Use of a gel-like polymer composition which can be obtained by polymerizing an acid group-containing monomer in the presence of a polyether compound in formulations for automatic dishwashing

Patent metadata

Field	Value
Publication number	US-10647945-B2
Application number	US-201414902487-A
Country	US
Kind code	B2
Filing date	Jul 2, 2014
Priority date	Jul 3, 2013
Publication date	May 12, 2020
Grant date	May 12, 2020

Abstract

The invention relates to the use of a gel-like polymer composition, which is produced by means of a radical polymerization of an [alpha],[beta]-ethylenically unsaturated acid in the presence of at least one polyether component, in formulations for automatic dishwashing (ADW).

First claim

The invention claimed is:

1. A machine dishwashing formulation which comprises a polymer composition in gel form, obtainable by a process in which
a) Providing a monomer composition M) consisting of
A) at least one α,β-ethylenically unsaturated acid, and
B) 0% to 0.1% by weight, based on the total weight of the monomer composition M), of crosslinking monomers having two or more than two polymerizable α,β-ethylenically unsaturated double bonds per molecule,

b) Subjecting the monomer composition M) provided in step a) to a free-radical polymerization in the presence of at least one polyether component PE) selected from polyetherols having a number-average molecular weight of at least 200 g/mol and the mono- and di-(C 1 -C 6 -alkyl ethers) thereof, surfactants containing polyether groups and mixtures thereof.

2. The formulation according to claim 1 , with the proviso that, when the polyether component PE) comprises a polyetherol having repeat propylene oxide units or a mono- or di-(C 1 -C 6 -alkyl ether) of a polyetherol having repeat propylene oxide units, the proportion of these repeat propylene oxide units averages not more than 18 units per molecule.

3. The formulation according to claim 1 , wherein the free-radical polymerization in step b) is additionally effected in the presence of a solvent S) selected from water, C 1 -C 6 -alkanols, polyols other than PE), the mono- and dialkyl ethers thereof, and mixtures thereof.

4. The formulation according to claim 1 , wherein the polymerization in step b) is effected in feed mode, by initially charging at least a portion of the polyether component PE) and optionally, if present, at least a portion of the solvent S), and supplying at least a portion of the monomer composition provided in step a) and at least one free-radical initiator FRI) to the initial charge.

5. The formulation according to claim 3 , wherein the free-radical polymerization in step b) is additionally effected in the presence of a solvent S) and
the reaction mixture at the start of the reaction in step b) comprises the solvent S) in an amount of 0.1% to 70% by weight, based on the total weight of the reaction mixture,
the reaction mixture after conclusion of the reaction in step b) comprises the solvent S) in an amount 0.1% to 40% by weight, based on the total weight of the reaction mixture.

6. The formulation according to claim 3 , wherein the free-radical polymerization in step b) is effected in the presence of a solvent S) selected from propylene glycol, dipropylene glycol, water and mixtures thereof.

7. The formulation according to claim 1 , wherein the polymerization in step b) is effected at a temperature in the range from 20 to 150° C.

8. The formulation according to claim 1 , wherein the monomer composition provided in step a) consist of acrylic acid A1) and optionally at least one further α,β-ethylenically unsaturated acid A2).

9. The formulation according to claim 8 , wherein the further α,β-ethylenically unsaturated acid A2) is selected from carboxylic acids, sulfonic acids, phosphoric acids and mixtures thereof.

10. The formulation according to claim 8 , wherein the further α,β-ethylenically unsaturated acid A2) is selected from methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloyloxypropylsulfonic acid, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, allylphosphonic acid and mixtures thereof.

11. The formulation according to claim 7 , wherein the monomer composition M) consists exclusively of acrylic acid.

12. The formulation according to claim 1 , wherein the free-radical polymerization is performed in the presence of a chain transfer agent.

13. The formulation according to claim 1 , wherein the polyether component PE) comprises at least one polyetherol having a number-average molecular weight in the range from about 200 to 100 000 or a mono- or di-(C 1 -C 2 -alkyl ether) thereof.

14. The formulation according to claim 1 , wherein the polyether component PE) comprises or consists of at least one polyetherol or a mono- or di-(C 1 -C 2 -alkyl ether) thereof comprising exclusively ethylene oxide units incorporated as alkylene oxide units.

15. The formulation according to claim 1 , wherein the polyether component PE) comprises at least one surfactant containing polyether groups, selected from alkyl polyoxyalkylene ethers, aryl polyoxyalkylene ethers, alkylaryl polyoxyalkylene ethers, alkoxylated animal and/or vegetable fats and/or oils, fatty amine alkoxylates, fatty acid amide alkoxylates, fatty acid diethanolamide alkoxylates, polyoxyethylene sorbitan fatty acid esters, alkyl polyether sulfates, aryl polyether sulfates, alkylaryl polyether sulfates, alkyl polyether sulfonates, aryl polyether sulfonates, alkylaryl polyether sulfonates, alkyl polyether phosphates, aryl polyether phosphates, alkylaryl polyether phosphates, glyceryl ether sulfonates, glyceryl ether sulfates, monoglyceride (ether) sulfates, fatty acid amide ether sulfates, polyoxyalkylene sorbitan fatty acid esters and mixtures thereof.

16. The formulation according to claim 1 , wherein the polyether component PE) comprises at least one surfactant containing polyether groups, selected from:
alkyl polyoxyalkylene ethers of the general formula (VI)
R 10 —O—(CH 2 CH 2 O) x —(CHR 11 CH 2 O) y —R 12

in which R 10 is a linear or branched alkyl radical having 8 to 22 carbon atoms,
R 11 and R 12 are each independently hydrogen or a linear or branched alkyl radical having 1-10 carbon atoms or H, where R 12 is methyl, and
x and y are each independently 0 to 300, where the sum of x and y is >0;
surfactants containing hydroxyl groups of the general formula (VII)
R 13 —O—(CH 2 CH 2 O) s —(CH 2 CH 2 CH 2 O) t —(CH 2 CH 2 CH 2 CH 2 O) u —(CH 2 CHR 14 O) v —CH 2 CH(OH)R 15

where
the sequence of the alkylene oxide units in the compounds of the formula (VII) is arbitrary,
s, t, u and v are each independently an integer from 0 to 500, where the sum of s, t, u and v is >0,
R 13 and R 15 are each independently a straight-chain or branched saturated C 1 -C 40 -alkyl radical or a mono- or polyunsaturated C 2 -C 40 -alkenyl radical, and
R 14 is selected from methyl, ethyl, n-propyl, isopropyl and n-butyl; and
fatty alcohol polyoxyalkylene esters of the general formula (VIII)
R 16 —O—(CH 2 CH 2 O) p —(CH 2 CHR 17 ) q —C(═O)R 18

where
the sequence of the alkylene oxide units in the compounds of the formula (VIII) is arbitrary,
p and q are each independently an integer from 0 to 500, where the sum of p and q is >0,
R 16 and R 18 are each independently a straight-chain or branched saturated C 1 -C 40 -alkyl radical or a mono- or polyunsaturated C 2 -C 40 -alkenyl radical, and
R 17 is selected from methyl, ethyl, n-propyl, isopropyl and n-butyl.

17. The formulation according to claim 1 , wherein the polymer composition has a content of acid groups of 1.5 mmol/g to 15 mmol/g.

18. The formulation according to claim 1 , wherein the polymer composition has a transparency, reported as the T L measured at 500 nm, of at least 85% based on the transparency of water.

19. The formulation according to claim 1 , wherein up to 80 mol % of the acid groups, in the polymer compositi

Assignees

• Basf Se

Inventors

• Weber Heike
• Fuchs Yannick
• Witteler Helmut
• Boehn Roland
• Rieger Ralph

Classifications

• C09D4/06

  {Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00 · CPC title

• C11D3/3757 Primary

  (Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions · CPC title

• C08F283/06 Primary

  on to polyethers, polyoxymethylenes or polyacetals {(C08F283/004 takes precedence)} · CPC title

• C11D3/386

  Preparations containing enzymes {, e.g. protease or amylase} · CPC title

• A61K8/8152

  Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers · CPC title