/Carbonate Powder

Salt/Carbonate Powder

Hand Dish Wash

Claims

1. A home or personal care detergent composition comprising: from 0.5 to 50 wt.%, preferably from 0.75 to 40 wt.%, more preferably from 1 to 30 wt.% of a furan-based surfactant having the following structure:

2. A home or personal care detergent composition according to claim 1 , wherein the furan-based surfactant has the following structure:

3. A home or personal care detergent composition according to claim 1 or claim 2, wherein the R group is a C12 to C carbon chain.

4. A home or personal care detergent composition according to any preceding claim, wherein the R group is a saturated alkyl chain. A home or personal care detergent composition according to any preceding claim, wherein the furan-based surfactant is selected from:

A home or personal care detergent composition according to any preceding claim, wherein the R group is a linear carbon chain. A home or personal care detergent composition according to any preceding claim, additionally comprising a fragrance, preferably from 0.0001 to 5 wt.% of a fragrance. A home or personal care detergent composition according to any preceding claim, comprising one or more additional surfactants selected from anionic and nonionic surfactants, wherein if present, then the anionic surfactant is present at a level of from 1 to 80 wt.%, preferably from 2 to 50 wt.%, more preferably from 3 to 30 wt.% and is preferably selected linear alkyl benzenesulphonate, secondary alkane sulphonate, laureth ether sulphate, lauryl sulphate, anionic alkyl polyglycosides, isethionates, alpha olefin sulphonate, internal olefin sulphonate, methyl ester sulphonate, oleyl sulphate, oleyl ether sulphate and rhamnolipids, most preferably selected from linear alkyl benzenesulphonate, secondary alkane sulphonate, laureth ether sulphate, lauryl sulphate, methyl ester sulphonate, oleyl sulphate, oleyl ether sulphate and rhamnolipids; wherein if present, then the nonionic surfactant is present at a level of from 1 to 80 wt.%, preferably from 2 to 50 wt.%, more preferably from 3 to 30 wt.% and is preferably selected from an alcohol ethoxylate, an alcohol propoxylate, a methyl ester ethoxylate, and an alkyl poly glycoside.; A home or personal care detergent composition according to any preceding claim, wherein said composition is a home care detergent composition, preferably a hand dish wash detergent composition or a laundry detergent composition, more preferably a laundry detergent composition. A home care detergent composition, preferably a laundry detergent composition according to claim 9, wherein the composition is in the form of a liquid, solid, powder, pastille, bead or paste. A home care detergent composition according to claim 9 or claim 10, additionally comprising an enzyme, preferably comprising from 0.05 to 5 wt.%, more preferably from 0.1 to 4 wt.%, more preferably from 0.5 to 3 wt.% of an enzyme, wherein the enzyme is preferably selected from one or more of a protease, amylase, mannanase, cellulase, lipase, pectate lyase, laccase, phosphodiesterase and mixtures thereof. A home care detergent composition according to any one of claims 9 to 11 , wherein the composition comprises from 0.5 to 15 wt.%, more preferably from 0.75 to 15 wt.%, even more preferably from 1 to 12 wt.%, most preferably from 1.5 to 10 wt.% of cleaning boosters selected from antiredeposition polymers, soil release polymers, alkoxylated polycarboxylic acid esters and mixtures thereof, more preferably selected from antiredeposition polymers, and soil release polymers. A home care detergent composition, preferably a laundry detergent composition according to any one of claims 9 to 12, additionally comprising from 0.05 to 8 wt.%, preferably from 0.1 to 5 wt.%, more preferably from 0.5 to 2 wt.% of a sequestrant, preferably the sequestrant is preferably selected from HEDP, DTPMP, EDTA, MGDA, GLDA or citric acid. Use of a furan-based surfactant as defined in any of the claims 1 to 13 in a laundry process to improve soil removal from fabrics.