Cleaning boosters and liquid laundry detergents

Abstract

A cleaning enhancer of Formula I is provided, wherein X is (II), (III), or (IV) wherein a = 1-30; b + c = 4; R 4 is hydrogen or C 1‑4 alkyl; R 5 is hydrogen or C 1‑4 alkyl; R 6 is hydrogen or C 7 alkyl; R 1 is a bond or a bridging group having 1 to 8 carbons; * in (II), (III), and (IV) indicates a bond to R 2 ; R 1 is (V) wherein d = 5-150; R 8 and R 9 are hydrogen or C 1‑2 alkyl, with the proviso that in each subunit d, at least one of R 8 and R 9 is hydrogen; R 10 is hydrogen or C 1‑22 alkyl; * in (V) indicates a bond to X; R 2 is (VI) wherein e = 5-150; R 11 and R 12 are hydrogen or C 1‑2 alkyl, with the proviso that in each subunit e, at least one of R 11 and R 12 is hydrogen; * in (VI) indicates a bond to X or R 3 ; and R 3 is hydrogen or C 1‑22 alkyl.

Description

[0001] This invention relates to a cleaning enhancer. Specifically, this invention relates to a cleaning enhancer for cleaning clothes, wherein the cleaning enhancer has Formula I, wherein a is 1 to 30; wherein each X is independently selected from the group consisting of Formulas II, III, and IV; wherein b is 0 to 4; wherein c is 0 to 4; wherein b + c = 4; wherein each R 4 Independently selected from hydrogen and C 1-4 alkyl groups; wherein each R 5 Independently selected from hydrogen and C 1-4 alkyl groups; wherein each R 6 Independently selected from hydrogen and methyl groups; wherein R 7 Choose from the group consisting of single bonds and bridging groups having 1 to 8 carbon atoms; and wherein each * in formulas II, III and IV represents a group with R 1 or R 2 The key; where R 1 It has the formula V; where d is from 5 to 150; where each R 8 and R 9 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit d, R 8 and R 9 At least one of them is hydrogen; where R 10 Choose freely from hydrogen and C 1-22 A group consisting of alkyl groups; and wherein * in formula V represents a bond with X; wherein each R 2 Independently possessing formula VI; where e is 5 to 150; and where each R 11 and R 12 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit e, R 11 and R 12 At least one of them is hydrogen; and each * in formula VI represents a combination with X or R. 3 The key; and where R 3 Choose freely from hydrogen and C 1-22 The group consisting of alkyl groups; and the condition is that 10 mol% to 100 mol% of X in Formula I has Formula II; and the condition is that 40 mol% to 100 mol% of R in Formula I is present. 1 and R 2 The functional groups are ethylene oxide and C 3-8 Copolymers of epoxides, wherein each copolymer contains 25 mol% to 99 mol% ethylene oxide.

[0002] Consumers expect laundry detergents in both liquid and gel forms to provide excellent overall cleaning. These detergents typically include surfactants among other ingredients to deliver the desired cleaning benefits. However, due to increasing environmental sensitivity and rising material costs, there is a growing trend to reduce the use of surfactants in laundry detergents. Therefore, detergent manufacturers are seeking ways to reduce the amount of surfactant per unit dose while maintaining overall cleaning performance.

[0003] One method to reduce the unit dosage of surfactant is to incorporate polymers into liquid detergent formulations, as described by Boutique et al. in U.S. Patent Application Publication No. 20090005288. Boutique et al. disclosed graft copolymers of polyethylene, polypropylene, or polybutane with vinyl acetate in a weight ratio of about 1:0.2 to about 1:10, for use in liquid or gel laundry detergent formulations having about 2% to about 20% by weight of surfactant.

[0004] Nevertheless, there is still a need for new cleaning enhancer compositions and liquid laundry detergent formulations containing them, particularly those compositions that are resistant to hydrolysis and readily biodegradable according to the OECD 301F scheme.

[0005] This invention provides a cleaning enhancer for cleaning clothes, wherein the cleaning enhancer has Formula I

[0006]

[0007] Where a is 1 to 30; where each X is independently selected from the group consisting of formulas II, III and IV.

[0008]

[0009] Where b is between 0 and 4; where c is between 0 and 4; where b + c = 4; where each R 4 Independently selected from hydrogen and C 1-4 alkyl groups; wherein each R 5 Independently selected from hydrogen and C 1-4 alkyl groups; wherein each R 6 Independently selected from hydrogen and methyl groups; wherein R 7 Choose from the group consisting of single bonds and bridging groups having 1 to 8 carbon atoms; and wherein each * in formulas II, III and IV represents a group with R 1 or R 2 The combination of; where R 1 Having V

[0010]

[0011] Where d ranges from 5 to 150; where each R 8 and R 9 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit d, R 8 and R 9 At least one of them is hydrogen; where R 10 Choose freely from hydrogen and C 1-22 A group consisting of alkyl groups; and wherein * in formula V indicates a combination with X; wherein each R 2 Independently possessing a VI

[0012]

[0013] Where e is between 5 and 150; and where each R 11 and R 12 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit e, R 11 and R 12 At least one of them is hydrogen; and each * in formula VI represents a combination with X or R. 3 The combination of; and where R 3 Choose freely from hydrogen and C 1-22 The group consisting of alkyl groups; and the condition is that 10 mol% to 100 mol% of X in Formula I has Formula II; and the condition is that 40 mol% to 100 mol% of R in Formula I is present. 1 and R 2 The functional groups are ethylene oxide and C 3-8 Copolymers of epoxides, wherein each copolymer contains 25 mol% to 99 mol% ethylene oxide.

[0014] The present invention provides a liquid laundry detergent formulation comprising: 25% to 98.9% by weight of a liquid carrier based on the weight of the liquid laundry detergent formulation; 1% to 60% by weight of a cleaning surfactant based on the weight of the liquid laundry detergent formulation; and 0.1% to 50% by weight of the cleaning enhancer of the present invention based on the weight of the liquid laundry detergent formulation.

[0015] The present invention provides a method for washing soiled fabric articles, the method comprising: providing the soiled fabric articles; providing the liquid laundry detergent formulation of the present invention; providing washing water; and applying the washing water and the liquid laundry detergent formulation to the soiled fabric articles to provide cleaned fabric articles. Detailed Implementation

[0016] It has been unexpectedly discovered that materials according to Formula I, having a six-membered saturated hydrocarbon ring (in which two carbon atoms have been replaced by nitrogen atoms, and each nitrogen atom is further linked to a -C(O)O- group via a -CH2- segment), are resistant to hydrolysis, providing effective detergency to liquid laundry detergent formulations containing them, especially for the removal of oily and greasy stains (e.g., sebum stains) from cotton-containing fabrics (e.g., polyester-cotton blends) at low temperatures (i.e., as low as 22°C), and as an additional beneficial effect, exhibiting readily biodegradable properties according to the OECD 301F procedure.

[0017] Unless otherwise specified, ratios, percentages, parts, etc., are all by weight. The weight percentage (or weight %) in the composition is a percentage of dry weight, that is, excluding any water that may be present in the composition.

[0018] As used herein, unless otherwise specified, the phrase "molecular weight" or MW refers to the weight-average molecular weight as measured in a conventional manner using gel permeation chromatography (GPC) and conventional standards, such as polystyrene molecular weight 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.

[0019] Preferably, the cleaning enhancer for cleaning clothes of the present invention has Formula I

[0020]

[0021] Where a is 1 to 30 (preferably 1 to 25; more preferably 1 to 20; most preferably 2 to 15); wherein each X is independently selected from the group consisting of Formula II, Formula III and Formula IV.

[0022]

[0023]

[0024] Where b is 0 to 4 (preferably 2) (when b is 0, there is a direct bond between the two nitrogen atoms); where c is 0 to 4 (preferably 2) (when c is 0, there is a direct bond between the two nitrogen atoms); where b + c = 4; where each R 4Independently selected from hydrogen and C 1-4 alkyl groups (preferably, wherein each R 4 Independently selected from hydrogen and C 1-3 Alkyl groups; more preferably, wherein each R 4 Independently selected from hydrogen, ethyl, and methyl groups; most preferably, wherein each R 4 (for hydrogen) (optionally both R 4 Groups can link together to form a polycyclic diamine structure); where each R 5 Independently selected from hydrogen and C 1-4 alkyl groups (preferably, wherein each R 5 Independently selected from hydrogen and C 1-3 Alkyl groups; more preferably, wherein each R 5 Independently selected from hydrogen, ethyl, and methyl groups; most preferably, wherein each R 5 (for hydrogen); where each R 6 Independently selected from hydrogen and methyl groups (preferably, wherein each R...) 6 (for hydrogen); where R 7 Selected from the group consisting of single bonds and bridging groups having 1 to 8 carbon atoms (preferably, wherein R 7 The group consisting of single bonds and bridging groups having 1 to 5 carbon atoms is selected; more preferably, wherein R 7 Selected from the group consisting of bridging groups having 1 to 5 carbon atoms; most preferably, wherein R 7 (Selected from the group consisting of -CH2CH2- groups and -CH2CH2CH2- groups), and wherein each * in formulas II, III and IV represents R. 1 or R 2 The key; where R 1 Having V

[0025]

[0026] Where d is 5 to 150 (preferably 5 to 100; more preferably 5 to 50; most preferably 5 to 25); wherein each R 8 and R 9 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit d, R 8 and R 9 At least one of them is hydrogen; where R 10 Choose freely from hydrogen and C 1-22 The group consisting of alkyl groups (preferably, hydrogen and C) 1-4 Alkyl groups; more preferably, hydrogen and methyl groups; most preferably, hydrogen); and wherein * in formula V represents a bond with X (i.e., with formula II, III or IV); wherein each R2 Independently possessing a VI

[0027]

[0028] Where e is 5 to 150 (preferably 5 to 100; more preferably 5 to 50; most preferably 5 to 25); and where each R 11 and R 12 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit e, R 11 and R 12 At least one of them is hydrogen; and each * in formula VI represents a combination with X (i.e., with formula II, formula III or formula IV) or R. 3 The key; and where R 3 Choose freely from hydrogen and C 1-22 The group consisting of alkyl groups (preferably, hydrogen and C) 1-4 Alkyl groups; more preferably, hydrogen and methyl groups; most preferably, hydrogen); and the condition is that X of formula I has 10 mol% to 100 mol% (preferably, 25 mol% to 100 mol%; more preferably, 40 mol% to 100 mol%; most preferably, 45 mol% to 100 mol%) of formula I; and the condition is that R of formula I has 40 mol% to 100 mol% (preferably, 45 mol% to 75 mol%; more preferably, 46 mol% to 60 mol%; most preferably, 47 mol% to 55 mol%) of formula I. 1 and R 2 The functional groups are ethylene oxide and C 3-8 A copolymer of epoxides (preferably, a copolymer of ethylene oxide and propylene oxide), wherein each copolymer contains 25 mol% to 99 mol% (preferably, 50 mol% to 95 mol%; more preferably, 60 mol% to 90 mol%; most preferably, 75 mol% to 85 mol%) of ethylene oxide.

[0029] Preferably, the liquid laundry detergent formulation of the present invention comprises: 25% to 98.9% by weight (preferably 30% to 97.8% by weight; more preferably 40% to 96.75% by weight; still more preferably 45% to 91.7% by weight; most preferably 50% to 87.5% by weight) of a liquid carrier based on the weight of the liquid laundry detergent formulation; 1% to 60% by weight (preferably 2% to 50% by weight; more preferably 2.5% to 40% by weight; still more preferably 7.5% to 35% by weight; most preferably 10% to 30% by weight) of a cleaning surfactant based on the weight of the liquid laundry detergent formulation; and a liquid carrier based on the weight of the liquid laundry detergent formulation. The detergent formulation contains 0.1% to 50% by weight (preferably 0.5% to 25% by weight; more preferably 0.75% to 20% by weight; still more preferably 0.8% to 15% by weight; most preferably 2.5% to 7.5% by weight) of a cleaning enhancer of formula I; wherein a is 1 to 30 (preferably 1 to 25; more preferably 1 to 20; most preferably 2 to 15); wherein each X is independently selected from the group consisting of formulas II, III and IV; wherein b is 0 to 4 (preferably 2) (when b is 0, there is a direct bond between the two nitrogen atoms); wherein c is 0 to 4 (preferably 2) (when c is 0, there is a direct bond between the two nitrogen atoms); wherein b + c = 4; wherein each R 4 Independently selected from hydrogen and C 1-4 alkyl groups (preferably, wherein each R 4 Independently selected from hydrogen and C 1-3 Alkyl groups; more preferably, wherein each R 4 Independently selected from hydrogen, ethyl, and methyl groups; most preferably, wherein each R 4 (for hydrogen) (optionally both R 4 Groups can link together to form a polycyclic diamine structure); where each R 5 Independently selected from hydrogen and C 1-4 alkyl groups (preferably, wherein each R 5 Independently selected from hydrogen and C 1-3 Alkyl groups; more preferably, wherein each R 5 Independently selected from hydrogen, ethyl, and methyl groups; most preferably, wherein each R 5 (for hydrogen); where each R 6 Independently selected from hydrogen and methyl groups (preferably, wherein each R...) 6 (for hydrogen); where R 7 Selected from the group consisting of single bonds and bridging groups having 1 to 8 carbon atoms (preferably, wherein R 7The group consisting of single bonds and bridging groups having 1 to 5 carbon atoms is selected; more preferably, wherein R 7 Selected from the group consisting of bridging groups having 1 to 5 carbon atoms; most preferably, wherein R 7 (Selected from the group consisting of -CH2CH2- groups and -CH2CH2CH2- groups), and wherein each * in formulas II, III and IV represents R. 1 or R 2 The key; where R 1 It has the formula V; where d is 5 to 150 (preferably 5 to 100; more preferably 5 to 50; most preferably 5 to 25); where each R 8 and R 9 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit d, R 8 and R 9 At least one of them is hydrogen; where R 10 Choose freely from hydrogen and C 1-22 The group consisting of alkyl groups (preferably, hydrogen and C) 1-4 Alkyl groups; more preferably, hydrogen and methyl groups; most preferably, hydrogen); and wherein * in formula V represents a bond with X (i.e., with formula II, III or IV); wherein each R 2 Independently having formula VI; wherein e is 5 to 150 (preferably 5 to 100; more preferably 5 to 50; most preferably 5 to 25); and wherein each R 11 and R 12 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit e, R 11 and R 12 At least one of them is hydrogen; and each * in formula VI represents a combination with X (i.e., with formula II, formula III or formula IV) or R. 3 The key; and where R 3 Choose freely from hydrogen and C 1-22 The group consisting of alkyl groups (preferably, hydrogen and C) 1-4 Alkyl groups; more preferably, hydrogen and methyl groups; most preferably, hydrogen); and the condition is that X of formula I has 10 mol% to 100 mol% (preferably, 25 mol% to 100 mol%; more preferably, 40 mol% to 100 mol%; most preferably, 45 mol% to 100 mol%) of formula I; and the condition is that R of formula I has 40 mol% to 100 mol% (preferably, 45 mol% to 75 mol%; more preferably, 46 mol% to 60 mol%; most preferably, 47 mol% to 55 mol%) of formula I. 1 and R 2 The functional groups are ethylene oxide and C3-8 A copolymer of epoxides (preferably, a copolymer of ethylene oxide and propylene oxide), wherein each copolymer contains 25 mol% to 99 mol% (preferably, 50 mol% to 95 mol%; more preferably, 60 mol% to 90 mol%; most preferably, 75 mol% to 85 mol%) of ethylene oxide.

[0030] Preferably, the liquid laundry detergent formulation of the present invention comprises a liquid carrier. More preferably, the liquid laundry detergent formulation provided by the method of the present invention comprises 25% to 98.9% by weight (preferably 30% to 97.8% by weight; more preferably 40% to 96.75% by weight; still more preferably 45% to 91.7% by weight; most preferably 50% to 87.5% by weight) of a liquid carrier based on the weight of the liquid laundry detergent formulation. Still more preferably, the liquid laundry detergent formulation of the present invention comprises 25% to 98.9% by weight (preferably 30% to 97.8% by weight; more preferably 40% to 96.75% by weight; still more preferably 45% to 91.7% by weight; most preferably 50% to 87.5% by weight) of a liquid carrier based on the weight of the liquid laundry detergent formulation; wherein the liquid carrier comprises water. Most preferably, the liquid laundry detergent formulation of the present invention comprises 25% to 98.9% by weight (preferably, 30% to 97.8% by weight; more preferably, 40% to 96.75% by weight; still more preferably, 45% to 91.7% by weight; most preferably, 50% to 87.5% by weight) of a liquid carrier based on the weight of the liquid laundry detergent formulation; wherein the liquid carrier is water.

[0031] Preferably, the liquid carrier may comprise a water-miscible liquid, such as C 1-3 Alkaneolamines and C 1-3 Alkyl alcohol. More preferably, the liquid carrier used in the method of the present invention comprises 0% to 8% by weight (preferably 0.2% to 8% by weight; more preferably 0.5% to 5% by weight) of a water-miscible liquid based on the weight of the liquid carrier; wherein the water-miscible liquid is selected from C 1-3 Alkylamines, C 1-3 The group consisting of alkanols and mixtures thereof.

[0032] Preferably, the liquid laundry detergent formulation of the present invention comprises: 1% to 60% by weight (preferably 2% to 50% by weight; more preferably 2.5% to 40% by weight; still more preferably 7.5% to 35% by weight; most preferably 10% to 30% by weight) of a cleaning surfactant based on the weight of the liquid laundry detergent formulation. More preferably, the liquid laundry detergent formulation of the present invention comprises: 1% to 60% by weight (preferably 2% to 50% by weight; more preferably 2.5% to 40% by weight; still more preferably 7.5% to 35% by weight; most preferably 10% to 30% by weight) of a cleaning surfactant based on the weight of the liquid laundry detergent formulation; wherein the cleaning surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof. More preferably, the liquid laundry detergent formulation of the present invention comprises: 1% to 60% by weight (preferably 2% to 50% by weight; more preferably 2.5% to 40% by weight; still more preferably 7.5% to 35% by weight; most preferably 10% to 30% by weight) of a cleaning surfactant based on the weight of the liquid laundry detergent formulation; wherein the cleaning surfactant comprises anionic surfactants. Furthermore, still more preferably, the liquid laundry detergent formulation provided by the method of the present invention comprises: 1% to 60% by weight (preferably 2% to 50% by weight; more preferably 2.5% to 40% by weight; still more preferably 7.5% to 35% by weight; most preferably 10% to 30% by weight) of a cleaning surfactant based on the weight of the liquid laundry detergent formulation; wherein the cleaning surfactant comprises a mixture of anionic and nonionic surfactants. Most preferably, the liquid laundry detergent formulation of the present invention comprises: 1% to 60% by weight (preferably 2% to 50% by weight; more preferably 2.5% to 40% by weight; still more preferably 7.5% to 35% by weight; most preferably 10% to 30% by weight) of a cleaning surfactant based on the weight of the liquid laundry detergent formulation; wherein the cleaning surfactant comprises a mixture of linear alkylbenzene sulfonate and sodium lauryl polyoxyethylene ether sulfate.

[0033] Anionic surfactants include alkyl sulfates, alkylbenzene sulfates, alkylbenzene sulfonic acids, alkylbenzene sulfonates, alkyl polyoxyethylene ether sulfates, alkoxylated alcohols, alkane sulfonic acids, alkane sulfonates, olefin sulfonic acids, olefin sulfonates, α-sulfonocarboxylates, α-sulfonocarboxyl esters, alkyl glycerol ether sulfonic acids, alkyl glycerol ether sulfonates, fatty acid sulfates, fatty acid sulfonates, fatty acid ester sulfonates, alkylphenols, alkylphenol polyoxyethylene ether sulfates, 2-acryloyloxy-alkane-1-sulfonic acid, 2-acryloyloxy-alkane-1-sulfonate, β-alkoxyalkane sulfonic acid, β-alkoxyalkane sulfonate, amine oxides, and mixtures thereof. Preferred anionic surfactants include 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, alkoxylated alcohols, C 8-20 Alkylphenols, amine oxides, sulfonates of fatty acids, sulfonates of fatty acid esters, C 8-10 Alkyl polyethoxysulfates and mixtures thereof. More preferred anionic surfactants include C... 12-16 Alkylbenzenesulfonic acid, C 12-16 Alkylbenzene sulfonates, C 12-18 Paraffin-sulfonic acid, C 12-18 Paraffin-sulfonate, C 12-16 Alkyl polyethoxysulfates and mixtures thereof.

[0034] Nonionic surfactants include alkoxylated surfactants (e.g., 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 fatty alcohol polyethylene glycol ethers. More preferred nonionic surfactants include secondary alcohol ethoxylated surfactants, ethoxylated 2-ethylhexanol, ethoxylated seed oils, butanol-terminated ethoxylated 2-ethylhexanol, and mixtures thereof. Most preferred nonionic surfactants include secondary alcohol ethoxylated surfactants.

[0035] Cationic surfactants include quaternary surfactant compounds. Preferred cationic surfactants include quaternary surfactant compounds having at least one of ammonium, sulfonium, phosphonium, iodonium, and thiocyanate groups. More preferred cationic surfactants include at least one of dialkyldimethylammonium chloride and alkyldimethylbenzylammonium chloride. Even more preferred cationic surfactants include at least one of: C 16-18 Dialkyldimethylammonium chloride, C 8-18 Alkyl dimethyl benzyl ammonium chloride and dimethyl ditrude ammonium chloride. The most preferred cationic surfactant includes dimethyl ditrude ammonium chloride.

[0036] Amphoteric surfactants include betaine, amine oxides, alkylamide-alkylamines, alkyl-substituted amine oxides, acylated amino acids, derivatives of aliphatic quaternary ammonium compounds, and mixtures thereof. Preferred amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds. More preferred amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds having long-chain groups (having 8 to 18 carbon atoms). Even more preferred amphoteric surfactants include at least one of the following: C 12-14 Alkyl dimethylamine oxide, 3-(N,N-dimethyl-N-hexadecyl-ammonium)propane-1-sulfonate, 3-(N,N-dimethyl-N-hexadecyl-ammonium)-2-hydroxypropane-1-sulfonate. The most preferred amphoteric surfactants include C... 12-14 At least one of alkyl dimethylamine oxides.

[0037] Preferably, the liquid laundry detergent formulation of the present invention comprises 0.1% to 50% by weight (preferably 0.5% to 25% by weight; more preferably 0.75% to 20% by weight; still more preferably 0.8% to 15% by weight; most preferably 2.5% to 7.5% by weight) of a cleaning enhancer of formula I; wherein a is 1 to 30 (preferably 1 to 25; more preferably 1 to 20; most preferably 2 to 15); wherein each X is independently selected from the group consisting of formulas II, III and IV; wherein b is 0 to 4 (preferably 2) (when b is 0, there is a direct bond between the two nitrogen atoms); wherein c is 0 to 4 (preferably 2) (when c is 0, there is a direct bond between the two nitrogen atoms); wherein b + c = 4; wherein each R 4 Independently selected from hydrogen and C 1-4 alkyl groups (preferably, wherein each R 4 Independently selected from hydrogen and C 1-3 Alkyl groups; more preferably, wherein each R 4 Independently selected from hydrogen, ethyl, and methyl groups; most preferably, wherein each R 4 (for hydrogen) (optionally both R 4 Groups can link together to form a polycyclic diamine structure); where each R 5 Independently selected from hydrogen and C 1-4 alkyl groups (preferably, wherein each R 5 Independently selected from hydrogen and C 1-3 Alkyl groups; more preferably, wherein each R 5 Independently selected from hydrogen, ethyl, and methyl groups; most preferably, wherein each R 5 (for hydrogen); where each R 6 Independently selected from hydrogen and methyl groups (preferably, wherein each R...) 6 (for hydrogen); where R 7Selected from the group consisting of single bonds and bridging groups having 1 to 8 carbon atoms (preferably, wherein R 7 The group consisting of single bonds and bridging groups having 1 to 5 carbon atoms is selected; more preferably, wherein R 7 Selected from the group consisting of bridging groups having 1 to 5 carbon atoms; most preferably, wherein R 7 (Selected from the group consisting of -CH2CH2- groups and -CH2CH2CH2- groups), and wherein each * in formulas II, III and IV represents R. 1 or R 2 The key; where R 1 It has the formula V; where d is 5 to 150 (preferably 5 to 100; more preferably 5 to 50; most preferably 5 to 25); where each R 8 and R 9 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit d, R 8 and R 9 At least one of them is hydrogen; where R 10 Choose freely from hydrogen and C 1-22 The group consisting of alkyl groups (preferably, hydrogen and C) 1-4 Alkyl groups; more preferably, hydrogen and methyl groups; most preferably, hydrogen); and wherein * in formula V represents a bond with X (i.e., with formula II, III or IV); wherein each R 2 Independently having formula VI; wherein e is 5 to 150 (preferably 5 to 100; more preferably 5 to 50; most preferably 5 to 25); and wherein each R 11 and R 12 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit e, R 11 and R 12 At least one of them is hydrogen; and each * in formula VI represents a combination with X (i.e., with formula II, formula III or formula IV) or R. 3 The key; and where R 3 Choose freely from hydrogen and C 1-22 The group consisting of alkyl groups (preferably, hydrogen and C) 1-4Alkyl groups; more preferably, hydrogen and methyl groups; most preferably, hydrogen); and the condition is that X of formula I has 10 mol% to 100 mol% (preferably, 25 mol% to 100 mol%; more preferably, 40 mol% to 100 mol%; most preferably, 45 mol% to 100 mol%) of formula I; and the condition is that R of formula I has 40 mol% to 100 mol% (preferably, 45 mol% to 75 mol%; more preferably, 46 mol% to 60 mol%; most preferably, 47 mol% to 55 mol%) of formula I. 1 and R 2 The functional groups are ethylene oxide and C 3-8 A copolymer of epoxides (preferably, a copolymer of ethylene oxide and propylene oxide), wherein each copolymer contains 25 mol% to 99 mol% (preferably, 50 mol% to 95 mol%; more preferably, 60 mol% to 90 mol%; most preferably, 75 mol% to 85 mol%) of ethylene oxide.

[0038] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises additives selected from the group consisting of: builders (e.g., sodium bicarbonate, sodium carbonate, zeolite, sodium citrate, sodium tripolyphosphate, and aminocarboxylates (such as methylglycine diacetate or its sodium salt, or glutamate diacetate or its sodium salt)); water-soluble growth promoters (e.g., sodium xylenesulfonate); foam control formulations (e.g., fatty acids, polydimethylsiloxane); enzymes (e.g., proteases, cellulases, lipases, amylases, mannanases); preservatives; fragrances (e.g., essential oils, such as D-limonene); optical brighteners; bleaching agents (e.g., sodium percarbonate, sodium perborate, sodium hypochlorite); dyes; additive polymers (e.g., dispersant polymers, such as acrylic homopolymers and copolymers of acrylic acid with maleic acid, sulfonated monomers, and / or ethyl acrylate); and mixtures thereof.

[0039] Preferably, the liquid laundry detergent formulation of the present invention further comprises a water-soluble growth promoter. More preferably, the liquid laundry detergent formulation of the present invention further comprises 0% to 10% by weight (preferably 0.1% to 10% by weight; more preferably 0.2% to 8% by weight; most preferably 0.5% to 7.5% by weight) of a water-soluble growth promoter based on the weight of the liquid laundry detergent formulation. Still more preferably, the liquid laundry detergent formulation of the present invention further comprises 0% to 10% by weight (preferably 0.1% to 10% by weight; more preferably 0.2% to 8% by weight; most preferably 0.5% to 7.5% by weight) of a water-soluble growth promoter based on the weight of the liquid laundry detergent formulation; wherein the water-soluble growth promoter is selected from: calcium, sodium, potassium, ammonium and alkanol ammonium salts of xylenesulfonic acid, toluenesulfonic acid, ethylbenzenesulfonic acid, naphthalenesulfonic acid and isopropylbenzenesulfonic acid; their salts and mixtures thereof. More preferably, the liquid laundry detergent formulation of the present invention further comprises 0% to 10% by weight (preferably 0.1% to 10% by weight; more preferably 0.2% to 8% by weight; most preferably 0.5% to 7.5% by weight) of a water-soluble growth promoter based on the weight of the liquid laundry detergent formulation; wherein the water-soluble growth promoter is selected from the group consisting of: sodium toluenesulfonate, potassium toluenesulfonate, sodium xylenesulfonate, ammonium xylenesulfonate, potassium xylenesulfonate, calcium xylenesulfonate, sodium cumenesulfonate, ammonium cumenesulfonate, and mixtures thereof. Most preferably, the liquid laundry detergent formulation of the present invention further comprises 0% to 10% by weight (preferably 0.1% to 10% by weight; more preferably 0.2% to 8% by weight; most preferably 0.5% to 7.5% by weight) of a water-soluble growth promoter based on the weight of the liquid laundry detergent formulation; wherein the water-soluble growth promoter is sodium xylenesulfonate.

[0040] Preferably, the liquid laundry detergent formulation of the present invention further comprises a washing aid. More preferably, the liquid laundry detergent formulation of the present invention further comprises 0% to 30% by weight (preferably 1% to 20% by weight; more preferably 2.5% to 10% by weight) of the washing aid based on the weight of the liquid laundry detergent formulation. More preferably, the liquid laundry detergent formulation of the present invention further comprises 0% to 30% by weight (preferably 1% to 25% by weight; more preferably 2.5% to 10% by weight) of a builder based on the weight of the liquid laundry detergent formulation; wherein the builder is selected from the group consisting of: inorganic builders (e.g., tripolyphosphates, pyrophosphates); alkali metal carbonates; borates; bicarbonates; hydroxides; zeolites; citrates (e.g., sodium citrate); polycarboxylates; monocarboxylates; aminotrimethylenephosphonic acid; salts of aminotrimethylenephosphonic acid; hydroxyethylidene diphosphonic acid; salts of hydroxyethylidene diphosphonic acid; diethylenetriaminepenta (methylenephosphonic acid); salts of diethylenetriaminepenta (methylenephosphonic acid); ethylenediaminetetraethylenephosphonic acid; salts of ethylenediaminetetraethylenephosphonic acid; oligophosphonates; polymeric phosphonates; mixtures thereof. Most preferably, the liquid laundry detergent formulation of the present invention further comprises 0% to 30% by weight (preferably 1% to 25% by weight; more preferably 2.5% to 10% by weight) of a detergent builder based on the weight of the liquid laundry detergent formulation; wherein the detergent builder comprises sodium citrate.

[0041] Preferably, the liquid laundry detergent formulation of the present invention further comprises a fragrance. More preferably, the liquid laundry detergent formulation of the present invention further comprises 0% to 10% by weight (preferably 0.001% to 5% by weight; more preferably 0.005% to 3% by weight; most preferably 0.01% to 2.5% by weight) of fragrance based on the weight of the liquid laundry detergent formulation.

[0042] Preferably, the liquid laundry detergent formulation of the present invention further comprises a fabric softener. More preferably, the liquid laundry detergent formulation of the present invention further comprises 0% to 10% by weight (preferably 0.5% to 10% by weight) of a fabric softener based on the weight of the liquid laundry detergent formulation. Most preferably, the liquid laundry detergent formulation of the present invention further comprises 0% to 10% by weight (preferably 0.5% to 10% by weight) of a fabric softener based on the weight of the liquid laundry detergent formulation; wherein the fabric softener is a cationic coagulating polymer (e.g., cationic hydroxyethyl cellulose; polyquaternary ammonium salt polymers and combinations thereof).

[0043] Preferably, the liquid laundry detergent formulation of the present invention further comprises a pH adjuster. More preferably, the liquid laundry detergent formulation of the present invention further comprises a pH adjuster; wherein the pH of the liquid laundry detergent formulation is 6 to 12.5 (preferably 6.5 to 11; more preferably 7.5 to 10). The base used for adjusting the pH includes mineral bases such as sodium hydroxide (including soda ash) and potassium hydroxide; sodium bicarbonate; sodium silicate; ammonium hydroxide; and organic bases (e.g., monoethanolamine, diethanolamine, or triethanolamine; and 2-dimethylamino-2-methyl-1-propanol (DMAMP)). The acid used for adjusting the pH includes inorganic acids (e.g., hydrochloric acid, phosphorous acid, and sulfuric acid) and organic acids (e.g., acetic acid, citric acid).

[0044] Preferably, the method for washing soiled fabric articles according to the present invention includes: providing the soiled fabric article (preferably, wherein the soiled fabric article is soiled with oil and grease; more preferably, wherein the soiled fabric article is soiled with sebum) (preferably, wherein the soiled fabric article is soiled cotton fabric; more preferably, wherein the soiled fabric article is soiled polyester-cotton fabric); providing the liquid laundry detergent formulation of the present invention; providing washing water; and applying the washing water and the liquid laundry detergent formulation to the soiled fabric to provide a cleaned fabric article (preferably, wherein the temperature of the washing water is ≤35°C (preferably, 10°C to 35°C; more preferably, 15°C to 30°C; most preferably, 20°C to 25°C)). More preferably, the method for washing soiled fabric articles according to the present invention includes: providing the soiled fabric article (preferably, wherein the soiled fabric article is soiled with oil and grease; more preferably, wherein the soiled fabric article is soiled with sebum) (preferably, wherein the soiled fabric article is soiled cotton fabric; more preferably, wherein the soiled fabric article is soiled polyester-cotton fabric); providing the liquid laundry detergent formulation of the present invention; providing washing water; providing rinsing water; applying the washing water and the liquid laundry detergent formulation to the soiled fabric to provide a cleaned fabric article; wherein the washing water is at ≤35°C (preferably, 10°C to 35°C; more preferably, 15°C to 30°C; most preferably, 20°C to 25°C); and then applying rinsing water to the cleaned fabric article to remove the liquid laundry detergent formulation from the cleaned fabric article.

[0045] Some embodiments of the present invention will now be described in detail in the following examples.

[0046]

[0047]

[0048]

[0049] GPC Analysis :

[0050] Molecular weight determination was performed using a Waters ACQUITY UPLC H-Class system (with differential refractive index detector) equipped with an Agilent Plgel 3 μm MiniMixed-E 4.6 × 250 mm column. The mobile phase was THF containing 0.1% DEEN, and the flow rate was 0.3 mL / min. The injection volume was 5 μL. Each sample was injected twice. The polymer solution was dissolved at approximately 5 mg / mL and filtered through a 0.45 μm PTFE filter before analysis. Calibration was performed using PS standards (molecular weights from 580 Daltons to 377,400 Daltons).

[0051] Synthesize S1: pip-DAME

[0052] Pip-DAME was prepared by reacting piperazine with methyl bromoacetate according to a literature method (see Chamorro-Arenas, D.; Osorio-Nieto, U.; Quintero, L.; Hernández-García, L.; Sartillo-Piscel, F., J. Org. Chem. 2018, 83, ). 15,333-346. Methyl bromoacetate (21.73 g; 142 mmol) was added in small portions via pipette to a dispersion of piperazine (5.493 g; 64 mmol) and sodium carbonate (16.885 g; 160 mmol) in 250 mL of acetonitrile. The reaction mixture was heated from 20 °C to 30 °C during the addition. After standing overnight at room temperature, the sample was filtered through a vacuum-assisted sintered glass funnel. The filtrate was concentrated using a rotary evaporator. The resulting solid mass (15.678 g) was cooled and stirred in 200 mL of hexane for 4 hours. Two batches of product were collected, yielding a total of 3.5 g of white crystals. 1 ¹H NMR (δ, CDCl₃): 3.65 (s, 6H), 3.16 (s, 4H), 2.59 (br s, 8H). Repeating the preparation process under similar conditions yielded the same... 1 Materials with H NMR spectra and the following data: 13 C NMR (126MHz, CDCl3) δ 170.61, 59.31, 52.75, 51.64.

[0053] Synthesis of S2: pip-DAME-EO-PO diol

[0054] pip-DAME-EO-PO diol was prepared in a flask equipped with a heating mantle, a Vigro fractionating column, a vacuum line, and a stir bar. Pip-DAME (1.053 g; 4.57 mmol) and EO-PO diol (5.825 g; 5.94 mmol; UCON) prepared according to synthesis S1 were charged into the flask. ™ 75-H-450). The contents of the flask were bubbled with nitrogen and heated in a heating mantle at 149°C to 150°C for 2.5 hours. After heating, titanium isopropoxide (65 mg; 0.23 mmol) was injected into the contents of the flask using a syringe. The heating mantle was maintained at 150°C under vacuum (pressure gradually reduced from 157 Torr to 53 Torr) for approximately 3.3 hours. After cooling to room temperature under nitrogen, additional pip-DAME (0.197 g; 0.86 mmol) was added to the contents of the flask. The mixture was again heated under vacuum (pressure gradually reduced from 217 Torr to 49 Torr) at 150°C under a heating mantle for approximately 3.5 hours. Based on the integral ratios of protons in the secondary and primary alcohol esters to those in the pip-DAME ring (1.00 : 1.42 : 8.00, at 5.07 ppm, 4.23 ppm, and 2.61 ppm, respectively), the conversion of methyl ester was calculated to be 86%. The number-average molecular weight M of the product... n and weight average molecular weight M w The values ​​were measured by GPC as Mn = 4,086 Daltons and Mw = 13,008 Daltons.

[0055] Synthesis of S3: pip-DAME-EO-PO diol / PPG

[0056] pip-DAME-EO-PO diol / PPG was prepared in a flask equipped with a heating mantle, a Vigro fractionating column, a vacuum line, and a stir bar. The flask was loaded with pip-DAME (1.004 g; 4.36 mmol) and EO-PO diol (2.795 g; 2.85 mmol; UCON) prepared according to synthesis S1. ™75-H-450) and polypropylene glycol (1.140 g; 2.85 mmol; PPG-400). The contents of the flask were bubbled with nitrogen and heated in a heating mantle, the temperature of which increased from 34 °C to 57 °C over approximately 2 hours. Titanium isopropoxide (69 mg / 0.24 mmol) was then injected into the contents of the flask via a syringe. The contents of the flask were then heated in a heating mantle at 140 °C to 141 °C for 4 hours. After cooling overnight at room temperature, the contents of the flask were heated in a heating mantle at 141 °C and placed under vacuum (pressure gradually decreased from 202 Torr to 183 Torr) for approximately 3 hours. Based on the integral ratio of protons of secondary alcohol esters to protons of primary alcohol esters to protons of the pip-DAME ring (1.62 : 0.87 : 8.00, at 5.02 ppm, 4.19 ppm, and 2.58 ppm, respectively), the conversion of methyl esters was estimated to be substantially complete. Number-average molecular weight M of the product n and weight average molecular weight M w The values ​​were measured by GPC as Mn = 3,484 Daltons and Mw = 11,778 Daltons.

[0057] Synthesis of S4: pip-DAME / DMA-EO-PO diol / PPG

[0058] pip-DAME / DMA-EO-PO diol / PPG was prepared in a flask equipped with a heating mantle, a Vigro distillation column, a vacuum line, and a stir bar. EO-PO diol (5.545 g; 5.66 mmol; UCON) was added to the flask. ™ 75-H-450) and polypropylene glycol (2.250 g; 5.63 mmol; PPG-400). The contents of the flask were bubbled with nitrogen and heated in a heating mantle, the temperature of which increased from 58 °C to 114 °C over approximately 50 minutes. Then, pip-DAME (1.010 g; 4.39 mmol), dimethyl maleate (0.765 g; 4.39 mmol), and titanium isopropoxide (123 mg; 0.43 mmol) prepared according to synthesis S1 were added to the contents of the flask. Nitrogen bubbling was repeated, and the contents of the flask were heated in a heating mantle at a temperature of 144 °C to 145 °C for approximately 1.5 hours. The contents of the flask were then placed under partial vacuum (pressure gradually reduced from 194 Torr to 7 Torr) for approximately 3 hours. After cooling overnight at room temperature under nitrogen, the contents of the flask were heated in a heating mantle at 141°C to 155°C under controlled pressure (gradually decreasing from 196 Torr to 2.9 Torr) for approximately 6 hours. Based on the integral ratios of the protons of the secondary and primary alcohol esters, the protons of the pip-DAME ring, and the protons at positions 3 and 4 of dimethyl maleate (3.09 : 1.69 : 8.00 : 4.15, at 5.0 ppm, 4.15 ppm, 2.58 ppm, and 1.58 ppm, respectively), the conversion of methyl ester was estimated to be 96%. The number-average molecular weight M of the product is...n and weight average molecular weight M w The values ​​were measured by GPC as Mn = 3,278 Daltons and Mw = 9,541 Daltons.

[0059] Synthesis of S5: pip-DAME / DMTP-EO-PO diol / PPG

[0060] pip-DAME / DMTP-EO-PO diol / PPG was prepared in a flask equipped with a heating mantle, a Vigro distillation column, a vacuum line, and a stir bar. EO-PO diol (5.600 g; 5.71 mmol; UCON) was added to the flask. ™ 75-H-450) and polypropylene glycol (2.296 g; 5.74 mmol; PPG-400). The contents of the flask were bubbled under nitrogen in a heated oil bath at a temperature between 89°C and 99°C for about 100 minutes. Then, pip-DAME (1.016 g; 4.41 mmol) and dimethyl terephthalate (0.854 g; 4.40 mmol) prepared according to synthesis S1 were added to the contents of the flask. The contents of the flask were bubbled again for another 10 minutes, and then titanium isopropoxide (137 mg; 0.48 mmol) was injected into the contents of the flask. The contents of the flask were then heated under nitrogen in an oil bath at a temperature of 114°C for 0.5 hours. The contents of the flask were then placed under partial vacuum (188 Torr to 196 Torr) for about 5.3 hours. The contents of the flask were then cooled to room temperature. Based on the integral ratios of protons in secondary and primary alcohol esters, protons in the pip-DAME ring, and aromatic protons in dimethyl terephthalate (3.16 : 1.87 : 8.00 : 4.25, respectively, at 4.9 ppm to 5.3 ppm, 4.1 ppm to 4.4 ppm, and 8.0 ppm), the conversion of methyl esters was found to be essentially quantitative. The number-average molecular weight M of the product was... n and weight average molecular weight M w The values ​​were measured by GPC as Mn = 3,040 Daltons and Mw = 7,775 Daltons.

[0061] Synthesizing S6: pyr-DMM

[0062] Pyr-DMM was prepared in a flask equipped with a heating mantle and stirrer. Dimethyl maleate (10.057 g; 70 mmol) and methanol (10.06 g) were added to the flask. The contents of the flask were placed under nitrogen in a heating mantle. Then, pyrrolidine (4.4 g; 62 mmol) was slowly added to the contents of the flask using a syringe. The contents of the flask were then maintained at 45°C to 50°C for approximately 7 hours. The methanol was then removed from the contents of the flask by rotary evaporation. The contents of the flask were then cooled by immersion in a 50°C water bath. The recovered product was then processed... 1¹H NMR (500MHz, CDCl₃) δ 3.80 – 3.73 (m, 2H), 3.68 (s, 3H), 3.63 (s, 3H), 2.83 (dd, J = 16.1, 9.0Hz, 1H), 2.70 – 2.51 (m, 5H), 1.78 – 1.62 (m, 4H) and quantitative analysis. 13 The values ​​of C NMR (126MHz, CDCl3) were 171.80 (1C), 171.63 (1C), 60.82 (1C), 51.73 (1C), 51.54 (1C), 49.75 (2C), 35.40 (1C), and 23.56 (2C) ppm.

[0063] Synthesis of S7: pyr-DMI

[0064] pyr-DMI was prepared by charging a flask with dimethyl itaconic acid (10.80 g; 68 mmol) and methanol (10 g). Pyrrolidine (4.4 g; 62 mmol) was then slowly added to the flask contents via syringe at room temperature. During the addition of pyrrolidine, the temperature of the flask contents increased from 21 °C to 27 °C. After standing overnight at room temperature under nitrogen, the flask contents were concentrated by rotary evaporation and then dried under vacuum for 3 hours. The recovered product was then processed... 1 ¹H NMR (500MHz, CDCl₃) δ 3.57 (s, 3H), 3.53 (s, 3H), 2.91 (m, 1H), 2.46–2.58 (m, 4H), 2.36 (m, 4H), 1.60 (s, 4H) and quantitative analysis. 13 The values ​​were analyzed by C NMR (126MHz, CDCl3) δ 174.35 (1C), 172.39 (1C), 57.16 (1C), 53.91 (2C), 51.65 (1C), 51.44 (1C), 41.27 (1C), 34.15 (1C), 23.50 (2C) ppm.

[0065] Synthesis of S8: pyr-DMM / DMS-PEG / PPG

[0066] Pyr-DMM / DMS-PEG / PPG was prepared in a flask equipped with a heating mantle, vacuum line, and stir bar. Pyr-DMM (4.201 g; 19.5 mmol) and polyethylene glycol (6.515 g; 21.7 mmol; PEG-300) prepared according to synthesis S7 were added to the flask. The contents of the flask were bubbled with nitrogen and heated in a heating mantle. Then, titanium isopropoxide (0.232 g; 0.82 mmol) was added to the contents of the flask, and the reaction was carried out under vacuum at 101 °C to 113 °C for approximately 3 hours. The contents of the flask were then cooled to room temperature. Dimethyl succinate (2.965 g; 20.3 mmol) and polyethylene glycol (9.008 g; 22.5 mmol; PPG-400) were added to the contents of the flask. The contents of the flask were then heated under vacuum at 101 °C to 113 °C for approximately 4 hours. The contents of the flask were then cooled to room temperature. Additional titanium isopropoxide (0.278 g; 0.98 mmol) was added to the contents of the flask. The contents of the flask were then held under partial vacuum at 101°C to 113°C for approximately 6.5 hours. 1 The integral ratios of the nonmethyl ester to diester in the 1H NMR spectra at 4.9 ppm (2.00, secondary ester), 4.0 ppm to 4.2 ppm (4.73, primary ester), 2.3 ppm to 2.8 ppm (11.90, contributions from 6 protons from pyr-DMM and 4 protons from DMS), and 1.6 ppm (4 protons from pyr-DMM) were estimated to be (2 + (4.73 / 2)) : ((4 / 4) + (10.67-6) / 4) = 4.37 : 2.16, indicating that the transformation was essentially complete. The number-average molecular weight M of the product was... n and weight average molecular weight M w The values ​​were measured by GPC as Mn = 1,485 Daltons and Mw = 2,679 Daltons.

[0067] Synthesis of S9: pyr-DMI-PEG / PPG

[0068] pyr-DMI-PEG / PPG was prepared in a flask equipped with a heating mantle, vacuum line, and stir bar. EO-PO diol (8.274 g; 8.44 mmol; UCON) was added to the flask. ™75-H-450) and polypropylene glycol (3.383 g; 8.46 mmol; PPG-400). The contents of the flask were bubbled with nitrogen and heated in a heating mantle, the temperature of which increased from 25 °C to 117 °C over approximately 2.5 hours. Then, pyr-DMI (3.020 g; 19.5 mmol) and titanium isopropoxide (188 mg; 0.66 mmol) prepared according to synthesis S8 were added to the contents of the flask. The contents of the flask were then heated under controlled vacuum (set point 45 Torr) in a heating mantle at 135 °C to 140 °C for approximately 3.9 hours. The contents of the flask were then cooled to room temperature. Then, pyr-DMI (0.755 g; 3.3 mmol) was added to the contents of the flask. The contents of the flask were then heated under controlled vacuum (set point 200 Torr) in a heating mantle at 141 °C for approximately 2.2 hours. The contents of the flask were then cooled to room temperature. Then, pyr-DMI (0.798 g; 3.5 mmol) and titanium isopropoxide (95 mg, 0.33 mmol) were added to the contents of the flask. The contents were then heated under controlled vacuum (set point gradually decreasing from 200 Torr to 15 Torr) at 121 °C with a heating mantle for approximately 3.5 hours. The contents were then cooled overnight at room temperature under nitrogen. Finally, the contents were heated under controlled vacuum (set point gradually decreasing from 15 Torr to 0.8 Torr) at 140 °C with a heating mantle for approximately 5.3 hours. 1 The integral ratios of the nonmethyl ester to diester in the 1H NMR spectra at 4.8 ppm to 5.1 ppm (1.58, secondary ester), 4.0 ppm to 4.3 ppm (1.13, primary ester), and 1.6 ppm (4.00, 4 protons from pyr-DMI) were estimated to be (1.58 + (1.13 / 2)) : ((4 / 4) = 2.15 : 1, indicating that the conversion was essentially complete. The number-average molecular weight M of the product was... n and weight average molecular weight M w The values ​​were measured by GPC as Mn = 2,282 Daltons and Mw = 4,368 Daltons.

[0069] Synthesis of S10: DMA / BHE-pip-EO-PO diol

[0070] DMA / BHE-pip-EO-PO diol was prepared in a flask equipped with a heating mantle, vacuum line, and stir bar. EO-PO diol (12.252 g; 12.50 mmol; UCON) was added to the flask. ™75-H-450). The contents of the flask were bubbled with nitrogen and heated in a heating mantle, the temperature of which increased from 42°C to 100°C over approximately 2 hours. Dimethyl adipate (3.563 g; 20.45 mmol) and zirconium acetylacetonate (IV) (190 mg; 0.39 mmol) were then added to the contents of the flask. The contents of the flask were then heated in a heating mantle under controlled vacuum (set point gradually decreased from 170 Torr to 44 Torr), the temperature of which increased from 98°C to 139°C over approximately 3.2 hours. The contents of the flask were then cooled to room temperature. 1,1'-(piperazine-1,4-diyl)bis(propane-2-ol) (2.203 g; 12.64 mmol; BHE-pip) were then added to the contents of the flask. The contents of the flask were then heated in a heating mantle under controlled vacuum (set point 200 Torr) at 121°C to 122°C for approximately 2.2 hours. The contents of the flask were then cooled overnight at room temperature under nitrogen. The contents were then heated for approximately 2.5 hours under a controlled vacuum (setpoint gradually decreasing from 200 Torr to 15 Torr) with a heating mantle at 121°C to 122°C. The contents were then cooled overnight at room temperature under nitrogen. The contents were then heated for approximately 5.7 hours under a controlled vacuum (setpoint gradually decreasing from 200 Torr to 15 Torr) with a heating mantle at 140°C. The contents were then cooled overnight at room temperature under nitrogen. The contents were then heated for approximately 4 hours under a controlled vacuum (setpoint gradually decreasing from 227 Torr to 0.07 Torr) with a heating mantle at 140°C. 1 The integral ratios of the nonmethyl ester to diester in the 1H NMR spectra at 4.9 ppm to 5.1 ppm (0.44, secondary ester), 4.0 ppm to 4.1 ppm (2.54, primary ester), and 1.5 ppm (4.00, four protons at positions 3 and 4 of dimethyl adipate (DMA)) were estimated to be (0.44 + (2.54 / 2)): ((4 / 4) = 1.71 : 1, indicating a conversion of 86%. The number-average molecular weight M of the product was... n and weight average molecular weight M w The values ​​were measured by GPC as Mn = 2,163 Daltons and Mw = 3,613 Daltons.

[0071] Synthetic S11: BHP-pip

[0072] The synthesis of 1,1'-(piperazine-1,4-diyl)bis(propane-2-ol) (BHP-pip) was carried out in a 48-position stainless steel parallel pressure reactor equipped with a glass liner and mechanical stirring. Piperazine (1.29 g; 15 mmol) was added to each reaction site. The reactor was sealed, and the temperature setpoint was raised to 110 °C to melt the piperazine. Propylene oxide (2.21 mL; 31.5 mmol) was injected into each reaction site; the temperature setpoint was raised to 130 °C, and the reactor contents were stirred for 20 hours. Leaks were found in four reactors, and the products from these leaks were not included in subsequent work. The contents of the remaining reactors were combined to give 124.8 g of BHP-pip. 1 ¹H NMR (d, CDCl₃), ppm: 3.78 (m, 2H), 3.40 (s, 2H), 2.14–2.74 (br, 12H), 1.10, 1.08 (two s, 6H). 13 C NMR (DMSO) δ 65.99, 63.11, 53.43, 21.76 ppm.

[0073] Synthesis of S12: DMA / BHP-pip-EO-PO diol

[0074] DMA / BHP-pip-EO-PO diol was prepared in a flask equipped with a heating mantle, vacuum line, and stir bar. EO-PO diol (12.125 g; 12.37 mmol; UCON) was added to the flask. ™75-H-450) and BHP-pip (2.507 g; 12.39 mmol) prepared according to synthesis S11. The contents of the flask were bubbled with nitrogen and heated in a heating mantle, the temperature of which increased from 65 °C to 125 °C over approximately 2 hours. Dimethyl maleate (DMA) (3.436 g; 19.72 mmol) and titanium isopropoxide (279 mg; 0.98 mmol) were then added to the contents of the flask. The contents of the flask were then heated in a heating mantle under controlled vacuum (gradually decreasing from 198 Torr to 81 Torr), the temperature of which increased from 129 °C to 149 °C over approximately 4.2 hours. The contents of the flask were then cooled overnight at room temperature under nitrogen. The contents of the flask were then heated in a heating mantle under controlled vacuum (set point 200 Torr) at a temperature of 153 °C to 154 °C for approximately 4.8 hours. The contents of the flask were then cooled overnight at room temperature under nitrogen again. The contents of the flask were then heated under a controlled vacuum (gradually decreasing from 200 Torr to 50 Torr) with a heating mantle, the temperature of which increased from 132°C to 151°C over approximately 6.2 hours. The contents were then cooled again overnight at room temperature under nitrogen. The contents were then heated under a controlled vacuum (gradually decreasing from 200 Torr to 50 Torr) with a heating mantle at 160°C to 162°C for approximately 3.5 hours. The contents were then cooled to room temperature. 1 The integral ratios of the nonmethyl ester to diester in the ¹H NMR spectra at 4.8 ppm to 5.1 ppm (1.45, secondary ester), 4.0 ppm to 4.2 ppm (0.83, primary ester), and 1.4 ppm to 1.7 ppm (4.00, four protons at positions 3 and 4 of dimethyl adipate (DMA)) were estimated to be (1.45 + (0.83 / 2)) : ((4 / 4) = 1.87 : 1, indicating a conversion of 93%. The number-average molecular weight M of the product was... n and weight average molecular weight M w The values ​​were measured by GPC as Mn = 3,015 Daltons and Mw = 6,940 Daltons.

[0075] Synthetic S13: pip-MA

[0076] The synthesis of 1,4-dimethyl 1,4-piperazine dipropionate (pip-MA) was carried out in a flask equipped with an internal vapor thermocouple, a feeding funnel, a condenser, a stir bar, and a distillation receiver. Methyl acrylate (MA) (82.5 g; 0.96 mol) was added to the flask. A solution of piperazine (43 g; 0.50 mol) in methanol (120 g) was added to the feeding funnel. The contents of the flask were heated to 50 °C, and the piperazine / methanol solution in the feeding funnel was added over 130 minutes. The temperature of the contents of the flask was raised to 56 °C, and after the addition of the piperazine / methanol solution, the contents of the flask were stirred for another 30 minutes. The contents of the flask were then distilled at a temperature of 34 °C to 60 °C to remove methanol, while the pressure on the contents of the flask was slowly reduced from 200 Torr to 2 Torr. A white, lumpy solid product (123.3 g) was recovered; the distillate recovery was 120.0 g. 1 ¹H NMR (500MHz, CDCl₃) δ 3.60 (s, 6H), 2.61 (dd, J = 6.89, 7.96Hz, 4H), 2.42 (m, 12H) and quantitative analysis. 13 C NMR (126MHz, DMSO-d6) δ 172.30 (2C), 53.09 (2C), 52.41 (4C), 51.16 (2C), 31.55 (2C).

[0077] Synthesis of S14: pip-MA-EO-PO diol

[0078] pip-MA-EO-PO diol was prepared in a flask equipped with a heating mantle, vacuum line, and stir bar. EO-PO diol (6.615 g; 5.73 mmol; UCON) was added to the flask. ™(75-H-450). The contents of the flask were bubbled with nitrogen and heated in a heating mantle, the temperature of which increased from 79°C to 103°C in about 1.6 hours. Then, pip-MA (1.293 g; 5.01 mmol) and titanium isopropoxide (64 mg; 0.23 mmol) prepared according to synthesis S13 were added to the contents of the flask. The contents of the flask were then heated in a heating mantle under controlled vacuum (from 185 Torr to 200 Torr), the temperature of which increased from 148°C to 153°C in about 5 hours. The contents of the flask were then cooled overnight at room temperature under nitrogen. The contents of the flask were then heated in a heating mantle under controlled vacuum (set point 190 Torr) at a temperature of 150°C to 152°C for about 7.5 hours. The contents of the flask were then cooled overnight at room temperature under nitrogen again. Titanium isopropoxide (61 mg; 0.21 mmol) was then added to the contents of the flask. The contents of the flask were then heated under a controlled vacuum (gradually decreasing from 200 Torr to 50 Torr) at 150°C for approximately 3.3 hours with a heating mantle. The contents were then cooled again overnight at room temperature under nitrogen. The contents were then heated under a controlled vacuum (200 Torr to 210 Torr) at 153°C for approximately 3.5 hours with a heating mantle. The contents were then cooled again overnight at room temperature under nitrogen. The contents were then heated again under a controlled vacuum (gradually decreasing from 200 Torr to 50 Torr) at 153°C with a heating mantle for approximately 5.3 hours. The contents were then cooled to room temperature. 1 The integral ratios of the nonmethyl ester to diester in the ¹H NMR spectra at 4.8 ppm to 5.0 ppm (1.03, secondary ester), 4.0 ppm to 4.2 ppm (1.52, primary ester), and 2.0 ppm to 2.7 ppm (16.00, pip-MA) are estimated to be (1.03 + (1.52 / 2)) : ((16 / 16) = 1.79 : 1, indicating a conversion of 90%. The number-average molecular weight M of the product is... n and weight average molecular weight M w The values ​​were measured by GPC as Mn = 2,770 Daltons and Mw = 5,790 Daltons.

[0079] Synthesis of S15: pip-MA / DMA-EO-PO diol / PPG

[0080] pip-MA / DMA-EO-PO diol / PPG was prepared in a flask equipped with a heating mantle, vacuum line, and stir bar. EO-PO diol (5.636 g; 5.73 mmol; UCON) was added to the flask. ™75-H-450) and polypropylene glycol (2.313 g; 5.78 mmol; PPG-400). The contents of the flask were bubbled with nitrogen and heated in a heating mantle, the temperature of which increased from 23 °C to 105 °C in about 2.3 hours. Then, pip-MA (1.202 g; 4.65 mmol), dimethyl adipate (DMA) (0.787 g; 4.52 mmol), and titanium isopropoxide (121 mg; 0.23 mmol) prepared according to synthesis S13 were added to the contents of the flask. The contents of the flask were then heated in a heating mantle under controlled vacuum (200 Torr to 210 Torr), the temperature of which increased from 151 °C to 155 °C in about 3.5 hours. The contents of the flask were then cooled overnight under nitrogen. The contents of the flask were then heated in a heating mantle at 155 °C for about 5.3 hours under controlled vacuum (from 200 Torr to 50 Torr). Based on 1 The integral ratios of the nonmethyl ester to diester in the ¹H NMR spectra at 4.8 ppm to 5.0 ppm (2.92, secondary ester), 4.0 ppm to 4.2 ppm (1.71, primary ester), 2.1 ppm to 2.6 ppm (18.75, pip-MA), and 1.4 ppm to 1.6 ppm (4.00, 4 protons of DMA) were estimated to be (2.92 + (1.71 / 2)) : ((18.75 / 16) + (4 / 4) = 1.74 : 1, indicating a conversion of 87%. The number-average molecular weight M of the product was... n and weight average molecular weight M w The values ​​were measured by GPC as Mn = 2,925 Daltons and Mw = 6,950 Daltons.

[0081] Synthesis of S16: Piperidine-DMM

[0082] Dimethyl 2-(piperidin-1-yl)succinate (piperidine-DMM) was prepared in a flask equipped with a heating mantle, vacuum line, and stir bar. Piperidine (5.320 g; 62.47 mmol) and methanol (19.9 g) were added to the flask contents over a period of 9 minutes. Dimethyl maleate (DMM) (10.014 g; 69.5 mmol) formed. After standing overnight at room temperature, the solvent was removed by a nitrogen stream, and the white precipitate was recovered. 1 ¹H NMR (500MHz, CDCl₃) δ 3.61 (s, 3H), 3.58 (s, 3H), 2.73 (m, 1H), 2.51 (m, 3H), 2.29 (m, 2H), 1.42 (br, 4H), 1.29 (m, 2H). (via ¹H NMR) 1¹H NMR analysis revealed that the recovered product contained 13 mol% (9 wt%) dimethyl fumarate. Quantitative analysis was performed. 13 C NMR (126MHz, CDCl3) δ 171.81 (1C), 171.20 (1C), 64.13 (1C), 51.51 (1C), 51.14 (1C), 50.84 (2C), 34.05 (1C), 26.38 (2C), 24.27 (1C) ppm.

[0083] Synthesis of S17: Piperidine-DMM-EO-PO diol

[0084] Piperidine-DMM-EO-PO diol was prepared in a flask equipped with a heating mantle, vacuum line, and stir bar. EO-PO diol (5.531 g; 5.64 mmol; UCON) was added to the flask. ™ 75-H-450). The contents of the flask were bubbled with nitrogen and heated in a heating mantle, the temperature of which increased from 68°C to 111°C over approximately 1.3 hours. The contents of the flask were then cooled to room temperature. Piperidine-DMM (0.939 g; 4.10 mmol) and titanium isopropoxide (68 mg; 0.24 mmol) prepared according to synthesis S16 were then added to the contents of the flask. The contents of the flask were then heated in a controlled vacuum (200 Torr) at 150°C in an oil bath for approximately 5 hours. The contents of the flask were then cooled overnight at room temperature under nitrogen. The contents of the flask were then heated in a controlled vacuum (46 Torr) at 155°C with a heating mantle for approximately 7 hours. Based on 1 The integral ratios in the ¹H NMR spectrum at 4.9 ppm to 5.2 ppm (1.18, secondary ester), 4.1 ppm to 4.4 ppm (1.69, primary ester), 1.46 ppm to 1.35 ppm (6.00, protons at positions 3, 4, and 5 on the piperidine-DMM ring), and 6.8 ppm (0.23, fumarate =CH- proton) indicate a methyl ester conversion of 90%. The number-average molecular weight M of the product is... n and weight average molecular weight M w The values ​​were measured by GPC as Mn = 2,920 Daltons and Mw = 6,210 Daltons.

[0085] Polymer hydrolysis

[0086] The stability of polymer products derived from synthesized S2-S5 (in this invention) and synthesized S8-10, S12, S14-S15 and S17 (comparative examples) was evaluated by measuring ester retention after 4 days at pH 8.25 and 20°C using the following NMR procedure. The results are provided in Table 1.

[0087] NMR method for estimating the degree of hydrolysis using proton NMR spectroscopyA 1% (w / w) solution of each analyte was prepared by dissolving 0.10 g of the analyte in 9.9 g of 10 mM Tris buffer at pH 8.25. A time = 0 spectrum was obtained by transferring approximately 0.75 mL of the test solution to a 5 mm NMR tube and adding 4 drops of D₂O. The relaxation time was 20 seconds at 40 °C. 1 H(zg30) and water inhibition ( 1 H; Noesygppr1d) experiment. The test solution was stored at 20°C, and after 4 days, another portion of the test solution was aliquoted to record another spectrum. The peaks at approximately 5.4 ppm (corresponding to secondary-C(O)OCH- esters) and approximately 4.5 ppm (corresponding to primary-C(O)OCH2- esters) were integrated and normalized to peak integrals or receiver gains from 1.0 ppm to 1.4 ppm. Comparing the integrals of these two peaks between the spectra at t = 0 and t = 4 provides the percentage of each type of ester retained in the tested polymer. Total ester retention (%) was calculated on a molar basis. In this document, the terms “primary ester” and “primary alcohol ester” should be understood to exclude methyl esters.

[0088]

[0089] Comparative Examples CF1-CF5 and Examples F1-F4: Liquid Laundry Detergent

[0090] The liquid laundry detergent formulations used in the cleaning tests of subsequent examples CF1-CF5 and Examples F1-F4 were prepared according to the general formulations described in Table 2, wherein the cleaning enhancers are shown in Table 3, and were neutralized to pH 8.5 with sodium hydroxide using standard liquid laundry detergent formulation preparation procedures.

[0091]

[0092]

[0093] Primary cleaning performance

[0094] The primary cleaning performance of the liquid laundry detergent formulations of Comparative Examples CF1-CF5 and Examples F1-F4 was evaluated in a Launder-Ometer (SDL Atlas, Model M228AA) using an 18-minute wash cycle at a set test temperature of 22°C. Twenty 1.2-liter tanks were used per run, each filled with 500 mL of Ca at 100 ppm by weight. 2+ :Mg 2+Water with a hardness adjusted to a molar ratio of 2:1. Add liquid laundry detergent (2.16 g) as shown in Table 4. Washed fabrics were rinsed at ambient temperature in an Eberbach E6000 reciprocating shaker at 300 mL of 100 ppm (2 / 1 Ca) solution. 2+ / Mg 2+ The samples were rinsed for 5 minutes at 260 osc / min pm in hardness-adjusted water. The soiled fabric and soiled ballast used in the tests were Testfabrics' PCS-S-132 High Resolution Sebum BEY Pigment and PCS-S-94 Sebum / Dust ASTM Stains, sewn onto pre-shrinked double-cotton fabric. The double-cotton fabric was 5×5 cm in size. The soiled sample was 2.5×3 cm. A 5×5 cm cut SBL-CFT soiled ballast was added to each tank to provide a baseline soil for the washing solution.

[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:

[0098]

[0099] 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

[0100]

[0101] The ΔSRI values ​​provided in Table 4 show the difference between the SRI measured in the noted examples and the SRI measured in Comparative Example CF1. Positive values ​​indicate enhanced detergency compared to Comparative Example CF1.

[0102]

Claims

1. A cleaning enhancer for cleaning clothes, wherein the cleaning enhancer has Formula I Where a is 1 to 30; where each X is independently selected from the group consisting of formulas II, III and IV. Where b is between 0 and 4; where c is between 0 and 4; where b + c = 4; where each R 4 Independently selected from hydrogen and C 1-4 alkyl groups; wherein each R 5 Independently selected from hydrogen and C 1-4 alkyl groups; wherein each R 6 Independently selected from hydrogen and methyl groups; wherein R 7 Choose from the group consisting of single bonds and bridging groups having 1 to 8 carbon atoms; and wherein each * in formulas II, III and IV represents a group with R 1 or R 2 The key; Where R 1 Having V Where d ranges from 5 to 150; where each R 8 and R 9 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit d, R 8 and R 9 At least one of them is hydrogen; where R 10 Choose freely from hydrogen and C 1-22 A group consisting of alkyl groups; and wherein * in formula V represents a bond with X; Each R 2 Independently possessing a VI Where e is between 5 and 150; and where each R 11 and R 12 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit e, R 11 and R 12 At least one of them is hydrogen; and each * in formula VI represents a combination with X or R. 3 The key; and Where R 3 Choose freely from hydrogen and C 1-22 Groups composed of alkyl groups; The condition is that X in Equation I, ranging from 10 mol% to 100 mol%, has the properties of Equation II; and The condition is that R exists in Equation I at a rate of 40 mol% to 100 mol%. 1 and R 2 The functional groups are ethylene oxide and C 3-8 Copolymers of epoxides, wherein each copolymer contains 25 mol% to 99 mol% ethylene oxide.

2. A liquid laundry detergent formulation, comprising: The liquid carrier comprises 25% to 98.9% by weight of the liquid laundry detergent formulation. Based on the liquid laundry detergent formulation, 1% to 60% by weight of a cleaning surfactant; and The cleaning enhancer according to claim 1 comprises 0.1% to 50% by weight of the liquid laundry detergent formulation.

3. The liquid laundry detergent formulation according to claim 2, wherein the cleaning surfactant comprises anionic surfactant.

4. The liquid laundry detergent formulation according to claim 3, wherein the liquid carrier comprises water.

5. The liquid laundry detergent formulation according to claim 4, wherein the liquid carrier further comprises a water-miscible liquid.

6. The liquid laundry detergent formulation according to claim 5, wherein the liquid laundry detergent formulation further comprises a water-soluble growth promoter.

7. The liquid laundry detergent formulation according to claim 6, wherein 45 mol% to 100 mol% of X in formula I has formula II.

8. The liquid laundry detergent formulation according to claim 7, wherein 40 mol% to 100 mol% of said R is present in formula I. 1 and R 2 The group is a copolymer of ethylene oxide and propylene oxide.

9. The liquid laundry detergent formulation according to claim 8, wherein a is 2 to 15; wherein b is 2; wherein c is 2; wherein each R 4 R 5 and R 6 It is hydrogen; where d is 5 to 25; and where e is 5 to 25.

10. A method for washing soiled textile articles, the method comprising: Provide soiled textile products; Provides a liquid laundry detergent formulation according to claim 9; Provide washing water; as well as The washing water and the liquid laundry detergent formulation are applied to the soiled fabric to provide a cleaned fabric.

Images