Cleaning enhancer

Abstract

The present invention provides a cleaning enhancer for cleaning dirty laundry wherein the cleaning enhancer has formula (I) wherein A1 is a divalent linking group having from 4 to 24 carbon atoms and R1 has formula (II), formula (III) or formula (IV); wherein * is the point of attachment to formula (I); a is 1 to 2; b is 1 to 2; and R2 has formula (V); wherein * is a connection point with the related basic formula; r3 is selected from hydrogen and a C1-22 alkyl group; r4 and R5 are independently selected from the group consisting of hydrogen and a C1-2 alkyl group, with the proviso that in each subunit c, at least one of R4 and R5 is hydrogen; and wherein c is 0 to 30; and with the proviso that when the divalent linking group A1 has 4 carbon atoms, the divalent linking group A1 comprises a ring. R1-A1-R1 (I) # imgabs0 # # imgabs1 #

Description

[0001] The present invention relates to a cleaning enhancer for cleaning dirty clothes. Specifically, the present invention relates to a cleaning enhancer for cleaning dirty clothes, wherein the cleaning enhancer has formula (I):

[0002] R 1 —A 1 —R 1 (I)

[0003] Among them A 1 is a divalent linking group having 4 to 24 carbon atoms; and wherein each R 1 Independently selected from the group consisting of formula (II), formula (III) and formula (IV)

[0004]

[0005] wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 Independently have formula (V)

[0006]

[0007] Wherein the * in formula (V) is the connection point with the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30; and provided that when the divalent linking group A 1 When it has 4 carbon atoms, the divalent linking group A 1 Including ring.

[0008] One approach to reducing 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. disclose graft copolymers of polyethylene, polypropylene or polybutylene oxide 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 wt % to about 20 wt % surfactant.

[0009] Nevertheless, there continues to be a continuing need for cleaning enhancers that promote laundry detergent formulations (particularly in liquid or gel laundry detergent formulations and unit dose formulations) that maintain primary cleaning performance while reducing surfactant load; preferably, while also providing improved anti-redeposition properties. There also continues to be a need for new cleaning enhancers that have improved biodegradability according to the OECD 301F protocol compared to conventional cleaning enhancers.

[0010] The present invention provides a cleaning enhancer for cleaning dirty laundry, wherein the cleaning enhancer has formula (I)

[0011] R 1 —A 1 —R 1 (I)

[0012] Among them A 1 is a divalent linking group having 4 to 24 carbon atoms; and wherein each R 1 Independently selected from the group consisting of formula (II), formula (III) and formula (IV)

[0013]

[0014]

[0015] wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 Independently have formula (V)

[0016]

[0017] Wherein the * in formula (V) is the connection point with the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30; and provided that when the divalent linking group A 1 When it has 4 carbon atoms, the divalent linking group A 1 Including ring.

[0018] The present invention provides a cleaning enhancer for cleaning dirty laundry, wherein the cleaning enhancer has formula (Ia)

[0019] R 1 —(CH2)n —R 1 (Ia)

[0020] wherein n is 5 to 24; and wherein each R 1 is independently selected from the group consisting of formula (II), formula (III) and formula (IV); wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 independently have the formula (V); wherein the * in the formula (V) is the point of attachment to the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30; and provided that when the divalent linking group A 1 When it has 4 carbon atoms, the divalent linking group A 1 Including ring.

[0021] The present invention provides a cleaning enhancer for cleaning dirty laundry, wherein the cleaning enhancer has formula (Ib)

[0022]

[0023] wherein p and r are independently 1 to 4; and wherein each R 1 is independently selected from the group consisting of formula (II), formula (III) and formula (IV); wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 independently have the formula (V); wherein the * in the formula (V) is the point of attachment to the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30; and provided that when the divalent linking group A 1 When the divalent linking group A has 4 carbon atoms, 1 Including ring.

[0024] The present invention provides a cleaning enhancer for cleaning dirty laundry, wherein the cleaning enhancer has formula (Ic):

[0025]

[0026] Among them A 2 is a divalent linking group having 2 to 22 carbon atoms; and wherein each R 1 is independently selected from the group consisting of formula (II), formula (III) and formula (IV); wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 independently have the formula (V); wherein the * in the formula (V) is the point of attachment to the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30; and provided that when the divalent linking group A 1 When it has 4 carbon atoms, the divalent linking group A 1 Including ring.

[0027] The present invention provides a cleaning enhancer for cleaning dirty laundry, wherein the cleaning enhancer has formula (Id):

[0028]

[0029] wherein t is 2 to 10; and wherein each R 1 is independently selected from the group consisting of formula (II), formula (III) and formula (IV); wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 independently have the formula (V); wherein the * in the formula (V) is the point of attachment to the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30; and provided that when the divalent linking group A 1When it has 4 carbon atoms, the divalent linking group A 1 Including ring.

[0030] The present invention provides a laundry detergent additive comprising a mixture of the cleaning enhancer of the present invention and water. DETAILED DESCRIPTION

[0031] It has surprisingly been found that the cleaning enhancers as described herein help improve primary cleaning performance for sebum soil removal while imparting good anti-redeposition properties of dust sebum and clay, and also exhibit a desirable biodegradability profile according to the OECD 301F protocol.

[0032] Preferably, the cleaning enhancer for cleaning dirty clothes of the present invention has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib))

[0033] R 1 —A 1 —R 1 (I)

[0034] Among them A 1 is a divalent linking group having 4 to 24 carbon atoms (preferably, wherein the divalent linking group A 1 is a divalent cyclic or non-cyclic, straight or branched aliphatic hydrocarbon having 4 to 24 carbon atoms (preferably 4 to 12 carbon atoms); and wherein each R 1 Independently selected from the group consisting of formula (II), formula (III) and formula (IV) (preferably, formula (II) and formula (III); most preferably, formula (III));

[0035]

[0036] wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2 (preferably, 1); wherein b is 1 or 2 (preferably, 1); (preferably, wherein a=b) and wherein each R 2 independently have formula (V) (ie, R 2 The individual occurrences of in formula (II), formula (III) and formula (IV) may be the same or different from each other)

[0037]

[0038] Wherein the * in formula (V) is the connection point with the relevant basic formula (i.e., formula (II), formula (III) or formula (IV)); wherein R 3 Selected from hydrogen and C 1-22The group consisting of alkyl groups (preferably hydrogen and C 1-5 alkyl group; more preferably, a methyl group, an ethyl group and a butyl group; still more preferably, a methyl group and an n-butyl group; most preferably, an n-butyl group); wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30 (preferably, with the proviso that in the cleaning enhancer, in the following mol % of the appearance of formula (V), c is 2 to 30 (preferably, 2 to 25; more preferably, 2 to 17; most preferably, 4 to 12): 70 mol % to 100 mol % (preferably, 80 mol % to 100 mol %; more preferably, 90 mol % to 100 mol %; most preferably, 95 mol % to 100 mol %); and with the proviso that when the divalent linking group A 1 When it has 4 carbon atoms, the divalent linking group A 1 including a ring (preferably, provided that when the divalent linking group A 1 When having 4 carbon atoms, the cleaning enhancer of formula (I) is selected from the group consisting of formula (Ib), formula (Ic) and formula (Id)).

[0039] Preferably, the cleaning enhancer for cleaning dirty clothes of the present invention has formula (I); wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib))

[0040] R 1 —(CH2) n —R 1 (Ia)

[0041]

[0042] wherein n is 5 to 24 (preferably, 5 to 12); wherein p and r are independently 1 to 4 (preferably, 1 to 2; more preferably, wherein p and r are 2) (preferably, wherein the sum of p+r is 2 to 6 (preferably, 2 to 5; more preferably, 4)); wherein A 2 is a divalent linking group having 2 to 22 carbon atoms (preferably, wherein the divalent linking group A 2 is a divalent cyclic or acyclic, straight or branched aliphatic hydrocarbon having 2 to 22 carbon atoms (preferably, 2 to 10 carbon atoms; more preferably, 3 to 6 carbon atoms; most preferably, 4 carbon atoms); more preferably, wherein the divalent linking group A 2is an alkanediyl group having 2 to 22 carbon atoms (preferably, 2 to 10 carbon atoms; more preferably, 3 to 6 carbon atoms; still more preferably, 3 to 5 carbon atoms; most preferably, 4 carbon atoms); and wherein t is 2 to 10 (preferably, 3 to 6; more preferably, 3 to 5; most preferably, 4).

[0043] Preferably, the cleaning enhancer for cleaning dirty clothes of the present invention has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib)); wherein each R 1 Independently selected from the group consisting of formula (II), formula (III) and formula (IV) (preferably, formula (II) and formula (III); most preferably, formula (III));

[0044]

[0045] wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2 (preferably, 1); wherein b is 1 or 2 (preferably, 1); (preferably, wherein a=b) and wherein each R 2 independently have formula (V) (ie, R 2 The individual occurrences of in formula (II), formula (III) and formula (IV) may be the same or different from each other);

[0046]

[0047] Wherein the * in formula (V) is the connection point with the relevant basic formula (i.e., formula (II), formula (III) or formula (IV)); wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-5 alkyl group; more preferably, a methyl group, an ethyl group and a butyl group; still more preferably, a methyl group and an n-butyl group; most preferably, an n-butyl group); wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5At least one of is hydrogen; and wherein c is 0 to 30 (preferably, provided that c is 2 to 30 (preferably, 2 to 25; more preferably, 2 to 17; most preferably, 4 to 12) in the following mol % occurrences of formula (V) in the cleaning enhancer: 70 mol % to 100 mol % (preferably, 80 mol % to 100 mol %; more preferably, 90 mol % to 100 mol %; most preferably, 95 mol % to 100 mol %).

[0048] Preferably, the cleaning enhancer for cleaning dirty laundry of the present invention has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib)); wherein for R of formula (V) with an average value of 70 mol% to 100 mol% (preferably, 80 mol% to 100 mol%; more preferably, 90 mol% to 100 mol%; most preferably, 95 mol% to 100 mol%) 2 Group, c is 2 to 30. More preferably, the cleaning enhancer for cleaning dirty laundry of the present invention has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib)); wherein the average value is 70 mol% to 100 mol% (preferably, 80 mol% to 100 mol%; more preferably, 90 mol% to 100 mol%; most preferably, 95 mol% to 100 mol%) of formula (V) 2 The group has the formula (Va)

[0049] R 6 —O—[CH2CH(R 7 )O] y —* (Va)

[0050] Wherein the * in formula (Va) is the connection point with the relevant basic formula (i.e., formula (II), formula (III) or formula (IV)); wherein R 6 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-5 alkyl group; more preferably, a methyl group, an ethyl group and a butyl group; still more preferably, a methyl group and an n-butyl group; most preferably, an n-butyl group); wherein each R 7 independently selected from hydrogen and C 1-2alkyl groups; and wherein y is 2 to 30. Most preferably, the cleaning enhancer for cleaning dirty laundry of the present invention has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib)); wherein the average value is 70 mol% to 100 mol% (preferably, 80 mol% to 100 mol%; more preferably, 90 mol% to 100 mol%; most preferably, 95 mol% to 100 mol%) of R of formula (V) 2 The group has the formula (Vb)

[0051] R 8 —O—(EO) h —(PO) i —(EO) j —* (Vb)

[0052] Wherein the * in formula (Vb) is the connection point with the relevant basic formula (i.e., formula (II), formula (III) or formula (IV)); wherein R 8 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-5 alkyl group; more preferably, a methyl group, an ethyl group and a butyl group; still more preferably, a methyl group and an n-butyl group; most preferably, an n-butyl group); wherein EO is an ethylene oxide group; wherein PO is a propylene oxide group; wherein h is 0 to 30 (preferably, 0 to 1); wherein i is 0 to 30 (preferably, 2 to 5); wherein j is 0 to 30 (preferably, 2 to 6); and wherein h+i+j is 2 to 30 (preferably, 4 to 12).

[0053] Preferably, the laundry detergent additive of the present invention comprises a mixture of the cleaning enhancer of the present invention and water. More preferably, the laundry detergent additive of the present invention is a mixture comprising: based on the weight of the laundry detergent additive, 0.1 wt % to 99 wt % (preferably, 0.2 wt % to 98 wt %; more preferably, 0.5 wt % to 95 wt %; most preferably, 0.75 wt % to 90 wt %) of the cleaning enhancer of the present invention; and based on the weight of the laundry detergent additive, 1 wt % to 99.9 wt % (preferably, 2 wt % to 99.8 wt %; more preferably, 5 wt % to 99.5 wt %; most preferably, 10 wt % to 99.25 wt %) of water. Most preferably, the laundry detergent additive of the present invention is a mixture comprising: 0.1 wt % to 99 wt % (preferably, 0.2 wt % to 98 wt %; more preferably, 0.5 wt % to 95 wt %; most preferably, 0.75 wt % to 90 wt %) of the cleaning enhancer of the present invention, based on the weight of the laundry detergent additive; and 1 wt % to 99.9 wt % (preferably, 2 wt % to 99.8 wt %; more preferably, 5 wt % to 99.5 wt %; most preferably, 10 wt % to 99.25 wt %) of water, based on the weight of the laundry detergent additive; wherein the laundry detergent additive is a liquid (preferably, wherein the laundry detergent additive is a liquid at 21° C. and 1 standard atmosphere).

[0054] Some embodiments of the present invention will now be described in detail in the following examples.

[0055] Synthesis S1: Michael Addition of 1,3-Diaminopropane to Dimethyl Maleate

[0056] 1,3-diaminopropane (15.217 g, 202 mmol, from Tokyo Chemical Industry Co., Ltd., USA, >98.0%) and ethanol (64 mL) were loaded into a 250 mL 3-neck glass round bottom flask equipped with a magnetic stirring bar. Gentle mixing was started, and the flask was equipped with a cold water condenser connected to an oil bubbler. The condenser was sealed to the center neck with silicone grease, and the flask was further sealed with 2 rubber septa. The flask was then cooled by immersion in an ice-water bath to absorb the heat of reaction. A thermocouple was inserted into a septum to track the temperature during the reaction. Dimethyl maleate (60.263 g, 404 mmol, from Tokyo Chemical Industry Co., Ltd., USA, 97%) was slowly added to the contents of the flask via a syringe over 22 minutes. A large exotherm was observed during the addition of dimethyl maleate. Once the temperature stopped rising, the flask was then placed on a reaction block heater and stirred at 60 ° C for 4.5 hours. pass 1 H and 13The progress of the reaction was monitored by C NMR spectroscopy. When the amine was completely converted into the disubstituted adduct, the ethanol was distilled off in a rotary evaporator to obtain a slightly viscous light yellow adduct. 1 HNMR (500 MHz, methanol-d4) δ 3.75 (s, 6H), 3.70 (s, 6H), 2.74 (m, 6.5H), 2.58 (m, 2.3H), 1.65 (p, 2.2H), 1.3 (m, 1H); 13 C NMR (500MHz, CDCl3) δ: 175.1(2C), 172.8(2C), 58.7(1C), 58.6(1C); 52.6(2C), 52.3(2C), 47.2(1C), 47.0(1C), 38.2(1C), 38.1(1C).

[0057] Synthesis S2: Michael Addition of 1,6-Diaminohexane to Dimethyl Maleate

[0058] 1,6-Diaminohexane (1.776 g, 15.1 mmol, from Sigma Aldrich, ≥99%) and ethanol (16 mL) were charged into a 100 mL 3-neck glass round bottom flask equipped with a magnetic stir bar. Gentle mixing was initiated and the flask was equipped with a cold water condenser connected to an oil bubbler. The condenser was sealed to the center neck with silicone grease and the flask was further sealed with 2 rubber septa. The flask was then cooled by immersion in an ice water bath to absorb the heat of reaction. A thermocouple was inserted into one of the septa to track the temperature during the reaction. Dimethyl maleate (4.445 g, 29.9 mmol, from Tokyo Chemical Industry Co., Ltd. America Branch, 97%) was slowly added to the contents of the flask via a syringe over 2 minutes. Exotherm was observed during the addition of dimethyl maleate and after 3 minutes. Once the temperature stopped rising, the flask was then placed on a reaction block heater and stirred at 60°C for 7 hours. By 1 H and 13 The progress of the reaction was monitored by C NMR spectroscopy. When the amine was completely converted into the disubstituted adduct, the ethanol was distilled off in a rotary evaporator to obtain a slightly viscous light yellow adduct. 1 H NMR (500MHz, CDCl3) δ3.65 (s, 6H), 3.60 (s, 7H), 3.58–3.48 (m, 2H), 2.64 (dd, J=15.8, 6.0Hz, 2H), 2.59–2.47 (m, 5H), 2.40 (ddd, J=11.1, 7.9, 6.3Hz, 2H), 1.35 (p, J=6.2Hz, 5H), 1.28–1.06 (m, 7H); 13C NMR (500MHz, CDCl3) δ: 174.1(2C), 171.2(2C), 57.6(2C), 52.2(2C), 51.7(2C), 47.9(2C), 37.7(2C), 29.9(2C), 26.9(2C).

[0059] Synthesis S3: Michael Addition of 1,12-Diaminododecane to Dimethyl Maleate

[0060] 1,12-Diaminododecane (6.861 g, 34.2 mmol, from Tokyo Chemical Industry Co., Ltd. America, 99.8%) and ethanol (32 mL) were charged into a 250 mL 3-neck glass round bottom flask equipped with a magnetic stir bar. Gentle mixing was initiated and the flask was equipped with a cold water condenser connected to an oil bubbler. The condenser was sealed to the center neck with silicone grease and the flask was further sealed with 2 rubber septa. The flask was then cooled by immersion in an ice water bath to absorb the heat of reaction. A thermocouple was inserted into one of the septa to track the temperature during the reaction. Dimethyl maleate (10.148 g, 68.3 mmol, from Tokyo Chemical Industry Co., Ltd. America, 97%) was slowly added to the contents of the flask via a syringe over 7 minutes. Exothermic events were observed during the addition of dimethyl maleate and after 4 minutes. Once the temperature stopped rising, the flask was then placed on a reaction block heater and stirred at 60°C for 4 hours. By 1 H and 13 The progress of the reaction was monitored by C NMR spectroscopy. When the amine was completely converted into the disubstituted adduct, the ethanol was distilled off in a rotary evaporator to obtain a slightly viscous light yellow adduct. 1 H NMR (500MHz, CDCl3) δ3.64 (s, 6H), 3.59 (s, 6H), 3.61–3.50 (m, 3H), 2.63 (dd, J=15.8, 6.1Hz, 2H), 2.60 –2.49 (m, 5H), 2.39 (ddd, J=11.1, 8.0, 6.3Hz, 2H), 1.41–1.28 (m, 5H), 1.20 (s, 2H), 1.21–1.08 (m, 18H); 13 C NMR (500MHz, CDCl3) δ: 174.1(2C), 171.2(2C), 57.6(2C), 51.9(2C), 51.6(2C), 48.0(2C), 37.6(2C), 29.9(2C), 29.4(m, 6C), 27.0(2C).

[0061] Synthesis S4: Michael Addition of trans-1,4-diaminocyclohexane with dimethyl maleate

[0062] Trans-1,4-diaminocyclohexane (3.945 g, 34.2 mmol, from Tokyo Chemical Industry Co., Ltd. USA, >98%) and methanol (38 mL) were loaded into a 250 mL 3-neck glass round bottom flask equipped with a magnetic stirring bar. Gentle mixing was started, and the flask was equipped with a short-path distillation head with a Vigreux column connected to an oil bubbler and equipped with a 50 mL collection flask. The distillation head was sealed to the center neck with silicone grease, and the flask was further sealed with 1 rubber septum and adapter to enable nitrogen purging. The flask was then cooled by immersion in an ice-water bath to absorb the heat of reaction. A thermocouple was inserted into the septum to track the temperature during the reaction. While nitrogen was purged into the distillation head, dimethyl maleate (10.110 g, 68.0 mmol, 97% from Tokyo Chemical Industry Co., Ltd. USA) was slowly added to the contents of the flask via syringe injection over 26 minutes. A slight exotherm was observed during the addition of dimethyl maleate. Once the temperature stopped rising, the flask was then placed in a heated water bath and stirred and refluxed and distilled for 4 hours. The resulting clear orange solution was removed from the nitrogen and exposed to air, and became cloudy when precipitation began to occur. The precipitate was collected by partially removing methanol via rotary evaporation until a slightly viscous slurry was formed, and the slurry was then dried in a crystallization tray in a 50°C oven for 16 hours. The resulting slurry was then dried in a 50°C oven in a crystallization tray. 1 H and 13 C NMR confirmed the disubstituted adduct and it was used without further purification. 1 H NMR (500MHz, CDCl3) δ3.54–3.47 (m, 4H), 3.45 (s, 3H), 3.16 (s, 4H), 2.55–2.3 3 (m, 2H), 2.18 (tt, J=10.4, 3.6Hz, 1H), 1.79–1.46 (m, 2H), 1.04–0.71 (m, 2H). 1 H NMR (500MHz, CDCl3) δ174.3(2C), 171.2(2C), 51.7(2C), 51.3(2C), 38.0(2C), 31.7(1C), 31.5(1C), 30.7(1C), 30.4(1C).

[0063] Synthesis S5: Michael Addition of 1,7-Diaminoheptane to Dimethyl Maleate

[0064] 1,7-Diaminoheptane (4.5 g, 34 mmol, from Sigma-Aldrich, 98%) and ethanol (14 mL) were charged into a 100 mL 3-neck glass round bottom flask with a magnetic stirring bar. Gentle mixing was initiated and the flask was equipped with a cold water condenser connected to an oil bubbler and sealed with silicone grease and 2 rubber septa. The flask was then cooled by immersion in an ice water bath to absorb the heat of reaction. A needle-type thermocouple was inserted into one of the septa to track the temperature during the reaction. Dimethyl maleate (10.1 g, 68 mmol, from Tokyo Chemical Industry Co., Ltd. USA, 97%) was slowly added to the contents of the flask via a syringe. A large exotherm was observed during the addition of dimethyl maleate. The resulting solution was then placed on a block heater and stirred at 60 ° C for five hours. By 1 H and 13 The progress of the reaction was monitored by C NMR spectroscopy. When the amine was completely converted into the disubstituted adduct, the ethanol was distilled off in a rotary evaporator to obtain a slightly viscous light yellow adduct. 1 H NMR (500MHz, CDCl3) δ3.62 (s, 6H), 3.57 (s, 6H), 3.52 (t, J=6.5Hz, 2H), 2.62 (d, J=6.1Hz, 1H), 2.59 (d, J= 6.1Hz, 1H), 2.56–2.47 (m, 4H), 2.36 (ddd, J=11.1, 7.9, 6.3Hz, 2H), 1.40–1.25 (m, 4H), 1.24–1.12 (m, 7H); 13 C NMR (500MHz, CDCl3) δ174.1(2C), 171.2(2C), 57.6(2C), 51.9(2C), 51.7(2C), 47.9(2C), 37.7(2C), 29.9(2C), 29.1(1C), 26,9(2C).

[0065] Synthesis S6: Michael Addition of 1,7-Diaminoheptane to Dimethyl Maleate

[0066] 1,7-Diaminoheptane (20.7 g, 155 mmol, from Sigma-Aldrich, 98%) and ethanol (50 mL) were loaded into a 250 mL 3-neck glass round bottom flask with a magnetic stirring bar. Gentle mixing was started and the flask was equipped with a cold water condenser connected to an oil bubbler and sealed with silicone grease and 2 rubber septa. The flask was then cooled by immersion in an ice water bath to absorb the heat of reaction. A needle-type thermocouple was inserted into one of the septa to track the temperature during the reaction. Dimethyl maleate (46.1 g, 310 mmol, from Tokyo Chemical Industry Co., Ltd. USA, 97%) was slowly added to the contents of the flask via a syringe. A large exotherm was observed during the addition of dimethyl maleate. The resulting solution was then placed on a block heater and stirred at 60 ° C for five hours. By 1 H and 13 The progress of the reaction was monitored by C NMR spectroscopy. When the amine was completely converted into the disubstituted adduct, the ethanol was distilled off in a rotary evaporator to obtain a slightly viscous light yellow adduct. 13 C NMR (500MHz, CDCl3) δ174.09, 173.58, 171.22, 165.18, 133.27, 60.87, 57.77, 57.68, 57.59, 5 2.16 (d, J=4.1Hz), 51.92, 51.68, 47.93, 37.66, 29.85, 29.12, 26.92, 18.28, 14.15–13.93 (m).

[0067] Synthesis S7 to Synthesis S10: Preparation of Alkoxylate Polymers

[0068] In Syntheses S7 to S10, the reaction mixture was stirred in a Symyx parallel pressure reactor with a glass insert and equipped with a removable polyetheretherketone (PEEK) paddle for mechanical stirring. Prepared according to the formula CH3O-(EO) with the values ​​of m and n as shown in Table 1 m (PO) n The glass insert and removable PEEK stirring blade were dried in a vacuum oven at 125°C overnight before the reaction. Preparation of CH3O-(EO) by ethoxylation of 2-methoxyethanol (from Sigma-Aldrich) m -H-type ethoxylated intermediate. A stock solution was prepared by dissolving potassium hydride in an amount of about 3 wt % based on the weight of 2-methoxyethanol in 2-methoxyethanol under nitrogen. The calculated amount of stock solution was then added to a glass insert under nitrogen. The glass insert was then loaded into a reactor, after which a stirring blade was attached.

[0069] The reactor was then sealed, heated to 120°C, and pressurized to 345 kPa with nitrogen. Ethylene oxide was then delivered to the reactor in several injections via an Isco syringe pump equipped with a robotically controlled needle and a compressed gas microvalve connected to the reactor. The total amount of ethylene oxide added to the reactor was calculated to provide the desired length of (EO) n Block, assuming complete consumption of the ethylene oxide added to the reactor. After the addition of ethylene oxide, the temperature was maintained at 120°C and the reaction mixture was stirred for 4 hours. The reactor contents were then cooled. The reactor was vented and purged with nitrogen to remove any residual ethylene oxide.

[0070] The reactor was then heated to 50°C and pressurized with nitrogen to a pressure of 345 kPa. Propylene oxide was then added to the reactor via an Isco syringe pump. The amount of propylene oxide added to the reactor was calculated to correspond to the desired length (PO) of the target material. n block, assuming complete consumption of the propylene oxide added to the reactor. After the addition of propylene oxide, the temperature was raised to 115°C and maintained at that temperature while stirring the contents of the reactor for 20 hours. The reactor contents were then cooled. The reactor was vented and purged with nitrogen to remove any residual ethylene oxide. The product from the reactor was used without further purification. The molecular weight of the collected product was determined by GPC, as reported in Table 1 by quantitative 13- The composition was determined by C NMR.

[0071] Table 1

[0072]

[0073] Comparative Example C1: Preparation of transesterification products

[0074] In Comparative Example C1, the transesterification product of the following general formula

[0075]

[0076] Prepared by: Alkoxylate polymer (R-OH) (14.2490 g, 27.4 mmol, 4.4 equiv., in UCON TM 50-HB-100 from Dow Chemical Company), material prepared according to Synthesis S1 (2.3113 g, 6.2 mmol), and titanium isopropoxide (0.234 g, 0.82 mmol, 13.2 mol %, from Sigma-Aldrich, 99.999%) were charged into a 250 mL flask with a magnetic stir bar. The flask was sealed with a septum inserted with a needle probe thermocouple, connected to a Schlenk line, and then connected to an IKA magnetic heating plate. The reaction block was heated with a set point temperature of 120°C while under a nitrogen blanket. After 35 minutes, the temperature reached 118.3°C and a vacuum was applied to the flask contents via a mechanical pump having an intermediate solvent trap housed in a Dewar flask and immersed in a bed of dry ice. When the contents of the flask were heated to account for viscosity changes, the mixing speed was adjusted from a set value of 200rpm to 300rpm. The flask contents were maintained at a temperature of 118.3°C to 125.3°C for seven hours under vacuum. The flask contents were then cooled and characterized by NMR to confirm that the reaction was complete. Based on the ratio of total carbonyl carbon integrals (peaks at 173.1ppm, 170.2ppm) to the residual methyl ester carbon peak at 51ppm being about 28:1, it was estimated that the conversion of methyl esters was >95%.

[0077] Example 1: Preparation of cleaning enhancer

[0078] In Example 1, the transesterification product cleaning enhancer of the following general formula

[0079]

[0080] Prepared by: Alkoxylate polymer (R-OH) (9.6139 g, 18.5 mmol, 4.6 eq., in UCON TM 50-HB-100 from The Dow Chemical Company), material prepared according to Synthesis S2 (1.6793 g, 4.0 mmol), and titanium isopropoxide (0.142 g, 0.50 mmol, 12.5 mol %, from Sigma-Aldrich, 99.999%) were charged into a 250 mL flask with a magnetic stir bar. The flask was sealed with a septum into which a needle probe thermocouple was inserted, connected to a Schlenk line, and then in a Schlenk tube connected to an IKA magnetic hotplate. The reaction block was heated with a set point temperature of 120°C while under a nitrogen blanket. After 34 minutes, the temperature reached 112.7°C and a vacuum was applied to the flask contents via a mechanical pump having an intermediate solvent trap housed in a Dewar flask and immersed in a bed of dry ice. The mixing speed was adjusted to 280rpm. The flask contents were maintained at a temperature of 117.9°C to 119.9°C for nine hours under vacuum. The flask contents were then cooled and characterized by NMR to confirm that the reaction was complete. Based on a ratio of total carbonyl carbon integrals (peaks at 173.1ppm, 170.2ppm) to the residual methyl ester carbon peak at 51ppm of >50:1, it was estimated that the conversion of methyl esters was >98%.

[0081] Example 2: Preparation of cleaning enhancer

[0082] In Example 2, the transesterification product cleaning enhancer of the following general formula

[0083]

[0084] Prepared by: Alkoxylate polymer (R-OH) (7.2037 g, 13.9 mmol, 4.5 eq., in UCON TM 50-HB-100 from The Dow Chemical Company), material prepared according to Synthesis S3 (1.5627 g, 3.1 mmol), and titanium isopropoxide (0.191 g, 0.67 mmol, 21.6 mol %, from Sigma-Aldrich, 99.999%) were charged into a 50 mL flask with a magnetic stir bar. The flask was sealed with a septum into which a needle probe thermocouple was inserted, connected to a Schlenk line, and then in a Schlenk tube connected to an IKA magnetic hotplate. The reaction block was heated with a set point temperature of 120°C while under a nitrogen blanket. After 48 minutes, the temperature reached 90.5°C and a vacuum was applied to the flask contents via a mechanical pump having an intermediate solvent trap housed in a Dewar flask and immersed in a bed of dry ice. The mixing speed was adjusted to 450rpm. The flask contents were maintained at a temperature of 113.8°C to 121.4°C for five hours under vacuum. The flask contents were then cooled and characterized by NMR to confirm that the reaction was complete. The ratio of the total carbonyl carbon integral (peaks at 173.0ppm, 170.1ppm) to the residual methyl ester carbon peak at 51ppm was about 29:1, and the conversion of the methyl esters was estimated to be >95%.

[0085] Example 3: Preparation of cleaning enhancer

[0086] In Example 3, the transesterification product cleaning enhancer of the following general formula

[0087]

[0088] Prepared by: Alkoxylate polymer (R-OH) (8.5855 g, 16.5 mmol, 4.3 eq., in UCON TM 50-HB-100 from Dow Chemical Company), material prepared according to Synthesis S4 (1.5268 g, 3.8 mmol), and titanium isopropoxide (0.180 g, 0.63 mmol, 16.6 mol %, from Sigma-Aldrich, 99.999%) were charged into a 250 mL flask with a magnetic stir bar. The flask was sealed with a septum into which a needle probe thermocouple was inserted, connected to a Schlenk line, and then in a Schlenk tube connected to an IKA magnetic hotplate. The reaction block was heated with a set point temperature of 120 ° C while under a nitrogen blanket. After 32 minutes, the temperature reached 118.3 ° C, and the sample changed from a turbid slurry to a clear solution. The flask contents were then vacuumed via a mechanical pump having an intermediate solvent trap housed in a Dewar flask and immersed in a bed of dry ice. The mixing speed was constantly maintained at 320 rpm. The flask contents were maintained at a temperature of 116.1 ° C to 120.4 ° C for 12.5 hours under vacuum. The flask contents were then cooled and characterized by NMR to confirm that the reaction was complete. Based on the total carbonyl carbon integral (peaks at 173.7 ppm, 173.5 ppm, 171.1 ppm, 170.2 ppm, 170.1 ppm) and the residual methyl ester carbon peak at 51 ppm, the ratio was about 12: 1, and the estimated conversion rate of methyl esters was about 90%.

[0089] Example 4: Preparation of cleaning enhancer

[0090] In Example 4, the transesterification product cleaning enhancer of the following general formula

[0091]

[0092] Prepared by: Alkoxylate polymer (R-OH) (10.2631 g, 19.7 mmol, 4.4 eq., in UCON TM 50-HB-100 from Dow Chemical Company), material prepared according to Synthesis S5 (1.9334 g, 4.5 mmol), and titanium isopropoxide (0.1685 g, 0.59 mmol, 13 mol %, from Sigma-Aldrich, 99.999%) were charged into a 250 mL flask with a magnetic stir bar and a needle probe thermometer attached via a septum. The flask was sealed with silicone grease, purged with nitrogen, and then placed on an IKA magnetic hot plate. The reaction block was heated at a set point temperature of 120°C. After the contents of the flask reached an internal temperature of 120°C, a vacuum was applied to the contents of the flask via a mechanical pump having an intermediate solvent trap cooled via dry ice in a Dewar flask. The mixing speed was set constant at 230rpm because the contents of the flask maintained a constant viscosity over the heating duration. The contents of the flask were kept at a temperature of 119°C to 121°C for 8.5 hours under vacuum. The contents of the flask were then cooled and characterized. The degree of replacement of the methyl ester group was estimated by the integral peaks of the methyl (51.5ppm) of the methyl ester and the α-methylene group (38.1ppm) on the heptanediamine-dimethyl maleate adduct in the quantitative 13C NMR spectrum. The ratio was 0.12:1, and since the initially unreacted heptanediamine-dimethyl maleate adduct had a methyl ester: α-methylene ratio of 2.18:1, this indicated that about 94% of the methyl groups had been converted.

[0093] Example 5: Preparation of cleaning enhancer

[0094] In Example 5, the transesterified cleaning enhancer of the following formula

[0095]

[0096] Prepared by charging the alkoxylate polymer product (R-OH) of Synthesis S7 (42.6 g, 110 mmol, 5.7 eq.) into a 250 mL Chemglass with a magnetic stir bar and a needle probe thermometer attached via a septum. The flask was sealed with silicone grease, purged with nitrogen, and then placed in a The reaction block is heated at room temperature with a set point of 400rpm. After starting to mix, a vacuum is applied via a mechanical pump having an intermediate solvent trap cooled by a dry ice bed. After vacuum stripping for 1 hour, the flask is disconnected from the vacuum source and refilled with nitrogen. The product (8.2913g, 19.4mmol) and titanium isopropoxide (0.9364g, 3.29mmol, 17 mol %, from Sigma-Aldrich, 99.999%) of synthetic S6 are added to the flask, and the flask is resealed with a diaphragm. The flask is then heated and stirred at a set point temperature of 120°C and 400rpm. After heating and mixing for 1 hour, a vacuum is applied for 7 hours, and the final decompression is 0.1 Torr. The product is cooled and characterized using NMR. 13 C NMR showed 100% conversion of the methyl ester to the tetrasubstituted product. 13C NMR (126MHz, CDCl3) δ75.87–74.12(m), 73.54–72.30(m), 72.00–70.98(m), 70.77–69.23(m), 58.89, 17.43–15.75(m).

[0097] Example 6 to Example 8: Preparation of cleaning enhancer

[0098] In Examples 6 to 8, the transesterification product cleaning enhancer of the following general formula

[0099]

[0100] Prepared by charging the alkoxylate polymer type and amount shown in Table 2 into a 250 mL Chemglass with a magnetic stir bar and a needle probe thermometer attached via a septum. The flask was sealed with silicone grease, purged with nitrogen, and then placed in a The reaction block was heated at room temperature with a set point of 400rpm. After starting to mix, a vacuum was applied via a mechanical pump having an intermediate solvent trap cooled by a dry ice bed. After vacuum stripping for 1 hour, the flask was disconnected from the vacuum source and refilled with nitrogen. The synthetic S6 product and titanium isopropoxide (from Sigma-Aldrich, 99.999%) of the amount shown in Table 2 were added to the flask and the flask was resealed with a septum. The flask was then heated and stirred at a set point temperature of 120°C and 400rpm. After heating and mixing for 1 hour, a vacuum was applied for 7 hours, and the final decompression was 0.1 Torr. The product was collected.

[0101] Table 2

[0102]

[0103] Comparative Examples CF1-CF3 and Examples F1-F3: Liquid Laundry Detergents

[0104] Liquid laundry detergent formulations used in the cleaning tests in the subsequent examples were prepared by standard liquid laundry formulation preparation procedures, having a general formula as described in Table 3, with cleaning enhancers as shown in Table 4, neutralized to pH 8.5.

[0105] Table 3

[0106]

[0107] Table 4

[0108]

[0109] Primary cleaning performance

[0110] The primary cleaning performance of the liquid laundry detergent formulations of Comparative Examples CF1 to CF2 and Examples F1 to F3 was evaluated in a Launder-Ometer (SDL Atlas, Model M228AA) at a set test temperature of 22°C using an 18 minute wash cycle. Twenty 1.2 liter cans were used for each run, which were filled with 500 mL of 100 ppm by mass of Ca 2+ Mg 2+ The washed fabrics were stirred at ambient temperature in an Eberbach E6000 reciprocating shaker in 300 mL of 100 ppm (2 / 1 Ca 2+ / Mg 2+ ) hardness adjusted water at 260 osc / min for 5 minutes. The soiled fabric and soil ballast used in the test were PCS-S-132 High Resolution Sebum BEY Pigment and PCS-S-94 Sebum / Dust ASTM Stain from Testfabrics sewn to pre-shrunk double cotton fabric. The dimensions of the double cotton were 5×5 cm. The soiled sample was 2.5×3 cm. A 5×5 cm cut SBL-CFT soil ballast was added to each tank to provide a baseline soil for the wash solution. The total surfactant concentration in the wash solution was 200 ppm.

[0111] Reflectance Measurement and Soil Removal Index (SRI)

[0112] The Soil 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 taken from 8 samples for each condition (two samples per kettle, 4 kettles) is provided in Table 5.

[0113] L of stained fabric * 、a * and b * The values ​​were measured before and after washing using a Mach 5 spectrophotometer from Colour Consult. * 、a * and b * Values ​​are measured in the SRI calculation as follows:

[0114]

[0115] Where US is the unwashed stain area, UF is the unwashed (unstained) fabric area, WS is the washed stain area, ΔE * (US-UF)is the ΔE between the unwashed stain and the unwashed fabric * Chromatic aberration, and ΔE * (WS-UF) is the ΔE between the washed stain and the unwashed fabric * Color difference. ΔE * The value of is calculated as

[0116] ΔE * =(ΔL *2 +Δa *2 +Δb *2 ) 1 / 2

[0117] The ΔSRI values ​​provided in Table 5 give the difference between the SRI measurements of the indicated examples and the SRI measurements of Comparative Example CF1. Positive values ​​indicate enhanced soil removal relative to Comparative Example CF1.

[0118] Table 5

[0119]

[0120] Comparative Examples CF4-CF6 and Examples F4-F6: Liquid Laundry Detergents

[0121] Liquid laundry detergent formulations of Comparative Examples CF4-CF6 and Examples F4-F6 used in subsequent cleaning tests were prepared by combining 0.5 g of a standard liquid laundry detergent formulation adjusted to pH 8.5 as described in Table 6 with 1.5 g of a 1 wt % aqueous solution of the cleaning enhancer shown in Table 7.

[0122] Table 6

[0123]

[0124] Table 7

[0125]

[0126] Anti-redeposition

[0127] The anti-redeposition performance of the standard liquid laundry detergent + cleaning enhancer combinations of Comparative Examples CF4-CF6 and Examples F4-F6 was evaluated in a Terg-o-tometer Model 7243ES under the conditions shown in Table 8 at 90 cycles per minute agitation.

[0128] Table 8

[0129]

[0130] The anti-redeposition performance was determined by calculating the ΔE measured with a MACH 5+ instrument (L, a & b). The results are reported in Table 9, where ΔE * According to the following equation:

[0131] ΔE * =ΔE aw -ΔE bw

[0132] where ΔE aw Measured from washed fabrics, and ΔE bw Measure from fabric before washing.

[0133] Higher ΔE * Corresponding to better anti-redeposition performance.

[0134] Table 9

[0135]

[0136] Comparative Examples CF7-CF8 and Examples F8-F11: Unit Dose of Laundry Detergent

[0137] Unit dose laundry detergent formulations of Comparative Examples CF7 to CF8 and Examples F8 to F11 used in subsequent cleaning tests were prepared by standard laundry formulation preparation procedures, having a general formula as described in Table 10, having a cleaning enhancer as shown in Table 11, and neutralized to pH 8.5.

[0138] Table 10

[0139]

[0140] Table 11

[0141]

[0142] Primary cleaning performance

[0143] The primary cleaning performance of the unit dose formulations of Comparative Examples CF7-CF8 and Examples F8-F11 was evaluated in a Terg-O-Tometer Model 7243ES under the conditions shown in Table 12 using a tank (2L) stirred at 85 cycles per minute.

[0144] Table 12

[0145]

[0146] Reflectance Measurement and Soil Removal Index (SRI)

[0147] The Soil 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 taken from 8 samples for each condition (two samples per kettle, 4 kettles) is provided in Table 13.

[0148] L of stained fabric * 、a * and b * The values ​​were measured before and after washing using a Mach 5 spectrophotometer from Colour Consult. * value, a * Value and b * Values ​​are measured in the SRI calculation as follows:

[0149]

[0150] Where US is the unwashed stain area, UF is the unwashed (unstained) fabric area, WS is the washed stain area, ΔE * (US-UF) is the ΔE between the unwashed stain and the unwashed fabric * Chromatic aberration, and ΔE * (WS-UF) is the ΔE between the washed stain and the unwashed fabric * Color difference. ΔE * The value of is calculated as

[0151] ΔE * =(ΔL *2 +Δa *2 +Δb *2 ) 1 / 2

[0152] Table 13

[0153]

Claims

1. A cleaning enhancer for cleaning dirty clothes, wherein the cleaning enhancer has formula (I) R 1 —A 1 —R 1 (I) Among them A 1 is a divalent linking group having 4 to 24 carbon atoms; and wherein each R 1 Independently selected from the group consisting of formula (II), formula (III) and formula (IV) wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 Independently have formula (V) Wherein the * in formula (V) is the connection point with the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30; and provided that when the divalent linking group A 1 When the divalent linking group A has 4 carbon atoms, 1 Including ring.

2. The cleaning enhancer according to claim 1, wherein the cleaning enhancer of formula (I) has formula (Ia): R 1 —(CH2) n —R 1 (Ia) Where n is 5 to 24.

3. The cleaning enhancer according to claim 1, wherein the cleaning enhancer of formula (I) has formula (Ib): wherein p and r are independently 1 to 4.

4. The cleaning enhancer according to claim 1, wherein the cleaning enhancer of formula (I) has formula (Ic): Among them A 2 It is a divalent linking group having 2 to 22 carbon atoms.

5. The cleaning enhancer according to claim 1, wherein the cleaning enhancer of formula (I) has formula (Id): wherein t is from 2 to 10.

6. The cleaning enhancer according to claim 1, wherein in the cleaning enhancer, 70 mol % to 100 mol % of R 2 In the occurrence of , c is 2 to 30.

7. The cleaning enhancer according to claim 1, wherein 70 mol % to 100 mol % of the R 2 The group has the formula (Va) R 6 —O—[CH2CH(R 7 )O] y —*(Va) Wherein the * in formula (Va) is the point of connection with the relevant base formula; Where R 6 Selected from hydrogen and C 1-22 A group consisting of alkyl groups; Each R 7 independently selected from hydrogen and C 1-2 The group consisting of an alkyl group; and wherein y is 2 to 30.

8. The cleaning enhancer according to claim 1, wherein 70 mol % to 100 mol % of the R 2 The group has the formula (Vb) R 8 —O—(EO) h —(PO) i -(IS) j —*(Vb) Wherein the * in formula (Vb) is the point of connection with the relevant base formula; Where R 8 Selected from hydrogen and C 1-22 A group consisting of alkyl groups; wherein EO is an ethylene oxide group; wherein PO is a propylene oxide group; wherein h is 0 to 30; wherein i is 0 to 30; wherein j is 0 and 30; and wherein h+i+j is 2 to 30.

9. A laundry detergent additive comprising a mixture of the cleaning enhancer according to claim 1 and water.

10. The laundry detergent additive according to claim 9, wherein the laundry detergent additive is a liquid.

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