Thickener comprising at least one cationic polymer preparable by inverse emulsion polymerization
The present invention relates to a thickener preparable by a process which comprises obtaining a cationic polymer by inverse emulsion polymerization of a) at least one water-soluble ethylenically unsaturated monomer comprising at least one cationic monomer, optionally at least one anionic monomer and/or optionally at least one nonionic monomer, b) at least one ethylenically unsaturated associative monomer, c) optionally at least one crosslinker, d) optionally at least one chain transfer agent, the temperature being kept constant during the inverse emulsion polymerization and being at least 40° C., preferably 50 to 90° C., and after the inverse emulsion polymerization has ended, activator being added to obtain the thickener.
1. A thickener prepared by a process which comprises obtaining a cationic polymer by inverse emulsion polymerization of
a) 20 to 99.99% by weight, based on the cationic polymer, of at least one water-soluble ethylenically unsaturated monomer comprising at least one cationic monomer, wherein the at least one cationic monomer is a compound of the formula (II)
wherein
R 1 is H or C 1 -C 4 -alkyl,
R 2 is H or methyl,
R 3 is C 1 -C 4 -alkylene,
R 4 , R 5 and R 6 are each independently H or C 1 -C 30 -alkyl,
X is —O— or —NH—, and
Y is Cl, Br, I, hydrogensulfate, or methosulfate,
b) 0.01 to 80% by weight, based on the cationic polymer, of at least one ethylenically unsaturated associative monomer, wherein the at least one ethylenically unsaturated associative monomer is a compound of the formula (I)
R—O—(CH 2 —CHR′—O) n —CO—CR″═CH 2 (I)
wherein
R is C 6 -C 50 -alkyl,
R′ is H or C 1 -C 4 -alkyl,
R″ is H or methyl, and
n is an integer from 0 to 100,
and
d) 0 to 0.3% by weight, based on the cationic polymer, of at least one chain transfer agent,
the temperature being kept constant during the inverse emulsion polymerization and being at least 40° C. and, after the inverse emulsion polymerization has ended, an activator is added to obtain the thickener;
wherein the thickener is in a surfactant-containing acidic formulation, the formulation having a pH of from 1 to <7;
wherein no crosslinker is used in the inverse emulsion polymerization of the cationic polymer.
2. The thickener according to claim 1 , wherein the temperature during the inverse emulsion polymerization is 50 to 90° C.
3. The thickener according to claim 1 , wherein an oil phase is present during the inverse emulsion polymerization, and wherein the inverse emulsion polymerization is followed and the activator addition is preceded by distillative removal of at least a portion of water and at least a portion of one or more low-boiling constituents of the oil phase selected from the group consisting of dearomatized aliphatic hydrocarbons and mineral oils of low viscosity.
4. The thickener according to claim 3 , wherein the distillative removal is performed by means of liquid dispersion polymer (LDP) technology.
5. The thickener according to claim 1 , wherein component b) is added to an oil phase in the inverse emulsion polymerization.
6. The thickener according to claim 1 , wherein the activator is selected from fatty alcohol alcoxylates, alkyl glycosides, alkyl carboxylates, alkylbenzenesulfonates, secondary alkanesulfonates and fatty alcohol sulfates.
7. The thickener according to claim 6 , wherein the activator is selected from fatty alcohol alcoxylates.
8. The thickener according to claim 1 , wherein a mixture of at least two activators is used, at least one activator having an HLB (hydrophilic-lipophilic balance) value of >12 to 20 and at least one activator an HLB value of 1 to 12.
9. The thickener according to claim 1 , wherein the cationic polymer is present dispersed in an oil phase, wherein the oil phase is present during the inverse emulsion polymerization.
10. The thickener according to claim 9 , wherein the cationic polymer is present dispersed in an inverse dispersion, water-in-oil dispersion, or a dispersed anhydrous cationic polymer in oil.
11. The thickener according to claim 1 , wherein more than 25% by weight (based on the total weight of the cationic polymer) of the cationic polymer is soluble in water.
12. The thickener according to claim 1 , wherein, in the at least one cationic monomer of the formula (II),
i) R 1 and R 2 are each H, or
ii) R 1 is H and R 2 is CH 3 .
13. The thickener according to claim 1 , wherein the component a) in the cationic polymer comprises at least one nonionic monomer, the at least one nonionic monomer being selected from N-vinylpyrrolidone, N-vinylimidazole or a compound of the formula
where
R 7 is H or C 1 -C 4 -alkyl,
R 8 is H or methyl, and
R 9 and R 10 are each independently H or C 1 -C 30 -alkyl.
14. The thickener according to claim 1 , wherein component a) in the cationic polymer comprises 30 to 99.5% by weight of at least one cationic monomer and 0.5 to 70% by weight of at least one nonionic monomer.
15. The thickener according to claim 1 , wherein the at least one chain transfer agent (component d) in the cationic polymer is selected from mercaptans, lactic acid, formic acid, isopropanol or hypophosphites.
16. The thickener according to claim 1 , wherein the ratio of activator to cationic polymer is >10 to 100 [% by weight/% by weight].
17. A thickener according to claim 1 to be used as a viscosity modifier, for optimization of shear dilution, as a thickening agent, for stabilization of suspended constituents having a size in the range from nanometers to millimeters or in surfactant-containing acidic or alkaline formulations.
18. The thickener according to claim 1 , wherein a) the at least one water-soluble ethylenically unsaturated monomer further comprises at least one anionic monomer or at least one nonionic monomer.
19. The thickener according to claim 1 , wherein component a) is at least one water-soluble ethylenically unsaturated monomer consisting of at least one cationic monomer and optionally of at least one anionic monomer and wherein any anionic monomer present in component a) is selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid or a salt thereof.
20. The thickener according to claim 1 , wherein component a) is at least one water-soluble ethylenically unsaturated monomer comprising at least one cationic monomer and optionally of at least one anionic monomer and wherein any anionic monomer present in component a) is selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid or a salt thereof.
21. A surfactant-containing acidic formulation comprising at least one thickener prepared by a process which comprises obtaining a cationic polymer by inverse emulsion polymerization of
a) 20 to 99.99% by weight, based on the cationic polymer, of at least one water-soluble ethylenically unsaturated monomer comprising at least one cationic monomer, wherein the at least one cationic monomer is a compound of the formula (II)
wherein
R 1 is H or C 1 -C 4 -alkyl,
R 2 is H or methyl,
R 3 is C 1 -C 4 -alkylene,
R 4 , R 5 and R 6 are each independently H or C 1 -C 30 -alkyl,
X is —O— or —NH—, and
Y is Cl, Br, I, hydrogensulfate, or methosulfate,
b) 0.01 to 80% by weight, based on the cationic polymer, of at least one ethylenically unsaturated associative monomer, wherein the at least one ethylenically unsaturated associative monomer is a compound of the formula (I)
R—O—(CH 2 —CHR′—O) n —CO—CR″═CH 2 (I)
wherein
R is C 6 -C 50 -alkyl,
R′ is H or C 1 -C 4 -alkyl,
R″ is H or methyl, and
n is an integer from 0 to 100,
and
d) 0 to 0.3% by weight, based on the cationic polymer, of at least one chain transfer agent,
the temperature being kept constant during the inverse emulsion polymerization and being at least 40° C. and, after the inverse emulsion polymerization has ended, an activator is added to obtain the at least one thickener, the pH of the formulation being 1 to <7;
wherein no crosslinker is used in the inverse emulsion polymerization of the cationic polymer.
22. A surfactant-containing acidic formulation according to claim 21 to be used in hair cosmetics, in hair styling, as a shampoo, as a softener, as a conditioner, as a skin cream, as a shower gel, as a fabric softener for laundry, or as an acidic detergent.
23. A surfactant-containing alkaline formulation comprising at least one thickener, the pH of the formulation being 7 to 13, wherein the at least one thickener is prepared by a process which comprises obtaining a cationic polymer by inverse emulsion polymerization of
a) 20 to 99.99% by weight, based on the cationic polymer, of at least one water-soluble ethylenically unsaturated monomer comprising at least one cationic monomer, wherein the at least one cationic monomer is a compound of the formula (II)
wherein
R 1 is H or C 1 -C 4 -alkyl,
R 2 is H or methyl,
R 3 is C 1 -C 4 -alkylene,
R 4 , R 5 and R 6 are each independently H or C 1 -C 30 -alkyl,
X is —O— or —NH—, and
Y is Cl, Br, I, hydrogensulfate, or methosulfate,
b) 0.01 to 80% by weight, based on the cationic polymer, of at least one ethylenically unsaturated associative monomer, wherein the at least one ethylenically unsaturated associative monomer is a compound of the formula (I)
R—O—(CH 2 —CHR′—O) n —CO—CR″═CH 2 (I)
wherein
R is C 6 -C 50 -alkyl,
R′ is H or C 1 -C 4 -alkyl,
R″ is H or methyl, and
n is an integer from 0 to 100,
and
d) 0 to 0.3% by weight, based on the cationic polymer, of at least one chain transfer agent,
the temperature being kept constant during the inverse emulsion polymerization and being at least 40° C. and, after the inverse emulsion polymerization has ended, an activator is added to obtain the at least one thickener;
wherein no crosslinker is used in the inverse emulsion polymerization of the cationic polymer.
24. A surfactant-containing alkaline formulation according to claim 23 to be used as a liquid washing composition or as a machine or manual dishwashing detergent.