Cleaning booster and liquid laundry detergent

Abstract

A cleaning booster of (I) is provided, wherein X is (II), (III) or (IV), wherein a=1-30; b+c=4; R4 is hydrogen or C1‑4 alkyl; R5 is hydrogen or C1-4 alkyl; R6 is hydrogen or methyl; R7 is bond or bridging group with 1-8 carbons; * in (II), (III) and (IV) represents bond to R1 or R2; R1 is (V), wherein d=5-150; R8 and R9 are hydrogen or C1‑2 alkyl, with proviso at least one of R8 and R9 is hydrogen in each subunit d; R10 is hydrogen or C1‑22 alkyl; * in (V) represents bond to X; R2 is (VI), wherein e=5-150; R11 and R12 are hydrogen or C1‑2 alkyl, with proviso at least one of R11 and R12 is hydrogen in each subunit e; * in (VI) represents a bond to X or R3; and R3 is hydrogen or C1‑22 alkyl.

Description

Attorney Docket No. 85777-WO-PCTCLEANING BOOSTER AND LIQUID LAUNDRY DETERGENT

[0001] The present invention is related to a cleaning booster. In particular, the present invention relatesbooster is of formula I, wherein a is 1 to 30; wherein each X is independently selected from the group consisting of formula II, formula III and formula IV; wherein b is 0 to 4; wherein c is 0 to 4; wherein b + c = 4; wherein each R4is independently selected from a hydrogen and a C1-4alkyl group; wherein each R5is independently selected from a hydrogen and a C1-4 alkyl group; wherein each R6is independently selected from a hydrogen and a methyl group; wherein R7is selected from the group consisting of a single bond and a bridging group with 1 to 8 carbon atoms; and wherein each * in formula II, formula III and formula IV represents a bond to R1or R2; wherein R1is of formula V; wherein d is 5 to 150; wherein each R8and R9is independently selected from the group consisting of a hydrogen and a C1-2 alkyl group, with the proviso that at least one of R8and R9is a hydrogen in each subunit d; wherein R10is selected from the group consisting of a hydrogen and a C1-22 alkyl group; and wherein the * in formula V represents a bond to X; wherein each R2is independently of formula VI; wherein e is 5 to 150; and wherein each R11and R12is independently selected from the group consisting of a hydrogen and a C1-2alkyl group, with the proviso that at least one of R11and R12is a hydrogen in each subunit e; and wherein each * in formula VI represents a bond to X or R3; and wherein R3is selected from the group consisting of a hydrogen and a C1-22alkyl group; and with the proviso that 10 to 100 mol% of the Xs in formula I are of formula II; and with the proviso that 40 to 100 mol% of the R1and R2groups present in formula I are copolymers of ethylene oxide and a C3-8 alkylene oxide, wherein each copolymer is 25 to 99 mol% ethylene oxide.

[0002] Laundry detergents in liquid and gel forms providing excellent overall cleaning are desirable to consumers. Such laundry detergents typically include surfactants among other components to deliver the consumer desired cleaning benefits. Nevertheless, due to increasing sensitivity for the environment and rising material costs, a move to reduce the utilization of surfactants in laundry detergents is growing. Consequently, detergent manufactures are seeking ways to reduce the amount of surfactant per unit dose of the laundry detergent while maintaining overall cleaning performance.

[0003] One approach for reducing the unit dose of surfactant is to incorporate polymers into the liquid detergent formulations as described by Boutique et al. in U.S. Patent Application Publication No.20090005288. Boutique et al. disclose a graft copolymer of polyethylene, polypropylene or polybutylene oxide with vinyl acetate in a weight ratio of from about 1:0.2Attorney Docket No. 85777-WO-PCTto about 1:10 for use in liquid or gel laundry detergent formulations having about 2 to about 20 wt% surfactant.

[0004] Notwithstanding, there remains a need for new cleaning booster compositions and liquid laundry detergent formulations comprising same, particularly wherein the cleaning booster composition possess resistance to hydrolysis while being readily biodegradable according to OECD 301F protocol.

[0005] The present invention provides a cleaning booster for cleaning laundry, wherein the cleaning booster is of formula I (I) wherein a is 1 to 30; wherein eachformula II, formula III and formula (II) wherein b is 0selected from a hydrogen and a C1-4alkyl group; wherein each R5is independently selected from a hydrogen and a C1-4 alkyl group; wherein each R6is independently selected from a hydrogen and a methyl group; wherein R7is selected from the group consisting of a single bond and a bridging group with 1 to 8 carbon atoms; and wherein each * in formula II, formula III and formula IV represents a bound to R1or R2; wherein R1is of formula VAttorney Docket No. 85777-WO-PCTwherein d is 5 to 150; consisting of a hydrogen andR9is a hydrogen in each subunit d; wherein R10is selected from the group consisting of a hydrogen and a C1-22alkyl group; and wherein the * in formula V represents a bound to X; wherein each R2is independently of formula VI wherein e is 5 to 150; andconsisting of a hydrogen and a 2 group, one R12is a hydrogen in each subunit e; and wherein each * in formula VI represents a bound to X or R3; and wherein R3is selected from the group consisting of a hydrogen and a C1-22 alkyl group; and with the proviso that 10 to 100 mol% of the Xs in formula I are of formula II; and with the proviso that 40 to 100 mol% of the R1and R2groups present in formula I are copolymers of ethylene oxide and a C3-8alkylene oxide, wherein each copolymer is 25 to 99 mol% ethylene oxide.

[0006] The present invention provides a liquid laundry detergent formulation, comprising: 25 to 98.9 wt%, based on weight of the liquid laundry detergent formulation, of a liquid carrier; 1 to 60 wt%, based on weight of the liquid laundry detergent formulation, of a cleaning surfactant; and 0.1 to 50 wt%, based on weight of the liquid laundry detergent formulation, of a cleaning booster of the present invention.

[0007] The present invention provides a method of washing a soiled fabric article, comprising: providing a soiled fabric article; providing a liquid laundry detergent formulation of the present invention; providing a wash water; and applying the wash water and the liquid laundry detergent formulation to the soiled fabric article to provide a cleaned fabric article. DETAILED DESCRIPTION

[0008] It has been surprisingly found that the materials according to Formula I having a six membered saturated hydrocarbon ring in which two of the carbon atoms have been replaced by a nitrogen atom where each of the nitrogen atoms is further linked to a -C(O)O- group byAttorney Docket No. 85777-WO-PCTa -CH2- segment, possess resistance to hydrolysis, provide effective soil release benefits to liquid laundry detergent formulations comprising same, especially oil- and grease borne soil (e.g., sebum soils), from cotton containing fabrics (e.g., polycotton blends) at low temperatures (i.e., as 22 °C) and as an added benefit exhibit ready biodegradability following the procedure of OECD 301F.

[0009] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight. Weight percentages (or wt%) in the composition are percentages of dry weight, i.e., excluding any water that may be present in the composition.

[0010] As used herein, unless otherwise indicated, the phrase "molecular weight" or MW refers to the weight average molecular weight as measured in a conventional manner with 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, Second Edition, A.M. Striegel, W. W. Yau, J. J. Kirkland, D. D. Bly; John Wiley & Sons, Inc.2009. Molecular weights are reported herein in units of Daltons, or equivalently, g / mol.

[0011] Preferably, the cleaning booster for cleaning laundry of the present invention is of formula I (I) wherein a is 1 to 30 (preferably, 1; wherein each X is independently selected from the group consisting of formula II, formula III and formula IV (II)Attorney Docket No. 85777-WO-PCTwherein b is 0 to 4nitrogens); wherein c is 0 two nitrogens); wherein b + c = 4; wherein each R4is independently selected from a hydrogen and a C1-4alkyl group (preferably, wherein each R4is independently selected from a hydrogen and a C1-3 alkyl group; more preferably, wherein each R4is independently selected from a hydrogen an ethyl group and a methyl group; most preferably, wherein each R4is a hydrogen)(optionally two R4groups can be joined together to form a polycyclic diamine structure); wherein each R5is independently selected from a hydrogen and a C1-4 alkyl group (preferably, wherein each R5is independently selected from a hydrogen and a C1- 3 alkyl group; more preferably, wherein each R5is independently selected from a hydrogen an ethyl group and a methyl group; most preferably, wherein each R5is a hydrogen); wherein each R6is independently selected from a hydrogen and a methyl group (preferably, wherein each R6is a hydrogen); wherein R7is selected from the group consisting of a single bond and a bridging group with 1 to 8 carbon atoms (preferably, wherein R7is selected from the group consisting of a single bond and a bridging group with 1 to 5 carbon atoms; more preferably, wherein R7is selected from the group consisting of a bridging group of 1 to 5 carbon atoms; most preferably, wherein R7is selected from the group consisting of a -CH2CH2- group and a -CH2CH2CH2- group); and wherein each * in formula II, formula III and formula IV represents a bond to R1or R2; wherein R1is of formula V wherein d is 5 to 15025); wherein each R8and R9is independently selected from the group consisting of a hydrogen and a C1-2alkyl group, with the proviso that at least one of R8and R9is a hydrogenAttorney Docket No. 85777-WO-PCTin each subunit d; wherein R10is selected from the group consisting of a hydrogen and a C1-22alkyl group (preferably, a hydrogen and a C1-4alkyl group; more preferably, a hydrogen and a methyl group; most preferably, a hydrogen); and wherein the * in formula V represents a bond to X (i.e., to formula II, formula III or formula IV); wherein each R2is independently of formula VI wherein e is 5 to 150 ; 11 12and wherein each R and R hydrogen and a C1-2 alkyl group, with the proviso that at least one of R11and R12is a hydrogen in each subunit e; and wherein each * in formula VI represents a bond to X (i.e., to formula II, formula III or formula IV) or R3; and wherein R3is selected from the group consisting of a hydrogen and a C1-22alkyl group (preferably, a hydrogen and a C1-4alkyl group; more preferably, a hydrogen and a methyl group; most preferably, a hydrogen); and with the proviso that 10 to 100 mol% (preferably, 25 to 100 mol%; more preferably, 40 to 100 mol%; most preferably, 45 to 100 mol%) of the Xs in formula I are of formula II; and with the proviso that 40 to 100 mol% (preferably, 45 to 75 mol%; more preferably, 46 to 60 mol%; most preferably, 47 to 55 mol%) of the R1and R2groups present in formula I are copolymers of ethylene oxide and a C3-8 alkylene oxide (preferably, copolymers of ethylene oxide and propylene oxide), wherein each copolymer is 25 to 99 mol% (preferably, 50 to 95 mol%; more preferably, 60 to 90 mol%; most preferably, 75 to 85 mol%) ethylene oxide.

[0012] Preferably, the liquid laundry detergent formulation of the present invention comprises: 25 to 98.9 wt% (preferably, 30 to 97.8 wt%; more preferably, 40 to 96.75 wt%; still more preferably, 45 to 91.7 wt%; most preferably, 50 to 87.5 wt%), based on weight of the liquid laundry detergent formulation, of a liquid carrier; 1 to 60 wt% (preferably, 2 to 50 wt%; more preferably, 2.5 to 40 wt%; still more preferably, 7.5 to 35 wt%; most preferably, 10 to 30 wt%), based on weight of the liquid laundry detergent formulation, of a cleaning surfactant; and 0.1 to 50 wt% (preferably, 0.5 to 25 wt%; more preferably, 0.75 to 20 wt%; still more preferably, 0.8 to 15 wt%; most preferably 2.5 to 7.5 wt%), based on weight of the liquid laundry detergent formulation, of a cleaning booster 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 formula II, formula III and formula IV;Attorney Docket No. 85777-WO-PCTwherein b is 0 to 4 (preferably, 2)(when b is O, there is a direct bound between the two nitrogens); wherein c is 0 to 4 (preferably, 2)(when c is O, there is a direct bound between the two nitrogens); wherein b + c = 4; wherein each R4is independently selected from a hydrogen and a C1-4alkyl group (preferably, wherein each R4is independently selected from a hydrogen and a C1-3 alkyl group; more preferably, wherein each R4is independently selected from a hydrogen an ethyl group and a methyl group; most preferably, wherein each R4is a hydrogen)(optionally two R4groups can be joined together to form a polycyclic diamine structure); wherein each R5is independently selected from a hydrogen and a C1-4alkyl group (preferably, wherein each R5is independently selected from a hydrogen and a C1-3alkyl group; more preferably, wherein each R5is independently selected from a hydrogen an ethyl group and a methyl group; most preferably, wherein each R5is a hydrogen); wherein each R6is independently selected from a hydrogen and a methyl group (preferably, wherein each R6is a hydrogen); wherein R7is selected from the group consisting of a single bond and a bridging group with 1 to 8 carbon atoms (preferably, wherein R7is selected from the group consisting of a single bond and a bridging group with 1 to 5 carbon atoms; more preferably, wherein R7is selected from the group consisting of a bridging group of 1 to 5 carbon atoms; most preferably, wherein R7is selected from the group consisting of a -CH2CH2- group and a -CH2CH2CH2- group); and wherein each * in formula II, formula III and formula IV represents a bond to R1or R2; wherein R1is of formula V; wherein d is 5 to 150 (preferably, 5 to 100; more preferably, 5 to 50; most preferably, 5 to 25); wherein each R8and R9is independently selected from the group consisting of a hydrogen and a C1-2alkyl group, with the proviso that at least one of R8and R9is a hydrogen in each subunit d; wherein R10is selected from the group consisting of a hydrogen and a C1-22alkyl group (preferably, a hydrogen and a C1-4 alkyl group; more preferably, a hydrogen and a methyl group; most preferably, a hydrogen); and wherein the * in formula V represents a bond to X (i.e., to formula II, formula III or formula IV); wherein each R2is independently of 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 R11and R12is independently selected from the group consisting of a hydrogen and a C1-2 alkyl group, with the proviso that at least one of R11and R12is a hydrogen in each subunit e; and wherein each * in formula VI represents a bond to X (i.e., to formula II, formula III or formula IV) or R3; and wherein R3is selected from the group consisting of a hydrogen and a C1-22alkyl group (preferably, a hydrogen and a C1-4alkyl group; more preferably, a hydrogen and a methyl group; most preferably, a hydrogen); and with the proviso that 10 to 100 mol% (preferably, 25 to 100 mol%; more preferably, 40 toAttorney Docket No. 85777-WO-PCT100 mol%; most preferably, 45 to 100 mol%) of the Xs in formula I are of formula II; and with the proviso that 40 to 100 mol% (preferably, 45 to 75 mol%; more preferably, 46 to 60 mol%; most preferably, 47 to 55 mol%) of the R1and R2groups present in formula I are copolymers of ethylene oxide and a C3-8alkylene oxide (preferably, copolymers of ethylene oxide and propylene oxide), wherein each copolymer is 25 to 99 mol% (preferably, 50 to 95 mol%; more preferably, 60 to 90 mol%; most preferably, 75 to 85 mol%) ethylene oxide.

[0013] 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 wt% (preferably, 30 to 97.8 wt%; more preferably, 40 to 96.75 wt%; still more preferably, 45 to 91.7 wt%; most preferably, 50 to 87.5 wt%), based on weight of the liquid laundry detergent formulation, of the liquid carrier. Still more preferably, the liquid laundry detergent formulation of the present invention comprises 25 to 98.9 wt% (preferably, 30 to 97.8 wt%; more preferably, 40 to 96.75 wt%; still more preferably, 45 to 91.7 wt%; most preferably, 50 to 87.5 wt%), based on weight of the liquid laundry detergent formulation, of a liquid carrier; wherein the liquid carrier comprises water. Most preferably, the liquid laundry detergent formulation of the present invention comprises 25 to 98.9 wt% (preferably, 30 to 97.8 wt%; more preferably, 40 to 96.75 wt%; still more preferably, 45 to 91.7 wt%; most preferably, 50 to 87.5 wt%), based on weight of the liquid laundry detergent formulation, of a liquid carrier; wherein the liquid carrier is water.

[0014] Preferably, the liquid carrier can include water miscible liquids, such as, C1-3alkanolamines and C1-3 alkanols. More preferably, the liquid carrier used in the method of the present invention includes 0 to 8 wt% (preferably, 0.2 to 8 wt%; more preferably, 0.5 to 5 wt%), based on weight of the liquid carrier, of water miscible liquids; wherein the water miscible liquids are selected from the group consisting of C1-3alkanolamines, C1-3alkanols and mixtures thereof.

[0015] Preferably, the liquid laundry detergent formulation of the present invention, comprises: 1 to 60 wt% (preferably, 2 to 50 wt%; more preferably, 2.5 to 40 wt%; still more preferably, 7.5 to 35 wt%; most preferably, 10 to 30 wt%), based on weight of the liquid laundry detergent formulation, of a cleaning surfactant. More preferably, the liquid laundry detergent formulation of the present invention, comprises: 1 to 60 wt% (preferably, 2 to 50 wt%; more preferably, 2.5 to 40 wt%; still more preferably, 7.5 to 35 wt%; most preferably, 10 to 30 wt%), based on weight of the liquid laundry detergent formulation, of a cleaning surfactant; wherein the cleaning surfactant is selected from the group consisting of anionicAttorney Docket No. 85777-WO-PCTsurfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof. Yet more preferably, the liquid laundry detergent formulation of the present invention, comprises: 1 to 60 wt% (preferably, 2 to 50 wt%; more preferably, 2.5 to 40 wt%; still more preferably, 7.5 to 35 wt%; most preferably, 10 to 30 wt%), based on weight of the liquid laundry detergent formulation, of a cleaning surfactant; wherein the cleaning surfactant includes an anionic surfactant. Yet still more preferably, the liquid laundry detergent formulation provided by the method of the present invention, comprises: 1 to 60 wt% (preferably, 2 to 50 wt%; more preferably, 2.5 to 40 wt%; still more preferably, 7.5 to 35 wt%; most preferably, 10 to 30 wt%), based on weight of the liquid laundry detergent formulation, of a cleaning surfactant; wherein the cleaning surfactant includes a mixture of an anionic surfactant and a non-ionic surfactant. Most preferably, the liquid laundry detergent formulation of the present invention, comprises: 1 to 60 wt% (preferably, 2 to 50 wt%; more preferably, 2.5 to 40 wt%; still more preferably, 7.5 to 35 wt%; most preferably, 10 to 30 wt%), based on weight of the liquid laundry detergent formulation, of a cleaning surfactant; wherein the cleaning surfactant includes a mixture of a linear alkyl benzene sulfonate and a sodium lauryl ethoxysulfate.

[0016] Anionic surfactants include alkyl sulfates, alkyl benzene sulfates, alkyl benzene sulfonic acids, alkyl benzene sulfonates, alkyl polyethoxy sulfates, alkoxylated alcohols, paraffin sulfonic acids, paraffin sulfonates, olefin sulfonic acids, olefin sulfonates, alpha-sulfocarboxylates, esters of alpha-sulfocarboxylates, alkyl glyceryl ether sulfonic acids, alkyl glyceryl ether sulfonates, sulfates of fatty acids, sulfonates of fatty acids, sulfonates of fatty acid esters, alkyl phenols, alkyl phenol polyethoxy ether sulfates, 2-acryloxy-alkane-1-sulfonic acid, 2-acryloxy-alkane-1-sulfonate, beta-alkyloxy alkane sulfonic acid, beta-alkyloxy alkane sulfonate, amine oxides and mixtures thereof. Preferred anionic surfactants include C8-20alkyl benzene sulfates, C8-20alkyl benzene sulfonic acid, C8-20 alkyl benzene sulfonate, paraffin sulfonic acid, paraffin sulfonate, alpha-olefin sulfonic acid, alpha-olefin sulfonate, alkoxylated alcohols, C8-20 alkyl phenols, amine oxides, sulfonates of fatty acids, sulfonates of fatty acid esters, C8-10alkyl polyethoxy sulfates and mixtures thereof. More preferred anionic surfactants include C12-16 alkyl benzene sulfonic acid, C12-16alkyl benzene sulfonate, C12-18paraffin-sulfonic acid, C12-18paraffin-sulfonate, C12-16 alkyl polyethoxy sulfate and mixtures thereof.

[0017] Non-ionic surfactants include alkoxylates (e.g., polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end group capped polyglycol ethers, mixed ethers, hydroxy mixed ethers, fatty acid polyglycol esters and mixtures thereof. PreferredAttorney Docket No. 85777-WO-PCTnon-ionic surfactants include fatty alcohol polyglycol ethers. More preferred non-ionic surfactants include secondary alcohol ethoxylates, ethoxylated 2-ethylhexanol, ethoxylated seed oils, butanol caped ethoxylated 2-ethylhexanol and mixtures thereof. Most preferred non-ionic surfactants include secondary alcohol ethoxylates.

[0018] Cationic surfactants include quaternary surface active compounds. Preferred cationic surfactants include quaternary surface active compounds having at least one of an ammonium group, a sulfonium group, a phosphonium group, an iodonium group and an arsonium group. More preferred cationic surfactants include at least one of a dialkyldimethylammonium chloride and alkyl dimethyl benzyl ammonium chloride. Still more preferred cationic surfactants include at least one of C16-18dialkyldimethylammonium chloride, a C8-18alkyl dimethyl benzyl ammonium chloride and dimethyl ditallow ammonium chloride. Most preferred cationic surfactant includes dimethyl ditallow ammonium chloride.

[0019] Amphoteric surfactants include betaines, amine oxides, alkylamidoalkylamines, 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 with a long chain group having 8 to 18 carbon atoms. Still more preferred amphoteric surfactants include at least one of C12-14alkyldimethylamine oxide, 3-(N,N-dimethyl-N-hexadecyl-ammonio)propane-1-sulfonate, 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate. Most preferred amphoteric surfactants include at least one of C12-14 alkyldimethylamine oxide.

[0020] Preferably, the liquid laundry detergent formulation of the present invention comprises 0.1 to 50 wt% (preferably, 0.5 to 25 wt%; more preferably, 0.75 to 20 wt%; still more preferably, 0.8 to 15 wt%; most preferably 2.5 to 7.5 wt%), of a cleaning booster 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 formula II, formula III and formula IV; wherein b is 0 to 4 (preferably, 2)(when b is O, there is a direct bound between the two nitrogens); wherein c is 0 to 4 (preferably, 2)(when c is O, there is a direct bound between the two nitrogens); wherein b + c = 4; wherein each R4is independently selected from a hydrogen and a C1-4 alkyl group (preferably, wherein each R4is independently selected from a hydrogen and a C1-3alkyl group; more preferably, wherein each R4is independently selected from a hydrogen an ethyl group and a methyl group; most preferably, wherein each R4is a hydrogen)(optionally two R4groups can be joined together toAttorney Docket No. 85777-WO-PCTform a polycyclic diamine structure); wherein each R5is independently selected from a hydrogen and a C1-4alkyl group (preferably, wherein each R5is independently selected from a hydrogen and a C1-3 alkyl group; more preferably, wherein each R5is independently selected from a hydrogen an ethyl group and a methyl group; most preferably, wherein each R5is a hydrogen); wherein each R6is independently selected from a hydrogen and a methyl group (preferably, wherein each R6is a hydrogen); wherein R7is selected from the group consisting of a single bond and a bridging group with 1 to 8 carbon atoms (preferably, wherein R7is selected from the group consisting of a single bond and a bridging group with 1 to 5 carbon atoms; more preferably, wherein R7is selected from the group consisting of a bridging group of 1 to 5 carbon atoms; most preferably, wherein R7is selected from the group consisting of a -CH2CH2- group and a -CH2CH2CH2- group); and wherein each * in formula II, formula III and formula IV represents a bond to R1or R2; wherein R1is of formula V; wherein d is 5 to 150 (preferably, 5 to 100; more preferably, 5 to 50; most preferably, 5 to 25); wherein each R8and R9is independently selected from the group consisting of a hydrogen and a C1-2 alkyl group, with the proviso that at least one of R8and R9is a hydrogen in each subunit d; wherein R10is selected from the group consisting of a hydrogen and a C1-22 alkyl group (preferably, a hydrogen and a C1-4alkyl group; more preferably, a hydrogen and a methyl group; most preferably, a hydrogen); and wherein the * in formula V represents a bond to X (i.e., to formula II, formula III or formula IV); wherein each R2is independently of 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 R11and R12is independently selected from the group consisting of a hydrogen and a C1-2 alkyl group, with the proviso that at least one of R11and R12is a hydrogen in each subunit e; and wherein each * in formula VI represents a bond to X (i.e., to formula II, formula III or formula IV) or R3; and wherein R3is selected from the group consisting of a hydrogen and a C1-22alkyl group (preferably, a hydrogen and a C1-4alkyl group; more preferably, a hydrogen and a methyl group; most preferably, a hydrogen); and with the proviso that 10 to 100 mol% (preferably, 25 to 100 mol%; more preferably, 40 to 100 mol%; most preferably, 45 to 100 mol%) of the Xs in formula I are of formula II; and with the proviso that 40 to 100 mol% (preferably, 45 to 75 mol%; more preferably, 46 to 60 mol%; most preferably, 47 to 55 mol%) of the R1and R2groups present in formula I are copolymers of ethylene oxide and a C3-8 alkylene oxide (preferably, copolymers of ethylene oxide and propylene oxide), wherein each copolymer is 25 to 99 mol% (preferably, 50 to 95 mol%; more preferably, 60 to 90 mol%; most preferably, 75 to 85 mol%) ethylene oxide.Attorney Docket No. 85777-WO-PCT

[0021] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises an additive selected from the group consisting of builders (e.g., sodium bicarbonate, sodium carbonate, zeolites, sodium citrate, sodium tripolyphosphate and aminocarboxylates (such as methylglycine diacetic acid, sodium salt or glutamic acid diacetic acid, sodium salt)); hydrotropes (e.g., sodium xylene sulfonate); foam control agents (e.g., fatty acids, polydimethylsiloxane); enzymes (e.g., protease, cellulases, lipase, amylase, mannanases); preservatives; perfumes (e.g., essential oils such as D-limonene); fluorescent whitening agents; bleach (e.g., sodium percarbonate, sodium perborate, sodium hypochlorite); dyes; additive polymers (e.g., dispersant polymers such as acrylic acid homopolymers and copolymers of acrylic acid with maleic acid, sulfonated monomer and / or ethyl acrylate); and mixtures thereof.

[0022] Preferably, the liquid laundry detergent formulation of the present invention, further comprises a hydrotrope. More preferably, the liquid laundry detergent formulation of the present invention, further comprises 0 to 10 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.2 to 8 wt%; most preferably, 0.5 to 7.5 wt%), based on the weight of the liquid laundry detergent formulation, of a hydrotrope. Still more preferably, the liquid laundry detergent formulation of the present invention, further comprises 0 to 10 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.2 to 8 wt%; most preferably, 0.5 to 7.5 wt%), based on the weight of the liquid laundry detergent formulation, of a hydrotrope; wherein the hydrotrope is selected from the group consisting of calcium, sodium, potassium, ammonium and alkanol ammonium salts of xylene sulfonic acid, toluene sulfonic acid, ethylbenzene sulfonic acid, naphthalene sulfonic acid and cumene sulfonic acid; salts thereof and mixtures thereof. Yet more preferably, the liquid laundry detergent formulation of the present invention, further comprises 0 to 10 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.2 to 8 wt%; most preferably, 0.5 to 7.5 wt%), based on the weight of the liquid laundry detergent formulation, of a hydrotrope; wherein the hydrotrope is selected from the group consisting of sodium toluene sulfonate, potassium toluene sulfonate, sodium xylene sulfonate, ammonium xylene sulfonate, potassium xylene sulfonate, calcium xylene sulfonate, sodium cumene sulfonate, ammonium cumene sulfonate and mixtures thereof. Most preferably, the liquid laundry detergent formulation of the present invention, further comprises 0 to 10 wt% (preferably, 0.1 to 10 wt%; more preferably, 0.2 to 8 wt%; most preferably, 0.5 to 7.5 wt%), based on the weight of the liquid laundry detergent formulation, of a hydrotrope; wherein the hydrotrope is sodium xylene sulfonate.Attorney Docket No. 85777-WO-PCT

[0023] Preferably, the liquid laundry detergent formulation of the present invention, further comprises a builder. More preferably, the liquid laundry detergent formulation of the present invention, further comprises 0 to 30 wt% (preferably, 1 to 20 wt%; more preferably, 2.5 to 10 wt%), based on the weight of the liquid laundry detergent formulation, of a builder. Still more preferably, the liquid laundry detergent formulation of the present invention, further comprises 0 to 30 wt% (preferably, 1 to 25 wt%; more preferably, 2.5 to 10 wt%), based on the weight of the liquid laundry detergent formulation, of a builder; wherein the builder is selected from the group consisting of inorganic builders (e.g., tripolyphosphate, pyrophosphate); alkali metal carbonates; borates; bicarbonates; hydroxides; zeolites; citrates (e.g., sodium citrate); polycarboxylates; monocarboxylates; aminotrismethylenephosphonic acid; salts of aminotrismethylenephosphonic acid; hydroxyethanediphosphonic acid; salts of hydroxyethanediphosphonic acid; diethylenetriaminepenta(methylenephosphonic acid); salts of diethylenetriaminepenta(methylenephosphonic acid); ethylenediaminetetraethylene-phosphonic acid; salts of ethylenediaminetetraethylene-phosphonic acid; oligomeric phosphonates; polymeric phosphonates; mixtures thereof. Most preferably, the liquid laundry detergent formulation of the present invention, further comprises 0 to 30 wt% 0 to 30 wt% (preferably, 1 to 25 wt%; more preferably, 2.5 to 10 wt%), based on the weight of the liquid laundry detergent formulation, of a builder; wherein the builder includes sodium citrate.

[0024] 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 wt% (preferably, 0.001 to 5 wt%; more preferably, 0.005 to 3 wt%; most preferably, 0.01 to 2.5 wt%), based on the weight of the liquid laundry detergent formulation, of the fragrance.

[0025] 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 wt% (preferably, 0.5 to 10 wt%), based on the weight of the liquid laundry detergent formulation, of a fabric softener. Most preferably, the liquid laundry detergent formulation of the present invention, further comprises 0 to 10 wt% (preferably, 0.5 to 10 wt%), based on the weight of the liquid laundry detergent formulation, of the fabric softener; wherein the fabric softener is a cationic coacervating polymer (e.g., cationic hydroxyl ethyl cellulose; polyquaternium polymers and combinations thereof).

[0026] Preferably, the liquid laundry detergent formulation of the present invention, further comprises a pH adjusting agent. More preferably, the liquid laundry detergent formulation ofAttorney Docket No. 85777-WO-PCTthe present invention, further comprising a pH adjusting agent; wherein the liquid laundry detergent formulation has a pH of 6 to 12.5 (preferably, 6.5 to 11; more preferably, 7.5 to 10). Bases for adjusting pH include mineral bases such as sodium hydroxide (including soda ash) and potassium hydroxide; sodium bicarbonate; sodium silicate; ammonium hydroxide; and organic bases (e.g., mono-, di- or tri-ethanolamine; and 2-dimethylamino-2-methyl-1- propanol (DMAMP)). Acids to adjust the pH include mineral acids (e.g., hydrochloric acid, phosphorus acid and sulfuric acid) and organic acids (e.g., acetic acid, citric acid).

[0027] Preferably, the method of washing a soiled fabric article of the present invention, comprises: providing a soiled fabric article (preferably, wherein the soiled fabric article is soiled with oil and grease borne soil; more preferably, wherein the soiled fabric article is soiled with sebum oils)(preferably, wherein the soiled fabric article is stained cotton fabric; more preferably, wherein the soiled fabric article is stained polycotton fabric); providing a liquid laundry detergent formulation of the present invention; providing a wash water; and applying the wash water and the liquid laundry detergent formulation to the soiled fabric to provide a cleaned fabric article (preferably, wherein the wash water is at a temperature of ≤ 35 °C (preferably, 10 to 35 °C; more preferably, 15 to 30 °C; most preferably, 20 to 25 °C)). More preferably, the method of washing a soiled fabric article of the present invention, comprises: providing a soiled fabric article (preferably, wherein the soiled fabric article is soiled with oil and grease borne soil; more preferably, wherein the soiled fabric article is soiled with sebum oils)(preferably, wherein the soiled fabric article is stained cotton fabric; more preferably, wherein the soiled fabric article is stained polycotton fabric); providing a liquid laundry detergent formulation of the present invention; providing a wash water; providing a rinse water; applying the wash water and the liquid laundry detergent formulation to the soiled fabric to provide a cleaned fabric article; wherein the wash water is at a temperature of ≤ 35 °C (preferably, 10 to 35 °C; more preferably, 15 to 30 °C; most preferably, 20 to 25 °C); and then applying the rinse water to the cleaned fabric article to remove the liquid laundry detergent formulation from the cleaned fabric article.

[0028] Some embodiments of the present invention will now be described in detail in the following Examples.Attorney Docket No. 85777-WO-PCT

[0029] Reagents Structure 1,4-bis(2-hydroxyethyl)piperazine (“BHE-pip”)Attorney Docket No. 85777-WO-PCTdimethyl 2-(piperidin-1-yl)succinate (“piperadine-DMM”) Product of Synthesis S16 [00

[0031] A Waters ACQUITY UPLC H-Class System with Refractive Index Detector, equipped with an Agilent Plgel 3 μm MiniMixed-E 4.6 x 250 mm column was used for molecular weight determinations. The mobile phase was THF with 0.1% DEEN, at a flow rate of 0.3 mL / min. The injection volume was 5 μL. Each sample was injected twice. Polymer solutions were dissolved at ~ 5 mg / mL and filtered through a 0.45 μm PTFE filter before analysis. Calibration used PS standards (molecular weight 580 - 377,400 Daltons).Attorney Docket No. 85777-WO-PCTSynthesis S1: pip-DAME

[0032] Pip-DAME was prepared by reaction of piperazine with methyl bromoacetate following a literature method (cf. 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 acetonitrile. The reaction mixture increased from 20 to 30 °C during the addition. After standing overnight at room temperature, the sample was filtered through a fritted funnel with vacuum assistance. The filtrate was reduced by rotary evaporator. The solid mass that resulted after cooling (15.678 g) was stirred in 200 mL hexanes for 4 hrs. Two crops were recovered, for a total of 3.5 g white crystals.1H NMR (δ, CDCl3): 3.65 (s, 6H), 3.16 (s, 4H), 2.59 (br s, 8H). The preparation was repeated under similar conditions, yielding a material with identical1H NMR spectrum and following:13C NMR (126 MHz, CDCl3) δ 170.61, 59.31, 52.75, 51.64. Synthesis S2: pip-DAME-EO-PO diol

[0033] A pip-DAME-EO-PO diol was prepared in a flask outfitted with a heating block, a Vigreux column, a vacuum line and a stir bar. To the flask was charged pip-DAME (1.053 g; 4.57 mmol) prepared according to Synthesis S1 and an EO-PO diol (5.825 g; 5.94 mmol; UCONTM75-H-450). The flask contents were sparged with nitrogen and heating in a block with a temperature of 149-150 °C for 2.5 hrs. After heating, titanium isopropoxide (65 mg; 0.23 mmol) was injected via syringe to the flask contents. The heating block was maintained at a temperature of 150 °C for ~3.3 hr under vacuum (pressure gradually reduced from 157 to 53 Torr). After cooling to room temperature under nitrogen, an additional pip-DAME (0.197g; 0.86 mmol) was added to the flask contents. The mixture was again heated, with a block temperature of 150 °C for ~3.5 hr under vacuum (pressure gradually reduced from 217 to 49 Torr). Based on the ratios of integrals for the secondary alcohol ester protons to primary alcohol ester protons to pip-DAME ring protons (1.00 : 1.42 : 8.00, at 5.07, 4.23, and 2.61 ppm, respectively), the conversion of methyl esters was calculated to be 86 %. The number average molecular weight, Mn, and the weight average molecular weight, Mw, of the product were measured by GPC as Mn = 4,086 Daltons and Mw = 13,008 Daltons. Synthesis S3: pip-DAME-EO-PO diol / PPG

[0034] A pip-DAME-EO-PO diol / PPG was prepared in a flask outfitted with a heating block, a Vigreux column, a vacuum line and a stir bar. To the flask was charged pip-DAME (1.004 g; 4.36 mmol) prepared according to Synthesis S1, an EO-PO diol (2.795 g; 2.85 mmol;Attorney Docket No. 85777-WO-PCTUCONTM75-H-450) and a poly(propylene glycol) (1.140 g; 2.85 mmol; PPG-400). The flask contents were sparged with nitrogen and heating in a block whose temperature was raised from 34 to 57 °C over ~2 hrs. Then titanium isopropoxide (69 mg / 0.24 mmol) was injected via syringe to the flask contents. The flask contents were then heated in a block with a temperature of 140-141°C for 4 hrs. After cooling overnight at room temperature, the flask contents were heated in a heating block at 141°C and placed under vacuum (pressure gradually reduced from 202 to 183 Torr) for ~ 3 hrs. Based on the ratios of integrals for the secondary alcohol ester protons to primary alcohol ester protons to pip-DAME ring protons (1.62 : 0.87 : 8.00, at 5.02, 4.19, and 2.58 ppm, respectively), the conversion of methyl esters was estimated to be essentially complete. The number average molecular weight, Mn, and the weight average molecular weight, Mw, of the product were measured by GPC as Mn = 3,484 Daltons and Mw = 11,778 Daltons. Synthesis S4: pip-DAME / DMA-EO-PO diol / PPG

[0035] A pip-DAME / DMA-EO-PO diol / PPG was prepared in a flask outfitted with a heating block, a Vigreux column, a vacuum line and a stir bar. To the flask was charged an EO-PO diol (5.545 g; 5.66 mmol; UCONTM75-H-450) and a poly(propylene glycol) (2.250 g; 5.63 mmol; PPG-400). The flask contents were sparged with nitrogen and heating in a block whose temperature was raised from 58 to 114 °C over ~50 min. Then pip-DAME (1.010 g; 4.39 mmol) prepared according to Synthesis S1, dimethyl maleate (0.765 g; 4.39 mmol) and titanium isopropoxide (123 mg; 0.43 mmol) were added to the flask contents. Nitrogen sparging was resumed and the flask contents were heated in a block with a temperature of 144-145 °C for ~1.5 hrs. The flask contents were then placed under partial vacuum (pressure gradually reduced from 194 to 7 Torr) for ~3 hrs. After cooling overnight at room temperature under nitrogen, the flask contents were heated in a heating block at 141-155 °C for ~6 hr at controlled pressure (gradually reduced from 196 to 2.9 Torr). Based on the ratios of integrals for the secondary alcohol ester protons to primary alcohol ester protons to pip-DAME ring protons to protons at the 3 and 4 positions of dimethyl maleate (3.09 : 1.69 : 8.00 : 4.15, at 5.0, 4.15, 2.58 and 1.58 ppm, respectively), the conversion of methyl esters was estimated to be 96%. The number average molecular weight, Mn, and the weight average molecular weight, Mw, of the product were measured by GPC as Mn = 3,278 Daltons and Mw = 9,541 Daltons. Synthesis S5: pip-DAME / DMTP-EO-PO diol / PPG

[0036] A pip-DAME / DMTP-EO-PO diol / PPG was prepared in a flask outfitted with a heating block, a Vigreux column, a vacuum line and a stir bar. To the flask was charged anAttorney Docket No. 85777-WO-PCTEO-PO diol (5.600 g; 5.71 mmol; UCONTM75-H-450) and a poly(propylene glycol) (2.296 g; 5.74 mmol; PPG-400). The flask contents were sparged with nitrogen in a heating oil bath at a temperature between 89 to 99 °C for ~100 min. Then pip-DAME (1.016 g; 4.41 mmol) prepared according to Synthesis S1 and dimethyl terephthalate (0.854 g; 4.40 mmol) were added to the flask contents. Sparging of the flask contents was resumed for another 10 min. before titanium isopropoxide (137 mg; 0.48 mmol) was injected to the flask contents. The flask contents were then heated in an oil bath with a temperature of 114 °C under nitrogen for 0.5 hrs. The flask contents were then placed under a partial vacuum (188-196 Torr) for ~5.3 hrs. The flask contents were then allowed to cool to room temperature. Based on the ratios of integrals for the secondary alcohol ester protons to primary alcohol ester protons to pip-DAME ring protons to aromatic protons of dimethyl terephthalate (3.16 : 1.87 : 8.00 : 4.25, at 4.9-5.3, 4.1-4.4 and 8.0 ppm, respectively), the conversion of methyl esters was found to be essentially quantitative. The number average molecular weight, Mn, and the weight average molecular weight, Mw, of the product were measured by GPC as Mn = 3,040 Daltons and Mw = 7,775 Daltons. Synthesis S6: pyr-DMM

[0037] A pyr-DMM was prepared in a flask outfitted with a heating block and a stir bar. To the flask was charged dimethyl maleate (10.057 g; 70 mmol) and methanol (10.06 g). The flask contents were placed under nitrogen in a heating block. Then pyrrolidine (4.4 g; 62 mmol) was slowly added to the flask contents via syringe. The flask contents then maintained at a temperature of 45 to 50 °C for ~7 hrs. Then the methanol was removed from the flask contents by rotary evaporator. The flask contents were then cooled by immersing the flask in a 50 °C water bath. The product recovered was analyzed by1H NMR (500 MHz, CDCl3) δ 3.80 – 3.73 (m, 2H), 3.68 (s, 3H), 3.63 (s, 3H), 2.83 (dd, J = 16.1, 9.0 Hz, 1H), 2.70 – 2.51 (m, 5H), 1.78 – 1.62 (m, 4H) and quantitative13C NMR (126 MHz, CDCl3) δ 171.80 (1C), 171.63 (1C), 60.82 (1C), 51.73 (1C), 51.54 (1C), 49.75 (2C), 35.40 (1C), 23.56 (2C) ppm. Synthesis S7: pyr-DMI

[0038] A pyr-DMI was by charging dimethyl itaconate (10.80 g; 68 mmol) and methanol (10 g) to a flask. Then pyrrolidine (4.4 g; 62 mmol) was slowly added to the flask contents via syringe at room temperature. During course of the addition of pyrrolidine the temperature of the flask contents rose from 21 to 27 °C. After standing overnight at room temperature under nitrogen, the flask contents were then reduced by rotary evaporation and then by drying under vacuum for 3 hrs. The product recovered was analyzed by1H NMR (500 MHz, CDCl3) δAttorney Docket No. 85777-WO-PCT3.57 (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 quantitative13C NMR (126 MHz, 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. Synthesis S8: pyr-DMM / DMS-PEG / PPG

[0039] A pyr-DMM / DMS-PEG / PPG was prepared in a flask outfitted with a heating block, a vacuum line and a stir bar. To the flask was charged pyr-DMM (4.201 g; 19.5 mmol) prepared according to Synthesis S7 and poly(ethylene glycol) (6.515 g; 21.7 mmol; PEG- 300). The flask contents were sparged with nitrogen and heated in a heating block. Then titanium isopropoxide (0.232 g; 0.82 mmol) was injected into the flask contents and the reaction was allowed to proceed under vacuum with a temperature of 101 to 113 °C for ~3 hrs. The flask contents were then cooled to room temperature. Dimethyl succinate (2.965 g, 20.3 mmol) and poly(propylene glycol) (9.008 g; 22.5 mmol; PPG-400) were added to the flask contents. The flask contents were then heated under vacuum at 101 to 113 °C for ~ 4 hrs. The flask contents were then allowed to cool to room temperature. Additional titanium isopropoxide (0.278 g; 0.98 mmol) was injected to the flask contents. The flask contents were then maintained at 101 to 113 °C under partial vacuum for ~6.5 hrs. Based on the ratios of integrals in the1H NMR spectrum at 4.9 ppm (2.00, secondary ester), 4.0-4.2 ppm (4.73, primary ester), 2.3-2.8 ppm (11.90, contributiosn from 6 protons of pyr-DMM and 4 protons from DMS), and 1.6 ppm (4 protons from pyr-DMM) the total ratio of non-methyl ester to diester was estimated to be (2+(4.73 / 2)) : ((4 / 4) + (10.67-6) / 4) = 4.37 : 2.16, which indicates essentially complete conversion. The number average molecular weight, Mn, and the weight average molecular weight, Mw, of the product were measured by GPC as Mn = 1,485 Daltons and Mw = 2,679 Daltons. Synthesis S9: pyr-DMI-PEG / PPG

[0040] A pyr-DMI-PEG / PPG was prepared in a flask outfitted with a heating block, a vacuum line and a stir bar. To the flask was charged an EO-PO diol (8.274 g; 8.44 mmol; UCONTM75-H-450) and a poly(propylene glycol) (3.383 g; 8.46 mmol; PPG-400). The flask contents were sparged with nitrogen and heated with a block whose temperature was raised from 25 to 117 °C over ~2.5 hrs. Then pyr-DMI (3.020 g; 19.5 mmol) prepared according to Synthesis S8 and titanium isopropoxide (188 mg; 0.66 mmol) were added to the flask contents. The flask contents were then heated with a heating block at 135-140 °C under controlled vacuum (setpoint 45 Torr) for ~3.9 hrs. The flask contents were then allowed to cool to room temperature. Then pyr-DMI (0.755 g; 3.3 mmol) was added to the flask contents. The flask contents were then heated with the heating block at 141 °C underAttorney Docket No. 85777-WO-PCTcontrolled vacuum (setpoint 200 Torr) for ~2.2 hrs. The flask contents were then allowed to cool to room temperature. Then pyr-DMI (0.798 g; 3.5 mmol) and titanium isopropoxide (95 mg, 0.33 mmol) were added to the flask contents. The flask contents were then heated with the heating block at 121 °C under controlled vacuum (setpoint gradually reduced from 200 to 15 Torr) for ~3.5 hrs. The flask contents were allowed to cool overnight at room temperature under nitrogen. The flask contents were then heated with a heating block temperature of 140 °C under controlled vacuum (setpoint gradually reduced from 15 to 0.8 Torr) for ~5.3 hrs. Based on the ratios of integrals in the1H NMR spectrum at 4.8-5.1 ppm (1.58, secondary ester), 4.0-4.3 ppm (1.13, primary ester), and 1.6 ppm (4.00, 4 protons from pyr-DMI) the total ratio of non-methyl ester to diester was estimated to be (1.58 + (1.13 / 2)) : ((4 / 4) = 2.15 : 1, which indicates essentially complete conversion. The number average molecular weight, Mn, and the weight average molecular weight, Mw, of the product were measured by GPC as Mn = 2,282 Daltons and Mw = 4,368 Daltons. Synthesis S10: DMA / BHE-pip-EO-PO diol

[0041] A DMA / BHE-pip-EO-PO diol was prepared in a flask outfitted with a heating block, a vacuum line and a stir bar. To the flask was charged an EO-PO diol (12.252 g; 12.50 mmol; UCONTM75-H-450). The flask contents were sparged with nitrogen and heated with a block whose temperature was raised from 42 to 100 °C over ~2 hrs. Then dimethyl adipate (3.563 g; 20.45 mmol) and zirconium(IV) acetylacetonate (190 mg; 0.39 mmol) were added to the flask contents. The flask contents were then heated with a heating block whose temperature was raised from 98 to 139 °C under controlled vacuum (setpoint gradually reduced from 170 to 44 Torr) over ~3.2 hrs. The flask contents were then allowed to cool to room temperature. Then 1,1’-(piperazine-1,4-diyl)bis(propan-2-ol) (2.203 g; 12.64 mmol; BHE-pip) was added to the flask contents. The flask contents were then heated with the heating block at 121-122 °C under controlled vacuum (setpoint 200 Torr) for ~2.2 hrs. The flask contents were then allowed to cool overnight at room temperature under nitrogen. Then the flask contents were then heated with the heating block at 121-122 °C under controlled vacuum (setpoint gradually reduced from 200 to 15 Torr) for ~2.5 hrs. The flask contents were allowed to cool overnight at room temperature under nitrogen. The flask contents were then heated with a heating block temperature of 140 °C under controlled vacuum (setpoint gradually reduced from 200 to 15 Torr) for ~5.7 hrs. The flask contents were allowed to cool overnight at room temperature under nitrogen. The flask contents were then heated with a heating block temperature of 140 °C under controlled vacuum (setpoint gradually reduced from 227 to 0.07 Torr) for ~4 hrs. Based on the ratios of integrals in the1H NMR spectrumAttorney Docket No. 85777-WO-PCTat 4.9-5.1 ppm (0.44, secondary ester), 4.0-4.1 ppm (2.54, primary ester), and 1.5 ppm (4.00, 4 protons at the 3 and 4 positions of dimethyl adipate (DMA)) the total ratio of non-methyl ester to diester was estimated to be (0.44 + (2.54 / 2)) : ((4 / 4) = 1.71 : 1, which indicates 86% conversion. The number average molecular weight, Mn, and the weight average molecular weight, Mw, of the product were measured by GPC as Mn = 2,163 Daltons and Mw = 3,613 Daltons. Synthesis S11: BHP-pip

[0042] Synthesis of 1,1’-(piperazine-1,4-diyl)bis(propan-2-ol) (BHP-pip) was performed in a 48 cell stainless steel parallel pressure reactors with glass inserts and with mechanical agitation. Piperazine (1.29 g; 15 mmol) was added to each cell. The reactors were sealed and then the temperature set point was raised to 110 °C to melt the piperazine. Propylene oxide (2.21 mL; 31.5 mmol) was injected into each cell; the temperature set point was raised to 130 °C and the reactor contents were stirred for 20 hrs. Four of the reactors were determined to have leaks and their products were not included in further work. The contents of the other reactors were combined to yield 124.8 g of BHP-pip.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).13C NMR (DMSO) δ 65.99, 63.11, 53.43, 21.76 ppm. Synthesis S12: DMA / BHP-pip-EO-PO diol

[0043] A DMA / BHP-pip-EO-PO diol was prepared in a flask outfitted with a heating block, a vacuum line and a stir bar. To the flask was charged an EO-PO diol (12.125 g; 12.37 mmol; UCONTM75-H-450) and BHP-pip (2.507 g; 12.39 mmol) prepared according to Synthesis S11. The flask contents were sparged with nitrogen and heated with a block whose temperature was raised from 65 to 125 °C over ~2 hrs. Then dimethyl maleate (DMA) (3.436 g; 19.72 mmol) and titanium isopropoxide (279 mg; 0.98 mmol) were added to the flask contents. The flask contents were then heated with a heating block whose temperature was raised from 129-149 °C under controlled vacuum (gradually reduced from 198 to 81 Torr) over ~4.2 hrs. The flask contents were then allowed to cool overnight at room temperature under nitrogen. The flask contents were then heated with the heating block temperature of 153-154 °C under controlled vacuum (setpoint 200 Torr) for ~4.8 hrs. The flask contents were than again allowed to cool overnight at room temperature under nitrogen. The flask contents were then heated with the heating block whose temperature was raised from 132 to 151 °C under controlled vacuum (gradually reduced from 200 to 50 Torr) over ~6.2 hrs. The flask contents were than again allowed to cool overnight at room temperature under nitrogen. The flask contents were then heated with the heating block temperature of 160-162 °C underAttorney Docket No. 85777-WO-PCTcontrolled vacuum (gradually reduced from 200 to 50 Torr) for ~3.5 hrs. The flask contents were then allowed to cool to room temperature. Based on the ratios of integrals in the1H NMR spectrum at 4.8-5.1 ppm (1.45, secondary ester), 4.0-4.2 ppm (0.83, primary ester), and 1.4-1.7 ppm (4.00, 4 protons at the 3 and 4 positions of dimethyl adipate (DMA)) the total ratio of non-methyl ester to diester was estimated to be (1.45 + (0.83 / 2)) : ((4 / 4) = 1.87 : 1, which indicates 93% conversion. The number average molecular weight, Mn, and the weight average molecular weight, Mw, of the product were measured by GPC as Mn = 3,015 Daltons and Mw = 6,940 Daltons. Synthesis S13: pip-MA

[0044] Synthesis of 1,4-piperazinedipropanoic acid, 1,4-dimethyl ester (pip-MA) was performed in a flask fitted to an internal vapor thermocouple, addition funnel, condenser, stirbar and distillation receiver. To the flask was added methyl acrylate (MA)(82.5 g; 0.96 mol). The addition funnel was charged with a solution of piperazine (43 g; 0.50 mol) in methanol (120 g). The flask contents were heated to 50 °C and the piparizine / methanol solution in the addition funnel was added over the course of 130 min. The temperature of the flask contents rose to 56 °C, and after addition of the piparizine / methanol solution was complete, the flask contents were stirred for an additional 30 min. The flask contents were then distilled to remove methanol with a flask temperature of 34-60 °C, while the pressure on the flask contents was slowly reduced from 200 to 2 Torr. A white solid mass product was recovered (123.3 g); with a distillate recovery of 120.0 g.1H NMR (500 MHz, CDCl3) δ 3.60 (s, 6H), 2.61 (dd, J = 6.89, 7.96 Hz, 4H), 2.42 (m, 12H) and quantitative13C NMR (126 MHz, DMSO-d6) δ 172.30 (2C), 53.09 (2C), 52.41 (4C), 51.16 (2C), 31.55 (2C). Synthesis S14: pip-MA-EO-PO diol

[0045] A pip-MA-EO-PO diol was prepared in a flask outfitted with a heating block, a vacuum line and a stir bar. To the flask was charged an EO-PO diol (6.615 g; 5.73 mmol; UCONTM75-H-450). The flask contents were sparged with nitrogen and heated with a block whose temperature was raised from 79 to 103 °C over ~1.6 hrs. Then pip-MA (1.293 g; 5.01 mmol) prepared according to Synthesis S13 and titanium isopropoxide (64 mg; 0.23 mmol) were added to the flask contents. The flask contents were then heated with a heating block whose temperature was raised from 148-153 °C under controlled vacuum (185 to 200 Torr) over ~5 hrs. The flask contents were then allowed to cool overnight at room temperature under nitrogen. The flask contents were then heated with the heating block temperature of 150-152 °C under controlled vacuum (setpoint 190 Torr) for ~7.5 hrs. The flask contents were than again allowed to cool overnight at room temperature under nitrogen. ThenAttorney Docket No. 85777-WO-PCTtitanium isopropoxide (61 mg; 0.21 mmol) was added to the flask contents. The flask contents were then heated with the heating block temperature of 150 °C under controlled vacuum (gradually reduced from 200 to 50 Torr) over ~3.3 hrs. The flask contents were than again allowed to cool overnight at room temperature under nitrogen. The flask contents were then heated with the heating block temperature of 153 °C under controlled vacuum (200-210 Torr) for ~3.5 hrs. The flask contents were than again allowed to cool overnight at room temperature under nitrogen. The flask contents were then again heated with the heating block temperature of 153 °C under controlled vacuum (gradually reduced from 200 to 50 Torr) over ~5.3 hrs. The flask contents were then allowed to cool to room temperature. Based on the ratios of integrals in the1H NMR spectrum at 4.8-5.0 ppm (1.03, secondary ester), 4.0-4.2 ppm (1.52, primary ester), and 2.0-2.7 ppm (16.00, pip-MA) the total ratio of non-methyl ester to diester was estimated to be (1.03 + (1.52 / 2)) : ((16 / 16) = 1.79 : 1, which indicates 90% conversion. The number average molecular weight, Mn, and the weight average molecular weight, Mw, of the product were measured by GPC as Mn = 2,770 Daltons and Mw = 5,790 Daltons. Synthesis S15: pip-MA / DMA-EO-PO diol / PPG

[0046] A pip-MA / DMA-EO-PO diol / PPG was prepared in a flask outfitted with a heating block, a vacuum line and a stir bar. To the flask was charged an EO-PO diol (5.636 g; 5.73 mmol; UCONTM75-H-450) and poly(propylene glycol) (2.313 g; 5.78 mmol; PPG-400). The flask contents were sparged with nitrogen and heated with a block whose temperature was raised from 23 to 105 °C over ~2.3 hrs. Then pip-MA (1.202 g; 4.65 mmol) prepared according to Synthesis S13, dimethyl adipate (DMA)(0.787 g; 4.52 mmol) and titanium isopropoxide (121 mg; 0.23 mmol) were added to the flask contents. The flask contents were then heated with a heating block whose temperature was raised from 151-155 °C under controlled vacuum (200 to 210 Torr) for ~3.5 hrs. The flask contents were then allowed to cool overnight under nitrogen. The flask contents were then heated with the heating block temperature of 155 °C under controlled vacuum (reduced from 200 to 50 Torr) over ~5.3 hrs. Based on the ratios of integrals in the1H NMR spectrum at 4.8-5.0 ppm (2.92, secondary ester), 4.0-4.2 ppm (1.71, primary ester), 2.1-2.6 ppm (18.75, pip-MA) and 1.4-1.6 ppm (4.00, 4 protons of DMA) the total ratio of non-methyl ester to diester was estimated to be (2.92 + (1.71 / 2)) : ((18.75 / 16) + (4 / 4) = 1.74 : 1, which indicates 87% conversion. The number average molecular weight, Mn, and the weight average molecular weight, Mw, of the product were measured by GPC as Mn = 2,925 Daltons and Mw = 6,950 Daltons.Attorney Docket No. 85777-WO-PCTSynthesis S16: piperidine-DMM

[0047] Dimethyl 2-(piperidin-1-yl)succinate (piperidine-DMM) was prepared in a flask outfitted with a heating block, a vacuum line and a stir bar. To the flask was charged piperidine (5.320 g; 62.47 mmol) and methanol (19.9 g). Dimethyl maleate (DMM) (10.014 g; 69.5 mmol) was slowly added to the flask contents over a period of 9 min. A white precipitate formed. After standing at room temperature overnight, the solvent was removed by nitrogen flow and the white precipitate was recovered.1H NMR (500 MHz, 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). By1H NMR analysis, the recovered product contained 13 mol% (9 wt%) dimethyl fumarate. Quantitative13C NMR (126 MHz, 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. Synthesis S17: piperidine-DMM-EO-PO diol

[0048] A piperidine-DMM-EO-PO diol was prepared in a flask outfitted with a heating block, a vacuum line and a stir bar. To the flask was charged an EO-PO diol (5.531 g; 5.64 mmol; UCONTM75-H-450). The flask contents were sparged with nitrogen and heated with a block whose temperature was raised from 68 to 111 °C over ~1.3 hrs. The flask contents were then allowed to cool to room temperature. Then piperidine-DMM (0.939 g; 4.10 mmol) prepared according to Synthesis S16 and titanium isopropoxide (68 mg; 0.24 mmol) were added to the flask contents. The flask contents were then heated in an oil bath at 150 °C under controlled vacuum (200 Torr) for ~5 hrs. The flask contents were then allowed to cool overnight at room temperature under nitrogen. The flask contents were then heated with the heating block temperature of 155 °C under controlled vacuum (46 Torr) for ~7 hrs. Based on the ratios of integrals in the1H NMR spectrum at 4.9-5.2 ppm (1.18, secondary ester), 4.1-4.4 ppm (1.69, primary ester), 1.46-1.35 ppm (6.00, piperidine-DMM ring protons at positions 3, 4 and 5) and 6.8 ppm (0.23, fumarate =CH- protons) indicates a 90% conversion of methyl esters. The number average molecular weight, Mn, and the weight average molecular weight, Mw, of the product were measured by GPC as Mn = 2,920 Daltons and Mw = 6,210 Daltons. Polymer Hydrolysis

[0049] Polymer products from Syntheses S2-S5 (inventive) and Syntheses S8-10, S12, S14- S15 and S17 (comparative) were evaluated for stability 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.

[0050] NMR Method of estimating the degree of hydrolysis by proton NMR spectroscopy: A 1 wt% solution of each polymer tested was made by dissolving the polymer to be testedAttorney Docket No. 85777-WO-PCT(0.10 g) in a 10 mM tris buffer (9.9 g) at pH of 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.1H (zg30) and water suppression (1H; noesygppr1d) experiments were run at 40 °C using a relaxation time of 20 sec. 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 at ~5.4 ppm (corresponding to the secondary -C(O)OCH- esters) and ~4.5 ppm (corresponding to the primary -C(O)OCH2- esters) were integrated and normalized to the integration of peaks from 1.0 to 1.4 ppm or to the receiver gain. Comparing the integrals of these two peaks between the t = 0 and t = 4 spectra provides the % esters of each type retained in the test polymer. The % total esters retained was calculated on a molar basis. Throughout this document the terms “primary ester” and “primary alcohol ester” are understood to exclude methyl esters. TABLE1 Ester retention (%) Polymer Inventive Primary Esters Secondary Esters Total Estersent

[0051] The liquid laundry detergent formulations of Comparative Examples CF1-CF5 and Examples F1-F4 used in the cleaning tests in the subsequent Examples were prepared having the generic formulation as described in TABLE2 with the cleaning booster as noted in TABLE3 neutralized to a pH of 8.5 with sodium hydroxide using standard liquid laundry formulation preparation procedures.Attorney Docket No. 85777-WO-PCTTABLE 2 Ingredient Commercial Name wt% Linear alkyl benzene sulfonate Nacconal 90G*2.0 *Comparative Example CF1 None

[0052] The primary cleaning performance of the liquid laundry detergent formulations of Comparative Examples CF1-CF5 and Examples F1-F4 were assessed in a Launder- Ometer (SDL Atlas, Model M228AA) at a set test temperature of 22 °C using an 18 minute wash cycle. Twenty of the 1.2 liter canisters were filled with 500 mL of hardness adjusted water at 100 ppm by mass with 2:1 Ca2+:Mg2+molar ratio were used for each run. Liquid laundry detergent (2.16 g) as noted in TABLE 4 was added. The washed fabrics were rinsed in 300 mL of 100 ppm (2 / 1 Ca2+ / Mg2+) hardness adjusted water at ambient temperature for 5 minutes at 260 osc / min pm on an Eberbach E6000 reciprocal shaker. The stained fabrics and soiled ballasts used in the tests were PCS-S-132 high discriminative sebum BEY pigment and PCS-S-94 sebum / dust ASTM stains from Testfabrics stitched to a pre-shrunk cotton interlock fabric. The size of the cotton interlock was 5x5 cm. The stained swatches were 2.5 x 3 cm. One 5 x 5 cm cut SBL-CFT soil ballast was added to each canister to provide baseline soil to the wash solution.Attorney Docket No. 85777-WO-PCTReflectance measurement and Stain Removal Index (SRI)

[0053] The soil removal index (SRI) for each of the Liquid Laundry Detergent formulations evaluated in Primary Cleaning Performance Test were determined using ASTM Method D4265-14. The average SRI taken from 8 swatches per condition (two swatches per pot, 4 pots) is provided in TABLE 4.

[0054] The L*, a*and b*values of the stained fabrics were measured pre and post wash with a Mach 5 spectrophotometer from Colour Consult. The L*, a*and b*values for the unwashed, unstained polycotton fabric was measured in the SRI calculations as follows: (∆^∗ − ∆^∗ ^^^ = (^^^^^) (^^^^^)∆^∗ × 100wherein US is the fabric area, WS is the *washed stain area, ΔE (US-UF) the unwashed stain and the unwashed fabric and ΔE*(WS-UF)is the ΔE*color difference between the washed stain and the unwashed fabric. The value of ΔE*is calculated as ΔE*= (ΔL*2+ Δa*2+ Δb*2)½The ΔSRI values provided in TABLE4 give the difference between the SRI measured for the noted example relative to the SRI measured for Comparative Example CF1. A positive value indicates an increase in soil removal relative to Comparative Example CF1. TABLE 4 ΔSRI Li id L ndr D t r nt Cl nin B t r PCS 94 PCS 132 C mbin d

Claims

Attorney Docket No. 85777-WO-PCTWe claim:

1. A cleaning booster for cleaning laundry, wherein the cleaning booster is of formula I (I) wherein a is 1 to 30; wherein each formula II, formula III andwherein b is 0selected from a hydrogen and a C1-4alkyl group; wherein each R5is independently selected from a hydrogen and a C1-4 alkyl group; wherein each R6is independently selected from a hydrogen and a methyl group; wherein R7is selected from the group consisting of a single bond and a bridging group with 1 to 8 carbon atoms; and wherein each * in formula II, formula III and formula IV represents a bond to R1or R2; wherein R1is of formula VAttorney Docket No. 85777-WO-PCTwherein d is 5 to 150; wherein each R8and R9is independently selected from the group consisting of a hydrogen and a C1-2alkyl group, with the proviso that at least one of R8and R9is a hydrogen in each subunit d; wherein R10is selected from the group consisting of a hydrogen and a C1-22alkyl group; and wherein the * in formula V represents a bond to X; wherein each R2is independently of formula VI wherein e is 5 to 150; andconsisting of a hydrogen and2R12is a hydrogen in each subunit e; and wherein each * in formula VI represents a bond to X or R3; and wherein R3is selected from the group consisting of a hydrogen and a C1-22 alkyl group; with the proviso that 10 to 100 mol% of the Xs in formula I are of formula II; and with the proviso that 40 to 100 mol% of the R1and R2groups present in formula I are copolymers of ethylene oxide and a C3-8alkylene oxide, wherein each copolymer is 25 to 99 mol% ethylene oxide.

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

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

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

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

6. The liquid laundry detergent formulation of claim 5, further comprising a hydrotrope.Attorney Docket No. 85777-WO-PCT7. The liquid laundry detergent formulation of claim 6, wherein 45 to 100 mol% of the Xs in formula I are of formula II.

8. The liquid laundry detergent formulation of claim 7, wherein 40 to 100 mol% of the R1and R2groups present in formula I are copolymers of ethylene oxide and propylene oxide.

9. The liquid laundry detergent formulation of claim 8, wherein a is 2 to 15; wherein b is 2; wherein c is 2; wherein each R4, R5and R6is hydrogen; wherein d is 5 to 25; and wherein e is 5 to 25.

10. A method of washing a soiled fabric article, comprising: providing a soiled fabric article; providing a liquid laundry detergent formulation according to claim 9; providing a wash water; and applying the wash water and the liquid laundry detergent formulation to the soiled fabric article to provide a cleaned fabric article.

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