# US 10,766,991 B2 · Sulfonate group-containing polymer and method of producing the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,766,991 B2 - Document ID: US10766991B2 - Status: Granted - Kind: B2 - Application number: 15/329,135 - Filed: 2014-09-25 - Published: 2017-08-31 - Granted: 2020-09-08 - Earliest claimed: 2014-09-25 - Assignees: Nippon Shokubai Co., Ltd. - Applicants: Nippon Shokubai Co., Ltd. - Inventors: Akiko Hemmi; Hirotaka Mizoguchi; Rika Matsumoto; Xiaoli Wang; Xianling Zhai; Peng Qin; Xiaoyan Liu - Web page: https://patentgrep.com/patent/US10766991B2 ## CPC - C08F 216/1416: {Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether} - C08F 216/14: Monomers containing only one unsaturated aliphatic radical - C08F 220/06: Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof - C08F 220/585: {and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]} - C11D 3/0036: {Soil deposition preventing compositions; Antiredeposition agents} - C08F 2800/20: as weight or mass percentages - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C11D: DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL ## Abstract A sulfonate group-containing copolymer is provided which comprising a structural unit (a) derived from a sulfonate group-containing monomer (A); a structural unit (b) derived from a (poly)oxyalkylene monomer (B); a structural unit (c) derived from a carboxyl group-containing monomer (C). The sulfonate group-containing copolymer comprises from 20% to 90% by mass in an acid form equivalent of the structural unit (c) in 100% by mass of all the structural units constituting the sulfonate group-containing copolymer. The product (P×Mw×n) of the ratio by mass P of the structural unit (b) to the structural unit (a) multiplied by the weight average molecular weight Mw of the sulfonate group-containing copolymer multiplied by the value n is from 950,000 to 800,000,000. ## Claims ### Claim 1 A sulfonate group-containing copolymer, comprising: a structural unit (a) derived from a sulfonate group-containing monomer (A); a structural unit (b) derived from a (poly)oxyalkylene monomer (B) represented by the following formula (1): wherein R1 represents a hydrogen atom or a methyl group; R2 represents a direct bond, CH2, or CH2CH2; and X0 represents a structural unit represented by the following formula (2): —Zn—OR0 (2) wherein Z may be the same or different and each represents a structural unit derived from a C2-C5 alkylene oxide; R0 represents hydrogen atom or a methyl group; and n is an integer of from 5 to 100; and a structural unit (c) derived from a carboxyl group-containing monomer (C) that is at least one selected from the group consisting of (meth)acrylic acid, maleic acid, maleic anhydride, and salts thereof, wherein the sulfonate group-containing copolymer comprises from 2% to 38% by mass of the structural unit (a), from 9% to 70% by mass of the structural unit (b), and from 20% to 90% by mass in an acid form equivalent of the structural unit (c) in 100% by mass of all the structural units constituting the sulfonate group-containing copolymer, wherein the product (P×Mw×n) of the ratio by mass P of the structural unit (b) to the structural unit (a) multiplied by the weight average molecular weight Mw of the sulfonate group-containing copolymer multiplied by the value n in the formula (2) is from 950,000 to 33,300,000, wherein the sulfonate group-containing monomer (A) is at least one of 2-acrylamide-2-methylpropanesulfonic acid and a compound represented by the following formula (3): wherein R3 represents a hydrogen atom or a methyl group; R4 represents a direct bond, CH2, or CH2CH2; X and Y each represent a hydroxy group or SO3M where M represents a hydrogen atom, Li, Na, or K, and at least one of X and Y is SO3M, wherein the sulfonate group-containing copolymer optionally comprises a structural unit (e) derived from a monomer (E) that is none of the monomer (A), the monomer (B), and the monomer (C) in an amount no more than 20% by mass based on 100% by mass of the structural units (a), (b), (c), and (e), and wherein the degree of neutralization of the sulfonate group-containing copolymer is 1 to 100 mol %, wherein an anti-redeposition property exhibited by the sulfonate group-containing copolymer, evaluated as follows, is 64.8% to 68.1%: In evaluation of anti-redeposition properties under high hardness condition, clay is used in item (4) as soil (1) A cotton cloth obtained from Testfabrics, Inc. is cut into 5 cm×5 cm to prepare white clothes and whiteness of each of the white clothes is previously measured as reflectance using colorimetry color difference meter SE6000 type produced by Nippon Denshoku Industries Co., Ltd. (2) Pure water is added to calcium chloride dihydrate (5.0 g) to prepare hard water (17 kg) (3) Pure water is added to polyoxyethylene (8) lauryl ether (4.0 g) to prepare an aqueous surfactant solution (100.0 g) and pH is controlled to 8.5 with sodium hydroxide (4) The temperature of a Terg-o-Tometer was set at 25° C., to a pot are added hard water (1 L), an aqueous surfactant solution (5 g), a 2% (solids content) aqueous polymer solution (1 g), and test powder 1 (class 11) (1 g) according to JIS Z 8901, the contents are stirred for 1 min at 100 rpm, five white cloths are put into the solution, and the solution is stirred for 10 min at 100 rpm (5) The white cloths are wrung by hand, and hard water (1 L) at 25° C. is charged into the pot, and is stirred for 2 min at 100 rpm (6) Each of the white cloths is pressed with a filler cloth to be dried while smoothing wrinkles, and the dried clothes are measured for whiteness again as reflectance with the above colorimetric difference meter (7) From the measurement results, the anti-redeposition performance is determined according to the following formula Anti-redeposition performance(%)=(whiteness after washing)/(whiteness of original white cloth)×100. ### Claim 2 (depends on 1) The sulfonate group-containing copolymer according to claim 1, wherein the sulfonate group-containing copolymer has a weight average molecular weight Mw of from 20,000 to 200,000. ### Claim 3 (depends on 1) The sulfonate group-containing copolymer according to claim 1, wherein the sulfonate group-containing copolymer has a ratio by mass P of the structural unit (b) to the structural unit (a) of from 1.2 to 20. ### Claim 4 (depends on 1) The sulfonate group-containing copolymer according to claim 1, wherein the degree of neutralization of the sulfonate group-containing copolymer is 70 to 99 mol %. ### Claim 5 (depends on 1) The sulfonate group-containing copolymer according to claim 1, wherein the amount of the optional structural unit (e) is no more than 10% by mass. ### Claim 6 (depends on 1) A method of producing the sulfonate group-containing copolymer of claim 1, the method comprising: copolymerizing monomer components including a sulfonate group-containing monomer (A), a (poly)oxyalkylene monomer (B), and a carboxyl group-containing monomer (C) that is at least one selected from the group consisting of (meth)acrylic acid, maleic acid, maleic anhydride, and salts thereof, the monomer (B) being represented by the following formula (1): wherein R1 represents a hydrogen atom or a methyl group; R2 represents a direct bond, CH2, or CH2CH2; and X0 represents a structural unit represented by the following formula (2): —Zn—OR0 (2) wherein Z may be the same or different and each represents a structural unit derived from a C2-C5 alkylene oxide; R0 represents a hydrogen atom or a methyl group; and n is an integer of from 5 to 100, wherein the monomer components comprise from 20% to 90% by mass in acid form equivalent of the carboxyl group-containing monomer (C) in 100% by mass of all the monomers in the monomer components, wherein the product (P×Mw×n) of the ratio by mass P of the structural unit (b) to the structural unit (a) multiplied by the weight average molecular weight Mw of the sulfonate group-containing copolymer multiplied by the value n in the formula (2) is from 950,000 to 33,300,000, wherein the sulfonate group-containing monomer (A) is at least one of 2-acrylamide-2-methylpropanesulfonic acid and a compound represented by the following formula (3): wherein R3 represents a hydrogen atom or a methyl group; R4 represents a direct bond, CH2, or CH2CH2; X and Y each represent a hydroxy group or SO3M where M represents a hydrogen atom, Li, Na, or K, and at least one of X and Y is SO3M, and wherein the degree of neutralization of the sulfonate group-containing copolymer is 1 to 100 mol %.