# US 8,540,974 B2 · Aqueous dispersions of water-soluble and/or water-swellable anionic polymers, method for their production and use thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,540,974 B2 - Document ID: US8540974B2 - Status: Granted - Kind: B2 - Application number: 11/573,210 - Filed: 2005-07-30 - Published: 2007-09-13 - Granted: 2013-09-24 - Earliest claimed: 2004-08-10 - Assignees: BASF SE - Applicants: Volker Braig; Werner Gauweiler; Pulakesh Mukherjee; Christian Hubert Weidl - Inventors: Volker Braig; Werner Gauweiler; Pulakesh Mukherjee; Christian Hubert Weidl - Web page: https://patentgrep.com/patent/US8540974B2 ## CPC - C08F 283/06: on to polyethers, polyoxymethylenes or polyacetals {(C08F283/004 takes precedence)} - C08F 2/20: with the aid of macromolecular dispersing agents - C08L 51/08: grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds - 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 - C08L 53/005: {Modified block copolymers} - C09D 7/43: Thickening agents - C09D 11/03: characterised by features other than the chemical nature of the binder - C14C 11/003: {using macromolecular compounds} - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - C14C: CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING (bleaching of leather or furs D06L; dyeing of leather or furs D06P) ## 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 ### Claim 1 An aqueous dispersion comprising water-soluble and/or water-swellable anionic polymers of ethylenically unsaturated, anionic monomers; an aqueous medium; and a stabilizer comprising: (a) at least one water-soluble polymer selected from the groups consisting of 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) at least one water-soluble copolymer comprising (b1) nonionic monoethylenically unsaturated monomers, (b2) cationic monoethylenically unsaturated monomers and optionally (b3) anionic monoethylenically unsaturated monomers, the fraction of the interpolymerized cationic monomers being greater than that of the anionic monomers. ### Claim 2 (depends on 1) An aqueous dispersion as claimed in claim 1, wherein polyalkylene glycols having molar masses MN 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 MN of from 100 to 100 000 are used as water-soluble polymers of group (a). ### Claim 3 (depends on 1) An aqueous dispersion as claimed in claim 1, wherein block copolymers of ethylene oxide and propylene oxide having a molar mass MN 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). ### Claim 4 (depends on 1) An aqueous dispersion as claimed in claim 1, wherein copolymers of (b1) acrylamide, methacrylamide, N-vinylformamide, 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 optionally (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). ### Claim 5 (depends on 1) An aqueous dispersion as claimed in claim 1, wherein stabilizer comprises (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 optionally further comprise up to 5 mol % of acrylic acid in interpolymerized form. ### Claim 6 (depends on 1) An aqueous dispersion as claimed in claim 1, wherein monoethylenically unsaturated C3- to C5-carboxylic acids, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid and/or the alkali metal or ammonium salts thereof are used as anionic monomers. ### Claim 7 (depends on 1) An aqueous dispersion as claimed in claim 1, wherein said water-soluble and/or water-swellable anionic polymers further comprise at least one other polymerized 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. ### Claim 8 (depends on 1) An aqueous dispersion as claimed in claim 1, wherein said water-soluble and/or water-swellable anionic polymer is crosslinked with at least one crosslinking agent. ### Claim 9 (depends on 8) An aqueous dispersion as claimed in claim 8, wherein the crosslinker used is pentaerythritol 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. ### Claim 10 (depends on 1) An aqueous dispersion as claimed in claim 1, wherein said ethylenically unsaturated, anionic monomers comprise acrylic acid. ### Claim 11 (depends on 1) An aqueous dispersion as claimed in claim 1, wherein said ethylenically unsaturated, anionic monomers comprise acrylic acid and/or methacrylic acid in the presence of penterythritol triallyl ether, N,N′-divinylethyleneurea or triallylamine and also mixtures thereof. ### Claim 12 (depends on 1) A process for the preparation of the aqueous dispersions of claim 1, comprising free radical polymerizing of ethylenically unsaturated, anionic monomers in an aqueous medium in the presence of a stabilizer comprising (a) at least one water-soluble polymer selected from the groups consisting of 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) at least one water-soluble copolymer comprising (b1) nonionic monoethylenically unsaturated monomers, (b2) cationic monoethylenically unsaturated monomers and (b3) anionic monoethylenically unsaturated monomers, the fraction of the interpolymerized cationic monomers being greater than that of the anionic monomers. ### Claim 13 (depends on 1) The method for thickening an aqueous system said method comprising using aqueous dispersion soluble polymer of claim 1. ### Claim 14 (depends on 13) The method of claim 13 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. ### Claim 15 (depends on 1) The aqueous dispersion as claimed in claim 1, comprising 1-70 wt. % of said water-soluble and/or water-swellable anionic polymers. ### Claim 16 (depends on 1) The aqueous dispersion as claimed in claim 1, comprising 15-20 wt. % of said water-soluble and/or water-swellable anionic polymers. ### Claim 17 (depends on 1) The aqueous dispersion as claimed in claim 1, comprising 1 to 40 wt. % of stabilizers (a) and (b). ### Claim 18 (depends on 1) The aqueous dispersion as claimed in claim 1, comprising 10 to 25 wt. % of stabilizers (a) and (b). ### Claim 19 (depends on 1) The aqueous dispersion as claimed in claim 1, wherein said dispersion has a viscosity of from 200 to 100,000 mPa·s as measured in a Brookfield viscometer at 20° C. ### Claim 20 (depends on 1) The aqueous dispersion as claimed in claim 1, wherein said dispersion has a viscosity of from 200 to 10,000 mPa·s as measured in a Brookfield viscometer at 20° C.