Concentrated laundry detergent composition

Abstract

The present invention provides a concentrated laundry detergent composition comprising: a solvent system wherein the solvent system is a mixture of water and a non-aqueous solvent; a cleaning surfactant; wherein the cleaning surfactant comprises a blend of: a nonionic surfactant; an anionic alcohol ethoxysulfate surfactant of formula I, wherein R1 and R2 are each independently a C1-16 alkyl group; wherein the sum of carbon atoms in R1 and R2 is from 7 to 17; wherein M + is a negatively charged cation that balances the-SO3-anion of formula I; and wherein n is 1 in 95 mol% to 100 mol% of the anionic alcohol ethoxysulfate surfactant of formula I; wherein the concentrated laundry detergent composition comprises lt based on the weight of the concentrated laundry detergent composition; and 10% by weight of water.

Description

[0001] This invention relates to a concentrated laundry detergent composition. Specifically, the invention relates to a concentrated laundry detergent composition comprising: a solvent system, wherein the solvent system is a mixture of water and a non-aqueous solvent; and a cleaning surfactant, wherein the cleaning surfactant comprises a blend of a nonionic surfactant and an anionic alcohol ethoxysulfate surfactant of formula I. Where R 1 and R 2 Each is C independently 1-16 alkyl groups; wherein R 1 and R 2 The total number of carbon atoms in the middle ranges from 7 to 17; of which M + It is the balanced I-SO3 - An anionic negatively charged cation; and wherein n is 1 in 95 mol% to 100 mol% of the anionic alcohol ethoxysulfate surfactant of formula I; wherein the concentrated laundry detergent composition contains <15 wt% water based on the weight of the concentrated laundry detergent composition.

[0002] Water-based laundry detergent formulations typically include alkyl ethoxysulfate anionic surfactants (e.g., alcohol ethoxysulfate surfactants). However, these surfactants are associated with undesirable 1,4-dioxane levels. Regulators have been tightening restrictions on the levels of 1,4-dioxane that may be present in consumer products. For example, New York State has banned all, but trace amounts, of 1,4-dioxane in cleaning products. Generally, the 1,4-dioxane content in consumer products must be below 10 parts per million (ppm) by weight to be compliant. One reason for the unintended inclusion of 1,4-dioxane in consumer products may be the introduction of alkyl ethoxysulfate anionic surfactants.

[0003] It is believed that conventional AES surfactants introduce 1,4-dioxane at multiple time points. The first time point of 1,4-dioxane formation in conventional AES surfactants is believed to occur during the sulfation process of alcohol ethoxylates, used to prepare alcohol ethoxysulfates. The alcohol ethoxylate intermediates used to produce conventional alcohol ethoxysulfate surfactants are prepared via ethoxylation (i.e., the reaction of an alcohol with ethylene oxide), which typically results in the distribution of alcohol ethoxylate oligomers. 1,4-Dioxane is believed to form under the sulfation process conditions during the preparation of conventional AES surfactants. A second time point of 1,4-dioxane formation associated with conventional AES surfactants is believed to occur during the treatment and processing of conventional AES surfactants. The treatment and processing of conventional AES surfactants typically involve acidic conditions at ambient temperature or high temperatures. Prolonged exposure of conventional AES surfactants and their alcohol ethoxylate precursors to acidic environments leads to the formation of 1,4-dioxane. Furthermore, exposure to high temperatures (e.g., up to 280°C) during processing, storage, and / or handling can cause conventional AES surfactants to decompose, leading to the formation of dioxanes.

[0004] Traditionally, the 1,4-dioxane content in conventional AES surfactants and products incorporating such surfactants has been controlled using stripping technology. For example, when the 1,4-dioxane concentration exceeds a target threshold, a stripping process is used to remove excess 1,4-dioxane from conventional AES surfactants or products incorporating such surfactants. This stripping process is not only expensive and time-consuming, but also cannot guarantee compliance with increasingly stringent regulatory requirements. Furthermore, because 1,4-dioxane can gradually form over time during the handling and further processing of conventional AES surfactants or related products, any previously employed stripping technology may become ineffective due to the generation of new 1,4-dioxane. Therefore, ensuring that products containing AES surfactants comply with relevant regulations when sold to end consumers is a significant challenge.

[0005] Furthermore, while standard (non-concentrated) liquid laundry detergents still dominate many markets, the use of concentrated laundry detergent formulations is becoming increasingly prevalent in consumer and institutional cleaning applications. Therefore, there remains a need for concentrated laundry detergent compositions containing anionic ethoxysulfate surfactants that resist the formation of 1,4-dioxanes during the sulfation process that forms the surfactant and subsequently when exposed to temperatures up to 280°C.

[0006] This invention provides a concentrated laundry detergent composition comprising: a solvent system, wherein the solvent system is a mixture of water and a non-aqueous solvent; a cleaning surfactant; wherein the cleaning surfactant comprises a blend of: a nonionic surfactant; and an anionic alcohol ethoxysulfate surfactant of formula I. Where R 1 and R 2 Each is C independently 1-16 alkyl groups; wherein R 1 and R 2 The total number of carbon atoms in the middle ranges from 7 to 17; of which M + It is the balanced I-SO3 - An anionic negatively charged cation; and wherein n is 1 in 95 mol% to 100 mol% of the anionic alcohol ethoxysulfate surfactant of formula I; wherein the concentrated laundry detergent composition contains <15 wt% water based on the weight of the concentrated laundry detergent composition.

[0007] This invention provides a concentrated laundry detergent composition comprising: a solvent system, wherein the solvent system is a mixture of water and a non-aqueous solvent; a fatty acid; a neutralizing agent; and a cleaning surfactant; wherein the cleaning surfactant comprises a blend of: a nonionic surfactant; and an anionic alcohol ethoxysulfate surfactant of formula I. Where R 1 and R 2 Each is C independently 1-16 alkyl groups; wherein R 1 and R 2 The total number of carbon atoms in the middle ranges from 7 to 17; of which M + It is the balanced I-SO3 - The anionic negatively charged cation; and wherein n is 1 in 95 mol% to 100 mol% of the anionic alcohol ethoxysulfate surfactant of Formula I; wherein the concentrated laundry detergent composition comprises 1 wt% to <10 wt% water based on the weight of the concentrated laundry detergent composition; and an additional anionic surfactant.

[0008] The present invention provides a method for washing soiled cotton articles, the method comprising: providing the soiled cotton articles; providing a laundry detergent composition according to the present invention; providing washing water; and applying the washing water and the laundry detergent composition to the soiled cotton articles to provide clean cotton articles. Detailed Implementation

[0009] Unexpectedly, it was found that anionic alcohol ethoxysulfate surfactants of Formula I resist the formation of 1,4-dioxanes during the sulfation process of forming anionic alcohol ethoxysulfate surfactants of Formula I, and subsequently when the anionic alcohol ethoxysulfate surfactants of Formula I are exposed to high temperatures up to 280°C during processing, storage and / or treatment; wherein R 1 and R 2 Each is C independently 1-16 alkyl groups; wherein R 1 and R 2 The total number of carbon atoms in the middle ranges from 7 to 17; of which M + It is -SO3 in equilibrium formula I - An anionic, negatively charged cation; and wherein n is 1 in 95 mol% to 100 mol% of the anionic alcohol ethoxysulfate surfactant of formula I.

[0010] Unexpectedly, it was also found that anionic alcohol ethoxysulfate surfactants of Formula I, when replacing conventional AES surfactants in aqueous laundry detergent formulations, provide comparable major cleaning performance and comparable improved anti-redeposition properties; wherein R 1 and R 2 Each is C independently 1-16 alkyl groups; wherein R 1 and R 2 The total number of carbon atoms in the middle ranges from 7 to 17; of which M + It is -SO3 in equilibrium formula I - An anionic, negatively charged cation; and wherein n is 1 in 95 mol% to 100 mol% of the anionic alcohol ethoxysulfate surfactant of formula I.

[0011] Unless otherwise specified, ratios, percentages, parts, etc. are all by weight (e.g., "ppm" means parts per million by weight).

[0012] As used herein and in the appended claims, the term "solid weight" in relation to concentrated laundry detergent compositions and anionic alcohol ethoxysulfate surfactants of Formula I means dry weight, i.e., excluding any water that may be present.

[0013] As used herein and in the appended claims, the terms “solvent,” “multiple solvents,” and “solvent system” in relation to concentrated laundry detergent compositions refer to one or more liquids used to dissolve or solvate other components in the composition. In some cases, the components may also be dispersed using a solvent / multiple solvents / solvent system (e.g., titanium dioxide in water). In some cases, the solvent may initially be present as a solid and subsequently dissolved in another solvent (e.g., polyethylene glycol in water). As used herein, the terms “solvent,” “multiple solvents,” and “solvent system” do not cover neutralizing agents (e.g., triethanolamine, monoethanolamine, and sodium hydroxide).

[0014] Preferably, the concentrated laundry detergent composition of the present invention comprises: a solvent system (preferably, 25% to 75% by weight (more preferably, 30% to 68.5% by weight; still more preferably, 35% to 61% by weight; most preferably, 37% to 53% by weight) based on the weight of the concentrated laundry detergent composition), wherein the solvent system is a mixture of water and non-aqueous solvents; optionally, fatty acids (preferably, 0% to 15% by weight (more preferably, 0.5% to 10% by weight; still more preferably, 1% to 7.5% by weight; most preferably, 2% to 4% by weight) based on the weight of the concentrated laundry detergent composition); optionally, a neutralizer (preferably, 0% to 15% by weight (more preferably, 1% to 12% by weight; still more preferably, 3% to 10% by weight; most preferably, 5% to 9% by weight) based on the weight of the concentrated laundry detergent composition); and a cleaning agent. The surfactant (preferably, 25% to 65% by weight (more preferably, 30% to 60% by weight; still more preferably, 35% to 55% by weight; most preferably, 40% to 50% by weight) of a concentrated laundry detergent composition), wherein the cleaning surfactant comprises blends of: nonionic surfactants (preferably, 1% to 35% by weight (more preferably, 2% to 20% by weight; still more preferably, 2% to 15% by weight; most preferably, 3% to 7% by weight) of a laundry detergent formulation); and anionic alcohol ethoxysulfate surfactants of Formula I (preferably, 2% to 25% by weight (more preferably, 5% to 20% by weight; still more preferably, 6% to 15% by weight; most preferably, 8% to 12% by weight) of anionic alcohol ethoxysulfate surfactants of Formula I, based on the weight of the laundry detergent formulation). Where R 1 and R 2 Each is C independently 1-16 alkyl group (preferably, C1-15 Alkyl groups; more preferably, C 1-14 Alkyl group; most preferably, straight-chain C 1-13 ); where R 1 and R 2 The total number of carbon atoms is 7 to 17 (preferably 10 to 16; more preferably 12 to 16; most preferably 14 to 16) (preferably, where R 1 and R 2 It is a straight-chain alkyl group; more preferably, wherein R 1 It is a methyl group, and R 2 It is a straight chain C 10-14 Alkyl group; most preferably, wherein R 1 It is a methyl group, and R 2 It is a straight chain C 12 alkyl groups or straight-chain C 14 alkyl groups); where M + It is -SO3 in equilibrium formula I - An anion with a negatively charged cation; (preferably, where M) + It is a cation selected from the group consisting of: nitrogen-containing cations (e.g., ammonium cations), metal cations (e.g., alkali metal cations, alkaline earth metal cations), boron-containing cations, and phosphorus-containing cations; more preferably, ammonium cations, alkali metal cations, and alkaline earth metal cations; still more preferably, ammonium cations, sodium cations, and calcium cations; most preferably, sodium cations); and wherein in the anionic alcohol ethoxysulfate surfactant of formula I, n is 1 (preferably, as in the case of 95 mol% to 100 mol% (preferably, 96 mol% to 100 mol%; more preferably, 97 mol% to 100 mol%; most preferably, 97.5 mol% to 100 mol%). 13 The concentrated laundry detergent composition contains, by weight of the concentrated laundry detergent composition, <15% by weight (preferably, 1% to 10% by weight; more preferably, 2% to 9.8% by weight; most preferably, 5% to 9.75% by weight), determined by nuclear magnetic resonance characterization; and optionally, an anionic surfactant (based on the weight of the laundry detergent formulation, preferably, 0% to 62% by weight (more preferably, 0% to 53% by weight; still more preferably, 5% to 47% by weight; most preferably, 21% to 25% by weight) of anionic surfactant); wherein the concentrated laundry detergent composition contains, based on the weight of the concentrated laundry detergent composition, <15% by weight (preferably, 1% to 10% by weight; more preferably, 2% to 9.8% by weight; most preferably, 5% to 9.75% by weight) of water.

[0015] Preferably, the concentrated laundry detergent composition of the present invention comprises 25% to 75% by weight (preferably 30% to 68.5% by weight; more preferably 35% to 61% by weight; most preferably 37% to 53% by weight) of a solvent system based on the weight of the concentrated laundry detergent composition, wherein the solvent system is a mixture of water and a non-aqueous solvent; and wherein the concentrated laundry detergent composition comprises <15% by weight (preferably 1% to 10% by weight; more preferably 2% to 9.8% by weight; most preferably 5% to 9.75% by weight) of water based on the weight of the concentrated laundry detergent composition. More preferably, the concentrated laundry detergent composition of the present invention comprises, based on the weight of the concentrated laundry detergent composition, 25% to 75% by weight (preferably, 30% to 68.5% by weight; more preferably, 35% to 61% by weight; most preferably, 37% to 53% by weight) of a solvent system, wherein the solvent system is a mixture of water and a non-aqueous solvent; wherein the non-aqueous solvent is selected from the group consisting of: polyols (e.g., propylene glycol, butylene glycol, pentanediol, hexanediol, heptanediol, octanediol, 2-methyl-1,3-propanediol, glycerol, xylitol, sorbitol, mannitol, diethylene glycol, triethylene glycol, glycerol, erythritol, euonymus alcohol, inositol, atorvastatin). Ionic liquids; glycol ethers (e.g., ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monopropyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether); epoxide copolymers (e.g., ethylene oxide co-epoxide polymers); polyethylene glycol (e.g., polyethylene glycol with a weight average molecular weight of 300 Daltons to 3,000 Daltons) and mixtures thereof; and wherein the concentrated laundry detergent composition comprises <15% by weight (preferably, 1% to 10% by weight; more preferably, 2% to 9.8% by weight; most preferably, 5% to 9.75% by weight) of water based on the weight of the concentrated laundry detergent composition.More preferably, the concentrated laundry detergent composition of the present invention comprises, based on the weight of the concentrated laundry detergent composition, 25% to 75% by weight (preferably, 30% to 68.5% by weight; more preferably, 35% to 61% by weight; most preferably, 37% to 53% by weight) of a solvent system, wherein the solvent system is a mixture of water and non-aqueous solvents; wherein the non-aqueous solvent comprises a polyol selected from the group consisting of: propylene glycol, butanediol, pentanediol, hexanediol, ... The concentrated laundry detergent composition comprises heptanediol, octanediol, 2-methyl-1,3-propanediol, glycerol, xylitol, sorbitol, mannitol, diethylene glycol, triethylene glycol, glycerol, erythritol, euonymol, inositol, edetol, and mixtures thereof; and wherein the concentrated laundry detergent composition comprises <15% by weight (preferably, 1% to 10% by weight; more preferably, 2% to 9.8% by weight; most preferably, 5% to 9.75% by weight) of water based on the weight of the concentrated laundry detergent composition. More preferably, the concentrated laundry detergent composition of the present invention comprises 25% to 75% by weight (preferably 30% to 68.5% by weight; more preferably 35% to 61% by weight; most preferably 37% to 53% by weight) of a solvent system based on the weight of the concentrated laundry detergent composition, wherein the solvent system is a mixture of water and a non-aqueous solvent; wherein the non-aqueous solvent includes a mixture of propylene glycol and glycerin; and wherein the concentrated laundry detergent composition comprises <15% by weight (preferably 1% to 10% by weight; more preferably 2% to 9.8% by weight; most preferably 5% to 9.75% by weight) of water based on the weight of the concentrated laundry detergent composition. Most preferably, the concentrated laundry detergent composition of the present invention comprises 25% to 75% by weight (preferably 30% to 68.5% by weight; more preferably 35% to 61% by weight; most preferably 37% to 53% by weight) of a solvent system based on the weight of the concentrated laundry detergent composition, wherein the solvent system is a mixture of water and a non-aqueous solvent; wherein the non-aqueous solvent is a mixture of propylene glycol and glycerin; and wherein the concentrated laundry detergent composition comprises <15% by weight (preferably 1% to 10% by weight; more preferably 2% to 9.8% by weight; most preferably 5% to 9.75% by weight) of water based on the weight of the concentrated laundry detergent composition.

[0016] Preferably, the concentrated laundry detergent composition of the present invention comprises 25% to 65% by weight (preferably 30% to 60% by weight; more preferably 35% to 55% by weight; most preferably 40% to 50% by weight) of a cleaning surfactant based on the weight of the concentrated laundry detergent composition; wherein the cleaning surfactant comprises a blend of a nonionic surfactant and an anionic alcohol ethoxysulfate surfactant of formula I; wherein R1 and R 2 Each is C independently 1-16 alkyl group (preferably, C 1-15 Alkyl groups; more preferably, C 1-14 Alkyl group; most preferably, straight-chain C 1-13 ); where R 1 and R 2 The total number of carbon atoms is 7 to 17 (preferably 10 to 16; more preferably 12 to 16; most preferably 14 to 16) (preferably, where R 1 and R 2 It is a straight-chain alkyl group; more preferably, wherein R 1 It is a methyl group, and R 2 It is a straight chain C 10-14 Alkyl group; most preferably, wherein R 1 It is a methyl group, and R 2 It is a straight chain C 12 alkyl groups or straight-chain C 14 alkyl groups); where M + It is the balanced I-SO3 - An anionic negatively charged cation; and wherein n is 1 in 95 mol% to 100 mol% of the anionic alcohol ethoxysulfate surfactant of Formula I. More preferably, the concentrated laundry detergent composition of the present invention comprises 25 wt% to 65 wt% (preferably 30 wt% to 60 wt%; more preferably 35 wt% to 55 wt%; most preferably 40 wt% to 50 wt%) of a cleaning surfactant based on the weight of the concentrated laundry detergent composition; wherein the cleaning surfactant comprises a blend of a nonionic surfactant and anionic surfactant; wherein the anionic surfactant comprises a mixture of an additional anionic surfactant and an anionic alcohol ethoxysulfate surfactant of Formula I; wherein R 1 and R 2 Each is C independently 1-16 alkyl group (preferably, C 1-15 Alkyl groups; more preferably, C 1-14 Alkyl group; most preferably, straight-chain C 1-13 ); where R 1 and R 2 The total number of carbon atoms is 7 to 17 (preferably 10 to 16; more preferably 12 to 16; most preferably 14 to 16) (preferably, where R 1 and R 2 It is a straight-chain alkyl group; more preferably, wherein R 1 It is a methyl group, and R 2 It is a straight chain C 10-14 Alkyl group; most preferably, wherein R1 It is a methyl group, and R 2 It is a straight chain C 12 alkyl groups or straight-chain C 14 alkyl groups); where M + It is the balanced I-SO3 - An anionic, negatively charged cation; and wherein n is 1 in 95 mol% to 100 mol% of the anionic alcohol ethoxysulfate surfactant of formula I.

[0017] Preferably, the concentrated laundry detergent composition of the present invention comprises 1% to 35% by weight (preferably 2% to 20% by weight; more preferably 2% to 15% by weight; most preferably 3% to 7% by weight) of a nonionic surfactant based on the weight of the concentrated laundry detergent composition. More preferably, the concentrated laundry detergent composition of the present invention comprises 1% to 35% by weight (preferably 2% to 20% by weight; more preferably 2% to 15% by weight; most preferably 3% to 7% by weight) of a nonionic surfactant based on the weight of the concentrated laundry detergent composition; wherein the nonionic surfactant is selected from the group consisting of alkoxylates, polyethylene glycol ethers, fatty alcohol polyethylene glycol ethers, alkylphenol polyethylene glycol ethers, end-capped polyethylene glycol ethers, mixed ethers, hydroxyl mixed ethers, fatty acid polyethylene glycol esters, and mixtures thereof. Preferred nonionic surfactants include alkoxylates. More preferably, the concentrated laundry detergent composition of the present invention comprises 1% to 35% by weight (preferably 2% to 20% by weight; more preferably 2% to 15% by weight; most preferably 3% to 7% by weight) of a nonionic surfactant based on the weight of the concentrated laundry detergent composition; wherein the nonionic surfactant is according to Formula A. Where w is an average value of 5 to 40 (preferably 7 to 27; more preferably 8 to 20; most preferably 7 to 12); where R 5 Choose the group consisting of: hydrogen and straight-chain or branched C. 1-20 Alkyl groups (preferably, hydrogen and straight-chain or branched C) 1-15 Alkyl groups; more preferably, straight-chain C 1-15 alkyl groups); where R 6 Choose from the following groups: straight chains or branches C 1-20 Alkyl groups and straight or branched C 1-4 Hydroxyalkyl groups (preferably straight-chain or branched C) 1-15 Alkyl groups and straight or branched C 1-4 Hydroxyalkyl group; more preferably, straight-chain C 1-15 Alkyl groups and straight or branched C 1-3Hydroxyalkyl group; most preferably, straight-chain C 1-15 alkyl groups); wherein each R 7 Independently selected from the group consisting of: hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-butyl group and 2-methyl-2-butyl group (preferably, hydrogen, methyl group and ethyl group; more preferably, hydrogen and methyl group; most preferably, hydrogen); and the condition is R 5 and R 6 The total number of carbon atoms in the surfactant is 5 to 21 (preferably 6 to 20 carbon atoms; more preferably 7 to 18 carbon atoms; most preferably 11 to 15 carbon atoms). Still more preferably, the nonionic surfactant is formulated according to Formula I; where w is an average value of 8 to 16; where R... 5 Choose from hydrogen and straight-chain C 1-15 The group consisting of alkyl groups; wherein R 6 Choose either a straight chain or a branched chain C. 1-15 Alkyl groups and straight or branched C 1-4 The group consisting of hydroxyalkyl groups; wherein R 7 Choose from the group consisting of: hydrogen, methyl group, and ethyl group; and the condition is R. 5 and R 6 The total number of carbon atoms in the surfactant is 6 to 20. The most preferred nonionic surfactant is according to formula I; where w is an average of 7 to 12; where R 5 Choose from hydrogen and straight-chain C 1-15 The group consisting of alkyl groups; wherein R 6 Choose free linear chain C 1-15 Alkyl groups and straight or branched C 1-3 The group consisting of hydroxyalkyl groups; wherein R 7 It is hydrogen; and the condition is R. 5 and R 6 The total number of carbon atoms in it ranges from 7 to 18.

[0018] Preferably, the concentrated laundry detergent composition of the present invention comprises 2% to 25% by weight (preferably 5% to 20% by weight; more preferably 6% to 15% by weight; most preferably 8% to 12% by weight) of an anionic alcohol ethoxysulfate surfactant of formula I, based on the weight of the concentrated laundry detergent composition; wherein R 1 and R 2 Each is C independently 1-16 alkyl group (preferably, C 1-15 Alkyl groups; more preferably, C 1-14 Alkyl group; most preferably, straight-chain C 1-13 ); where R 1 and R 2The total number of carbon atoms is 7 to 17 (preferably 10 to 16; more preferably 12 to 16; most preferably 14 to 16) (preferably, where R 1 and R 2 It is a straight-chain alkyl group; more preferably, wherein R 1 It is a methyl group, and R 2 It is a straight chain C 10-14 Alkyl group; most preferably, wherein R 1 It is a methyl group, and R 2 It is a straight chain C 12 alkyl groups or straight-chain C 14 alkyl groups); where M + It is -SO3 in equilibrium formula I - An anion with a negatively charged cation; (preferably, where M) + It is a cation selected from the group consisting of: nitrogen-containing cations (e.g., ammonium cations), metal cations (e.g., alkali metal cations, alkaline earth metal cations), boron-containing cations, and phosphorus-containing cations; more preferably, ammonium cations, alkali metal cations, and alkaline earth metal cations; still more preferably, ammonium cations, sodium cations, and calcium cations; most preferably, sodium cations); and wherein x is 1 in the anionic alcohol ethoxysulfate surfactant of formula I in 95 mol% to 100 mol% (preferably, 96 mol% to 100 mol%; more preferably, 97 mol% to 100 mol%; most preferably, 97.5 mol% to 100 mol%) (preferably, as in the case of using...). 13 (determined by C nuclear magnetic resonance characterization).

[0019] Preferably, the anionic alcohol ethoxysulfate surfactant of Formula I comprises <9 ppm (preferably, <8 ppm; more preferably, <7 ppm; still more preferably, <6 ppm; even more preferably, <5 ppm; still more preferably, <4 ppm; still more preferably, <3 ppm; even more preferably, <2 ppm; even more preferably, <1 ppm; even more preferably, <0.25 ppm; most preferably, below the detection limit) of 1,4-dioxane (preferably, wherein the 1,4-dioxane content is measured by liquid injection low-temperature gas chromatography-mass spectrometry analysis for the organic layer and liquid chromatography-mass spectrometry analysis for the aqueous layer).

[0020] Preferably, the anionic alcohol ethoxysulfate surfactant of Formula I contains <2% by weight (preferably <1.75% by weight; more preferably <1.5% by weight; still more preferably <1.25% by weight; even more preferably <1.1% by weight; most preferably ≤1% by weight) of the alcohol ethoxysulfate surfactant of Formula I based on the alcohol ethoxysulfate surfactant of Formula I. Where R 3 and R 4 Each is C independently 1-16 alkyl groups; wherein R 3 and R 4 The total number of carbon atoms in the middle ranges from 7 to 17; and A in this range... + It is -SO3 in equilibrium IV - An anion with a negatively charged cation; (preferably, where A) + It is a cation selected from the group consisting of: nitrogen-containing cations (e.g., ammonium cations), metal cations (e.g., alkali metal cations, alkaline earth metal cations), boron-containing cations, and phosphorus-containing cations; more preferably, ammonium cations, alkali metal cations, and alkaline earth metal cations; still more preferably, ammonium cations, sodium cations, and calcium cations; most preferably, sodium cations).

[0021] Preferably, the concentrated laundry detergent composition of the present invention comprises an anionic alcohol ethoxysulfate surfactant of formula I as described above, wherein the anionic alcohol ethoxysulfate surfactant of formula I has improved thermal stability. More preferably, the concentrated laundry detergent composition of the present invention comprises an anionic alcohol ethoxysulfate surfactant of formula I as described above, wherein the anionic alcohol ethoxysulfate surfactant of formula I has enhanced thermal stability. As used herein and in the appended claims, the term "improved thermal stability" refers to the presence of <9 ppm (preferably, <8 ppm; more preferably, <7 ppm; still more preferably, <6 ppm; even more preferably, <5 ppm; still more preferably, <4 ppm; even more preferably, <3 ppm; even more preferably, <2 ppm; even more preferably, <1 ppm; most preferably, <0.5 ppm) of 1,4-dioxane (preferably, the 1,4-dioxane content is measured by liquid injection low-temperature gas chromatography-mass spectrometry analysis for the organic layer and liquid chromatography-mass spectrometry analysis for the aqueous layer) of the anionic alcohol ethoxysulfate surfactant of Formula I when heated to 110°C. As used herein and in the appended claims, the term “enhanced thermal stability” means that when heated to 280°C, the anionic alcohol ethoxysulfate surfactant of Formula I contains <10 ppm of 1,4-dioxane by solid weight based on the anionic alcohol ethoxysulfate surfactant of Formula I (preferably, wherein the 1,4-dioxane content is measured by liquid chromatography-mass spectrometry for the organic layer and liquid chromatography-mass spectrometry for the aqueous layer).

[0022] Preferably, the concentrated laundry detergent composition of the present invention further comprises, based on the weight of the laundry detergent formulation, 0% to 62% by weight (preferably, 0% to 53% by weight; more preferably, 5% to 47% by weight; most preferably, 21% to 25% by weight) of an additional anionic surfactant; wherein the additional anionic surfactant is different from the anionic alcohol ethoxysulfate surfactant of Formula I. More preferably, the concentrated laundry detergent composition of the present invention further comprises, based on the weight of the laundry detergent formulation, 0% to 62% by weight (preferably 0% to 53% by weight; more preferably 5% to 47% by weight; most preferably 21% to 25% by weight) of an additional anionic surfactant; wherein the additional anionic surfactant is selected from the group consisting of: alkyl sulfates, alkylbenzene sulfates, alkylbenzene sulfonic acids, alkylbenzene sulfonates, paraffin sulfonic acids, paraffin sulfonates, olefin sulfonic acids, olefin sulfonates, α-sulfonylcarboxylates, esters of α-sulfonylcarboxylates, alkyl glycerol ether sulfonic acids, alkyl glycerol ether sulfonates, sulfates of fatty acids, sulfonates of fatty acids, sulfonates of fatty acid esters, alkylphenols, 2-acryloyloxy-alkane-1-sulfonic acids, 2-acryloyloxy-alkane-1-sulfonates, amine oxides, and mixtures thereof; and wherein the additional anionic surfactant is different from the anionic alcohol ethoxysulfate surfactant of Formula I. More preferably, the concentrated laundry detergent composition of the present invention further comprises, based on the weight of the laundry detergent formulation, 0% to 62% by weight (preferably 0% to 53% by weight; more preferably 5% to 47% by weight; most preferably 21% to 25% by weight) of an additional anionic surfactant; wherein the additional anionic surfactant is selected from the group consisting of: C 8-20 Alkylbenzene sulfate, C 8-20 Alkylbenzenesulfonic acid, C 8-20 Alkylbenzene sulfonates, paraffin sulfonates, paraffin sulfonates, α-olefin sulfonates, α-olefin sulfonates, C 8-20 Alkylphenols, amine oxides, sulfonates of fatty acids, sulfonates of fatty acid esters, and mixtures thereof. More preferably, the concentrated laundry detergent composition of the present invention further comprises, based on the weight of the laundry detergent formulation, 0% to 62% by weight (preferably 0% to 53% by weight; more preferably, 5% to 47% by weight; most preferably, 21% to 25% by weight) of an additional anionic surfactant; wherein the additional anionic surfactant is selected from the group consisting of: C 12-16 Alkylbenzenesulfonic acid, C 12-16 Alkylbenzene sulfonates, C 12-18 Paraffin-sulfonic acid, C 12-18Paraffin-sulfonates and mixtures thereof. Most preferably, the concentrated laundry detergent composition of the present invention further comprises, based on the weight of the laundry detergent formulation, 0% to 62% by weight (preferably 0% to 53% by weight; more preferably 5% to 47% by weight; most preferably 21% to 25% by weight) of an additional anionic surfactant; wherein the additional anionic surfactant is selected from the group consisting of: C 12-16 Alkylbenzenesulfonic acid, C 12-16 Alkylbenzene sulfonates and mixtures thereof.

[0023] Preferably, the concentrated laundry detergent composition of the present invention comprises 25% to 65% by weight (preferably 30% to 60% by weight; more preferably 35% to 55% by weight; most preferably 40% to 50% by weight) of a cleaning surfactant based on the weight of the concentrated laundry detergent composition; wherein the cleaning surfactant comprises a blend of a nonionic surfactant and anionic surfactant; wherein the anionic surfactant comprises anionic alcohol ethoxysulfate surfactant of formula I; and wherein the weight ratio of the nonionic surfactant to the anionic surfactant in the blend is 10:1 to 1:15 (preferably 5:1 to 1:12; more preferably 1:1 to 1:10, most preferably 1:6 to 1:10).

[0024] Preferably, the concentrated laundry detergent composition of the present invention comprises 0% to 15% by weight (preferably 0.5% to 10% by weight; more preferably 1% to 7.5% by weight; most preferably 2% to 4% by weight) of fatty acids (preferably oleic acid) based on the weight of the concentrated laundry detergent composition.

[0025] Preferably, the concentrated laundry detergent composition of the present invention comprises 0% to 15% by weight (preferably 1% to 12% by weight; more preferably 3% to 10% by weight; most preferably 5% to 9% by weight) of a neutralizing agent (e.g., triethanolamine, diethanolamine, monoethanolamine, sodium hydroxide) based on the weight of the concentrated laundry detergent composition. More preferably, the concentrated laundry detergent composition of the present invention comprises 0% to 15% by weight (preferably 1% to 12% by weight; more preferably 3% to 10% by weight; most preferably 5% to 9% by weight) of a neutralizing agent based on the weight of the concentrated laundry detergent composition; wherein the neutralizing agent is selected from the group consisting of triethanolamine, diethanolamine, monoethanolamine, sodium hydroxide, and mixtures thereof. Most preferably, the concentrated laundry detergent composition of the present invention comprises 0% to 15% by weight (preferably 1% to 12% by weight; more preferably 3% to 10% by weight; most preferably 5% to 9% by weight) of a neutralizing agent based on the weight of the concentrated laundry detergent composition; wherein the neutralizing agent comprises monoethanolamine.

[0026] Preferably, the concentrated laundry detergent composition of the present invention further comprises additives. Preferably, the concentrated laundry detergent composition of the present invention further comprises additives selected from the group consisting of: amphoteric / amphoionic surfactants; bleaching activators (tetraacetylethylenediamine (TAED)); bleaching agents (e.g., sodium percarbonate, sodium perborate, sodium hypochlorite); builders (e.g., sodium bicarbonate, sodium carbonate, zeolite, sodium citrate, sodium tripolyphosphate, and aminocarboxylates (such as sodium methylglycine diacetate or sodium glutamate diacetate)); cationic surfactants; colorants; conditioning agents; dyes; enzymes (e.g., proteases, cellulases, lipases, amylases, mannanases); fillers; fluorescent whitening agents; foam control agents (e.g., polydimethylsiloxane); fragrances (e.g., essential oils, such as D-limonene); water-soluble growth promoters (e.g., sodium xylenesulfonate); optical brighteners; pigments; pH buffers; preservatives; rheology modifiers; stabilizers; structural agents; softeners (e.g., softening silicones, cationic polymers) and mixtures thereof.

[0027] Preferably, the method of washing soiled cotton articles according to the present invention includes: providing soiled cotton articles; providing washing water; providing rinsing water; providing the concentrated laundry detergent composition of the present invention; applying the washing water and the concentrated laundry detergent composition to the soiled cotton articles to provide washed cotton articles; and then rinsing the washed cotton articles with rinsing water.

[0028] Preferably, in the method for washing soiled cotton articles according to the present invention, the soiled cotton articles are treated with a concentrated laundry detergent composition and wash water using well-known techniques. Preferably, the concentrated laundry detergent composition and wash water are mixed at a weight ratio of 1:100 to 1:1,000.

[0029] Some embodiments of the present invention will now be described in detail in the following examples.

[0030] Experimental materials

[0031]

[0032] Synthesis of S1:C 12 EO

[0033] In the etherification of 1-dodecene and monoethylene glycol using a catalyst, a 3-liter (L) three-necked round-bottom glass flask equipped with a top-mounted stirrer with stirring via the central neck, a reflux condenser, and a heating jacket was used. A paddle impeller was used for stirring to ensure good mixing. A reaction mixture of 551.7 g of ethylene glycol and 505.8 g of 1-dodecene was prepared and charged into the reactor at 23 °C along with 61 g of powdered catalyst. The impeller stirring rate was set to 400 rpm. The reactor was heated to 135 °C over 30 minutes and maintained at 135 °C for 18 hours, then cooled to 23 °C by shutting off the heater. The reaction mixture was separated into monoethylene glycol and catalyst phases and an olefin phase using a separatory funnel.

[0034] The distillation apparatus consisted of a 1-liter round-bottom flask connected to a short-path distillation head with a thermometer fitting and a condenser with a vacuum fitting at the outlet. The flask was heated in an aluminum block using an IKA heating stirrer. The combined olefin phase was added to the distillation vessel, followed by stirring and evacuation. Obvious boiling was observed, but no condensate was observed or collected. The temperature of the heating block was increased to 75°C, and unreacted dodecane was collected at a head temperature of 25°C to 50°C and a pressure of 13.3 Pa to 40 Pa. The temperature of the heating block was gradually increased to 140°C at a pressure of 13 Pa, and the middle fraction containing both monoether alcohol ethoxylate and dodecene was recovered as the head temperature increased from 50°C to 75°C. C2 was collected at a head temperature of 70°C to 115°C and a pressure of 6 Pa to 33 Pa. 12 EO. Gradually increase the temperature of the heating block to 200°C, and at a pressure of 6 Pa, collect the intermediate fraction containing both monoether alcohol ethoxylate and diether when the head temperature rises from 115°C to 130°C. Stop distillation and collect the diether retained in the vessel. [The text abruptly ends here, likely due to an incomplete translation or missing information.] 12The EO is fed to the next sulfation process to prepare sulfate anionic surfactants.

[0035] Synthesis of S2:C 14 EO

[0036] When using a catalyst to etherify 1-tetradecene and monoethylene glycol, a 300 mL Parr reactor with a heating jacket and controller was used. A paddle impeller was used for stirring to ensure good mixing.

[0037] A reaction mixture of 100.0 g monoethylene glycol and 100.0 g 1-tetradecene was prepared and charged into a reactor at 23 °C along with 10.0 g powdered catalyst. The impeller stirring rate was set to at least 600 rpm. The reactor was heated to 135 °C over 30 minutes and maintained at 135 °C for 6 hours, then cooled to room temperature by turning off the heater. The reaction mixture was separated using a separatory funnel. The reaction mixture was separated into monoethylene glycol and catalyst phases, as well as olefin phases, using a separatory funnel. Fifteen batches were produced; the olefin phases were collected and combined for distillation.

[0038] C was distilled using the same distillation apparatus as that used in synthesis S1. 14 EO. The product from the olefin phase generated during multiple batch reactor operations was charged into a distillation vessel, then stirred and evacuated. Obvious boiling was observed, but no condensate was observed or collected. The temperature of the heating block was increased to 95°C, and unreacted 1-tetradecene was collected at a head temperature of 30°C to 60°C and a pressure of 27 Pa to 5 Pa. The temperature of the heating block was gradually increased to 170°C, and at a pressure of 7 Pa to 5 Pa, the middle fraction containing both monoether and tetradecene was recovered when the head temperature increased from 60°C to 85°C. C was collected at a head temperature of 80°C to 115°C and a pressure of 8 Pa to 5 Pa. 14 EO. When the temperature of the distillation vessel is set to 170°C, distillation stops when no more material is distilled out.

[0039] Synthesis of S3:C 12 EO sulfate

[0040] All chemical operations were performed under a dry nitrogen atmosphere. Prior to the experiment, all glassware was heated in a laboratory oven to remove residual moisture. Dichloromethane (500 mL) and C2O2 prepared according to the synthesis of S1 were added to a 2 L three-necked round-bottom flask. 12EO (48.4 g, 0.21 mol, 1.0 equivalence). The reaction flask was equipped with a top-mounted mechanical stirrer, a feeding funnel, and a thermocouple. Next, chlorosulfonic acid (14.5 mL, 0.221 mol, 1.1 equivalence) was carefully loaded into the feeding funnel. The reaction flask was then immersed in an ice bath and cooled to 0°C for 20 minutes. After cooling, chlorosulfonic acid was added dropwise to the reaction flask over approximately 20 minutes at a rate of approximately 1.0 mL / min. During the addition of chlorosulfonic acid, the reaction temperature did not exceed 5°C. After the addition, the reactants were allowed to react, and the temperature was maintained between 0°C and 5°C for 3 hours. At this point, the reaction was neutralized by slowly adding dropwise an aqueous solution of NaOH (18.0 g of NaOH in 500 mL, 0.9 mol). The addition rate was slow enough that the temperature did not exceed 5°C during the addition. The addition of the NaOH aqueous solution continued until the reaction became alkaline. The dioxane content of the crude biphasic product was analyzed. Dichloromethane was then carefully removed from the crude two-phase product under vacuum. During the dichloromethane removal process, a large amount of foaming was observed. After dichloromethane removal, the remaining aqueous solution was placed in a freeze dryer / lyophilizer to obtain the secondary alcohol ethoxylate sulfate product, C. 12 EO sulfate, a white solid (47.7 g), was further purified by dissolving it in hot anhydrous ethanol (1 L), filtering, and recrystallizing upon cooling. The resulting solid was then dried in a vacuum oven. The purified product was used for performance and characteristic testing.

[0041] Synthesis of S4:C 14 EO sulfate

[0042] All chemical operations were performed under a dry nitrogen atmosphere. Prior to the experiment, all glassware was heated in a laboratory oven to remove residual moisture. Dichloromethane (500 mL) and C2 prepared according to the synthesis of S2 were added to a 2 L three-necked round-bottom flask. 14EO (49 g, 0.189 mol, 1.0 equivalence). The reaction flask was equipped with a top-mounted mechanical stirrer, a feeding funnel, and a thermocouple. Next, chlorosulfonic acid (13.0 mL, 0.199 mol, 1.1 equivalence) was carefully loaded into the feeding funnel. The reaction flask was then immersed in an ice bath and cooled to 0°C for 20 minutes. After cooling, chlorosulfonic acid was added dropwise to the reaction flask over approximately 20 minutes at a rate of approximately 1.0 mL / min. During the addition of chlorosulfonic acid, the reaction temperature did not exceed 5°C. After the addition, the reactants were allowed to react, and the temperature was maintained between 0°C and 5°C for 3 hours. At this point, the reaction was neutralized by slowly adding dropwise an aqueous solution of NaOH (18.0 g of NaOH in 500 mL, 0.9 mol). The addition rate was slow enough that the temperature did not exceed 5°C during the addition. The addition of the NaOH aqueous solution continued until the reaction became alkaline. The dioxane content of the crude biphasic product was analyzed. Dichloromethane was then carefully removed from the biphasic product under vacuum. A large amount of foaming was observed during the removal of DCM. After DCM removal, the remaining aqueous solution was placed in a freeze dryer / lyophilizer to obtain the secondary alcohol ethoxylate sulfate product. The product was then further purified by dissolving it in hot anhydrous ethanol (1 L), filtering, and recrystallizing upon cooling. The resulting solid was then dried in a vacuum oven. 14 The percentage of active sulfate in EO sulfate was determined by cation titration. The purified product was used for performance and characteristic testing.

[0043] Synthesis of S5: ALEO1 sulfate

[0044] ALEO1 sulfate was prepared from ALEO1 in the same manner as described in synthesis S3.

[0045] Synthesis of S6: SA3EO sulfate

[0046] SA3EO sulfate was prepared from SA3EO in the same manner as described in synthesis S3.

[0047] Synthesize S7:C 16 EO

[0048] A 2L glass reactor with a heating jacket and controller is used to etherify 1-tetradecene and monoethylene glycol using a catalyst. A paddle impeller is used for stirring to ensure good mixing.

[0049] A reaction mixture of 434.0 g monoethylene glycol and 537.0 g 1-hexadecene was prepared and charged into a reactor at 23 °C along with 48.0 g powdered catalyst. The impeller stirring rate was set to at least 600 rpm. The reactor was heated to 145 °C over 30 minutes and maintained at 145 °C for 7 hours, then cooled to room temperature by turning off the heater. The reaction mixture was separated using a separatory funnel. The reaction mixture was separated into monoethylene glycol and catalyst phases, as well as olefin phases, using a separatory funnel. Fifteen batches were produced, and the olefin phases were collected and combined for distillation.

[0050] C was distilled using the same distillation apparatus as used in synthesis S1. 16 EO. The product from the olefin phase generated during the operation of multiple batch reactors was charged into a distillation vessel, then stirred and evacuated. Obvious boiling was observed, but no condensate was observed or collected. The temperature of the heating block was increased to 250°C, and unreacted 1-hexadecene was collected under distillation head temperatures of 40°C to 130°C and a pressure of 5 mmHg. The temperature of the heating block was gradually increased to 320°C, and the intermediate fraction containing both monoether and hexadecene was recovered at a pressure of 1.13 mmHg as the head temperature increased from 40°C to 180°C. C was collected at a head temperature of 180°C and a pressure of 1.13 mmHg. 16 EO. When the temperature of the distillation vessel is set to 400°C, distillation stops when no more material is distilled out.

[0051] Synthesize S8:C 16 EO sulfate

[0052] All chemical operations were performed under a dry nitrogen atmosphere. Prior to the experiment, all glassware was heated in a laboratory oven to remove residual moisture. Dichloromethane (500 mL) and C2O2 prepared according to the synthesis of S7 were added to a 2 L three-necked round-bottom flask. 16EO (44.05 g, 0.154 mol, 1.0 equivalence). The reaction flask was equipped with a top-mounted mechanical stirrer, a feeding funnel, and a thermocouple. Next, chlorosulfonic acid (10.5 mL, 0.161 mol, 1.03 equivalence) was carefully loaded into the feeding funnel. The reaction flask was then immersed in an ice bath and cooled to 0°C for 20 minutes. After cooling, chlorosulfonic acid was added dropwise to the reaction flask over approximately 20 minutes at a rate of approximately 1.0 mL / min. During the addition of chlorosulfonic acid, the reaction temperature did not exceed 5°C. After the addition, the reactants were allowed to react, and the temperature was maintained between 0°C and 5°C for 3 hours. At this point, the reaction was neutralized by slowly adding dropwise an aqueous solution of NaOH (18.0 g of NaOH in 500 mL of aqueous solution, 0.9 mol). The addition rate was slow enough that the temperature did not exceed 5°C during the addition. NaOH was continued to be added until the reaction became alkaline. Dichloromethane was then carefully removed from the biphasic reactants under vacuum. A large amount of foaming was observed during the removal of DCM. After DCM removal, the remaining aqueous solution was placed in a freeze dryer to obtain the secondary alcohol ethoxylate sulfate product. The product was then further purified by dissolving it in hot anhydrous ethanol (1 L), filtering, and recrystallizing upon cooling. The resulting solid was then dried in a vacuum oven. 16 The percentage of active sulfate in EO sulfate was determined by cation titration.

[0053] Active sulfate (EO=0) content of surfactant

[0054] The concentrations of active sulfates in the surfactants indicated in Table 1 were determined using procedures improved from the following literature: Turney, ME, Cannell, DW, “Alkaline methylene blue method for determination of anionic surfactants and for amine oxides in detergents.”, J. Am. OilChem. Soc., Vol. 42, pp. 544-546 (1965); and Epton, SR, “A new method for the rapidtitrimetric analysis of sodium alkyl sulphates and related compounds.”, Trans. Faraday Soc., Vol. 44, pp. 226-230 (1948).

[0055] Number of moles of hyamine (Mol) H The determination of )

[0056] Sodium dioctyl sulfosuccinate (SDOSS), control solutionAdd 0.8 g (±0.1 mg) of sodium dioctyl sulfosuccinate of known purity (≥99%) to a 20 mL scintillation vial. Fill the vial with 10 mL of deionized water and transfer to a 250 mL volumetric flask. Repeat this process 3 to 5 times to ensure sample transfer. Once transfer is complete, dilute the sample to 250 mL with deionized water. Then stopper the flask and thoroughly mix the solution by repeatedly inverting the flask.

[0057] Methylene blue solution Add 0.050 g (±0.005 g) of methylene blue chloride to a 20 mL scintillation vial. Fill the vial with 10 mL of deionized water and transfer it to a 1 L graduated cylinder. Repeat this process 3 to 5 times to ensure sample transfer. Then dilute the methylene blue solution to 1 L with deionized water. Transfer this solution to a 2 L glass jar. After transfer, carefully add 10 mL of concentrated sulfuric acid and 50 g of anhydrous sodium sulfate to the methylene blue solution and mix thoroughly.

[0058] Hyamine 1622 solution Add 1.1 g of Hyamine 1622 to a 20 mL scintillation vial. Fill the vial with 10 mL of deionized water and transfer to a 1 L volumetric flask. Repeat this process 3 to 5 times to ensure sample transfer. Then dilute the sample to 1 L with deionized water. Thoroughly mix the solution by repeatedly inverting the flask, and then filter into a 1 L glass bottle.

[0059] Standardization of Hyamine Solution Pipette 5 mL of sodium dioctyl sulfosuccinate solution into a 100 mL glass bottle. Next, pipette 20 mL of methylene blue solution and 25 mL of chloroform. Cap the 100 mL bottle and shake vigorously for several seconds. Then, titrate the methylene blue / chloroform biphase mixture with Hyamine 1622 solution in 0.5 mL increments. After each addition, cap the bottle and shake vigorously. Continue adding Hyamine 1622 in 0.5 mL increments until the blue color of the chloroform layer (or lower layer) begins to migrate to the upper layer. At this point, reduce the increment of Hyamine 1622 to 0.1 mL and continue adding until the endpoint is reached. The endpoint is reached when the blue intensities of the two layers match. This standardization is performed in triplicate. Then, calculate the molar amount of Hyamine 1622 using the following formula. Mol H It is the number of moles of hyamine; CS Vol This is the volume of the control solution used in the test (i.e., 5 mL); CS mass It is the total number of grams of the control (SDOSS) added to the control solution; H CSVol This is the amount (mL) of hyamine solution required to reach the endpoint; CSMW This is the molecular weight of the control solution SDOSS (i.e., 444.56 g / mol).

[0060] Determination of active sulfates in surfactants

[0061] Weigh 0.9 to 1.1 g of surfactant sample, accurate to 0.1 mg, into a 20 mL scintillation vial. Fill the vial with 10 mL of deionized water and transfer to a 250 mL volumetric flask. Repeat this process 3 to 5 times to ensure proper sample transfer. After transfer, dilute the sample to 250 mL with deionized water. Stopper the flask and thoroughly mix the solution by repeatedly inverting it. Next, pipette 5 mL of the test sample solution into a 100 mL vial. Then, pipette 20 mL of methylene blue solution and 25 mL of chloroform into the 100 mL vial. Cover the vial and shake vigorously for a few seconds. Then, titrate the methylene blue / chloroform biphase mixture with Hyamine 1622 solution in 0.5 mL increments. After each addition, cover the vial and shake vigorously. Continue adding Hyamine 1622 in 0.5 mL increments until the blue color of the chloroform layer (or lower layer) begins to migrate upwards. At this point, reduce the incremental addition of Hyamine 1622 to 0.1 mL and continue adding until the endpoint is reached. The endpoint is the point where the color intensity of the two layers matches. Each sample is repeated in triplicate. The percentage of active sulfate (wt%) is calculated using the following formula: Where H SVol This refers to the volume (mL) of hyamine solution required to reach the endpoint; Mol H This is the number of moles of hyamine (determined from the standard solution described above); S MW It is the weight-average molecular weight (g / mol) of the surfactant; S Vol This is the volume of the surfactant being tested (i.e., 5 mL); S mass This represents the total number of grams (g) of surfactant added to 250 mL of solution. The results are provided in Table 1.

[0062] EO distribution of surfactants

[0063] The distribution of EO adducts in the surfactants listed in Table 1 was determined by NMR or UHPLC-MS, as indicated by the methods described below, and the results are provided in Table 1.

[0064] Nuclear magnetic resonance (NMR) characterization of EO distribution

[0065] The surfactant sample was prepared by dissolving the surfactant in deuterated dimethyl sulfoxide containing 0.025 M chromium acetylacetonate (III). The NMR spectrum of the sample was then acquired using a Bruker AVANCE 400 MHz NMR spectrometer equipped with a 10 mm cryogenic probe (set temperature 25 °C). 13 The C NMR parameters were set as follows: 90° pulse, reverse gating decoupling, 1.38 sec acquisition time, and 6.4 sec cycle delay. 2048 scans were collected. Data were processed in MNOVA, with chemical shifts based on the solvent peak at 39.52 ppm. DEPT-135 experiments were also conducted using the same parameters, but with a 2.0 sec cycle delay and 2048 scans. The proportions of different EO adducts were calculated by accumulating and comparing the intensities of ethylene oxide alcohol terminal groups (approximately 60 ppm to 61 ppm), ethylene oxide backbone groups (approximately 69 ppm to 70 ppm), ethylene oxide terminal ether peaks (approximately 71 ppm to 72 ppm), unreacted primary alcohol peaks (approximately 60 ppm to 61 ppm), and unreacted secondary alcohol peaks (approximately 65 ppm to 66 ppm).

[0066] Analysis of sodium lauryl ether sulfate by UHPLC-MS

[0067] Ultra-high performance liquid chromatography-mass spectrometry (UHPLC-MS) conditions:

[0068]

[0069] program Compositions containing commercially available surfactants were analyzed using ultra-high performance liquid chromatography-mass spectrometry (UHPLC-MS) equipped with electrospray ionization (ESI). For analysis, a stock solution of 25 ppm was prepared in a 50 / 50 methanol / water mixture. The alcohol ethoxylate samples were diluted 1:100 (two parallel samples) with a 50 / 50 methanol / water mixture and vortexed for several seconds. They were then diluted 1:10 with a 50 / 50 methanol / water mixture to obtain a final dilution of 1:1,000. ® LA-4 is used as a standard for 1 mole of commercially available sodium lauryl polyoxyethylene ether sulfate, and Ethal ® LA-7 is used as a commercially available 3 mol sodium lauryl polyoxyethylene ether sulfate standard. Calibration standards with concentrations of 10 ppm, 5 ppm, 2 ppm, and 1 ppm are prepared in a 50 / 50 methanol / water solution.

[0070] Alkyl sulfates were diluted from a 1:1,000 preparation solution with a 50 / 50 methanol / water solution to obtain a final solution of 1:20,000. POLYSTEP ®BN-5 is used as a standard for alkyl sulfate analysis. Standards with concentrations of 5 ppm, 2 ppm, 1 ppm, and 0.5 ppm are prepared in a 50 / 50 methanol / water solution.

[0071] Waters ACQUITY was used with a Waters BEH C18 1.7μm 1×50mm column. ® Samples were analyzed using a UPLC system. Mass spectrometry analysis was performed using a Waters LCT Premier TOF mass spectrometer equipped with ESI. Measurements were performed in both positive and negative ion modes. Each sample preparation solution was injected three times for analysis. The proportions of different EO adducts were calculated based on peak areas, and the results are recorded in Table 1.

[0072] Table 1

[0073]

[0074] In the products of synthesizing S4 and S5, at least 95 mol% of the oligomer has n=1, and no more than 5 mol% of the oligomer has n≥2. Specifically, in the products of synthesizing S4 and S5, ≥98 mol% of the oligomer has n=1, and ≤2 mol% of the oligomer has n≥2.

[0075] 1,4-Dioxane content of surfactant

[0076] The 1,4-dioxane content of the surfactants listed in Table 2 was measured by low-temperature gas chromatography-mass spectrometry (GC-MS) for the organic layer and liquid chromatography-mass spectrometry (LC-MS) for the aqueous layer, as detailed below, and the results are provided in Table 2.

[0077] Used for the determination of 1,4-dioxane in organic layers Gas chromatography-mass spectrometry (GC-MS) conditions :

[0078]

[0079] The standard was prepared by adding a solution of dioxane in tetrahydrofuran (“THF”) and diluting it to 0.1 ppm to 100 ppm.

[0080] Samples were prepared by mixing 3.3 g of the crude processed organic (DCM) layer with 6.7 g of THF, followed by shaking the solution for approximately 20 minutes. The solids were then centrifuged to the bottom, and the supernatant was transferred to an autosampler vial. Spiked samples were prepared by adding a THF solution of dioxane standard at 5 ppm to 10 ppm to individual samples.

[0081] Used for the determination of 1,4-dioxane content in aquatic layers. Liquid chromatography-mass spectrometry (LC-MS) conditions :

[0082]

[0083] Samples were injected either in pure form or after dilution with water at a ratio of 1:4. Standards were prepared by preparing a THF stock solution of dioxane and diluting it with water to a concentration of 0.1 ppm to 100 ppm.

[0084] Calculation of dioxane content relative to solids

[0085] The dioxane content relative to the solid content in the sample (ppm) is calculated using the following equation.

[0086]

[0087] Table 2

[0088]

[0089] Gas chromatography results of SA3EO sulfate surfactants showed that secondary alcohols containing an average of 3 moles of ethylene oxide per molecule contained 2 ppm of 1,4-dioxane in the organic phase at 110 °C, indicating that structures with n ≥ 2 may produce 1,4-dioxane. Interestingly, when the inlet temperature was increased to 280 °C, the 1,4-dioxane content of SA3EO sulfate in the organic phase increased from 2 ppm to 1,471 ppm. This result indicates that sulfated surfactants with n ≥ 2 may produce observable 1,4-dioxane at 110 °C, but also suggests that such surfactants may be unstable at higher temperatures of 280 °C, leading to significant 1,4-dioxane formation. Similar to SA3EO sulfate, gas chromatography results of ALEO1 sulfate surfactants showed that at 110 °C, >9 ppm of 1,4-dioxane was formed relative to the solid. Furthermore, the ALEO1 sulfate surfactant also exhibited the formation of a large amount of 1,4-dioxane (259 ppm) at 280 °C, indicating that the ALEO1 sulfate surfactant lacks stability at high temperatures. The present invention C 12 EO sulfate surfactants (≥95 mol% n=1 and ≤5 mol% n=2) exhibit low 1,4-dioxane content. Surprisingly, the C of this invention... 12 The EO sulfate surfactant also exhibited extremely low 1,4-dioxane content, below the limits of detection (LOD) of both GC and LC methods. Based on the LOD, this indicates that at 110 °C, relative to the solid, C 12 The dioxane content of EO sulfate is <1.6 ppm. Interestingly, when the inlet temperature rises to 280°C, the C of this invention... 12 The 1,4-dioxane content in the EO sulfate material remained below 1 ppm (i.e., 0.58 ppm), indicating that, compared to the control material, the C content of the present invention...12 EO sulfate has higher thermal stability.

[0090] Comparative Examples CF1-CF2 and Examples F1-F8: Detergent Compositions

[0091] Concentrated laundry detergent compositions were prepared in each of Comparative Examples CF1-CF2 and Examples F1-F8. These aqueous laundry detergent compositions had formulations with a pH of 8-8.5 as described in Table 3 and were prepared using standard laundry detergent formulation preparation procedures. The formulation stability of the concentrated laundry detergent compositions was observed, and those exhibiting phase separation were identified as unstable. These observations are reported in Table 3.

[0092]

[0093] Primary cleaning performance

[0094] The primary cleaning performance of the liquid laundry detergent formulations of Comparative Examples CF1-CF4 and Examples F1-F8 was estimated in a Launder-Ometer (SDL Atlas, model M228AA) using a 30-minute wash cycle at a set test temperature of 22°C. Twenty 1.2-liter tanks were used per run, each tank filled with 500 mL of Ca at 100 ppm by weight. 2+ :Mg 2+ The hardness was adjusted to a molar ratio of 2:1. The washed fabrics were then rinsed at ambient temperature in an Eberbach E6000 reciprocating shaker at 300 mL of 100 ppm (2 / 1 Ca) water. 2+ / Mg 2+ The soiled fabric was rinsed for 5 minutes at 260 osc / min pm in hardness-adjusted water. The soiled fabric and soiled ballast used in the test were PCS-S-94 sebum / dust ASTM stains from Testfabrics sewn to pre-shrinked double cotton fabric. The double cotton fabric was 5x5 cm in size. The soiled sample was 2.5x3 cm. A 5x5 cm cut SBL-CFT soiled ballast was added to each tank to provide a baseline soiling for the wash solution. The total surfactant concentration in the wash solution was 200 ppm.

[0095] Reflectance measurement and Stain Removal Index (SRI)

[0096] The Stain Removal Index (SRI) of each liquid laundry detergent formulation evaluated in the primary cleaning performance test was determined using ASTM Method D4265-14. The average SRI obtained from eight samples (two samples per can, four cans) for each condition is provided in Table 4.

[0097] L of the soiled fabric * a* and b * The L value was measured before and after washing using a Mach 5 spectrophotometer from Colour Consult. L value for unwashed, uncontaminated polyester-cotton fabric. * a * and b * The value is measured in the following SRI calculation: Where US represents the area of ​​the unwashed stain, UF represents the area of ​​the unwashed (unstained) fabric, WS represents the area of ​​the washed stain, and ΔE * (US-UF) ΔE is the distance between the unwashed stain and the unwashed fabric. * Color difference, and ΔE * (WS-UF) ΔE is the distance between washed stains and unwashed fabric. * Color difference. ΔE * The value is calculated as .

[0098] Table 4

[0099]

[0100] Anti-redeposition

[0101] The anti-redeposition performance of the combination of standard liquid laundry detergent and cleaning enhancer in Comparative Examples CF1-CF4 and Examples F1-F8 was estimated in a Terg-o-tometer of model 7243ES under the conditions shown in Table 5 with 90 cycles of agitation per minute.

[0102] Table 5

[0103]

[0104] Redeposition resistance was determined by calculating ΔE, measured using a MACH 5+ instrument (L, a & b). The results are recorded in Table 6, where ΔE... * According to the following equation: Where ΔE aw Measured from the washed fabric, and ΔE bw Measured from the fabric before washing. Higher ΔE * This corresponds to better resistance to redeposition.

[0105] Table 6

[0106]

Claims

1. A concentrated laundry detergent composition, said concentrated laundry detergent composition comprising: A solvent system, wherein the solvent system is a mixture of water and non-aqueous solvents; Cleaning surfactant; wherein the cleaning surfactant comprises blends of the following: Nonionic surfactants; Anionic alcohol ethoxysulfate surfactant of formula I Where R 1 and R 2 Each is C independently 1-16 alkyl groups; wherein R 1 and R 2 The total number of carbon atoms in the middle ranges from 7 to 17; of which M + It is the balanced I-SO3 - An anion with a negatively charged cation; and wherein n is 1 in 95 mol% to 100 mol% of the anionic alcohol ethoxysulfate surfactant of formula I; and Optionally, an anionic surfactant may be added; and Optional fatty acids; and Optional neutralizing agent; The concentrated laundry detergent composition contains <15% by weight of water based on the weight of the concentrated laundry detergent composition.

2. The concentrated laundry detergent composition of claim 1, wherein the concentrated laundry detergent composition comprises 25% to 65.1% by weight of a non-aqueous solvent based on the weight of the concentrated laundry detergent composition.

3. The concentrated laundry detergent composition according to claim 2, wherein the anionic alcohol ethoxysulfate surfactant of formula I contains <9 ppm of 1,4-dioxane.

4. The concentrated laundry detergent composition according to claim 3, wherein the concentrated laundry detergent composition contains <1% by weight of an alcohol sulfate surfactant of formula II based on the solids weight of the concentrated laundry detergent composition. Where R 3 and R 4 Each is C independently 1-16 alkyl groups; wherein R 3 and R 4 The total number of carbon atoms in the middle ranges from 7 to 17; and A in this range... + It is -SO3 in Equilibrium II - An anion is a negatively charged cation.

5. The concentrated laundry detergent composition of claim 4, wherein the concentrated laundry detergent composition contains 1% to <10% by weight of water based on the weight of the concentrated laundry detergent composition; and wherein the concentrated laundry detergent composition further comprises: an additional anionic surfactant; a fatty acid; and a neutralizing agent.

6. The concentrated laundry detergent composition according to claim 5, wherein the laundry detergent formulation comprises: The solvent system comprises 35% to 61% by weight of the concentrated laundry detergent composition. The fatty acids comprise 1% to 7.5% by weight of the concentrated laundry detergent composition. The neutralizing agent comprises 3% to 10% by weight of the concentrated laundry detergent composition; and The cleaning surfactant comprises 35% to 55% by weight of the concentrated laundry detergent composition; wherein the cleaning surfactant comprises a blend of the following: The nonionic surfactant comprises 2% to 15% by weight of the laundry detergent formulation. Based on the laundry detergent formulation, 6% to 15% by weight of the anionic alcohol ethoxysulfate surfactant of Formula I; and The additional anionic surfactant is 5% to 47% by weight based on the weight of the laundry detergent formulation. The weight ratio of the nonionic surfactant to the anionic surfactant in the blend is 1:1 to 1:

10.

7. The concentrated laundry detergent composition according to claim 6, wherein the additional anionic surfactant is a linear alkylbenzene sulfonate surfactant.

8. The concentrated laundry detergent composition according to claim 7, further comprising an additive selected from the group consisting of: amphoteric / amphoionic surfactants; bleaching activators; bleaching agents; detergent builders; cationic surfactants; colorants; conditioning agents; dyes; enzymes; fillers; fluorescent whitening agents; foam control agents; fragrances; water-soluble growth promoters; optical brighteners; organic solvents; pigments; pH buffers; preservatives; rheology modifiers; stabilizers; structural agents; softeners; and mixtures thereof.

9. A method for washing soiled cotton products, the method comprising: Provide soiled cotton products; Provide a laundry detergent composition according to claim 1; Provide washing water; Provide rinsing water; The washing water and the laundry detergent composition are applied to the soiled cotton product to provide a washed cotton product; And to rinse the washed cotton products with the rinse water.

10. The method of claim 9, wherein the concentrated laundry detergent composition is the concentrated laundry detergent composition of claim 8.

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