# US 11,111,374 B2 · Multivalent cation-containing copolymer, process for production thereof and use thereof to treating aqueous dispersions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,111,374 B2 - Document ID: US11111374B2 - Status: Granted - Kind: B2 - Application number: 15/776,120 - Filed: 2016-11-14 - Published: 2018-11-15 - Granted: 2021-09-07 - Earliest claimed: 2015-11-16 - Assignees: BASF SE - Applicants: BASF SE - Inventors: Stephen John Adkins; Holger Misslitz; Mitchell Louis Catling - Web page: https://patentgrep.com/patent/US11111374B2 ## CPC - C02F 1/56: Macromolecular compounds - C02F 11/14: with addition of chemical agents - C02F 11/147: using organic substances (C02F11/148 takes precedence) - C08F 220/06: Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof - C08F 220/56: Acrylamide; Methacrylamide - C08L 33/26: Homopolymers or copolymers of acrylamide or methacrylamide - C09K 8/035: Organic additives - C02F 2103/10: from quarries or from mining activities - C08F 220/58: containing oxygen in addition to the carbonamido oxygen {, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine} - C08F 220/585: {and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]} - C08F 222/04: Anhydrides, e.g. cyclic anhydrides - C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes) - 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) - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE ## Abstract There is disclosed a multivalent cation containing copolymer derived from one or more ethylenically unsaturated acids. The copolymer has the following characteristics: (a) an intrinsic viscosity of at least about 3 dl/g when measured in 1 M Na Cl solution at 25° C.; (b) the copolymer is derived from a monomer mixture comprising an ethylenically unsaturated acid and at least one comonomer, the ethylenically unsaturated acid present in an amount in the range of from about % to about 65% by weight; and (c) a residual comonomer content is less than 1000 ppm when the comonomer is an acrylamide. The copolymer, inter alia, is useful as a flocculant for treating an aqueous slurry comprising particulate material, preferably tailings from a mining operation. ## Claims ### Claim 1 A multivalent cation containing copolymer, which is water-soluble and in particulate form, wherein the multivalent cation containing copolymer is derived from one or more ethylenically unsaturated acids, the copolymer having the following characteristics: (a) an intrinsic viscosity of at least about 3 dl/g when measured in 1 M NaCl solution at 25° C.; (b) the copolymer is a reaction product of a monomer mixture comprising an ethylenically unsaturated acid in an amount in the range of from about 5% to about 65% by weight and at least one comonomer selected from the group consisting of acrylamide, methacrylamide and any mixture thereof; and (c) a residual comonomer content is less than 1000 ppm when the comonomer is an acrylamide, wherein the multivalent cation containing copolymer has a gel content measurement of less than 50% gel. ### Claim 2 (depends on 1) The multivalent cation containing copolymer of claim 1, in the form of a calcium copolymer. ### Claim 3 (depends on 1) The multivalent cation containing copolymer of claim 1, in the form of a magnesium copolymer. ### Claim 4 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the at least one comonomer is acrylamide. ### Claim 5 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the ethylenically unsaturated acid is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, acrylamido tertiary butyl sulfonic acid (ATBS) and any mixture of two or more of these. ### Claim 6 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the ethylenically unsaturated acid is selected from the group consisting of acrylic acid, methacrylic acid, acrylamido tertiary butyl sulfonic acid (ATBS) and any mixture of two or more of these. ### Claim 7 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the ethylenically unsaturated acid is acrylic acid. ### Claim 8 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the ethylenically unsaturated acid is present in an amount in the range of from about 15% to about 65% by weight. ### Claim 9 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the ethylenically unsaturated acid is present in an amount in the range of from about 20% to about 65% by weight. ### Claim 10 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the ethylenically unsaturated acid is present in an amount in the range of from about 35% to about 65% by weight. ### Claim 11 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the intrinsic viscosity is in the range of from about 4 to about 25 dl/g when measured in 1 M NaCl solution at 25° C. ### Claim 12 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the intrinsic viscosity is in the range of from about 4 to about 20 dl/g when measured in 1 M NaCl solution at 25° C. ### Claim 13 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the intrinsic viscosity is in the range of from about 5 to about 15 dl/g when measured in 1 M NaCl solution at 25° C. ### Claim 14 (depends on 1) The multivalent cation containing copolymer of claim 1, in solid form. ### Claim 15 (depends on 1) The multivalent cation containing copolymer of claim 1, in substantially a spherical particulate form. ### Claim 16 (depends on 1) The multivalent cation containing copolymer of claim 1, in powder form. ### Claim 17 (depends on 1) The multivalent cation containing copolymer of claim 1, in bead form. ### Claim 18 (depends on 1) The multivalent cation containing copolymer of claim 1, in the form of a reverse-phase emulsion. ### Claim 19 (depends on 1) The multivalent cation containing copolymer of claim 1, in the form of a reverse-phase dispersion. ### Claim 20 (depends on 1) The multivalent cation containing copolymer of claim 1, in the form of an aqueous solution. ### Claim 21 (depends on 1) The multivalent cation containing copolymer of claim 1, in the form of an aqueous dispersion. ### Claim 22 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the residual comonomer (ACM) content is less than about 500 ppm when the comonomer is an acrylamide. ### Claim 23 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the residual comonomer (ACM) content is in the range of from about 300 ppm to about 500 ppm when the comonomer is an acrylamide. ### Claim 24 (depends on 1) The multivalent cation containing copolymer of claim 1, in a substantially pure form. ### Claim 25 (depends on 1) The multivalent cation containing copolymer of claim 1, in isolated form. ### Claim 26 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the copolymer has an anionic content in the range of from about 20 to about 65 weight percent. ### Claim 27 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the copolymer has an anionic content in the range of from about 25 to about 65 weight percent. ### Claim 28 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the copolymer has an anionic content in the range of from about 30 to about 65 weight percent. ### Claim 29 (depends on 1) The multivalent cation containing copolymer of claim 1, wherein the copolymer has an anionic content in the range of from about 40 to about 65 weight percent. ### Claim 30 (depends on 1) A process for treating an aqueous slurry comprising particulate material, the process comprising contacting the aqueous slurry with the multivalent cation containing copolymer of claim 1. ### Claim 31 (depends on 30) The process of claim 30, further comprising thickening the aqueous slurry. ### Claim 32 (depends on 30) The process of claim 30, further comprising sedimentation of the aqueous slurry. ### Claim 33 (depends on 30) The process of claim 30, further comprising dewatering the aqueous slurry. ### Claim 34 (depends on 30) The process of claim 30, further comprising compaction and/or consolidation of the aqueous slurry. ### Claim 35 (depends on 30) The process of claim 30, further comprising flocculation of the aqueous slurry. ### Claim 36 (depends on 30) The process of claim 30, further comprising coagulation of the aqueous slurry. ### Claim 37 (depends on 30) The process of claim 30, wherein the aqueous slurry comprises tailings. ### Claim 38 (depends on 30) The process of claim 30, wherein the aqueous slurry comprises mature fine tailings (MFT). ### Claim 39 (depends on 30) The process of claim 30, wherein the aqueous slurry comprises fluid fine tailings (FFT). ### Claim 40 (depends on 30) The process of claim 30, wherein the aqueous slurry comprises thin fine tailings (TFT). ### Claim 41 (depends on 30) The process defined in claim 30, wherein the aqueous slurry comprises whole tailings (WT). ### Claim 42 (depends on 1) A process for treating an aqueous slurry comprising particulate material, the process comprising contacting the aqueous slurry with an aqueous solution comprising the multivalent cation containing copolymer of claim 1. ### Claim 43 (depends on 1) A process for producing the multivalent cation containing copolymer of claim 1, comprising: contacting a multivalent cation containing ethylenically unsaturated acid and at least one comonomer to produce a monomer mixture comprising the multivalent cation containing ethylenically unsaturated acid present in an amount in the range of from about 5% to about 65% by weight; and contacting the monomer mixture with a thermal initiator to cause the multivalent cation containing ethylenically unsaturated acid and the at least one comonomer to react to produce the multivalent cation containing copolymer. ### Claim 44 (depends on 43) The process of claim 43, wherein the multivalent cation containing ethylenically unsaturated acid is a multivalent cation containing diacrylate. ### Claim 45 (depends on 43) The process of claim 43, wherein the thermal initiator comprises an azo compound. ### Claim 46 (depends on 43) The process of claim 43, wherein the thermal initiator is selected from the group consisting of azobisisobutyronitrile (AIBN), 4,4′-azobis-(4-cyanovalereic acid) (ACVA) and any mixture thereof. ### Claim 47 (depends on 43) The process of claim 43, further comprising contacting the monomer mixture with a redox initiator comprising a reducing compound and an oxidizing compound. ### Claim 48 (depends on 47) The process of claim 47, wherein the reducing compound is selected from the group consisting of sodium sulphite, sulphur dioxide, sodium metabisulphite and any mixture thereof. ### Claim 49 (depends on 47) The process of claim 47, wherein the oxidizing compound is selected from the group consisting of ammonium persulphate, tertiary butyl hydroperoxide and any mixture thereof.