Polymers containing S-vinylthio alkanols

Patent metadata

Field	Value
Publication number	US-11548965-B2
Application number	US-201916665881-A
Country	US
Kind code	B2
Filing date	Oct 28, 2019
Priority date	Oct 30, 2013
Publication date	Jan 10, 2023
Grant date	Jan 10, 2023

Abstract

Process for preparing polymers comprising S-vinylthioalkanol as monomer by radical polymerization, the polymerization being carried out in aqueous solution, with the proviso that no N-vinylpyrrolidone as monomer is used for preparing the polymers, and also polymers prepared by such processes. Copolymer consisting of S-vinyl-2-thioethan-1-ol and one or more ethylenically unsaturated monomers selected from the group consisting of acrylic acid, itaconic acid, maleic acid, maleic anhydride, and vinylphosphonic acid. Mixtures, preferably aqueous compositions, comprising polymers or copolymers. Use of polymers, copolymers, or aqueous compositions as concrete plasticizers, wetting agents, in cosmetics, as adhesive constituent, in emulsion polymerization, for metal surface treatment, in coatings applications, in paints, in laundry detergents, in washing detergents, as encapsulating material or as enveloping material.

First claim

The invention claimed is:

1. A polymer consisting of S-vinylthioalkanol as monomer and at least one further monomer, different from the S-vinylthioalkanol, being prepared by a process comprising carrying out polymerization in aqueous solution, with the proviso that no N-vinylpyrrolidone is used as monomer for preparing the polymer, and
wherein:
the at least one further monomer is selected from the group consisting of monoethylenically unsaturated water-soluble monomer having one or more acid groups, monoethylenically unsaturated water-soluble monomer having one or more anhydride groups, monoethylenically unsaturated water-soluble monomer having one or more quaternized nitrogen groups, and monoethylenically unsaturated water-soluble monomer having one or more heteroaromatic groups; and
the polymer is free from monoethylenically unsaturated water-soluble monomers having one or more ester groups.

2. The polymer according to claim 1 , wherein, as the S-vinylthioalkanol, unsaturated compounds of the general formula (I) are used

where
R 1 , R 2 , and R 3 independently of one another, identically or differently, are H or CH 3 and
R 4 is linear or branched C 1 -C 30 alkylene.

3. The polymer according to claim 1 , wherein the S-vinylthioalkanol is selected from the group consisting of S-vinyl-2-thioethan-1-ol, S-vinyl-2-thiopropan-1-ol, S-vinyl-1-thiopropan-2-ol, S-vinyl-2-thiobutan-1-ol, S-vinyl-1-thiobutan-2-ol, S-vinyl-2-thiopentan-1-ol, S-vinyl-1-thiopentan-2-ol, S-vinyl-2-thiocyclohexan-1-ol, S-vinyl-2-thio-(012-022)-1-0l, S-vinyl-1-thio-(C 12 -C 22 )-2-ol, S-vinyl-1-thiopropane-2,3-diol, S-vinyl-2-thiopropane-1,3-diol, 1-phenyl-S-vinyl-1-thioethan-2-ol, and 1-phenyl-S-vinyl-2-thioethan-1-ol.

4. The polymer according to claim 1 , wherein, as the at least one further monomer, acrylic acid is used.

5. The polymer according to claim 1 , wherein the polymer has an upper critical solution temperature in water of 0 to 99° C.

6. The polymer according to claim 1 , wherein from 1 to 99 mol % of S-vinylthioalkanol is used, based on the total amount of monomers.

7. The polymer according to claim 3 , wherein from 1 to 99 mol % of S-vinyl-2-thioethan-1-ol and from 99 to 1 mol % of the at least one further monomer are used, based on the total amount of monomers.

8. The polymer according to claim 1 , wherein the at least one further monomer is a monoethylenically unsaturated water-soluble monomer having one or more amide groups.

9. A mixture, comprising the polymer according to claim 1 .

10. An aqueous composition, comprising the polymer according to claim 1 .

11. A composition selected from the group consisting of concrete, a wetting agent, a cosmetic, an adhesive composition, an emulsion polymerization system, a metal surface treating agent, a coating composition, a paint, a laundry detergent, a washing detergent, an encapsulating material, and an enveloping material, the composition comprising the polymer according to claim 1 .

12. An article comprising:
a hot-dipped galvanized steel substrate; and
the polymer according to claim 1 as a coating on the hot-dipped galvanized steel substrate.

13. A copolymer comprising S-vinyl-2-thioethan-1-ol and one or more ethylenically unsaturated monomers selected from the group consisting of itaconic acid, maleic acid, maleic anhydride, and vinylphosphonic acid, and optionally comprising acrylic acid;
wherein:
from 10 to 50 mol. % of S-vinyl-2-thioethan-1-ol is used, based on the total amount of monomers;
from 50 to 90 mol. % of the one or more ethylenically unsaturated monomers and, optionally, the acrylic acid are used, based on the total amount of monomers;
the copolymer is free from monoethylenically unsaturated water-soluble monomers having one or more ester groups; and
the copolymer has an upper critical solution temperature in water of 0 to 99° C.

14. A polymer comprising S-vinylthioalkanol as monomer, monoethylenically unsaturated water-soluble monomer having one or more acid groups, and, optionally, at least one further monomer different from the S-vinylthioalkanol, being prepared by a process comprising carrying out polymerization in aqueous solution, with the proviso that no N-vinylpyrrolidone is used as monomer for preparing the polymer, and
wherein:
the at least one further monomer is selected from the group consisting of monoethylenically unsaturated water-soluble monomer having one or more anhydride groups, monoethylenically unsaturated water-soluble monomer having one or more quaternized nitrogen groups, and monoethylenically unsaturated water-soluble monomer having one or more heteroaromatic groups;
from 10 to 50 mol. % of S-vinylthioalkanol is used, based on the total amount of monomers;
from 50 to 90 mol. % of the monoethylenically unsaturated water-soluble monomer having one or more acid groups and, optionally, the at least one further monomer different from the S-vinylthioalkanol are used, based on the total amount of monomers;
the polymer is free from monoethylenically unsaturated water-soluble monomers having one or more ester groups;
the polymer has an upper critical solution temperature in water of 0 to 99° C.; and
as the S-vinylthioalkanol, unsaturated compounds of the general formula (I) are used

where
R 1 , R 2 , and R 3 independently of one another, identically or differently, are H or CH 3 , and
R 4 is linear or branched C 1 -C 30 alkylene.

15. The polymer according to claim 14 , wherein the S-vinylthioalkanol is selected from the group consisting of S-vinyl-2-thioethan-1-ol, S-vinyl-2-thiopropan-1-ol, S-vinyl-1-thiopropan-2-ol, S-vinyl-2-thiobutan-1-ol, S-vinyl-1-thiobutan-2-ol, S-vinyl-2-thiopentan-1-ol, S-vinyl-1-thiopentan-2-ol, S-vinyl-2-thiocyclohexan-1-ol, S-vinyl-2-thio-(C 12 -C 22 )-1-01, S-vinyl-1-thio-(C 12 -C 22 )-2-ol, S-vinyl-1-thiopropane-2,3-diol, S-vinyl-2-thiopropane-1,3-diol, 1-phenyl-S-vinyl-1-thioethan-2-ol, and 1-phenyl-S-vinyl-2-thioethan-1-ol.

16. The polymer according to claim 14 , wherein, as the monoethylenically unsaturated water-soluble monomer having one or more acid groups, acrylic acid is used.

17. The polymer according to claim 14 , wherein the polymer has an upper critical solution temperature in water of 30 to 80° C.

18. The polymer according to claim 15 , wherein the S-vinylthioalkanol is S-vinyl-2-thioethan-1-ol.

19. A mixture, comprising the polymer according to claim 14 .

20. An aqueous composition, comprising the polymer according to claim 14 .

21. A composition selected from the group consisting of concrete, a wetting agent, a cosmetic, an adhesive composition, an emulsion polymerization system, a metal surface treating agent, a coating composition, a paint, a laundry detergent, a washing detergent, an encapsulating material, and an enveloping material, the composition comprising the polymer according to claim 14 .

22. An article comprising:
a hot-dipped galvanized steel substrate; and
the polymer according to claim 14 as a coating on the hot-dipped galvanized steel substrate.

Assignees

• Basf Se

Inventors

• Fleischhaker Friederike
• Schade Christian

Classifications

• C08F220/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C08F228/04 Primary

  Thioethers · CPC title

• C09D133/02

  Homopolymers or copolymers of acids; Metal or ammonium salts thereof · CPC title

• C09D5/08

  Anti-corrosive paints · CPC title

• C08F228/02 Primary

  by a bond to sulfur · CPC title