Silicone-deposited laundry detergent formulations

Abstract

The present invention provides a laundry detergent formulation comprising: water; alcohol ethoxysulfate surfactants of formula (I) wherein R1 and R2 are C1-16 alkyl groups; 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 x is 1 in 95 mol% to 100 mol% of an alcohol ethoxysulfate surfactant of formula (I); fabric softening organic silicon; and a deposition aid polymer, wherein the deposition aid polymer is a dextran matrix polymer functionalized with a quaternary ammonium moiety; wherein the deposition aid polymer has a Kjeldahl nitrogen content TKN of from 0.5 wt% to 5 wt%; and wherein the deposition aid polymer comprises lt; and 0.1% of bonds, the bonds between glucose units in the deposition aid polymer being beta-1, 3 bonds.

Description

[0001] This invention relates to laundry detergent formulations. Specifically, this invention relates to a laundry detergent formulation comprising: water; an 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 x is 1 in 95 mol% to 100 mol% of an alcohol ethoxysulfate surfactant of formula I; a fabric softening silicone; and a deposition aid polymer, wherein the deposition aid polymer is a dextran-based polymer with quaternary ammonium partial functionalization; wherein the deposition aid polymer has a Kjeldahl nitrogen content (TKN) of 0.5 wt% to 5 wt%; and wherein the deposition aid polymer contains <0.1% bonds, wherein the bonds between the glucose units in the deposition aid polymer are β-1,3 bonds.

[0002] Laundry detergent formulations typically include anionic surfactants as the primary soap foam generator, as well as secondary surfactants. Alkyl ethoxysulfate anionic surfactants (e.g., alcohol ethoxysulfate surfactants (AES)) have established use in various laundry detergent formulations as conventional AES anionic surfactants; this is associated with undesirable 1,4-dioxane levels. Regulators have been tightening restrictions on the potential presence of 1,4-dioxane 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] Therefore, there is still a need for laundry detergent formulations containing anionic alcohol ethoxysulfate surfactants that resist the formation of 1,4-dioxanes during the sulfation process that forms the surfactant and subsequently when the alcohol ethoxysulfate surfactant is exposed to high temperatures up to 280°C.

[0006] This invention provides a laundry detergent formulation comprising: water; an alcohol ethoxysulfate surfactant of formula I; wherein R 1 and R 2 Each is C independently 1-16 alkyl groups; wherein R 1 and R2 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 x is 1 in 95 mol% to 100 mol% of an alcohol ethoxysulfate surfactant of formula I; a fabric softening silicone; and a deposition aid polymer, wherein the deposition aid polymer is a dextran-based polymer with quaternary ammonium partial functionalization; wherein the deposition aid polymer has a Kjeldahl nitrogen content (TKN) of 0.5 wt% to 5 wt%; and wherein the deposition aid polymer contains <0.1% bonds, wherein the bonds between the glucose units in the deposition aid polymer are β-1,3 bonds.

[0007] This invention provides a laundry detergent formulation comprising: water; an alcohol ethoxysulfate surfactant of formula I; 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 the balanced I-SO3 - An anion with a negatively charged cation; wherein x is 1 in 95 mol% to 100 mol% of an alcohol ethoxysulfate surfactant of formula I; a fabric softening silicone; and a deposition aid polymer, wherein the deposition aid polymer is a dextran-based polymer partially functionalized with quaternary ammonium; wherein the dextran-based polymer is a branched dextran polymer comprising multiple glucose structural units; wherein 90 mol% to 98 mol% of the glucose structural units are linked by α-D-1,6 bonds, and 2 mol% to 10 mol% of the glucose structural units are linked by α-1,3 bonds; wherein the dextran-based polymer has a weight-average molecular weight of 100,000 Daltons to 700,000 Daltons; wherein the deposition aid polymer has a Kjeldahl nitrogen content (TKN) of 0.5 wt% to 5 wt%; wherein the deposition aid polymer contains <0.1% β-1,3 bonds between the glucose units in the deposition aid polymer.

[0008] This invention provides a laundry detergent formulation comprising: water; an alcohol ethoxysulfate surfactant of formula I; 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 the balanced I-SO3 -An anionic, negatively charged cation; wherein x is 1 in 95 mol% to 100 mol% of an alcohol ethoxysulfate surfactant of Formula I; a fabric-softening silicone; and a deposition aid polymer, wherein the deposition aid polymer is a dextran-based polymer with quaternary ammonium partial functionalization of Formula II. in X is a pendant oxygen affixed to a dextran-based polymer; wherein X is a divalent linking group that bonds a quaternary ammonium nitrogen affixed to a pendant oxygen affixed to the dextran-based polymer; wherein the dextran-based polymer is a branched dextran polymer comprising multiple glucose structural units; wherein 90 mol% to 98 mol% of the glucose structural units are linked by α-D-1,6 bonds, and 2 mol% to 10 mol% of the glucose structural units are linked by α-1,3 bonds; wherein the dextran-based polymer has a weight-average molecular weight of 100,000 Daltons to 700,000 Daltons; wherein each R 7 Choose C independently 1-7 The group consisting of alkyl groups; and wherein R 8 Choose C freely 1-22 The group consisting of alkyl groups; wherein the deposition aid polymer has a Kjeldahl nitrogen content of 0.9% to 1.5% by weight (TKN); and wherein the deposition aid polymer contains <0.1% bonds, and the bonds between the glucose units in the deposition aid polymer are β-1,3 bonds.

[0009] This invention provides a laundry detergent formulation comprising: water; an alcohol ethoxysulfate surfactant of formula I; 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 the balanced I-SO3 - An anionic, negatively charged cation; wherein x is 1 in 95 mol% to 100 mol% of an alcohol ethoxysulfate surfactant of formula I; a fabric-softening silicone; and a deposition aid polymer, wherein the deposition aid polymer is a dextran-based polymer having a quaternary ammonium partial functionalization of formula III. in It is the pendant oxygen on the dextran-based polymer; where R 7 and R 8 Each is a methyl group; where R 11It is hydrogen; wherein the dextran matrix polymer is a branched dextran polymer containing multiple glucose structural units; wherein 90 mol% to 98 mol% of the glucose structural units are linked by α-D-1,6 bonds, and 2 mol% to 10 mol% of the glucose structural units are linked by α-1,3 bonds; wherein the dextran matrix polymer has a weight-average molecular weight of 100,000 Daltons to 700,000 Daltons; wherein the deposition aid polymer has a Kjeldahl nitrogen content (TKN) of 0.9 wt% to 1.5 wt%; and wherein the deposition aid polymer contains <0.1% β-1,3 bonds between the glucose units in the deposition aid polymer.

[0010] The present invention provides a method for depositing organosilicon on cotton, the method comprising: providing a soiled cotton garment article; selecting a laundry detergent formulation of the present invention having a synergistic combination of an alcohol ethoxysulfate surfactant of Formula I and a modified carbohydrate polymer; providing bath water; and applying the bath water and the laundry detergent formulation to the soiled cotton garment article to provide a clean cotton garment article; wherein fabric-softening organosilicon is associated with a clean cotton garment article. Detailed Implementation

[0011] In addition to resisting the formation of 1,4-dioxane during the sulfation process of the Formula I alcohol ethoxysulfate surfactant and subsequently when the Formula I alcohol ethoxysulfate surfactant is exposed to high temperatures up to 280°C during processing, storage and / or treatment; it was surprisingly found that the combination of this Formula I alcohol ethoxysulfate surfactant (as described herein) and the deposition aid polymer (as described herein) significantly improved the deposition of silicone from laundry detergent onto cotton fabrics during washing.

[0012] Unless otherwise specified, ratios, percentages, parts, etc. are all by weight (e.g., "ppm" means parts per million by weight).

[0013] As used herein and in the appended claims, the term "solid weight" in relation to laundry detergent formulations and alcohol ethoxysulfate surfactants of Formula I means dry weight, i.e., excluding any water that may be present.

[0014] As used herein, unless otherwise specified, the phrase "molecular weight" or M WThis refers to the weight-average molecular weight as measured using conventional methods with gel permeation chromatography (GPC) and conventional standards (such as polyethylene glycol standards). GPC techniques are discussed in detail in *Modern Size-Exclusion Liquid Chromatography – Practice of Gel Permeation and Gel Filtration Chromatography*, 2nd Edition, AM Striegel, WW Yau, JJ Kirkland, DD Bly; John Wiley & Sons, Inc. 2009. Molecular weights are reported in Daltons or, equivalently, g / mol.

[0015] Preferably, the laundry detergent formulation of the present invention comprises: water (preferably, 43% to 94.9% by weight based on the weight of the laundry detergent formulation; more preferably, 45% to 94% by weight; still more preferably, 57.5% to 85% by weight; most preferably, 70% to 75% by weight)); an alcohol ethoxysulfate surfactant of Formula I (preferably, 0.01% to 35% by weight based on the weight of the laundry detergent formulation; more preferably, 0.1% to 20% by weight; still more preferably, 1% to 15% by weight; most preferably, 2.5% to 10% by weight) of an alcohol ethoxysulfate surfactant of Formula I). Where R 1 and R 2 Each is C independently 1-16 Alkyl groups (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 11 to 15; still more preferably 11 to 13; most preferably 11 or 13) (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 10-12 Alkyl group; most preferably, wherein R 1 It is a methyl group, and R 2 It is a straight chain C 10 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 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 The following are determined by nuclear magnetic resonance characterization: fabric softening silicone (preferably, 0.05 wt% to 12 wt% (preferably, 0.1 wt% to 10 wt%; more preferably, 1 wt% to 7.5 wt%; most preferably, 3 wt% to 7 wt%) based on the weight of the laundry detergent formulation); and deposition aid polymer (preferably, 0.5 wt% to 10 wt% (preferably, 0.1 wt% to 8 wt% (more preferably, 0.5 wt% to 5 wt%; most preferably, 2 wt% to 3 wt%) based on the weight of the laundry detergent formulation), wherein the deposition aid polymer is a dextran-based polymer with quaternary ammonium partial functionalization (preferably, wherein the quaternary ammonium portion has Formula II). in X is a pendant oxygen on a dextran-based polymer; wherein X is a divalent linking group that bonds the quaternary ammonium nitrogen to the pendant oxygen on the dextran-based polymer (preferably, wherein X is selected from divalent hydrocarbon groups, which may optionally be replaced by (e.g., hydroxyl groups, alkoxy groups, ether groups); more preferably, wherein X is -CH2CH(OR) 11 CH2- group; wherein R 11 Choose the group consisting of: hydrogen and C 1-4 Alkyl groups (preferably hydrogen; most preferably, X is a -CH2CH(OH)CH2- group); wherein each R 7 Choose independently the group consisting of the following items: C 1-7 Alkyl groups (preferably, C 1-3 Alkyl groups; more preferably, methyl groups and ethyl groups; most preferably, methyl groups); and wherein each R 8 Choose independently the group consisting of the following items: C 1-22 Alkyl groups (preferably selected from the group consisting of: C 1-3 alkyl groups and C6-22 Alkyl groups; more preferably, methyl groups and ethyl groups; most preferably, methyl groups); (preferably, the dextran-based polymer has a weight-average molecular weight of 50,000 Daltons to 2,000,000 Daltons (preferably, 75,000 Daltons to 1,000,000 Daltons; more preferably, 80,000 Daltons to 750,000 Daltons; most preferably, 100,000 Daltons to 700,000 Daltons); wherein the deposition aid polymer has a Kjeldahl nitrogen content (TKN) of 0.5 wt% to 5 wt% (preferably, 0.75 wt% to 2.5 wt%; more preferably, 0.8 wt% to 2 wt%; most preferably, 0.9 wt% to 1.5 wt%); and wherein the deposition aid polymer contains <0.1% bonds, and the bonds between the glucose units in the deposition aid polymer are β-1,3 bonds.

[0016] Preferably, the laundry detergent formulation of the present invention comprises: 43% to 94.9% by weight (preferably 45% to 94% by weight; more preferably, 57.5% to 85% by weight; most preferably, 70% to 75% by weight) of water based on the weight of the laundry detergent formulation. More preferably, the laundry detergent formulation of the present invention comprises: 43% to 94.9% by weight (preferably 45% to 94% by weight; more preferably, 57.5% to 85% by weight; most preferably, 70% to 75% by weight) of water based on the weight of the laundry detergent formulation; wherein the water is at least one of distilled water, deionized water, and industrial soft water. Still more preferably, the laundry detergent formulation of the present invention comprises: 43% to 94.9% by weight (preferably 45% to 94% by weight; more preferably, 57.5% to 85% by weight; most preferably, 70% to 75% by weight) of water based on the weight of the laundry detergent formulation, wherein the water is distilled and deionized. Most preferably, the laundry detergent formulation of the present invention comprises: 43% to 94.9% by weight (preferably 45% to 94% by weight; more preferably 57.5% to 85% by weight; most preferably 70% to 75% by weight) of water based on the weight of the laundry detergent formulation, wherein the water is distilled, deionized and industrially softened to avoid introducing undesirable metal ions into the laundry detergent formulation.

[0017] Preferably, the laundry detergent formulation of the present invention comprises, based on the weight of the laundry detergent formulation, 0.01% to 35% (preferably 0.1% to 20%; more preferably 1% to 15%; most preferably 2.5% to 10%) of an alcohol ethoxysulfate surfactant of formula I; wherein R 1 and R 2 Each is C independently1-16 Alkyl groups (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 11 to 15; still more preferably 11 to 13; most preferably 11 or 13) (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 10-12 Alkyl group; most preferably, wherein R 1 It is a methyl group, and R 2 It is a straight chain C 10 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 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).

[0018] Preferably, the alcohol ethoxysulfate surfactant of Formula I comprises 1,4-dioxane (preferably, <8ppm; more preferably, <7ppm; still more preferably, <6ppm; even more preferably, <5ppm; still more preferably, <4ppm; still more preferably, <3ppm; even more preferably, <2ppm; even more preferably, <1ppm; even more preferably, <0.25ppm; most preferably, below the detection limit) based on a solid weight of <9ppm (preferably, <8ppm; more preferably, <7ppm; still more preferably, <6ppm; still more preferably, <5ppm; still more preferably, <4ppm; still more preferably, <3ppm; even more preferably, <2ppm; even more preferably, <1ppm; even more preferably, <0.25ppm; most preferably, below the detection limit) of the alcohol ethoxysulfate surfactant of Formula I.

[0019] Preferably, the alcohol ethoxysulfate surfactant of Formula I contains an alcohol sulfate surfactant of Formula IV with a solid weight of <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) based on the alcohol ethoxysulfate surfactant of Formula I. Where R 9 and R 10 Each is C independently 1-16 Alkyl groups (preferably, C 1-15 Alkyl groups; more preferably, C 1-14 Alkyl group; most preferably, straight-chain C 1-13 ); where R 9 and R 10 The total number of carbon atoms is 7 to 17 (preferably 10 to 16; more preferably 11 to 15; still more preferably 11 to 13; most preferably 11 or 13) (preferably, where R 7 and R 8 It is a straight-chain alkyl group; more preferably, wherein R 9 It is a methyl group, and R 10 It is a straight chain C 10-12 Alkyl group; most preferably, wherein R 9 It is a methyl group, and R 10 It is a straight chain C 10 alkyl group); and wherein A + It is the -SO3 in the 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).

[0020] Preferably, the laundry detergent formulation of the present invention comprises an alcohol ethoxysulfate surfactant of Formula I as described above, wherein the alcohol ethoxysulfate surfactant of Formula I has improved thermal stability. More preferably, the laundry detergent formulation of the present invention comprises an alcohol ethoxysulfate surfactant of Formula I as described above, wherein the 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 1,4-dioxane (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 the alcohol ethoxysulfate surfactant of Formula I at a solid weight of <9 ppm (preferably, <8 ppm; more preferably, <7 ppm; still more preferably, <6 ppm; still 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) 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 alcohol ethoxysulfate surfactant of Formula I contains <10 ppm of 1,4-dioxane by solid weight based on the 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).

[0021] Preferably, the laundry detergent formulation of the present invention comprises: 0.05% to 12% by weight (preferably 0.1% to 10% by weight; more preferably 0.1% to 7.5% by weight; most preferably 3% to 7% by weight) of fabric softening silicone based on the weight of the laundry detergent formulation; wherein the fabric softening silicone is selected from the group consisting of nitrogen-free silicone polymers, anionic silicone polymers, nonionic silicone polymers, and mixtures thereof. More preferably, the laundry detergent formulation of the present invention comprises: 0.05% to 12% by weight (preferably 0.1% to 10% by weight; more preferably 0.1% to 7.5% by weight; most preferably 3% to 7% by weight) of fabric softening silicone based on the weight of the laundry detergent formulation; wherein the fabric softening silicone is selected from the group consisting of nitrogen-free silicone polymers, anionic silicone polymers, nonionic silicone polymers, and mixtures thereof; and wherein the fabric softening silicone is in the form of an emulsion (preferably, wherein the silicone emulsion is a nonionic emulsion of high molecular weight polydimethylsiloxane, such as polydimethylsiloxane (and) lauryl polyoxyethylene ether-4 (and) lauryl polyoxyethylene ether-23).

[0022] Preferred nitrogen-free organosilicon polymers include nonionic nitrogen-free organosilicon polymers, zwitterionic nitrogen-free organosilicon polymers, zwitterionic nitrogen-free organosilicon polymers, and mixtures thereof. Preferred nitrogen-free organosilicon polymers have formula V, VI, or VII (preferably formula V or VII): Each R 4 Choose independently the group consisting of the following items: C 1-20 alkyl groups, C 2-20 alkenyl group, C 6-20 aryl group, C 7-20 arylalkyl group, C 7-20 alkylaryl group, C 7-20 aryl alkenyl groups and C 7-20 Alkenyl aryl group (preferably, wherein R 4 Select from the group consisting of: methyl groups, phenyl groups, and phenylalkyl groups); where each R 5 Independently select from the group consisting of: -OH group, C 1-20 alkyl groups, C 2-20 alkenyl group, C 6-20 aryl group, C 7-20 arylalkyl group, C 7-20 alkylaryl group, C 7-20aryl alkenyl group, C 7-20 Alkenyl aryl groups and poly(ethylene oxide / propylene oxide) copolymer groups having formula VIII Each R 6 Choose independently the group consisting of the following items: hydrogen, C 1-4 Alkyl groups and acetyl groups; wherein a has a value such that the viscosity of the nitrogen-free organosilicon polymer according to formula V or formula VII at 20°C is from 2 centiliters to 50,000,000 centiliters (preferably from 10,000 centiliters to 10,000,000 centiliters at 20°C); wherein b is from 1 to 50 (preferably from 1 to 30); wherein c is from 1 to 50 (preferably from 1 to 30); wherein n is from 1 to 50 (preferably from 3 to 5); wherein m is from 1 to 100 (preferably from 6 to 100); wherein p is from 0 to 14 (preferably from 0 to 3); wherein m + p is from 5 to 150 (preferably from 7 to 100) (preferably, wherein R 5 Select from the group consisting of: -OH groups, methyl groups, phenyl groups, phenylalkyl groups, and groups having formula VIII). The most preferred nitrogen-free organosilicon polymer has formula VII, wherein R 4 It is methyl and wherein a has a value that makes the viscosity of the nitrogen-free organosilicon polymer at 20°C between 60,000 centistokes and 5,000,000 centistokes.

[0023] Preferred nitrogen-free organosilicon polymers include anionic organosilicon polymers. Anionic organosilicon polymers are described, for example, in "The Encyclopedia of Polymer Science," Volume 11, page 765. Examples of anionic organosilicon polymers include organosilicon polymers incorporating functional groups of carboxylic acids, sulfates, sulfonic acids, phosphates, and / or phosphonates. Preferred anionic organosilicon polymers incorporate carboxyl functional groups (e.g., carboxylic acids or carboxylate anions). Preferred anionic organosilicon polymers have a weight-average molecular weight of 1,000 Daltons to 100,000 Daltons (preferably 2,000 Daltons to 50,000 Daltons; more preferably 5,000 Daltons to 50,000 Daltons; most preferably 10,000 Daltons to 50,000 Daltons). Preferably, the anionic organosilicon polymer has an anionic group content of at least 1 mol% (more preferably, at least 2 mol%). Preferably, the anionic groups on the anionic organosilicon polymer are not located at the end positions of the longest linear organosilicon chains. Preferred anionic silicone polymers have anionic groups at the mid-chain positions of the silicone. More preferred anionic silicone polymers have anionic groups located at least 5 silicone atoms from the end of the longest linear silicone chain in the anionic silicone polymer.

[0024] Preferably, the laundry detergent formulation of the present invention comprises a deposition aid polymer; wherein the deposition aid polymer is a quaternary ammonium partially functionalized dextran-based polymer; wherein the deposition aid polymer enhances the deposition of silicone from the laundry detergent formulation onto the fabric (preferably, cotton fabric). More preferably, the laundry detergent formulation of the present invention comprises 0.5% to 10.0% by weight (preferably 0.1% to 8% by weight; more preferably 0.5% to 5% by weight; most preferably 2% to 3% by weight) of a deposition aid polymer based on the weight of the laundry detergent formulation; wherein the deposition aid polymer is a quaternary ammonium partially functionalized dextran-based polymer; wherein the deposition aid polymer enhances the deposition of silicone from the laundry detergent formulation onto the fabric (preferably, cotton fabric). Most preferably, the laundry detergent formulation of the present invention comprises, by weight, 0.5% to 10.0% (preferably 0.1% to 8%; more preferably 0.5% to 5%; most preferably 2% to 3%) of a deposition aid polymer; wherein the deposition aid polymer is a dextran-based polymer partially functionalized with quaternary ammonium; wherein the deposition aid polymer reinforces the deposition of silicone from the laundry detergent formulation onto the fabric (preferably cotton); wherein the Kjeldahl nitrogen content (TKN) of the deposition aid polymer, corrected for ash and volatiles, is 0.5% to 5% (preferably 0.75% to 2.5%; more preferably 0.8% to 2%; most preferably 0.9% to 1.5%) (measured according to ASTM method D-2364); and wherein the deposition aid polymer reinforces the deposition of silicone from the laundry detergent formulation onto the fabric (preferably cotton).

[0025] Preferably, the deposition aid polymer is a quaternary ammonium partially functionalized dextran-based polymer. More preferably, the deposition aid polymer is a quaternary ammonium partially functionalized dextran-based polymer; wherein the dextran-based polymer is a branched dextran polymer. Still more preferably, the deposition aid polymer is a quaternary ammonium partially functionalized dextran polymer; wherein the dextran-based polymer includes a branched dextran polymer; wherein the branched dextran polymer contains a plurality of glucose structural units; wherein 90 mol% to 98 mol% (preferably, 92.5 mol% to 97.5 mol%; more preferably, 93 mol% to 97 mol%; most preferably, 94 mol% to 96 mol%) of glucose structural units are linked by α-D-1,6 bonds, and 2 mol% to 10 mol% (preferably, 2.5 mol% to 7.5 mol%; more preferably, 3 mol% to 7 mol%; most preferably, 4 mol% to 6 mol%) of glucose structural units are linked by α-1,3 bonds. Most preferably, the deposition aid polymer is a quaternary ammonium partially functionalized dextran-based polymer; wherein the dextran-based polymer is a branched dextran polymer; wherein the branched dextran polymer comprises a plurality of glucose structural units; wherein, according to Formula IX, 90 mol% to 98 mol% (preferably, 92.5 mol% to 97.5 mol%; more preferably, 93 mol% to 97 mol%; most preferably, 94 mol% to 96 mol%) of glucose structural units are linked by α-D-1,6 bonds, and 2 mol% to 10 mol% (preferably, 2.5 mol% to 7.5 mol%; more preferably, 3 mol% to 7 mol%; most preferably, 4 mol% to 6 mol%) of glucose structural units are linked by α-1,3 bonds. Where R is selected from hydrogen, C 1-4 alkyl groups and hydroxyl groups C 1-4 Alkyl groups; and wherein the average number of branches of the dextran polymer backbone is ≤3 dehydrated glucose units.

[0026] Preferably, the dextran-based polymer contains less than 0.01% by weight of alternating sugars based on the weight of the dextran-based polymer. More preferably, the dextran-based polymer contains less than 0.001% by weight of alternating sugars based on the weight of the dextran-based polymer. Most preferably, the dextran-based polymer contains alternating sugars below the detection limit.

[0027] Preferably, the deposition aid polymer is a dextran-based polymer with quaternary ammonium partial functionalization; wherein the quaternary ammonium moiety of Formula II is bonded to the dangling oxygen on the dextran-based polymer. in X is a pendant oxygen on the dextran-based polymer; wherein X is a divalent linking group that bonds the quaternary ammonium moiety to the pendant oxygen on the dextran-based polymer (preferably, wherein X is selected from a divalent hydrocarbon group, which may optionally be replaced by (e.g., a hydroxyl group, an alkoxy group, an ether group); more preferably, wherein X is -CH2CH(OR) 11 CH2- groups; wherein each R 11 Choose independently the group consisting of: hydrogen and C. 1-4 Alkyl groups (preferably hydrogen; most preferably, X is a -CH2CH(OH)CH2- group); wherein each R 7 Choose independently the group consisting of the following items: C 1-7 Alkyl groups (preferably, C 1-3 Alkyl groups; more preferably, methyl groups and ethyl groups; most preferably, methyl groups); and wherein each R 8 Choose independently the group consisting of the following items: C 1-22 Alkyl groups (preferably selected from the group consisting of: C 1-3 alkyl groups and C 6-22 Alkyl groups; more preferably, methyl groups and ethyl groups; most preferably, methyl groups). More preferably, the deposition aid polymer is a cationic dextran polymer; wherein the cationic dextran polymer comprises a dextran-based polymer functionalized with quaternary ammonium groups; wherein the quaternary ammonium groups of Formula III are bonded to the dangling oxygen on the dextran-based polymer. Each R 7 Choose independently the group consisting of the following items: C 1-7 Alkyl groups (preferably, C 1-3 Alkyl groups; more preferably, methyl groups and ethyl groups; most preferably, methyl groups); wherein each R 8 Choose independently the group consisting of the following items: C 1-22 Alkyl groups (preferably selected from the group consisting of: C 1-3 alkyl groups and C 6-22 Alkyl groups; more preferably, methyl groups and ethyl groups; most preferably, methyl groups); and wherein each R 11 Choose independently the group consisting of: hydrogen and C. 1-4 Alkyl groups (preferably hydrogen). Most preferably, the deposition aid polymer is a cationic dextran polymer; wherein the cationic dextran polymer comprises a dextran-based polymer functionalized with quaternary ammonium groups; wherein the quaternary ammonium groups having Formula III are bonded to the dangling oxygen on the dextran-based polymer; wherein R 11 It is hydrogen; and R is in this context. 7and R 8 Each of them is a methyl group.

[0028] Preferably, the deposition aid polymer contains aldehyde functional groups in amounts of <0.001 mg equivalence / g (preferably, <0.0001 mg equivalence / g; more preferably, <0.00001 meq / g; most preferably, <detectable limit).

[0029] Preferably, the deposition aid polymer contains <0.1% (preferably, <0.01%; more preferably, <0.001%; ​​most preferably, <detectable limit) of bonds, and the bonds between the glucose units in the deposition aid polymer are β-1,4 bonds.

[0030] Preferably, the deposition aid polymer contains <0.1% (preferably, <0.01%; more preferably, <0.001%; ​​most preferably, <detectable limit) of bonds, and these bonds between the individual glucose units in the deposition aid polymer are β-1,3 bonds.

[0031] Preferably, the deposition aid polymer contains <0.001 mg equivalence / g (preferably, <0.0001 mg equivalence / g; more preferably, <0.00001 meq / g; most preferably, <detectable limit) of functionalized organosilicon.

[0032] Preferably, the laundry detergent formulation of the present invention further comprises an additional cleaning surfactant. More preferably, the laundry detergent formulation of the present invention further comprises 0.01% to 35% by weight (preferably 0.1% to 20% by weight; more preferably 1% to 15% by weight; most preferably 2.5% to 10% by weight) of an additional cleaning surfactant based on the weight of the laundry detergent formulation, wherein the additional cleaning surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof. Still more preferably, the laundry detergent formulation of the present invention further comprises 0.01% to 35% by weight (preferably 0.1% to 20% by weight; more preferably 1% to 15% by weight; most preferably 2.5% to 10% by weight) of an additional cleaning surfactant based on the weight of the laundry detergent formulation; wherein the additional cleaning surfactant includes alkylbenzene sulfonic acid or a salt thereof. Most preferably, the laundry detergent formulation of the present invention further comprises, based on the weight of the laundry detergent formulation, 0.01% to 35% by weight (preferably, 0.1% to 20% by weight; more preferably, 1% to 15% by weight; most preferably, 2.5% to 10% by weight) of an additional cleaning surfactant; wherein the additional cleaning surfactant comprises a sodium salt of a linear alkylbenzene sulfonic acid.

[0033] Preferably, the laundry detergent formulation of the present invention further comprises additives. Preferably, the laundry detergent formulation of the present invention further comprises additives selected from the group consisting of: salts, detergent builders, enzymes, corrosion inhibitors, acids, bleaching agents, bleaching catalysts, abrasives, antimicrobial agents, chelating agents, pH adjusters, buffers, rheology modifiers, structural agents, fragrances, and mixtures thereof.

[0034] Preferably, a method for depositing silicone on cotton includes: providing a soiled cotton garment article; selecting a laundry detergent formulation of the present invention having a synergistic combination of an alcohol ethoxysulfate surfactant of Formula I and a modified carbohydrate polymer; providing bath water; and applying the bath water and the laundry detergent formulation to the soiled cotton garment article to provide a clean cotton garment article; wherein fabric-softening silicone is associated with a clean cotton garment article.

[0035] Some embodiments of the present invention will now be described in detail in the following examples.

[0036] Experimental materials

[0037]

[0038] Synthesis of S1:C 12 EO

[0039] 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.

[0040] 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.] 12 The EO is fed to the next sulfation process to prepare sulfate anionic surfactants.

[0041] Synthesis of S2:C 12 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 C2O2 prepared according to the synthesis of S1 were added to a 2 L three-necked round-bottom flask. 12 EO (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 purified secondary alcohol ethoxylate sulfate product, C12 EO sulfate, a white solid (47.7 g). The purified product was used for performance and characteristic tests.

[0043] Synthesis of S3: ALEO1 sulfate

[0044] ALEO1 sulfate was prepared from ALEO1 in the same manner as described in synthesis S2.

[0045] Synthesis of S4: SA3EO sulfate

[0046] SA3EO sulfate was prepared from SA3EO in the same manner as described in synthesis S2.

[0047] Synthesis of S5: Synthesis of cationic dextran polymers

[0048] Dextran-based polymer (400 g; Ultradex 530, from FermWorx) was added to a 1000 mL four-necked round-bottom flask equipped with a rubber whey cap, nitrogen inlet, pressure equalization feed funnel, agitator and motor, a ground thermocouple connected to a J-KEM controller, and a Friedrich condenser connected to a mineral oil bubbler. The weight-average molecular weight of the dextran-based polymer was 200,000 to 500,000 Daltons. 65% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride (63.8 g; QUAT) was added to the feed funnel. ® 188 (available from Dow Chemical). While stirring the contents of the flask, purge the system with nitrogen for one hour to replace any entrained oxygen. The nitrogen flow rate is approximately 1 bubble / second.

[0049] Using a plastic syringe, a 50% sodium hydroxide aqueous solution (24.7 g) was added to the contents of the flask over several minutes with stirring under nitrogen. The contents of the flask were then stirred under nitrogen for one hour. Then, with continuous stirring under nitrogen, the contents of a feeding funnel were added dropwise to the contents of the flask over several minutes. After transferring the contents of the feeding funnel to the contents of the flask, the mixture was stirred for 20 minutes. Heat was then applied to the contents of the flask using a heating mantle controlled by a J-KEM controller set at 55°C. The contents of the flask were heated to 70°C and maintained at that temperature for 4 hours.

[0050] The contents of the flask were then cooled in an ice-water bath while maintaining a positive nitrogen pressure. When the contents reached room temperature, glacial acetic acid (5.7 g) was added. The contents were then stirred under nitrogen for 10 minutes. The product solution was ready for use without further purification. The product polymer was characterized by nuclear magnetic resonance (¹H NMR) spectroscopy for structural analysis to determine the degree of substitution (DS). quatThe value is 0.171. The product contains 28% by weight of an aqueous solution of the polymeric active substance.

[0051] Synthetic S6: Hydroxyethyl cellulose

[0052] The pressure vessel was equipped with a mechanical agitator, a nitrogen inlet, a rubber cap, and a reflux condenser connected to a mineral oil bubbler. Biofloc 94 wood pulp (24.5 g; from Tembec Cellutions), isopropanol (223.2 g), and distilled water (31.8 g) were added to the vessel. While stirring the mixture, the vessel was purged with nitrogen for one hour to remove any entrained oxygen from the system. While stirring under nitrogen, a 50% sodium hydroxide aqueous solution (14.2 g) was added dropwise over five minutes using a syringe. The mixture was then stirred under nitrogen for 30 minutes. Ethylene oxide (30.1 g) was added to the reaction vessel with continuous stirring and sealed. The reactants were heated to 75°C and stirred for one hour. The mixture was then cooled to room temperature, optionally with the addition of hydrogen peroxide to adjust the viscosity, neutralized with glacial acetic acid (11.1 g), and stirred for 10 minutes. The polymer product was recovered by vacuum filtration and washing in a Waring blender: five washes with 250 mL of 4:1 (by volume) acetone / water, followed by two washes with 250 mL of pure acetone. The polymer product was treated with glyoxal by adding 40% aqueous glyoxal (0.40 g) and glacial acetic acid (0.25 g) to the final acetone drying. The polymer product was then vacuum dried overnight at 50 °C. The 2% aqueous viscosity (corrected for ash and volatiles) of the product polymer at 25.0 °C was measured at 500 mPa·s using a Brookfield LVT, 30 rpm, No. 4 spindle, and its weight-average molecular weight was 400,000 Daltons.

[0053] Synthesis of S7-S8: Cationic Modified Carbohydrate Polymers

[0054] A 500 mL four-necked round-bottom flask equipped with a 60 mL equalizing feed funnel connected to a nitrogen inlet, a rubber cap, a stirrer and motor, a Claisen adapter connected to a subsurface thermocouple connected to a J-KEM controller, and a Friedrich condenser connected to a mineral oil bubbler was loaded with Ag (hydroxyethyl cellulose prepared according to synthesis S6), Bg (isopropanol), and Cg (deionized water). Then, Dg (70% aqueous QUAB 151, glycidyltrimethylammonium chloride) was added to the 60 mL equalizing feed funnel. While stirring the contents of the flask, the top space of the flask was purged with a steady stream of nitrogen at approximately one bubble per second for one hour to remove any entrained oxygen. The values ​​for AD are provided in Table 1.

[0055] Under nitrogen atmosphere, the mixture was continuously stirred, and then 7.3 g of a 25% sodium hydroxide aqueous solution was added dropwise to the contents of the flask over approximately 1 minute using a plastic syringe. The contents of the flask were then stirred for 30 minutes, followed by the addition of QUAB 151 from the feeding funnel over 5 minutes. The contents of the flask were then stirred under nitrogen atmosphere for 10 minutes, and the temperature setpoint on the J-Kem controller was set to 55°C, with the heating element applied to the flask. The contents of the flask were maintained at 55°C for 3 hours with continuous stirring under nitrogen atmosphere.

[0056] The contents of the flask were then cooled by placing it in a cold water bath while maintaining a positive nitrogen pressure. The contents were then neutralized by adding 3.2 g of glacial acetic acid to the contents using a syringe and stirring for 10 minutes. The contents were then vacuum filtered through a large sintered Buchner funnel. The filter cake was washed three times in the Buchner funnel by stirring for three minutes each time, using a specified washing solvent, followed by vacuum removal of the washings: first with a washing solvent mixture of 246 g isopropanol and 54 g distilled water; second with a washing solvent mixture of 270 g isopropanol and 30 g distilled water; and third with a washing solvent mixture of 300 g isopropanol containing 0.4 g 40% glyoxal and 0.1 g glacial acetic acid. The product-modified hydroxyethyl cellulose washings were then recovered by vacuum filtration, briefly air-dried, and then vacuum-dried overnight at 50°C.

[0057] The Kjeldahl nitrogen content (TKN) of the obtained modified hydroxyethyl cellulose was evaluated (corrected for ash and volatile matter), and the results are provided in Table 1.

[0058]

[0059] Active sulfate (EO=0) content in surfactants

[0060] The concentrations of active sulfates in the surfactants indicated in Table 2 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).

[0061] Number of moles of hyamine (Mol) H The determination of )

[0062] Sodium dioctyl sulfosuccinate (SDOSS), control solution Add 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.

[0063] 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.

[0064] 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.

[0065] Standardization of Hyamine SolutionPipette 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; CS MW This is the molecular weight of the control solution SDOSS (i.e., 444.56 g / mol).

[0066] Determination of active sulfates in surfactants

[0067] 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 2.

[0068] EO distribution of surfactants

[0069] The distribution of EO adducts in the surfactants listed in Table 2 was determined by NMR or UHPLC-MS, as indicated by the methods described below, and the results are provided in Table 2.

[0070] Nuclear magnetic resonance (NMR) characterization of EO distribution

[0071] 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).

[0072] Analysis of sodium lauryl ether sulfate by UHPLC-MS

[0073] Ultra-high performance liquid chromatography-mass spectrometry (UHPLC-MS) conditions:

[0074]

[0075] programCompositions 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.

[0076] 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.

[0077] 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 ratios of different EO adducts were calculated by peak area and are reported in Table 2.

[0078]

[0079] In the product of S2 synthesis, 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 product of S2 synthesis, ≥98 mol% of the oligomer has n=1, and ≤2 mol% of the oligomer has n≥2.

[0080] 1,4-Dioxane content of surfactant

[0081] The 1,4-dioxane content of the surfactants listed in Table 3 was determined by low-temperature gas chromatography-mass spectrometry (GC-MS) for the organic layer and by liquid chromatography-mass spectrometry (LC-MS) for the aqueous layer, as indicated by the methods listed below, and the results are provided in Table 3.

[0082] Used for the determination of 1,4-dioxane in organic layers Gas chromatography-mass spectrometry (GC-MS) conditions :

[0083]

[0084] The standard was prepared by adding a solution of dioxane in tetrahydrofuran (“THF”) and diluting it to 0.1 ppm to 100 ppm.

[0085] 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.

[0086] Used for the determination of 1,4-dioxane content in aquatic layers. Liquid chromatography-mass spectrometry (LC-MS) conditions :

[0087]

[0088] 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.

[0089] Calculation of dioxane content relative to solids

[0090] The dioxane content relative to the solid content in the sample (ppm) is calculated using the following equation.

[0091]

[0092]

[0093] Gas chromatography results of SA3EO sulfate surfactants showed that secondary alcohols containing an average of 3 moles of ethylene oxide per molecule produced 2 ppm of 1,4-dioxane in the organic phase at 110 °C, indicating that substances with an n≥2 structure may generate 1,4-dioxane. Interestingly, when the inlet temperature 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 suggests that sulfated surfactants with n≥2 may produce observable 1,4-dioxane at 110 °C, and that such surfactants may be unstable at 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 generated relative to the solid. Furthermore, ALEO1 sulfate surfactants also generated a large amount of 1,4-dioxane (259 ppm) at 280 °C, indicating that ALEO1 sulfate surfactants lack stability at high temperatures. This invention C 12 EO sulfate surfactants (≥95 mol% n=1 and ≤5 mol% n=2) exhibited lower 1,4-dioxane content. Unexpectedly, the present invention C... 12 The EO sulfate surfactant exhibits extremely low 1,4-dioxane content, below the detection limits (LOD) of 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 present invention C... 12 The 1,4-dioxane content of EO sulfate remains below 1 ppm (i.e., 0.58 ppm), indicating that compared to the control material, the present invention C 12 EO sulfate has higher thermal stability.

[0094] Comparative Examples CF1-CF7 and Example F1 :

[0095] Laundry detergent formulation

[0096] The laundry detergent formulations of Comparative Examples CF1-CF7 and Example F1 were prepared by mixing together the components in the weight proportions indicated in Table 4, adjusted to pH 8 with sodium hydroxide (if necessary).

[0097]

[0098] Deposition of organosilicon on cotton fabrics

[0099] The organosilicon deposition on cotton fabrics by the laundry detergent formulations prepared according to Comparative Examples CF1-CF7 and Example F1 was quantified using X-ray photoelectron spectroscopy (XPS), which provides quantitative elemental and chemical state information from the top 10 nm of the cotton fabric.

[0100] Use a circular die and a hand-operated press to cut the cotton fabric into 0.5-inch diameter discs. Then add 20 mL of 200 ppm (3:1 Ca) solution. 2+ :Mg 2+ Water was added to a separate 25 mL vial for each laundry detergent formulation used in the laundry detergent formulation. A magnetic stir bar was added to each vial along with 0.2 g of the laundry detergent formulation prepared according to Comparative Examples CF1-CF7 and Example F1 to form a washing solution. The vials were placed on a 15-position stir plate and set to stir at 300 rpm. Three cotton discs were added to each vial and stirred in the washing solution for 16 minutes. The cotton discs were then transferred to a container with 20 mL of 200 ppm (3:1 Ca) water. 2+ :Mg 2+ Add water and a stirring rod to a fresh 25 mL vial. Stir the fresh vial for 3 minutes to rinse the cotton disc. Then remove the cotton disc from the vial and allow it to dry on a metal rack. Seal the dried cotton disc in a clean 25 mL vial. Then evaluate the silicone deposition on the cotton disc using XPS. The instrument parameters used are provided in Table 5. The molar percentage of silicone deposited on the cotton disc from the laundry detergent formulation is reported in Table 6.

[0101]

[0102]

Claims

1. A laundry detergent formulation, the laundry detergent formulation comprising: water; 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 x is 1 in 95 mol% to 100 mol% of the alcohol ethoxysulfate surfactant of Formula I; Fabric softening silicone; and A deposition aid polymer, wherein the deposition aid polymer is a dextran-based polymer partially functionalized with quaternary ammonium; wherein the deposition aid polymer has a Kjeldahl nitrogen content of 0.5% to 5% by weight (TKN); and wherein the deposition aid polymer contains <0.1% bonds, wherein the bonds between the glucose units in the deposition aid polymer are β-1,3 bonds.

2. The laundry detergent formulation according to claim 1, wherein R 1 It is a methyl group, and R 2 It is a straight chain C 10-12 Alkyl groups.

3. The laundry detergent formulation according to claim 2, wherein R 2 It is a straight chain C 10 Alkyl groups.

4. The laundry detergent formulation according to claim 3, wherein the dextran-based polymer is a branched dextran polymer comprising a plurality of glucose structural units; wherein 90 mol% to 98 mol% of the glucose structural units are linked by α-D-1,6 bonds, and 2 mol% to 10 mol% of the glucose structural units are linked by α-1,3 bonds; wherein the dextran-based polymer has a weight-average molecular weight of 100,000 Daltons to 700,000 Daltons.

5. The laundry detergent formulation according to claim 4, wherein the deposition aid polymer is a dextran-based polymer of formula II with quaternary ammonium partial functionalization. in X is the pendant oxygen on the dextran-based polymer; wherein X is a divalent linker that bonds the quaternary ammonium nitrogen to the pendant oxygen on the dextran-based polymer; wherein each R 7 Choose C independently 1-7 The group consisting of alkyl groups; and wherein R 8 Choose C freely 1-22 The group consisting of alkyl groups; wherein the deposition aid polymer has a Kjeldahl nitrogen content of 0.9% to 1.5% by weight (TKN).

6. The laundry detergent formulation of claim 5, wherein the deposition aid polymer is a dextran-based polymer having a quaternary ammonium partially functionalized form of formula III. in It is the pendant oxygen on the dextran-based polymer; wherein R 7 and R 8 Each is a methyl group; where R 11 It is hydrogen.

7. The laundry detergent formulation of claim 6, further comprising an additional cleaning surfactant; wherein the additional cleaning surfactant comprises a sodium salt of a linear alkylbenzene sulfonic acid.

8. The laundry detergent formulation according to claim 7, wherein the laundry detergent formulation comprises: Based on the weight of the laundry detergent formulation, 43% to 94.9% by weight of water; Based on the weight of the laundry detergent formulation, 0.01% to 35% by weight of the alcohol ethoxysulfate surfactant of Formula I; Based on the weight of the laundry detergent formulation, 0.05% to 12% by weight of the fabric softening silicone; Based on the weight of the laundry detergent formulation, 0.5% to 10% by weight of the deposition aid polymer; and Based on the weight of the laundry detergent formulation, the additional cleaning surfactant comprises 0.01% to 35% by weight.

9. The laundry detergent formulation according to claim 8, wherein the laundry detergent formulation comprises: Based on the weight of the laundry detergent formulation, 70% to 75% by weight of water; Based on the weight of the laundry detergent formulation, 2.5% to 10% by weight of the alcohol ethoxysulfate surfactant of Formula I; Based on the weight of the laundry detergent formulation, 3% to 7% by weight of the fabric softening silicone; Based on the weight of the laundry detergent formulation, 2% to 3% by weight of the deposition aid polymer; and Based on the weight of the laundry detergent formulation, 2.5% to 10% by weight of the additional cleaning surfactant.

10. A method for depositing organosilicon on cotton, the method comprising: Provide soiled cotton clothing and products; Choose the laundry detergent formulation according to claim 1, wherein the laundry detergent formulation has a synergistic combination of the alcohol ethoxysulfate surfactant of formula I and the deposition aid polymer; Provide bath water; as well as The bath water and the laundry detergent formulation are applied to the soiled cotton clothing to provide clean cotton clothing; wherein the fabric softening silicone is associated with the clean cotton clothing.

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