Lactone cleaning enhancer and liquid laundry detergent

Abstract

A cleaning enhancer (I) is provided, wherein a is 0 to 1; wherein b is 0 to 1; wherein c is 0 to 4; wherein d is 0 to 4; wherein c + d = 4; wherein R 1 It is hydrogen or C 1‑4 alkyl groups; wherein R 2 It is hydrogen or C 1‑4 alkyl groups; wherein R 3 It has Equation II, where e is 4 to 100; where f is 1 to 20; where g is 0 to 6; where h is 0 to 6; where g+h is 1 to 6; where R 4 C 1‑16 alkyl groups; wherein R 5 and R 6 It is hydrogen or C 1‑2 alkyl groups, provided that in each subunit e, R 5 and R 6 At least one of them is hydrogen; where R 7 It is hydrogen or C 1‑18 Alkyl group; and wherein the * in formula (II) represents a bond with formula (I).

Description

[0001] This invention relates to a cleaning enhancer. Specifically, this invention relates to a cleaning enhancer for cleaning clothing, wherein the cleaning enhancer has formula I.

[0002]

[0003] Where a is 0 or 1; where b is 0 or 1; where c is 0 to 4; where d is 0 to 4; where c + d = 4; where each R 1 Independently selected from hydrogen and C 1-4 alkyl groups; wherein each R 2 Independently selected from hydrogen and C 1-4 alkyl groups; wherein each R 3 Independently possessing Formula II

[0004]

[0005] Where e is 4 to 100; where f is 1 to 20; where g is 0 to 6; where h is 0 to 6; where g + h = 1 to 6; where R 4 C 1-16 alkyl groups; wherein each R 5 and R 6 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit e, R 5 and R 6 At least one of them is hydrogen; wherein each R 7 Independently selectable from hydrogen and C 1-18 A group consisting of alkyl groups; and wherein the * in formula II represents a bond with formula I.

[0006] 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.

[0007] 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.

[0008] 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 protocol.

[0009] This invention provides a cleaning enhancer for cleaning clothes, wherein the cleaning enhancer has Formula I

[0010]

[0011] Where a is 0 or 1; where b is 0 or 1; where c is 0 to 4; where d is 0 to 4; where c + d = 4; where each R 1 Independently selected from hydrogen and C 1-4 alkyl groups; wherein each R 2 Independently selected from hydrogen and C 1-4 alkyl groups; wherein each R 3 Independently possessing Formula II

[0012]

[0013] Where e is 4 to 100; where f is 1 to 20; where g is 0 to 6; where h is 0 to 6; where g + h = 1 to 6; where R 4 C 1-16 alkyl groups; wherein each R 5 and R 6 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit e, R 5 and R 6 At least one of them is hydrogen; wherein each R 7 Independently selectable from hydrogen and C 1-18 A group consisting of alkyl groups; and wherein the * in formula II represents a bond with formula I.

[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] This 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 a cleaning enhancer of formula Ia, based on the weight of the liquid laundry detergent formulation.

[0016]

[0017] Each R 3 Independently possessing Equation II; where e is 4 to 100; where f is 1 to 20; where g is 0 to 6; where h is 0 to 6; where g + h = 1 to 6; where R 4 C 1-16 alkyl groups; wherein each R 5 and R 6 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit e, R 5 and R 6 At least one of them is hydrogen; wherein each R 7 Independently selectable from hydrogen and C 1-18 A group consisting of alkyl groups; and wherein the * in formula II represents a bond with formula Ia.

[0018] This 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 a cleaning enhancer of formula Ia, based on the weight of the liquid laundry detergent formulation; wherein each R 3 Independently possessing formula IIa

[0019]

[0020] Where e is 4 to 100; where f is 1 to 20; where i is 2 to 7; where R 4 C 1-16 Alkyl groups; wherein the asterisk (*) in formula IIa indicates a bond with formula Ia.

[0021] The present invention provides a method for washing soiled textile articles, the method comprising: providing the soiled textile 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 textile articles to provide cleaned textile articles. Detailed Implementation

[0022] Surprisingly, it has been found that materials with a six-membered saturated hydrocarbon ring according to Formula I, in which two carbon atoms of the six-membered saturated hydrocarbon ring have been replaced by nitrogen atoms, wherein each nitrogen atom is further linked to a -C(O)O- group via a -CH2- segment, provide effective dirt-removing benefits for liquid laundry detergent formulations containing it, particularly at low temperatures (i.e., 22°C) to remove oil and grease-laden dirt (e.g., sebum dirt) from cotton fabrics (e.g., polyester-cotton blends), and as an additional benefit, the material exhibits readily biodegradable properties according to the OECD 301F procedure.

[0023] 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.

[0024] 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.

[0025] Preferably, the cleaning enhancer for cleaning clothes of the present invention has Formula I

[0026]

[0027] Where a is 0 or 1 (preferably 0); where b is 0 or 1 (preferably 0); where c is 0 to 4 (preferably 2) (when b is 0, there is a direct bond between the two nitrogen atoms); where d is 0 to 4 (preferably 2) (when c is 0, there is a direct bond between the two nitrogen atoms); where c + d = 4; where each R 1 Independently selected from hydrogen and C 1-4 alkyl groups (preferably, wherein each R 1 Independently selected from hydrogen and C 1-3 Alkyl groups; more preferably, wherein each R 1Independently selected from hydrogen and ethyl and methyl groups; most preferably, wherein each R 1 (It is hydrogen) (optionally any two of the Rs) 1 Groups can be linked together to form a ring); where each R 2 Independently selected from hydrogen and C 1-4 alkyl groups (preferably, wherein each R 2 Independently selected from hydrogen and C 1-3 Alkyl groups; more preferably, wherein each R 2 Independently selected from hydrogen and ethyl and methyl groups; most preferably, wherein each R 2 (for hydrogen); where each R 3 Independently possessing Formula II

[0028]

[0029] Where e is 4 to 100 (preferably 5 to 50; more preferably 6 to 30; most preferably 6 to 15); where f is 1 to 20 (preferably 1 to 10; more preferably 1 to 6; most preferably 1 to 3); where g is 0 to 6; where h is 0 to 6; where g + h = 1 to 6 (preferably 2 to 6; more preferably 3 to 5; most preferably 4); where R 4 C 1-16 alkyl group (preferably, C 1-14 Alkyl groups; more preferably, C 1-4 Alkyl groups; most preferably, methyl groups); wherein each R 5 and R 6 Choose independently the following groups: hydrogen and C 1-2 Alkyl groups (preferably hydrogen and methyl groups; most preferably, hydrogen), provided that in each subunit e, R 5 and R 6 At least one of them is hydrogen; wherein each R 7 Choose independently the following groups: hydrogen and C 1-18 Alkyl groups (preferably hydrogen and C) 1-12 Alkyl groups; more preferably, hydrogen and C 1-4 Alkyl group; most preferably, hydrogen); and wherein the * in formula II represents a bond with formula I.

[0030] 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; and 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 agent based on the weight of the liquid laundry detergent formulation. Surfactant; and a cleaning enhancer of Formula I, based on a liquid laundry detergent formulation, in an amount of 0.1 wt% to 50 wt% (preferably, 0.5 wt% to 25 wt%; more preferably, 0.75 wt% to 20 wt%; still more preferably, 0.8 wt% to 10 wt%; most preferably, 2.5 wt% to 7.5 wt%); wherein a is 0 or 1 (preferably 0); wherein b is 0 or 1 (preferably 0); wherein c is 0 to 4 (preferably 2) (when b is 0, there is a direct bond between the two nitrogen atoms); wherein d is 0 to 4 (preferably 2) (when c is 0, there is a direct bond between the two nitrogen atoms); wherein c + d = 4; wherein each R 1 Independently selected from hydrogen and C 1-4 alkyl groups (preferably, wherein each R 1 Independently selected from hydrogen and C 1-3 Alkyl groups; more preferably, wherein each R 1 Independently selected from hydrogen and ethyl and methyl groups; most preferably, wherein each R 1 (It is hydrogen) (optionally any two of the Rs) 1 Groups can be linked together to form a ring); where each R 2 Independently selected from hydrogen and C 1-4 alkyl groups (preferably, wherein each R 2 Independently selected from hydrogen and C 1-3 Alkyl groups; more preferably, wherein each R 2 Independently selected from hydrogen and ethyl and methyl groups; most preferably, wherein each R 2 (for hydrogen); where each R 3 Independently having formula II; wherein e is 4 to 100 (preferably 5 to 50; more preferably 6 to 30; most preferably 6 to 15); wherein f is 1 to 20 (preferably 1 to 10; more preferably 1 to 6; most preferably 1 to 3); wherein g is 0 to 6; wherein h is 0 to 6; wherein g + h = 1 to 6 (preferably 2 to 6; more preferably 3 to 5; most preferably 4); wherein R 4 C 1-16alkyl group (preferably, C 1-14 Alkyl groups; more preferably, C 1-4 Alkyl groups; most preferably, methyl groups); wherein each R 5 and R 6 Choose independently the following groups: hydrogen and C 1-2 Alkyl groups (preferably hydrogen and methyl groups; most preferably, hydrogen), provided that in each subunit e, R 5 and R 6 At least one of them is hydrogen; wherein each R 7 Choose independently the following groups: hydrogen and C 1-18 Alkyl groups (preferably hydrogen and C) 1-12 Alkyl groups; more preferably, hydrogen and C 1-4 Alkyl group; most preferably, hydrogen); and wherein the * in formula II represents a bond with formula I.

[0031] 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.

[0032] Preferably, the liquid carrier may comprise a water-miscible liquid, such as C 1-3 Alkaneolamines and C 1-3Alkaneols. 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 the group consisting of C1-3 alkanolamines, C1-3 alkanols, and mixtures thereof.

[0033] Preferably, the liquid laundry detergent formulation of the present invention comprises, 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. More preferably, the liquid laundry detergent formulation of the present invention comprises, 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; 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 includes 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 includes 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 ethoxysulfate.

[0034] Anionic surfactants include alkyl sulfates, alkylbenzene sulfates, alkylbenzene sulfonic acids, alkylbenzene sulfonates, alkyl polyethoxylates, alkoxylated alcohols, paraffin sulfonic acids, paraffin sulfonates, olefin sulfonic acids, olefin sulfonates, α-sulfonocarboxylates, esters of α-sulfonocarboxylates, alkyl glycerol ether sulfonic acids, alkyl glycerol ether sulfonates, sulfates of fatty acids, sulfonates of fatty acids, sulfonates of fatty acid esters, alkylphenols, alkylphenol polyethoxylate sulfates, 2-acryloyloxy-alkane-1-sulfonic acids, 2-acryloyloxy-alkane-1-sulfonates, β-alkoxyalkane sulfonic acids, β-alkoxyalkane sulfonates, 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] Preferably, the 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 10% by weight; most preferably, 2.5% to 7.5% by weight) of a cleaning enhancer of formula I; wherein a is 0 or 1 (preferably 0); wherein b is 0 or 1 (preferably 0); wherein c is 0 to 4 (preferably 2) (when b is 0, there is a direct bond between the two nitrogen atoms); wherein d is 0 to 4 (preferably 2) (when c is 0, there is a direct bond between the two nitrogen atoms); wherein c + d = 4; wherein each R 1 Independently selected from hydrogen and C 1-4 alkyl groups (preferably, wherein each R 1 Independently selected from hydrogen and C 1-3 Alkyl groups; more preferably, wherein each R 1 Independently selected from hydrogen and ethyl and methyl groups; most preferably, wherein each R 1 (It is hydrogen) (optionally any two of the Rs) 1 Groups can be linked together to form a ring); where each R 2 Independently selected from hydrogen and C 1-4 alkyl groups (preferably, wherein each R 2 Independently selected from hydrogen and C 1-3 Alkyl groups; more preferably, wherein each R 2 Independently selected from hydrogen and ethyl and methyl groups; most preferably, wherein each R 2 (for hydrogen); where each R 3Independently having formula II; wherein e is 4 to 100 (preferably 5 to 50; more preferably 6 to 30; most preferably 6 to 15); wherein f is 1 to 20 (preferably 1 to 10; more preferably 1 to 6; most preferably 1 to 3); wherein g is 0 to 6; wherein h is 0 to 6; wherein g + h = 1 to 6 (preferably 2 to 6; more preferably 3 to 5; most preferably 4); wherein R 4 C 1-16 alkyl group (preferably, C 1-14 Alkyl groups; more preferably, C 1-4 Alkyl groups; most preferably, methyl groups); wherein each R 5 and R 6 Choose independently the following groups: hydrogen and C 1-2 Alkyl groups (preferably hydrogen and methyl groups; most preferably, hydrogen), provided that in each subunit e, R 5 and R 6 At least one of them is hydrogen; wherein each R 7 Choose independently the following groups: hydrogen and C 1-18 Alkyl groups (preferably hydrogen and C) 1-12 Alkyl groups; more preferably, hydrogen and C 1-4 Alkyl groups; most preferably, hydrogen); and wherein the * in Formula II represents a bond with Formula I. More 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 10% by weight; most preferably, 2.5% to 7.5% by weight) of a cleaning enhancer of Formula Ia.

[0039]

[0040] Each R 3 Independently having formula II; wherein e is 4 to 100 (preferably 5 to 50; more preferably 6 to 30; most preferably 6 to 15); wherein f is 1 to 20 (preferably 1 to 10; more preferably 1 to 6; most preferably 1 to 3); wherein g is 0 to 6; wherein h is 0 to 6; wherein g + h = 1 to 6 (preferably 2 to 6; more preferably 3 to 5; most preferably 4); wherein R 4 C 1-16 alkyl group (preferably, C 1-14 Alkyl groups; more preferably, C 1-4 Alkyl groups; most preferably, methyl groups); wherein each R 5 and R 6 Choose independently the following groups: hydrogen and C 1-2Alkyl groups (preferably hydrogen and methyl groups; most preferably, hydrogen), provided that in each subunit e, R 5 and R 6 At least one of them is hydrogen; wherein each R 7 Choose independently the following groups: hydrogen and C 1-18 Alkyl groups (preferably hydrogen and C) 1-12 Alkyl groups; more preferably, hydrogen and C 1-4 Alkyl groups; most preferably, hydrogen); and wherein the * in formula II represents a bond with formula Ia. Most 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 10% by weight; most preferably, 2.5% to 7.5% by weight) of a cleaning enhancer of formula Ia; wherein each R 3 Independently possessing formula IIa

[0041]

[0042] Where e is 4 to 100 (preferably 5 to 50; more preferably 6 to 30; most preferably 6 to 15); where f is 1 to 20 (preferably 1 to 10; more preferably 1 to 6; most preferably 1 to 3); where i is 2 to 7 (preferably 3 to 7; more preferably 4 to 6; most preferably 5); where R 4 C 1-16 alkyl group (preferably, C 1-14 Alkyl groups; more preferably, C 1-4 Alkyl group; most preferably, methyl group); wherein the * in formula IIa represents a bond with formula Ia.

[0043] 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 sodium methylglycine diacetate or sodium glutamate diacetate)); 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.

[0044] 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 the 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 the 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, by weight, 0% to 10% (preferably 0.1% to 10%; more preferably 0.2% to 8%; most preferably 0.5% to 7.5%) of a water-soluble growth promoter based on 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, by weight, 0% to 10% (preferably 0.1% to 10%; more preferably 0.2% to 8%; most preferably 0.5% to 7.5%) of a water-soluble growth promoter based on the liquid laundry detergent formulation; wherein the water-soluble growth promoter is sodium xylenesulfonate.

[0045] 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, by weight, 0% to 30% (preferably, 1% to 20%; more preferably, 2.5% to 10%) of a 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, by weight, 0% to 30% (preferably 1% to 25%; more preferably 2.5% to 10%) of a builder based on 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; and mixtures thereof. Most preferably, the liquid laundry detergent formulation of the present invention further comprises, by weight, 0% to 30% (preferably, 1% to 25%; more preferably, 2.5% to 10%) of a detergent builder based on the liquid laundry detergent formulation; wherein the detergent builder comprises sodium citrate.

[0046] 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, based on the weight of the liquid laundry detergent formulation, 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 the fragrance.

[0047] 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).

[0048] 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). Bases used for pH adjustment include 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)). Acids used for pH adjustment include inorganic acids (e.g., hydrochloric acid, phosphoric acid, and sulfuric acid) and organic acids (e.g., acetic acid, citric acid).

[0049] Preferably, the method for washing the soiled fabric articles of the present invention comprises: providing the soiled fabric articles (preferably, wherein the soiled fabric articles are soiled by dirt carried by oil and grease; more preferably, wherein the soiled fabric articles are soiled by sebum oil) (preferably, wherein the soiled fabric articles are soiled cotton fabric; more preferably, wherein the soiled fabric articles are 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 clean fabric articles (preferably, wherein the washing water is at a temperature ≤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 of washing the soiled fabric article of the present invention comprises: providing the soiled fabric article (preferably, wherein the soiled fabric article is soiled by dirt carried by oil and grease; more preferably, wherein the soiled fabric article is soiled by sebum oil) (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.

[0050] Some embodiments of the present invention will now be described in detail in the following examples.

[0051] GPC Analysis :

[0052] Molecular weight was determined using a Waters ACQUITY UPLC H-Class system with a refractive index detector and an Agilent Plgel 3μm MiniMixed-E 4.6×250mm 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 weight 580 Daltons–377,400 Daltons).

[0053] Synthesis of S1: Tetramethyl 2,2'-(piperazine-1,4-diyl)disuccinate

[0054] Tetramethyl 2,2'-(piperazine-1,4-diyl)disuccinate was prepared as follows. Piperazine (9.277 g; 102.6 mmol) was dissolved in ethanol (329.8 g; 200 ABV) in a flask. The flask was then placed in an ice bath, and dimethyl maleate (31.623 g; 204.6 mmol; from TCI Corporation) was added to the flask contents over a 1-hour period using a syringe pump. After the addition of dimethyl maleate, the flask contents were held for 10 minutes, then a reflux condenser was attached to the flask, and the contents were heated to 60-65°C for approximately 3 hours. A white precipitate was collected from the flask contents by filtration. The collected precipitate was dried overnight in a vacuum oven to give 9.95 g of product. The second batch of precipitate was recovered by cooling the filtrate in a dry ice bed, filtering out the additional precipitate, and drying it overnight in a vacuum oven to obtain an additional 4.41 g of product. 1 H NMR (500MHz, CDCl-3) δ 3.71 (s, 8H); 3.66 (x, 6H); 2.83 (dd, J= 16.1; 8.9Hz; 2H); 2.70-2.55 (m, 6H); 2.47 (m, 4H). 13 C NMR (126MHz, CDCl3) δ171.69; 170.96; 77.43; 77.29; 77.08; 76.83; 63.37; 51.77; 51.53; 49.88; 33.98. 1 The peaks at 4.1 ppm (complex multiplet) and 1.2 ppm (two triplets) in the H spectrum indicate the presence of low levels of ethyl ester (based on a piperazine group of 5 mol%).

[0055] Synthesis of S2:R 3 Group

[0056] Prepare R with the following average structure3 Group:

[0057]

[0058] By adding mPEG 550 (17.014 g; 30.0 mmol; estimated number-average molecular weight M) to the flask... n The monomers were 567 Daltons (OH number; from TCI) and ε-caprolactone (10.289 g; 90.1 mmol; from TCI; 99.9%). The contents of the flask were then purged with nitrogen for 1.3 hours while heating at 79 °C. Titanium isopropoxide (0.488 g; 1.72 mmol; from Sigma Aldrich; 99.999%) was injected into the flask contents. The flask contents were heated at 120 °C for approximately 1.5 hours. Complete conversion of the monomer ε-caprolactone was achieved by... 13 The absence of a peak at 176.1 ppm in the C NMR spectrum confirmed this. The integral ratio of carbon (58.9 ppm), carbonyl group (172-174 ppm), CH2OH group of ε-caprolactone-terminated polymer (62.1 ppm), and CH2OH group of unterminated mPEG (61.5 ppm) for the mPEG methyl ether was 1.00:2.06:0.58:0.43. Each polymer had an average of 3.1 ε-caprolactone units, and approximately 60% of the chains had at least one ε-caprolactone unit. The number-average molecular weight of the product was calculated to be 899 Daltons.

[0059] Synthetic S3: Cleaning Enhancer

[0060] The cleaning enhancer of the present invention was prepared in a flask equipped with an egg-shaped magnetic stir bar, an oil bath, and a thermocouple immersed in the oil bath and attached to an Ohaus Guardian 7000 hot plate. R prepared according to synthesis S2 was added to the flask. 3 Materials (7.5511 g; 8.4 mmol) and tetramethyl 2,2'-(piperazine-1,4-diyl)disuccinate (0.7512 g; 2.0 mmol) prepared according to synthesis S1. The contents of the flask were then heated to 120-121 °C under vacuum (pressure gradually decreased from 190 Torr to 49 Torr) for approximately 3 hours. After cooling overnight at room temperature under nitrogen, the contents of the flask were heated at 160 °C under vacuum (pressure gradually decreased from 192 Torr to 49 Torr) for approximately 4 hours. After cooling overnight at room temperature under nitrogen, the contents of the flask were heated at 160 °C under vacuum (pressure gradually decreased from 192 Torr to 49 Torr) for approximately 5.3 hours. The final product was measured by quantitative analysis. 13Characterized by C NMR, and determined to have a methyl ester conversion of approximately 73% based on the integral ratio of methyl ester carbon (51.7; 51.4 ppm) to noncaprolactone ester carbonyl carbon (171.1; 170.3 ppm) of 1.2:4.0.

[0061] Synthesize S4:R 3 Group

[0062] Prepare R with the following average structure 3 Group:

[0063]

[0064] By adding mPEG 550 (17.035 g; 30.0 mmol; estimated number-average molecular weight M) to the flask... n The concentration was 567 Daltons (OH number; from TCI). The contents of the flask were then purged with nitrogen for 1.3 hours while heating at 121°C. γ-valerol (10.268 g; 102.6 mmol; from TCI; 99.6%) was then added to the flask contents. Titanium isopropoxide (0.488 g; 1.72 mmol; from Sigma-Aldrich; 99.999%) was subsequently added. The flask contents were heated at 121-123°C for approximately 6 hours. The product was then measured... 13 NMR characterization. Based on the integral ratio of carbon (58.9 ppm), carbonyl group (172 ppm–175 ppm), residual γ-valerolactone CH2OH group (171.2 ppm), γ-valerolactone-terminated polymer CH2OH group (61.9 ppm), and unterminated mPEG CH2OH group (61.6 ppm) of mPEG = 1.00:3.10:0.20:0.60:0.35, the conversion of γ-valerolactone was 94%. Each polymer had an average of 3.1 γ-valerolactone units, and approximately 60% of the chains had at least one γ-valerolactone unit. The number-average molecular weight of the product was calculated to be 860 Daltons.

[0065] Synthetic S5: Cleaning Enhancer

[0066] The cleaning enhancer of the present invention was prepared in a flask equipped with an egg-shaped magnetic stir bar, an oil bath, and a thermocouple immersed in the oil bath and attached to an Ohaus Guardian 7000 hot plate. The R prepared according to synthesis S4 was then added to the flask. 3Materials (7.211 g; 8.4 mmol) and tetramethyl 2,2'-(piperazine-1,4-diyl)disuccinate prepared according to synthesis S1 (0.7557 g; 2.02 mmol) were used. The contents of the flask were then heated to 120-121 °C under vacuum (pressure gradually reduced from 47 Torr to 8 Torr) for approximately 9 hours. After cooling overnight at room temperature under nitrogen, the contents of the flask were heated at 120-124 °C under vacuum (pressure gradually reduced from 49 Torr to 7.5 Torr) for approximately 8.3 hours. After cooling overnight at room temperature under nitrogen, titanium isopropoxide (56 mg; 0.19 mmol; from Sigma-Aldrich; ≥99%) was added to the contents of the flask, and the mixture was heated at 122-123 °C under vacuum (66 Torr) for approximately 6.4 hours. After cooling overnight at room temperature under nitrogen, titanium isopropoxide (45 mg; 0.16 mmol) was added to the flask contents, which were then heated under vacuum (65 Torr) at 122–123 °C for approximately 5.8 hours. After cooling overnight at room temperature under nitrogen, the flask contents were then heated under vacuum (65 Torr) at 122–123 °C for approximately 14.5 hours. The final product was measured... 13 Characterized by C NMR, and determined to have a methyl ester conversion of approximately 97% based on the integral ratio of methyl ester carbon (51 ppm–52 ppm) to non-valerolactone ester carbonyl carbon (171.1; 170.2 ppm) of 0.20:4.0.

[0067] Synthesis of S6: Tetramethyl 2,2'-(piperazine-1,4-diyl)disuccinate

[0068] Tetramethyl 2,2'-(piperazine-1,4-diyl)disuccinate was prepared as follows. Piperazine (8.92 g; 103.6 mmol) was dissolved in methanol (253.2 g) in a flask. The flask was then placed under nitrogen and dimethyl maleate (30.36 g; 210.7 mmol; from TCI) was added to the flask contents at room temperature over a 1-hour period using a syringe pump. After stirring overnight under nitrogen at room temperature, the flask contents were heated to reflux for approximately 1.5 hours. Then, after stirring overnight under nitrogen at room temperature, the mixture was heated to reflux again for 1 hour. The flask contents were then cooled to room temperature and immersed in an ice-water bath. The resulting solid precipitate was recovered by filtration and dried overnight in a vacuum oven to give 14.95 g. The NMR spectrum of the recovered product was substantially the same as that of the product obtained in synthesis S1, except that no ethyl ester peak was observed.

[0069] Synthesize S7:R 3 Group

[0070] Prepare R with the following average structure 3 Group:

[0071]

[0072] By adding mPEG 550 (16.707 g; 29.5 mmol; estimated number-average molecular weight M) to the flask... n The concentration was 567 Daltons (OH number; from TCI). The contents of the flask were then purged with nitrogen for 0.6 hours while heating at 116 °C. After cooling the contents to 46 °C, titanium isopropoxide (0.025 g; 0.088 mmol; from Sigma-Aldrich; 99.999%) and ε-caprolactone (6.753 g; 59.2 mmol; from TCI; 99.6%) were added to the contents. The contents were then heated at 120 °C for approximately 4 hours. 13 The conversion of monomeric ε-caprolactone was approximately 99% based on the integrals at 176 ppm and 173 ppm in the C NMR. The integral ratio of carbon in the mPEG methyl ether (58.8 ppm), carbonyl group (173 ppm), CH2OH group in the ε-caprolactone-terminated polymer (62.0 ppm), and CH2OH group in the unterminated mPEG (61.5 ppm) was 1.00:2.06:0.55:0.46, with each polymer having an average of 2.1 ε-caprolactone units, and approximately 54% of the chains having at least one ε-caprolactone unit. The number-average molecular weight of the product was calculated to be 802 Daltons.

[0073] Synthetic S8: Cleaning Enhancer

[0074] The cleaning enhancer of the present invention was prepared in a flask equipped with an egg-shaped magnetic stir bar, an oil bath, and a thermocouple immersed in the oil bath and attached to an Ohaus Guardian 7000 hot plate. The R prepared according to synthesis S7 was then added to the flask. 3Materials (7.741 g; 9.7 mmol) and tetramethyl 2,2'-(piperazine-1,4-diyl)disuccinate (0.7541 g; 2.01 mmol) prepared according to synthesis S6. Titanium isopropoxide (80 mg; 0.28 mmol) was injected into the flask contents, which were then heated to 120-123 °C under vacuum (pressure gradually decreased from 192 Torr to 6 Torr) over approximately 20.5 hours. After cooling the flask contents to 48 °C, titanium isopropoxide (40 mg; 0.14 mmol) was added, and the mixture was reheated under vacuum (50-62 Torr) at 121 °C for approximately 6 hours. After cooling the flask contents to 82 °C, titanium isopropoxide (43 mg; 0.15 mmol) was added, and the mixture was reheated under vacuum (50 Torr) at 121 °C for approximately 15 hours. Titanium isopropoxide (41 mg; 0.14 mmol) was added to the contents of the flask, and the mixture was heated under vacuum (48-49 Torr) at 120 °C for approximately 15.3 hours. The final product was then quantified. 13 Characterized by C NMR, and determined to have a methyl ester conversion of approximately 84% based on the integral ratio of methyl ester carbon (51.4 ppm) to noncaprolactone ester carbonyl carbon (171.1; 170.0 ppm) of 0.65:4.0.

[0075] Synthesize S9:R 3 Group

[0076] Prepare R with the following average structure 3 Group:

[0077]

[0078] By adding lauryl ether-9 (74.83 g; 128 mmol; estimated number-average molecular weight M) to a flask n The concentration was 582 Daltons; from Stepan; BIOSOFT 25-9. The contents of the flask were then purged with nitrogen for 2.5 hours while heating at 121 °C. After cooling the contents to 46 °C, titanium isopropoxide (0.093 g; 0.33 mmol; from Sigma-Aldrich; 99.999%) and ε-caprolactone (15.03 g; 131.5 mmol; from TCI; 99.6%) were added to the contents. The contents were then heated at 121 °C for approximately 3.5 hours. 13The conversion of monomeric ε-caprolactone was approximately 99% based on the integrals at 176 ppm and 173.5 ppm in C NMR. The integral ratio of carbon atoms in the lauryl methyl group (14.0 ppm), carbonyl group (173.5 ppm), CH2OH group in the ε-caprolactone-terminated polymer (62.1 ppm), and CH2OH group in the unterminated lauryl group (61.5 ppm) was 1.00:0.98:0.51:0.41, with each polymer having an average of 1.0 ε-caprolactone unit, and approximately 55% of the chains having at least one ε-caprolactone unit. The number-average molecular weight of the product was calculated to be 694 Daltons.

[0079] Synthetic S10: Cleaning Enhancer

[0080] The cleaning enhancer of the present invention was prepared in a flask equipped with an egg-shaped magnetic stir bar, an oil bath, and a thermocouple immersed in the oil bath and attached to an Ohaus Guardian 7000 hot plate. The R prepared according to synthesis S9 was then added to the flask. 3 Materials (20.019 g; 28.8 mmol) and tetramethyl 2,2'-(piperazine-1,4-diyl)disuccinate (2.587 g; 6.91 mmol) prepared according to synthesis S6. Titanium isopropoxide (168 mg; 0.59 mmol) was injected into the flask contents, which were then heated to 162 °C under nitrogen purging and aeration to remove methanol over approximately 5 hours. After cooling the flask contents to 49 °C, titanium isopropoxide (160 mg; 0.56 mmol) was added to the flask contents, and the mixture was reheated at 120 °C under vacuum (210 Torr) for approximately 14 hours. The final product was obtained by quantitative analysis. 13 Characterized by C NMR, and determined to have a methyl ester conversion of approximately 95% based on the integral ratio of methyl ester carbon (51.4 ppm) to noncaprolactone ester carbonyl carbon (171.0; 170.2 ppm) of 0.19:4.0.

[0081] Synthetic S11: Comparative material with f=0

[0082] Material of formula I was prepared in a flask, where f=0. mPEG 1000 (7.19 g; 7.26 mmol; estimated number-average molecular weight M) was added to the flask. nThe result was 991 Daltons (determined by NMR; from TCI). The contents of the flask were then purged with nitrogen for 1.5 hours while heating at 122 °C. The nitrogen flow to the flask was stopped, and a vacuum (50 Torr) was applied while cooling to 52 °C over 1.3 hours. The vapor space of the flask was refilled with nitrogen, and tetramethyl 2,2'-(piperazine-1,4-diyl)disuccinate (0.64 g; 1.71 mmol) prepared according to synthesis S6 was added to the contents of the flask. Titanium isopropoxide (0.075 g; 0.26 mmol) was then injected into the contents of the flask. The flask was then wrapped with insulating material and placed under a regulated vacuum (50 Torr) while heating at 120 °C–123 °C for 18.5 hours. The vapor space of the flask was refilled with nitrogen, and titanium isopropoxide (0.085 g; 0.30 mmol) was added to the contents of the flask. Vacuum was restored (50 Torr), and the contents of the flask were heated at 120 °C for 14.3 h. The vapor space of the flask was refilled with nitrogen, and titanium isopropoxide (0.048 g; 0.17 mmol) was added to the contents of the flask. Vacuum was restored (50 Torr), and the contents of the flask were heated at 120 °C for 18 h. The vapor space of the flask was refilled with nitrogen, and titanium isopropoxide (0.082 g; 0.29 mmol) was added to the contents of the flask. Vacuum was restored (50 Torr), and the contents of the flask were heated at 120 °C for 15.7 h. The vapor space of the flask was refilled with nitrogen, and titanium isopropoxide (0.063 g; 0.22 mmol) was added to the contents of the flask. Vacuum was restored (50 Torr), and the contents of the flask were heated at 151 °C for 5.8 h. The final product was measured by quantification. 13 Characterized by C10 NMR, and determined to have approximately 88% methyl ester conversion based on the integral ratio of methyl ester carbon (51.7; 51.4 ppm) to non-caprolactone ester carbon (171.5; 169.5 ppm) of 0.60:4.0. The integral ratio of methyl ether carbon (58.9 ppm) to piperazine ring carbon was 5.6:4.

[0083] Polymer hydrolysis

[0084] The stability of polymer products from synthesized S3 and S5 (in this invention) and synthesized S11 (comparative) was assessed 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.

[0085] NMR method for estimating the degree of hydrolysis by proton NMR spectroscopyA 1% (w / w) solution of each polymer was prepared by dissolving 0.10 g of the polymer to be tested in 9.9 g of 10 mM Tris buffer at pH 8.25. A time=0 NMR 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. 1 H(zg30) and water inhibition ( 1 The H;noesygppr1d) experiment was performed at 40 °C with a relaxation time of 20 seconds. The test solution was stored at 20 °C, and after 4 days, another aliquot of the test solution was removed to record another spectrum. The peak between 4.03 ppm and 4.35 ppm was integrated and normalized to the peak at approximately 1.4 ppm. Comparing the integrals of these two peaks between the spectra at t=0 and t=4 days provides the percentage of esters retained in the polymer. The percentage of total esters retained is calculated based on molar amounts.

[0086]

[0087] Polymer enzymatic hydrolysis

[0088] The stability and enzymatic hydrolysis of polymer products from synthesized S3 and S5 (in this invention) and synthesized S11 (comparative) were assessed by measuring ester retention after 4 days in the presence and absence of enzymes using the following NMR procedure (respectively). The results are provided in Table 2.

[0089] NMR method for estimating the degree of hydrolysis by proton NMR spectroscopy A 1% (w / w) solution of each polymer was prepared by dissolving 0.10 g of the polymer to be tested in 9.9 g of 10 mM Tris buffer at pH 7.0. A time=0 NMR 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. 1 H(zg30) and water inhibition ( 1 The H;noesygppr1d) experiment was performed at 40 °C with a relaxation time of 20 seconds. 2 wt% immobilized lipase (Novozyme 435) was added to one series of solutions, while another series did not accept the enzyme. The test solutions were stored at 20 °C, and after 4 days, another aliquot of the test solutions was removed to record another spectrum. The peaks between 4.03 ppm and 4.52 ppm were integrated and normalized to peaks between 1.53 and 2.00 ppm. Comparing the integrals of these two peaks between the spectra at t=0 and t=4 days provides the percentage of esters retained in the polymer. The percentage of total esters retained is calculated based on molar amounts.

[0090]

[0091] Comparative Examples CF1-CF2 and Examples F1-F3: Liquid Laundry Detergent

[0092] Liquid laundry detergent formulations of Comparative Examples CF1-CF2 and Examples F1-F3 used in the cleaning tests in the subsequent examples were prepared using standard liquid laundry formulation preparation procedures. These formulations had the general formulations described in Table 3, wherein the cleaning enhancers described in Table 4 were neutralized to pH 8.5 with sodium hydroxide.

[0093]

[0094] Primary cleaning performance

[0095] The primary cleaning performance of the liquid laundry detergent formulations of Comparative Examples CF1 to CF2 and Examples F1 to F3 was estimated 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 tank 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 described in Table 5. 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.

[0096] Reflectance measurement and Stain Removal Index (SRI)

[0097] 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 5.

[0098] 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:

[0099]

[0100] 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

[0101]

[0102] The ΔSRI values ​​provided in Table 5 show the difference between the SRI measurement values ​​of the illustrated embodiment and the SRI measurement values ​​of Comparative Example CF1. Positive values ​​indicate enhanced detergency compared to Comparative Example CF1.

[0103]

Claims

1. A cleaning enhancer for cleaning clothes, wherein the cleaning enhancer has Formula I Where a is 0 or 1; where b is 0 or 1; where c is 0 to 4; where d is 0 to 4; where c + d = 4; where each R 1 Independently selected from hydrogen and C 1-4 alkyl groups; wherein each R 2 Independently selected from hydrogen and C 1-4 alkyl groups; wherein each R 3 Independently possessing Formula II Where e is 4 to 100; where f is 1 to 20; where g is 0 to 6; where h is 0 to 6; where g + h = 1 to 6; where R 4 C 1-16 alkyl groups; wherein each R 5 and R 6 Independently selectable from hydrogen and C 1-2 A group consisting of alkyl groups, provided that in each subunit e, R 5 and R 6 At least one of them is hydrogen; wherein each R 7 Independently selectable from hydrogen and C 1-18 A group consisting of alkyl groups; and wherein the * in formula II represents a bond with formula I.

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

3. The liquid laundry detergent formulation according to claim 2, wherein the cleaning enhancer has formula Ia 。 4. The liquid laundry detergent formulation according to claim 3, wherein each R 3 Independently possessing formula IIa Where e is 4 to 100; where f is 1 to 20; where i is 2 to 7; where R 4 C 1-16 Alkyl group; wherein the * in formula IIa represents a bond with formula I or Ia.

5. The liquid laundry detergent formulation of claim 4, wherein the cleaning surfactant comprises a mixture of anionic and nonionic surfactants.

6. The liquid laundry detergent formulation according to claim 5, wherein the liquid carrier comprises water.

7. The liquid laundry detergent formulation according to claim 6, wherein the liquid carrier further comprises a water-miscible liquid.

8. The liquid laundry detergent formulation according to claim 7 further comprises a water-soluble growth promoter.

9. The liquid laundry detergent formulation according to claim 8, wherein e is 6 to 15; wherein f is 1 to 3; wherein i is 5; and wherein R 4 It is a methyl group.

10. A method for washing soiled textile articles, the method comprising: Provide soiled textile products; Provide a liquid laundry detergent formulation according to claim 2; 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.

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