AQUEOUS DISPERSIONS OF WATER-SOLUBLE AND/OR WATER-SWELLABLE ANIONIC POLYMERS, METHOD FOR THEIR PRODUCTION AND USE THEREOF

• US 20070212321A1
• Filed: 07/30/2005
• Published: 09/13/2007
• Est. Priority Date: 08/10/2004
• Status: Active Grant

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Braig, Volker, Gauweiler, Werner, Mukherjee, Pulakesh, Weidl, Christian
• Granted Patent: US 8,540,974 B2
• Time in Patent Office: Days
• US Class Current: 424/70.160
• CPC Class Codes: C08F 2/20 with the aid of macromolecular dispersing agents
• CPC Class Codes: C08F 283/06 on to polyethers, polyoxymethylenes or polyacetals C08F283/004 takes precedence
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 51/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 53/005 Modified block copolymers
• CPC Class Codes: C09D 11/03 characterised by features other than the chemical nature of the binder
• CPC Class Codes: C09D 7/43 Thickening agents
• CPC Class Codes: C14C 11/003 using macromolecular compounds

Abstract

Aqueous dispersions of water-soluble and/or water-swellable anionic polymers which are obtainable by free radical polymerization of ethylenically unsaturated, anionic monomers in an aqueous medium in the presence of at leas one stabilizer, the polymerization being carried out in the presence of at least one water-soluble polymer of the groups consisting of (a) graft polymers of vinyl acetate and/or vinyl propionate on (i) polyethylene glycols or (ii) polyethylene glycols or polypropylene glycols blocked at one or both terminal groups with alkyd carboxyl or amino groups, polyalkylene glycols, polyalkylene glycols blocked at one or both terminal groups with alkyl carboxy or amino groups and (b) water-soluble copolymers of (b1) nonionic monoethylenically unsaturated monomers, (b2) cationic monoethylenically unsaturated monomers and if appropriate (b3) anionic monoethylenically unsaturated monomers, the fraction of the interpolymerized cationic monomers being greater than that of the anionic monomers, as a stabilizer, said aqueous dispersions are prepared by free radical polymerization of the anionic monomers in an aqueous medium in the presence of the abovementioned water-soluble polymers (a) and (b) and said aqueous dispersions are used as thickeners for aqueous systems.

Claims

1. An aqueous dispersion of water-soluble and/or water-swellable anionic polymers which are obtainable by free radical polymerization of ethylenically unsaturated, an onic monomers in an aqueous medium in the presence of at least one stabilizer, wherein the polymerization is carried out in the presence of at least one water-soluble polymer from the groups consisting of

(a) graft polymers of vinyl acetate and/or vinyl propionate on polyethylene glycols or (ii) polyethylene glycols or polypropylene glycols blocked at one or both ter nal groups with alkyl, carboxyl or amino groups,

polyalkylene glycols, polyalkylene glycols blocked at one or both terminal groups with alkyl carboxyl or amino groups

and

(b) water-soluble copolymers of

(b1) nonionic monoethylenically unsaturated monomers,

(b2) cat onic monoethylenically unsaturated monomers and if appropriate

(b3) anionic monoethylenically unsaturated monomers, the fraction of the interpolymerized cationic monomers being greater than that of the anionic monomers, as a stabilizer.

2. An aqueous dispersion as claimed in claim 1, wherein polyalkylene glycols having molar masses M_N of from 100 to 100 000 and/or polyalkylene glycols blocked at one or both terminal groups with alkyl, carboxyl or amino groups and having molar masses M_N of from 100 to 100 000 are used as water-soluble polymers of group (a).

3. An aqueous dispersion as claimed claim 1, wherein block copolymers of ethylene oxide and propylene oxide having a molar mass M_N of from 500 to 20 000 g/mol and an ethylene oxide unit content of from 10 to 80 mol % are used as water-soluble polymers of group (a).

4. An aqueous dispersion as claimed in claim 1, wherein copolymers of

(b1) acrylamide, methacrylamide, N-vinylformamaide, N-vinylpyrrolidone and/or N-vinylcaprolactam,

(b2) dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, partially or fully neutralized dialkylaminoalkyl (meth)acrylates, quaternized dialkylaminoalkyl (meth)acrylates, dialkyldiallylammonium halides, N-vinylimidazole and quaternized N-vinylimidazole and if appropriate

(b3) acrylic acid, methacrylic acid, vinylsulfonic acid, vinylphosphonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and also the alkali metal and ammonium salts thereof.

are used as water-soluble polymers of group (b).

5. An aqueous dispersion as claimed in claim 1, wherein the stabilizer used is a combination of

(a) at least one block copolymer of ethylene oxide and propylene oxide and

(b) at least one copolymer of acrylamide and dimethylaminoethyl acrylate methochloride, which copolymer may if appropriate further comprise up to 5 mol % of acrylic acid in interpolymerized form.

6. An aqueous dispersion as claimed in claim 1, wherein monoethylenically unsaturated C₃- to C₅-carboxy ic acids, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid and/or the alkali metal or ammonium salts thereof are used as anionic monomers.

7. An aqueous dispersion as claimed in claim 1, wherein the polymerization of the anionic monomers is additionally carried out in the presence of at least one other monomer from the group consisting of acrylamide, methacrylamide, acrylic esters of monohydric alcohols of 1 to 20 carbon atoms, methacrylic esters of monohydric alcohols of 1 to 20 carbon atoms, vinyl acetate, vinyl propionate, dialkylaminoethyl (meth)acrylates, dialkylaminopropyl (meth)acrylates, diallyldimethylammonium chloride, vinylimidazole and quaternized vinylimidazole and also partially or fully acid-neutralized or quaternized dialkylaminoalkyl (meth)acrylates.

8. An aqueous dispersion as claimed in claim 1, wherein the polymerization of the anionic monomers is additionally carried out in the presence of at least one crosslinking agent.

9. An aqueous dispersion as claimed in claim 1, herein the crosslinker used is pentaerythrityl triallyl ether, N,N′

-divinylethyleneurea, at least doubly allyl-comprising allyl ethers of sugars, at least doubly vinyl-comprising vinyl ethers or triallylamine and also mixtures thereof.

10. An aqueous dispersion as claimed in claim 1, obtainable by polymerizing acrylic acid in the absence of other monomers.

11. An aqueous dispersion as claimed in claim 1, obtainable by polymerizing acrylic acid and/or methacrylic acid in the presence of pentaerythrityl triallyl ether N,N′

-divinylethyleneurea or triallylamine and also mixtures thereof.

15. The method for thickening an aqueous system said method consist using aqueous dispersion soluble polymer of claim 1.

16. The method of claim 15 wherein the aqueous dispersion is used as a thickener for paper coating slips, pigment print pastes aqueous colors, leather treatment compositions cosmetic formulations, pharmaceutical articles of manufacture and agrochemicals.

12. A process for the preparation of aqueous dispersions of water-soluble and/or water-swellable anionic polymers by free radical polymerization of ethylenically unsaturated, anionic monomers in an aqueous medium in the presence of at least one stabilizer, wherein the polymerization is carried out in the presence of at least one water-soluble polymer from the groups consisting of

(a) graft polymers of vinyl acetate and/or vinyl propionate on (i) polyethylene glycols or (ii) polyethylene glycols or polypropylene glycols blocked at one or both terminal groups with alkyl, carboxyl or amino groups,

polyalkylene glycols polyalkylene glycols blocked at one or both terminal groups with alkyl carboxyl or amino groups

and

(b) water-soluble copolymers of

(b1) nonionic monoethylenically unsaturated monomers,

(b2) cationic monoethylenically unsaturated monomers and if appropriate

(b3) anionic monoethylenically unsaturated monomers, the fraction of the interpolymerized cationic nonomers being greater than that of the anionic monomers,

as a stabilizer.

13-14. -14. (canceled)