# US 2018/0022979 A1 · Crosslinked polymer compositions and methods for use in subterranean formation operations > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2018/0022979 A1 - Document ID: US20180022979A1 - Status: Published application - Kind: A1 - Application number: 15/545,304 - Filed: 2015-02-23 - Published: 2018-01-25 - Earliest claimed: 2015-02-23 - Assignees: Halliburton Energy Services, Inc. - Applicants: Halliburton Energy Services, Inc. - Inventors: Hui ZHOU; Weibin ZHA - Web page: https://patentgrep.com/patent/US20180022979A1 ## CPC - C09K 8/24: Polymers - C08F 230/02: containing phosphorus - C09K 8/512: containing cross-linking agents - C09K 8/588: characterised by the use of specific polymers {(polymeric surfactants C09K8/584)} - C09K 8/685: {containing cross-linking agents} - C09K 8/887: {containing cross-linking agents} - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract A crosslinked polymer comprising reactants of a first repeating unit, a second repeating unit, and a crosslinker that react to form the crosslinked polymer, wherein the first repeating unit is a sulfonic acid-containing monomer present from 1% to 45% by weight of the reactants, wherein the second repeating unit is selected from the group consisting of an N-vinyl amide-contain ing monomer, a terminal double bond-containing monomer, and any combination thereof, and is present from 55% to 99% by weight of the reactants, and wherein the crosslinker comprises at least two olefinic bonds. ## Claims ### Claim 1 A crosslinked polymer comprising: reactants of a first repeating unit, a second repeating unit, and a crosslinker that react to form the crosslinked polymer, wherein the first repeating unit is a sulfonic acid-containing monomer present from 1% to 45% by weight of the reactants, wherein the second repeating unit is selected from the group consisting of an N-vinyl amide-containing monomer, a terminal double bond-containing monomer, and any combination thereof, and is present from 55% to 99% by weight of the reactants, and wherein the crosslinker comprises at least two olefinic bonds. ### Claim 2 (depends on 1) The crosslinked polymer of claim 1, wherein the sulfonic acid-containing monomer is selected from the group consisting of an acrylic sulfonic acid, a methylallyl sulfonic acid, an allyl sulfonic acid, a styrene sulfonic acid, a vinyl sulfonic acid, a vinyl aromatic sulfonic acid, any salt thereof, and any combination thereof. ### Claim 3 (depends on 1) The crosslinked polymer of claim 1, wherein the sulfonic acid-containing monomer is selected from the group consisting of 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, α-methyl styrenesulfonic acid, 2-sulfoethyl methacrylate, vinylbenzene sulfonic acid, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, any salt thereof, any ester thereof, and any combination thereof. ### Claim 4 (depends on 1) The crosslinked polymer of claim 1, wherein the N-vinyl amide-containing monomer is a pyrrolidone-containing N-vinyl amide, a piperidone-containing N-vinyl amide, a caprolactam-containing N-vinyl amide, an acrylate-containing N-vinyl amide, an alkyl-containing N-vinyl amide, and any combination thereof. ### Claim 5 (depends on 1) The crosslinked polymer of claim 1, wherein the N-vinyl amide-containing monomer is selected from the group consisting of N-vinyl-2-pyrrolidone; N-vinyl-2-caprolactam; N-vinyl-piperidone; N-vinyl-3-methyl pyrrolidone; N-vinyl-4-methylpyrrolidone; N-vinyl-5-methylpyrrolidone; N-vinyl-3-ethyl pyrrolidone; N-vinyl-3-butyl pyrrolidone; N-vinyl-3,3-dimethylpyrrolidone; N-vinyl-4, 5-dimethylpyrrolidone; N-vinyl-5,5-dimethylpyrrolidone; N-vinyl-3,3,5-trimethylpyrrolidone; N-vinyl-5-methyl-5-ethyl pyrrolidone; N-vinyl-3,4,5-trimethyl-3-ethyl pyrrolidone; N-vinyl-6-methyl-2-piperidone; N-vinyl-6-ethyl-2-piperidone; N-vinyl-3,5-dimethyl-2-piperidone; N-vinyl-4,4-dimethyl-2-piperidone; N-vinyl-6-propyl-2-piperidone; N-vinyl-3-octyl piperidone; N-vinyl-7-methyl caprolactam; N-vinyl-7-ethyl caprolactam; N-vinyl-4-isopropyl caprolactam; N-vinyl-5-isopropyl caprolactam; N-vinyl-4-butyl caprolactam; N-vinyl-5-butyl caprolactam; N-vinyl-4-butyl caprolactam; N-vinyl-5-tert-butyl caprolactam; N-vinyl-4-octyl caprolactam; N-vinyl-5-tert-octyl caprolactam; N-vinyl-4-nonyl caprolactam; N-vinyl-5-tert-nonyl caprolactam; N-vinyl-3,7-dimethyl caprolactam; N-vinyl-3,5-dimethyl caprolactam; N-vinyl-4,6-dimethyl caprolactam; N-vinyl-3,5,7-trimethyl caprolactam; N-vinyl-2-methyl-4-isopropyl caprolactam; N-vinyl-5-isopropyl-7-methyl caprolactam; N-vinylformamide; N-vinylacetamide; N-vinylpropanamide; N-vinyl-N-methylacetamide; and any combination thereof. ### Claim 6 (depends on 1) The crosslinked polymer of claim 1, wherein the terminal double bond-containing monomer is selected from the group consisting of acrylamide, N-substituted acrylamides, methacrylamide, N-substituted methacrylamides, acrylates, methacrylates, acrylic acid, methacrylic acid, N-allylamides, vinyl alcohol, vinyl ethers, vinyl esters, allyl alcohol, allyl ethers, allyl esters, vinylpyridine, vinylimidazole, allylimidazole, diallyldimethylammonium halide, any salt thereof, and any combination thereof. ### Claim 7 (depends on 1) The crosslinked polymer of claim 1, wherein the crosslinker is selected from the group consisting of a crosslinker with at least two vinyl groups; a crosslinker with at least two allyl groups; a crosslinker with at least two acrylate groups; a crosslinker with at least two methacrylate groups; a crosslinker with at least two acrylamide groups; a crosslinker with at least two methacrylamide groups; a crosslinker with at least two groups from at least two of a vinyl group, an allyl group, an acrylate, a methacrylate group, an acrylamide group, and a methacrylamide group; and any combination thereof. ### Claim 8 (depends on 7) The crosslinked polymer of claim 7, wherein the crosslinker with at least two vinyl groups is selected from the group consisting of divinyl ether; a divinyl ester; a divinyl ether of a polyglycol; a divinyl ether of a polyol; a vinyl ether of a polyol; ethylene glycol divinyl ether; triethylene glycol divinyl ether; poly(ethylene glycol) divinyl ether; 1,3-divinyl-2-imidazolidinone; divinylbenzene; ethylidene pyrrolidone; ethylidene bis(N-vinylpyrrolidone); and any combination thereof. ### Claim 9 (depends on 7) The crosslinked polymer of claim 7, wherein the crosslinker with at least two allyl groups is selected from the group consisting of diallyl ether; an allyl ether of a diallyl ether; a diallyl ester; an allyl ether of a polyglycol; an allyl ether of a polyol; an allyl amine; pentaerythritol allyl ether; trimethylolpropane diallyl ether; ethylene glycol diallyl ether; glycerol diallyl ether; triallyl-1,3,5-triazine-2,4,6-trione; 2,4,6-triallyloxy-1,3,5-triazine; and any combination thereof. ### Claim 10 (depends on 7) The crosslinked polymer of claim 7, wherein the crosslinker with at least two acrylate groups is selected from the group consisting of ethylene glycol diacrylate; diethylene glycol diacrylate; triethylene glycol diacrylate; pentaerythritol triacrylate; pentaerythritol tetraacrylate; 1,1,1-trimethylolpropane triacrylate; 1,6-hexanediol diacrylate; and any combination thereof. ### Claim 11 (depends on 7) The crosslinked polymer of claim 7, wherein the crosslinker with at least two methacrylate groups is selected from the group consisting of ethylene glycol dimethacrylate; poly(ethylene glycol) dimethacrylate; 1,1,1-trimethylolpropane trimethacrylate; pentaerythritol trimethacrylate; pentaerythritol tetramethacrylate; and any combination thereof. ### Claim 12 (depends on 7) The crosslinked polymer of claim 7, wherein the crosslinker with at least two acrylamide groups is selected from the group consisting of N,N′-substituted bisacrylamide; N,N′-methylenebis(acrylamide); and any combination thereof. ### Claim 13 (depends on 7) The crosslinked polymer of claim 7, wherein the crosslinker with at least two methacrylamide groups is selected from the group consisting of N,N′-ethylenebis(2-methylacrylamide); 1,4-dimethacrylolpiperazine; N,N′-methylenebis(2-methylacrylamide); 1,6-hexamethylene bis(2-methylacrylamide); and any combination thereof. ### Claim 14 (depends on 7) The crosslinked polymer of claim 7, wherein the crosslinker with at least two groups from at least two of a vinyl group, an allyl group, an acrylate group, a methacrylate group, an acrylamide group, and a methacrylamide group is selected from the group consisting of an allyl acrylate; N,N-diallylacrylamide; N-vinyl-3(E)-ethylidene pyrrolidone; and any combination thereof. ### Claim 15 (depends on 1) The crosslinked polymer of claim 1, wherein the crosslinker is present in the range of about 0.01% to about 25% by weight of the reactants. ### Claim 16 A method comprising: introducing a treatment fluid into a subterranean formation, wherein the treatment fluid comprises a base fluid and a crosslinked polymer, the crosslinked polymer comprising: reactants of a first repeating unit, a second repeating unit, and a crosslinker that react to form the crosslinked polymer, wherein the first repeating unit is a sulfonic acid-containing monomer present from 1% to 45% by weight of the reactants, wherein the second repeating unit is selected from the group consisting of an N-vinyl amide-containing monomer, a terminal double bond-containing monomer, and any combination thereof, and is present from 55% to 99% by weight of the reactants, and wherein the crosslinker comprises at least two olefinic bonds. ### Claim 17 (depends on 16) The method of claim 16, wherein the crosslinker is present in the range of about 0.01% to about 25% by weight of the reactants. ### Claim 18 (depends on 16) The method of claim 16, wherein the crosslinker is present in the range of about 9% to about 25% by weight of the reactants. ### Claim 19 A system comprising: a tubular extending into a wellbore in a subterranean formation; and a pump fluidly coupled to the tubular, the tubular containing a treatment fluid comprising a base fluid and a crosslinked polymer, wherein the crosslinked polymer comprises: reactants of a first repeating unit, a second repeating unit, and a crosslinker that react to form the crosslinked polymer, wherein the first repeating unit is a sulfonic acid-containing monomer present from 1% to 45% by weight of the reactants, wherein the second repeating unit selected from the group consisting of an N-vinyl amide-containing monomer, a terminal double bond-containing monomer, and any combination thereof, and is present from 55% to 99% by weight of the reactants, and wherein the crosslinker comprises at least two olefinic bonds. ### Claim 20 (depends on 19) The system of claim 19, wherein the crosslinker is present in the range of about 0.01% to about 25% by weight of the reactants.