阅读说明：本技术 烷氧基化的多羧酸酯 (Alkoxylated polycarboxylates ) 是由 K·穆齐 S·罗曼斯基 C·莎夫尔 C·布雷法 J·迪德里希斯 S·N·巴特舍勒 于 2018-06-11 设计创作，主要内容包括：提供了烷氧基化的多羧酸酯,其可通过如下获得：首先使含有至少三个羧酸单元的芳族多羧酸或由其衍生的酸酐,优选含有三个或四个羧酸单元的芳族多羧酸或由其衍生的酸酐,更优选含有三个羧酸单元的芳族多羧酸或由其衍生的酸酐,甚至更优选偏苯三酸或偏苯三酸酐,最优选偏苯三酸酐,与醇烷氧化物反应,并且在第二步骤中使所得的产物与醇或醇的混合物,优选与醇反应。(Alkoxylated polycarboxylates are provided, which are obtainable by: an aromatic polycarboxylic acid containing at least three carboxylic acid units or an anhydride derived therefrom, preferably an aromatic polycarboxylic acid containing three or four carboxylic acid units or an anhydride derived therefrom, more preferably an aromatic polycarboxylic acid containing three carboxylic acid units or an anhydride derived therefrom, even more preferably trimellitic acid or trimellitic anhydride, most preferably trimellitic anhydride, is first reacted with an alcohol alkoxylate and the resulting product is reacted in a second step with an alcohol or a mixture of alcohols, preferably with an alcohol.)

1. An alkoxylated polycarboxylic ester, obtainable by: an aromatic polycarboxylic acid containing at least three carboxylic acid units or an anhydride derived therefrom, preferably an aromatic polycarboxylic acid containing three or four carboxylic acid units or an anhydride derived therefrom, more preferably an aromatic polycarboxylic acid containing three carboxylic acid units or an anhydride derived therefrom, even more preferably trimellitic acid or trimellitic anhydride, most preferably trimellitic anhydride, is first reacted with an alcohol alkoxylate and the resulting product is reacted in a second step with an alcohol or a mixture of alcohols, preferably with an alcohol.

2. The alkoxylated polycarboxylate according to claim 1, wherein said alcohol alkoxylate is described by formula (I),

wherein R1 is a substituted or unsubstituted alkyl or alkenyl group having 1 to 20 carbon atoms, an aryl or alkylaryl group having 6 to 20 carbon atoms or H, preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 12 carbon atoms or an aryl or alkylaryl group having 6 to 13 carbon atoms, more preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 6 carbon atoms, and most preferably a methyl group,

r2 to R5 independently of one another are hydrogen or an alkyl radical having 1 to 4 carbon atoms, preferably hydrogen or methyl,

wherein the substituents R2 to R5 are selected such that both R2 and R3 or both R4 and R5 are hydrogen and at least one of the other substituents is not hydrogen, preferably such that three of the substituents R2 to R5 are hydrogen, and even more preferably such that three of the substituents R2 to R5 are hydrogen and the other substituent is a methyl group,

n and m are, independently of one another, a number from 0 to 100, on a molar average, such that n + m is from 4 to 100, preferably from 8 to 70, more preferably from 10 to 60, and even more preferably from 12 to 50,

wherein in the case where both R2 and R3 are hydrogen, n is a number from 4 to 100 and m is a number from 0 to 50, preferably n is from 8 to 70 and m is from 0 to 30, more preferably n is from 10 to 60 and m is from 0 to 25, and even more preferably n is from 12 to 50 and m is from 0 to 20, and when m >0, the ratio of n to m is greater than 1, preferably at least 2, more preferably at least 3, and even more preferably at least 4,

wherein in the case where both R4 and R5 are hydrogen, m is a number from 4 to 100 and n is a number from 0 to 50, preferably m is from 8 to 70 and n is from 0 to 30, more preferably m is from 10 to 60 and n is from 0 to 25, and even more preferably m is from 12 to 50 and n is from 0 to 20, and when n >0, the ratio of m to n is greater than 1, preferably at least 2, more preferably at least 3, and even more preferably at least 4,

wherein in case both n and m >0, the units are distributed blockwise, alternately, periodically and/or randomly,

r6 and R7 are each independently of the other hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or methyl, and at least one of R6 and R7 is methyl, and

y is OH.

3. The alkoxylated polycarboxylic ester according to claim 1 or 2, characterised in that said alcohol alkoxylate is an ethoxylated alcohol or an ethoxylated and propoxylated alcohol wherein the ratio of ethylene oxide units to propylene oxide units is greater than 1, preferably at least 2, more preferably at least 3, and even more preferably at least 4, and is preferably an ethoxylated and propoxylated alcohol.

4. The alkoxylated polycarboxylic ester according to one or more of claims 1 to 3, characterized in that the alcohol alkoxylate of formula (I) is a polyethylene glycol monomethyl ether or an alcohol-terminated methyl-ethoxylated-propoxylated polyether having a molecular mass Mn of from 252 to 4900, preferably having a molecular mass Mn of from 350 to 4000, even more preferably having a molecular mass Mn of from 450 to 3000 and especially preferably having a molecular mass Mn of from 500 to 2500, and preferably is a polyethylene glycol monomethyl ether having a molecular mass Mn of from 252 to 4400, preferably having a molecular mass Mn of from 350 to 4000, even more preferably having a molecular mass Mn of from 450 to 3000 and especially preferably having a molecular mass Mn of from 500 to 2500.

5. The alkoxylated polycarboxylic ester according to one or more of claims 1 to 4, characterized in that the alcohol or at least one alcohol from the mixture of alcohols used in step 2 of the reaction is an alkylaryl alcohol having from 7 to 13 carbon atoms or a substituted or unsubstituted alkyl or alkenyl alcohol having from 2 to 20 carbon atoms, preferably an alkylaryl alcohol having from 7 to 10 carbon atoms, a substituted or unsubstituted alkyl or alkenyl alcohol having from 12 to 18 carbon atoms or a substituted alkyl alcohol having from 2 to 4 carbon atoms, more preferably an alkylaryl alcohol having from 7 to 10 carbon atoms, an unsubstituted alkyl or alkenyl alcohol having from 12 to 18 carbon atoms, which is preferably linear, or an alkyl alcohol having from 2 or 3 carbon atoms substituted with an ether function, most preferably an unsubstituted alkyl alcohol having from 12 to 18 carbon atoms, or an alkyl alcohol having 2 carbon atoms substituted with a phenoxy or ethoxyphenoxy group, wherein the phenyl ring in the phenoxy group may additionally be substituted.

6. Alkoxylated polycarboxylic acid amides according to one or more of claims 1 to 5, characterized in that the alcohol or at least one alcohol from the mixture of alcohols used in step 2 of the reaction is selected from lauryl alcohol (dodecanol), myristyl alcohol (tetradecanol), a mixture of lauryl and myristyl alcohols, cetearyl alcohol (mixture of cetyl and stearyl alcohols), stearyl alcohol (stearyl alcohol) and coconut fatty alcohol (C)₆To C₁₈A mixture of alcohols), phenoxyethanol, phenylethyl alcohol and benzyl alcohol, and is preferably selected from lauryl/myristyl alcohol, cetearyl alcohol and phenoxyethanol, and more preferably from lauryl/myristyl alcohol and cetearyl alcohol.

7. Alkoxylated polycarboxylic esters according to formula (II), preferably in the form of a mixture and preferably obtainable by the reaction steps described in one or more of claims 1 to 6,

wherein R8, R9 and R10 are selected from (a) and (b) such that at least one of R8, R9 and R10 is (b) and at least one of R8, R9 and R10 is (a), preferably R8 is (a) and one or both of R9 and R10 is (b), more preferably R8 is (a) and one of R9 or R10 is (b) and the other is (a), wherein

(a) Is an alkylaryloxy group having from 7 to 13 carbon atoms or a substituted or unsubstituted alkoxy or alkenyloxy group having from 2 to 20 carbon atoms, preferably an alkylaryloxy group having from 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy or alkenyloxy group having from 12 to 18 carbon atoms or a substituted alkoxy or alkenyloxy group having from 2 to 4 carbon atoms, more preferably an alkylaryloxy group having from 7 to 10 carbon atoms or an unsubstituted alkoxy or alkenyloxy group having from 12 to 18 carbon atoms, which is preferably linear, or an alkoxy group having from 2 or 3 carbon atoms which is substituted by an ether group, most preferably an alkyl alcohol having from 12 to 18 carbon atoms which is unsubstituted, or an alkoxy group having 2 carbon atoms which is substituted by a phenoxy or ethoxyphenoxy group, wherein the phenyl ring in the phenoxy group may additionally be substituted, and

(b) is an alcohol alkoxylate group of the formula (I'),

wherein R1 is a substituted or unsubstituted alkyl or alkenyl group having 1 to 20 carbon atoms, an aryl or alkylaryl group having 6 to 20 carbon atoms or H, preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 12 carbon atoms or an aryl or alkylaryl group having 6 to 13 carbon atoms, more preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 6 carbon atoms, and most preferably a methyl group,

r2 to R5 independently of one another are hydrogen or an alkyl radical having 1 to 4 carbon atoms, preferably hydrogen or methyl,

wherein the substituents R2 to R5 are selected such that both R2 and R3 or both R4 and R5 are hydrogen and at least one of the other substituents is not hydrogen, preferably such that three of the substituents R2 to R5 are hydrogen, and even more preferably such that three of the substituents R2 to R5 are hydrogen and the other substituent is a methyl group,

n and m are, independently of one another, a number from 0 to 100, on a molar average, such that n + m is a number from 4 to 100, preferably from 8 to 70, more preferably from 10 to 60, and even more preferably from 12 to 50,

wherein in the case where both R2 and R3 are hydrogen, n is a number from 4 to 100 and m is a number from 0 to 50, preferably n is from 8 to 70 and m is from 0 to 30, more preferably n is from 10 to 60 and m is from 0 to 25, and even more preferably n is from 12 to 50 and m is from 0 to 20, and when m >0, the ratio of n to m is greater than 1, preferably at least 2, more preferably at least 3, and even more preferably at least 4,

wherein in the case where both R4 and R5 are hydrogen, m is a number from 4 to 100 and n is a number from 0 to 50, preferably m is from 8 to 70 and n is from 0 to 30, more preferably m is from 10 to 60 and n is from 0 to 25, and even more preferably m is from 12 to 50 and n is from 0 to 20, and when n >0, the ratio of m to n is greater than 1, preferably at least 2, more preferably at least 3, and even more preferably at least 4,

wherein in case both n and m are >0, the units are distributed blockwise, alternately, periodically and/or randomly,

r6 and R7 are each independently of the other hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or methyl, and at least one of R6 and R7 is methyl, and

y' is O.

8. The alkoxylated polycarboxylic ester according to claim 7, wherein formula (II) is characterized in that R8 is equal to one of R9 or R10 and is an alkylaryloxy group having 7 to 13 carbon atoms or a substituted or unsubstituted alkoxy or alkenyloxy group having 2 to 20 carbon atoms, preferably an alkylaryloxy group having 7 to 10 carbon atoms or a substituted or unsubstituted alkoxy or alkenyloxy group having 12 to 18 carbon atoms, more preferably an alkylaryloxy group having 7 to 10 carbon atoms.

9. Alkoxylated polycarboxylate according to claim 7 or 8, characterised in that R8 is equal to one of R9 or R10 and is a substituted or unsubstituted ethoxylated aromatic alcohol residue having 8 to 16 carbon atoms, preferably 8 to 12 carbon atoms.

10. The alkoxylated polycarboxylic ester according to one or more of claims 7 to 9, wherein (b) is characterized in that (b) is a polyethylene glycol monomethyl ether residue of formula (Γ) having a molecular mass Mn of 251 to 4400, preferably having a molecular mass Mn of 350 to 4000, even more preferably having a molecular mass Mn of 450 to 3000, and especially preferably having a molecular mass Mn of 500 to 2500.

11. Process for the production of an alkoxylated polycarboxylic ester according to one or more of claims 1 to 10, comprising the steps of: firstly reacting an aromatic polycarboxylic acid containing at least three carboxylic acid units or an anhydride derived therefrom with an alcohol alkoxylate and secondly reacting the resulting product with an alcohol or a mixture of alcohols, preferably with an alcohol.

12. The process according to claim 11, characterized in that the reaction of step 1 is carried out with 0.7 to 1.5 molar equivalents of the alcohol alkoxylate, preferably 0.8 to 1.4 molar equivalents, more preferably 0.9 to 1.3 molar equivalents, and most preferably 1.0 to 1.2 molar equivalents.

13. The process according to claim 11 or 12, characterized in that the reaction of step 1 is carried out at a temperature of 50 to 150 ℃, preferably at a temperature of 60 to 140 ℃, even more preferably at a temperature of 70 to 130 ℃, and most preferably at a temperature of 80 to 120 ℃.

14. The process according to one or more of claims 11 to 13, characterized in that the reaction of step 2 is carried out with 1.8 to 3.5 molar equivalents of the alcohol or mixture of alcohols, preferably 1.9 to 3.0 molar equivalents, and more preferably 2.0 to 2.8 molar equivalents.

Technical Field

The present invention relates to the field of alkoxylated aromatic polycarboxylates and processes for their preparation. Alkoxylated aromatic polycarboxylates may advantageously be used as anti-redeposition agents in laundry applications.

Background

Antiredeposition agents used in laundry detergents help prevent soil from redepositing on fabrics after it has been removed during washing. This can be achieved, for example, by dispersing the dirt in the wash liquid.

Washing soiled fabrics with laundry detergent compositions is essentially a two-step process. In the first stage, the detergent must remove the soil from the fabric and suspend it in the wash liquor. In the second stage, the detergent composition must prevent soil and other insoluble materials from redepositing on the cloth prior to removing the fabric from the wash or rinse liquor. Polymers are known to assist in two processes. For example, the soil release polymer enhances the removal of soil from the fabric, while the anti-redeposition polymer prevents the removed soil from redepositing on the fabric.

Examples of suitable anti-redeposition agents include fatty acid amides, fluorocarbon surfactants, complex phosphate esters, styrene maleic anhydride copolymers, and cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and the like.

For example, US 4,240,918 describes polymers with anti-fouling and anti-redeposition properties, such as hydrophilic polyurethanes, certain copolyesters and mixtures thereof.

However, many known anti-redeposition agents suffer from the disadvantage that their performance and whitening effect in washing or laundry applications is insufficient.

Disclosure of Invention

The problem to be solved by the present invention is therefore to provide new antiredeposition agents which have advantageous properties when used in washing or laundry applications and which result in an enhanced "whiteness".

It has surprisingly been found that this problem can be solved by specific alkoxylated polycarboxylates obtainable by: an aromatic polycarboxylic acid containing at least three carboxylic acid units or an anhydride derived therefrom is first reacted with an alcohol alkoxylate and the product obtained is reacted in a second step with an alcohol or a mixture of alcohols, preferably with an alcohol.

The present invention therefore provides specific alkoxylated polycarboxylates obtainable by: an aromatic polycarboxylic acid containing at least three carboxylic acid units or an anhydride derived therefrom, preferably an aromatic polycarboxylic acid containing three or four carboxylic acid units or an anhydride derived therefrom, more preferably an aromatic polycarboxylic acid containing three carboxylic acid units or an anhydride derived therefrom, even more preferably trimellitic acid or trimellitic anhydride, most preferably trimellitic anhydride, is first reacted with an alcohol alkoxylate, and the resulting product is reacted in a second step with an alcohol or a mixture of alcohols, preferably with an alcohol.

The specific alkoxylated polycarboxylates of the present invention exhibit advantageous properties as anti-redeposition agents in laundry or laundry applications. They additionally show advantageous properties as dispersants and in washing or laundry applications they lead to an enhanced "whiteness". In addition, the alkoxylated polycarboxylates of the present invention exhibit advantageous stability and additionally exhibit advantageous biodegradability.

Detailed Description

Polycarboxylic acid component

The aromatic polycarboxylic acid containing at least three carboxylic acid units or an anhydride derived therefrom is preferably an aromatic polycarboxylic acid containing three or four carboxylic acid units or an anhydride derived therefrom, more preferably an aromatic polycarboxylic acid containing three carboxylic acid units or an anhydride derived therefrom, even more preferably trimellitic acid or trimellitic anhydride, and most preferably trimellitic anhydride.

Examples of aromatic polycarboxylic acids containing at least three carboxylic acid units or anhydrides derived therefrom are trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, trimesic acid, mellitic acid and mellitic anhydride.

Trimellitic anhydride has the following structure:

alcohol alkoxylate component

In a preferred embodiment of the alkoxylated polycarboxylic esters of the invention, the alcohol alkoxylate is described by formula (I),

wherein R1 is a substituted or unsubstituted alkyl or alkenyl group having 1 to 20 carbon atoms, an aryl or alkylaryl group having 6 to 20 carbon atoms, or H, preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 12 carbon atoms or an aryl or alkylaryl group having 6 to 13 carbon atoms, more preferably a substituted or unsubstituted alkyl or alkenyl group having 1 to 6 carbon atoms, and most preferably a methyl group,

r2 to R5 independently of one another are hydrogen or an alkyl radical having 1 to 4 carbon atoms, preferably hydrogen or methyl,

wherein the substituents R2 to R5 are selected such that both R2 and R3 or both R4 and R5 are hydrogen and at least one of the other substituents is not hydrogen, preferably such that three of the substituents R2 to R5 are hydrogen, and even more preferably such that three of the substituents R2 to R5 are hydrogen and the other substituent is a methyl group,

n and m are, independently of one another, a number from 0 to 100, on a molar average, such that n + m is from 4 to 100, preferably from 8 to 70, more preferably from 10 to 60, and even more preferably from 12 to 50,

wherein in case both R2 and R3 are hydrogen, n is a number from 4 to 100 and m is a number from 0 to 50, preferably n is from 8 to 70 and m is from 0 to 30, more preferably n is from 10 to 60 and m is from 0 to 25, and even more preferably n is from 12 to 50 and m is from 0 to 20, and when m >0, the ratio of n to m is greater than 1, preferably at least 2, more preferably at least 3, and even more preferably at least 4,

wherein in the case where both R4 and R5 are hydrogen, m is a number from 4 to 100 and n is a number from 0 to 50, preferably m is from 8 to 70 and n is from 0 to 30, more preferably m is from 10 to 60 and n is from 0 to 25, and even more preferably m is from 12 to 50 and n is from 0 to 20, and when n >0, the ratio of m to n is greater than 1, preferably at least 2, more preferably at least 3, and even more preferably at least 4, and

wherein in case both n and m are >0, the units are distributed blockwise, alternately, periodically and/or randomly,

r6 and R7 are each independently of the other hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably both R6 and R7 are hydrogen, and

y is OH.

The value of n + m is the molar average number of alkoxy groups. The values of n and m can be determined using NMR and the value of n + m is from 4 to 100, preferably from 8 to 70, more preferably from 10 to 60, and even more preferably from 12 to 50. Within this preferred embodiment, the value of n + m may be 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50.

In a preferred embodiment, m is 0 and n is a number from 4 to 100.

In another preferred embodiment, both m and n are > 0.

In another preferred embodiment, n is 0 and m is a number from 4 to 100.

In a further preferred embodiment of the invention, R2 and R3 of formula (I) are both hydrogen, n is a number from 4 to 100 and m is a number from 0 or 1 to 50, preferably n is from 8 to 70 and m is from 0 or 1 to 30, more preferably n is from 10 to 60 and m is from 0 or 1 to 25, and even more preferably n is from 12 to 50 and m is from 0 or 1 to 20, and when m >0 is, the ratio of n to m is greater than 1, preferably at least 2, more preferably at least 3, and even more preferably at least 4.

In a further preferred embodiment of the invention, both R4 and R5 of formula (I) are hydrogen, m is a number from 4 to 100 and n is a number from 0 or 1 to 50, preferably m is from 8 to 70 and n is from 0 or 1 to 30, more preferably m is from 10 to 60 and n is from 0 or 1 to 25, and even more preferably m is from 12 to 50 and n is from 0 or 1 to 20, and when n >0 is, the ratio of m to n is greater than 1, preferably at least 2, more preferably at least 3, and even more preferably at least 4.

In a further preferred embodiment of the invention, three of R2, R3, R4 and R5 of formula (I) are hydrogen and the others are methyl and the values of both n and m are not zero. The groups represented by n and m are distributed blockwise, alternately, periodically and/or randomly.

In a preferred embodiment, the substituted or unsubstituted alkyl or alkenyl residue R1 is unsubstituted, and preferably is methyl.

In a further preferred embodiment, the substituted alkyl or alkenyl residue R1 is substituted with one or more halogen atoms, carbonyl groups, carboxyl groups, ester functions or ether functions.

In a further preferred embodiment, the substituted or unsubstituted alkyl or alkenyl residue R1 has a linear or branched carbon chain, preferably a linear carbon chain.

In a further preferred embodiment of the invention, the alcohol alkoxylate is an ethoxylated alcohol or an ethoxylated and propoxylated alcohol, preferably an alcohol of formula (I) wherein the ratio of ethylene oxide units to propylene oxide units is greater than 1, preferably at least 2, more preferably at least 3, and even more preferably at least 4, and preferably is an ethoxylated and propoxylated alcohol.

In a further preferred embodiment of the invention, the alcohol alkoxylate of the formula (I) is a polyethylene glycol monomethyl ether or an alcohol-terminated methyl-ethoxylated-propoxylated polyether having a molecular mass Mn of from 252 to 4900, preferably having a molecular mass Mn of from 350 to 4000, even more preferably having a molecular mass Mn of from 450 to 3000, and particularly preferably having a molecular mass Mn of from 500 to 2500; and is preferably polyethylene glycol monomethyl ether having a molecular mass Mn of 252 to 4400, preferably having a molecular mass Mn of 350 to 4000, even more preferably having a molecular mass Mn of 450 to 3000, and particularly preferably having a molecular mass Mn of 500 to 2500.

The molecular mass Mn is the number average molecular mass. The average molecular mass (Mn) of the alcohol alkoxylates can be determined by GPC (gel permeation chromatography) analogously to the method disclosed in WO 2016/075178A 1 (page 7/8)The assay, with preferred details, is as follows: injecting 10 μ l into the injection container

And 10 μm particle size on a 300x 8mm size PSS Suprema column. Detection was monitored at 235nm on a multi-wavelength detector. The eluent used was 1.25g/l of disodium hydrogen phosphate in 45/55% (v/v) water/acetonitrile mixture. The separation was carried out at a flow rate of 0.8 ml/min. Quantification was performed by external calibration of standard samples of polyethylene glycol of different molecular masses.

Alcohol component

In the alkoxylated polycarboxylic esters of the invention, the at least one alcohol of the alcohol or alcohol mixture used in step 2 of the reaction is generally an alkylaryl alcohol having from 7 to 13 carbon atoms or a substituted or unsubstituted alkyl or alkenyl alcohol having from 2 to 20 carbon atoms, preferably an alkylaryl alcohol having from 7 to 10 carbon atoms, a substituted or unsubstituted alkyl or alkenyl alcohol having from 12 to 18 carbon atoms or a substituted alkyl alcohol having from 2 to 4 carbon atoms, more preferably an alkylaryl alcohol having from 7 to 10 carbon atoms, an unsubstituted alkyl or alkenyl alcohol having from 12 to 18 carbon atoms, which is preferably linear, or an alkyl alcohol having from 2 or 3 carbon atoms substituted with ether functions, most preferably an unsubstituted alkyl alcohol having from 12 to 18 carbon atoms, or an alkyl alcohol having 2 carbon atoms substituted with a phenoxy or ethoxyphenoxy group, wherein the phenyl ring in the phenoxy group may be additionally substituted.

In the case where the alcohol is an alkylaryl substituent having from 7 to 13 carbon atoms, the number of carbon atoms specified includes aromatic rings.

In a preferred embodiment of the invention, the substituted alkyl or alkenyl alcohol is substituted with one or more halogen atoms, carbonyl groups, carboxyl groups, ester functions or ether functions.

In a further preferred embodiment of the invention, the substituted or unsubstituted alkyl or alkenyl alcohol has a linear or branched carbon chain, preferably a linear carbon chain.

In a further preferred embodiment of the invention, the alkyl or alkenyl alcohol substituted with an ether function is a substituted or unsubstituted ethoxylated aromatic alcohol, preferably having from 8 to 16 carbon atoms, more preferably from 8 to 12 carbon atoms.

In a further preferred embodiment of the invention, the alkyl or alkenyl alcohol substituted by an ether function is an etherified diol or oligodiol (oliglycol), such as ethylene glycol phenol ether (phenoxyethanol) or an ether of ethylene glycol and a substituted phenol (e.g. methylated, halogenated or methoxylated phenol).

In a preferred embodiment of the invention, at least one of the alcohols or one of the alcohol mixtures used in step 2 of the reaction is an alkylaryl alcohol having from 7 to 13, preferably from 7 to 10, in particular 7, carbon atoms (i.e. benzyl alcohol), or an unsubstituted alkyl alcohol having from 2 to 20, preferably from 2 to 18, carbon atoms, having a straight or branched, preferably straight, carbon chain, or a substituted alkyl alcohol having from 2 to 4, preferably 2, carbon atoms, substituted with an ether function, wherein the second part of the ether is derived from an unsubstituted or substituted phenol, which is preferably unsubstituted and, if substituted, preferably methylated, halogenated or methoxylated phenol, or an ethoxylated unsubstituted or substituted phenol, which is preferably unsubstituted and, if substituted, preferably methylated, Halogenated or methoxylated phenols.

In a particularly preferred embodiment of the invention, at least one of the alcohols or mixtures of alcohols used in step 2 of the reaction is selected from lauryl alcohol (dodecanol), myristyl alcohol (tetradecanol), a mixture of lauryl and myristyl alcohols, cetearyl alcohol (a mixture of cetyl and stearyl alcohols), stearyl alcohol (stearyl alcohol) and coconut fatty alcohol (a mixture of C6 to C18 alcohols), phenoxyethanol, phenylethyl alcohol and benzyl alcohol, and is preferably selected from phenoxyethanol, phenylethyl alcohol and benzyl alcohol.

In a particularly preferred embodiment of the present invention, the alkoxylated polycarboxylates of the present invention may be obtained by: trimellitic anhydride is first reacted with polyethylene glycol monomethyl ether having a molecular mass Mn of from 500 to 1500 and the resulting product is reacted in a second step with benzyl alcohol, phenoxyethanol or a mixture of benzyl alcohol and phenoxyethanol.

In another particularly preferred embodiment of the present invention, the alkoxylated polycarboxylates of the present invention may be obtained by: trimellitic anhydride is first reacted with polyethylene glycol monomethyl ether having a molecular mass Mn of from 500 to 1500 and the resulting product is reacted in a second step with unsubstituted alkyl alcohols having from 12 to 18 carbon atoms.

In a further preferred embodiment of the invention, the alkoxylated polycarboxylic esters according to the invention are compounds or mixtures of compounds of formula (II),

wherein R8, R9 and R10 are selected from (a) and (b) such that at least one of R8, R9 and R10 is (b) and at least one of R8, R9 and R10 is (a), preferably R8 is (a) and one or both of R9 and R10 is (b), more preferably R8 is (a) and one of R9 or R10 is (b) and the other is (a), wherein:

(a) is an alkylaryloxy group having from 7 to 13 carbon atoms or a substituted or unsubstituted alkoxy or alkenyloxy group having from 2 to 20 carbon atoms, preferably an alkylaryloxy group having from 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy or alkenyloxy group having from 12 to 18 carbon atoms or a substituted alkoxy or alkenyloxy group having from 2 to 4 carbon atoms, more preferably an alkylaryloxy group having from 7 to 10 carbon atoms or an unsubstituted alkoxy or alkenyloxy group having from 12 to 18 carbon atoms, which is preferably linear, or an alkoxy group having from 2 or 3 carbon atoms which is substituted by an ether group, most preferably an alkyl alcohol having from 12 to 18 carbon atoms which is unsubstituted, or an alkoxy group having 2 carbon atoms which is substituted by a phenoxy or ethoxyphenoxy group, wherein the phenyl ring in the phenoxy group may additionally be substituted, and

(b) is an alcohol alkoxylate group of the formula (I'),

wherein R1 to R7, m and n have the same and preferred meanings as in formula (I),

and

y' is O.

(a) The preferred meaning of (a) follows the preferred alcohols of the alcohol component.

In a further preferred embodiment of the invention, R8 of formula (II) is equal to one of R9 or R10 and is an alkylaryloxy group having from 7 to 13 carbon atoms or a substituted or unsubstituted alkoxy or alkenyloxy group having from 2 to 20 carbon atoms, preferably an alkylaryloxy group having from 7 to 10 carbon atoms or a substituted or unsubstituted alkoxy or alkenyloxy group having from 12 to 18 carbon atoms, more preferably an alkylaryloxy group having from 7 to 10 carbon atoms, especially benzyloxy, or an unsubstituted alkoxy group having from 12 to 18 carbon atoms, especially lauryl oxy, myristyloxy, a mixture of lauryl and myristyloxy, palmityl, stearyl, or a mixture of palmityl and stearyl (cetylstearyl).

In a further preferred embodiment of the invention, R8 of formula (II) is equal to one of R9 or R10 and is a substituted or unsubstituted ethoxylated aromatic alcohol residue having 8 to 16 carbon atoms, preferably 8 to 12 carbon atoms, especially phenoxyethoxy.

In a further preferred embodiment of the invention, formula (I') is a polyethylene glycol monomethyl ether residue having a molecular mass Mn of 251 to 4400, preferably having a molecular mass Mn of 350 to 4000, even more preferably having a molecular mass Mn of 450 to 3000, and especially preferably having a molecular mass Mn of 500 to 2500.

Further preferred embodiments of the present invention can be produced by a combination of the above-described preferred embodiments.

Preparation method

In a further aspect of the invention, there is provided a process for the production of the alkoxylated polycarboxylates of the present invention, preferably those of formula (II), comprising the steps of: firstly reacting an aromatic polycarboxylic acid containing at least three carboxylic acid units or an anhydride derived therefrom with an alcohol alkoxylate and secondly reacting the resulting product with an alcohol or a mixture of alcohols, preferably with an alcohol.

In the preparation of the alkoxylated polycarboxylic esters of the present invention, reaction step 1 is carried out in the presence or absence of an additional solvent, preferably in the absence of an additional solvent.

Solvents suitable for the reaction of alcohols with aromatic anhydrides are known to those skilled in the art. These solvents include, but are not limited to, aromatic hydrocarbons such as, but not limited to, benzene, toluene or xylene, aprotic polar solvents such as, but not limited to, anisole, aromatic ethers, high boiling alkyl ethers, dimethylformamide and dimethylsulfoxide.

In a preferred embodiment, the alcohol alkoxylate used as reactant, preferably of formula (I), may act as solvent at the reaction temperature.

In the preparation of the alkoxylated polycarboxylic esters of the invention, reaction step 1 is generally carried out with 0.7 to 1.5 molar equivalents of the alcohol alkoxylate, preferably 0.8 to 1.4 molar equivalents, more preferably 0.9 to 1.3 molar equivalents, and most preferably 1.0 to 1.2 molar equivalents.

Molar equivalents are defined herein with respect to the aromatic polycarboxylic acid.

In the preparation of the alkoxylated polycarboxylic esters of the present invention, reaction step 1 is carried out in the presence or absence of a catalyst, preferably in the absence of a catalyst.

Catalysts for the reaction of alcohols with anhydrides are known to those skilled in the art. These catalysts include, but are not limited to, Lewis acids such as zinc chloride and ferric chloride, Bronstedt acids such as sulfuric acid, perchloric acid and trifluoroacetic acid, and tertiary amines such as 4-dimethylaminopyridine.

In the preparation of the alkoxylated polycarboxylic esters of the invention, the reaction step 1 is generally carried out at a temperature of from 50 to 150 ℃, preferably at a temperature of from 60 to 140 ℃, even more preferably at a temperature of from 70 to 130 ℃ and most preferably at a temperature of from 80 to 120 ℃.

In the preparation of the alkoxylated polycarboxylic esters of the present invention, the reaction step 2 is carried out in the presence or absence of an additional solvent, preferably in the absence of an additional solvent.

Solvents suitable for the esterification of alcohols or mixtures of alcohols with carboxylic acids are known to the person skilled in the art. These solvents include, but are not limited to, aromatic hydrocarbons such as benzene, toluene or xylene, aprotic polar solvents such as anisole, aromatic ethers, high boiling alkyl ethers, dimethylformamide and dimethylsulfoxide.

In a preferred embodiment, the solvent used in the second step of the reaction is the same as the solvent used in the first step of the reaction.

In another preferred embodiment, the alcohol or mixture of alcohols used as reactants in the second step of the reaction acts as a solvent.

In another preferred embodiment, the reaction is carried out in a one-pot process without changing the solvent or reaction vessel between the first and second reaction steps.

In the preparation of the alkoxylated polycarboxylic esters of the present invention, reaction step 2 is carried out in the presence or absence of a catalyst, preferably in the presence of a bronsted or lewis acid catalyst.

Suitable catalysts for the esterification reaction are well known to those skilled in the art. These catalysts include, but are not limited to, sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid or other alkylbenzenesulfonic acids, sulfuric acid, perchloric acid, trifluoroacetic acid, phosphorus pentoxide, phosphinic acid, phosphoric acid, heteropolyacids, supported or soluble metal salts such as tin salts, zinc salts, iron salts or titanium alkoxides, ion exchange resins and zeolites.

In the preparation of the alkoxylated polycarboxylic esters of the invention, reaction step 2 is generally carried out with from 1.8 to 3.5 molar equivalents of alcohol or mixture of alcohols, preferably from 1.9 to 3.0 molar equivalents, and more preferably from 2.0 to 2.8 molar equivalents.

Molar equivalents are defined herein with respect to the aromatic polycarboxylic acid.

In the preparation of the alkoxylated polycarboxylic esters of the invention, the reaction step 2 is generally carried out at a temperature of from 130 to 250 ℃, preferably at a temperature of from 150 to 220 ℃, even more preferably at a temperature of from 160 to 200 ℃ and most preferably at a temperature of from 170 to 200 ℃.

The alkoxylated polycarboxylates of the present invention, especially those of formula (II), are used as anti-redeposition agents, especially in laundry or laundry compositions and applications.

The alkoxylated polycarboxylates of the present invention have additional utility as dispersants, especially in laundry or laundry compositions and applications.