# US 10,870,747 B2 · Method for producing acrylate rubber at reduced emulsifier concentration > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,870,747 B2 - Document ID: US10870747B2 - Status: Granted - Kind: B2 - Application number: 15/763,953 - Filed: 2016-09-23 - Published: 2019-02-21 - Granted: 2020-12-22 - Earliest claimed: 2015-09-30 - Assignees: Ineos Styrolution Group GmbH - Applicants: Ineos Styrolution Group GmbH - Inventors: Wolfgang Fischer; Tobias Schulz - Web page: https://patentgrep.com/patent/US10870747B2 ## CPC - C08L 25/12: with unsaturated nitriles - C08F 2/002: {Scale prevention in a polymerisation reactor or its auxiliary parts} - C08F 2/26: anionic - C08F 6/14: Treatment of polymer emulsions {(C08F6/001, C08F6/006, C08F6/008, C08F6/02, C08F6/04 take precedence)} - C08F 265/04: on to polymers of esters - C08J 5/18: Manufacture of films or sheets - C08L 51/003: {grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C08L51/04, C08L51/06 take precedence)} - C09D 5/022: {Emulsions, e.g. oil in water} - C09D 5/027: {Dispersing agents (anti-settling agents C09D7/45)} - C09D 125/12: with unsaturated nitriles - C08J 2325/12: with unsaturated nitriles - C08J 2351/00: Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers - C08J 2451/00: Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers - C08L 2201/52: Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C - C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure - C08L 2205/03: containing three or more polymers in a blend - C08L 2207/53: Core-shell polymer - C08L 2312/00: Crosslinking - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - 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) ## Abstract Method for producing a thermoplastic moulding compound containing: up to 40 wt. % of a graft copolymer A, containing 50-70 wt. % graft base A1 from an acrylic ester polymer and 30-50 wt. % of a graft shell A2, and 0-90 wt. % of a hard matrix B, wherein the reaction for producing the graft copolymer A is carried out in the presence of 0.01 to 4 times the molar amount of sodium carbonate, relative to the molar amount of initiator, wherein the reaction for producing copolymer A is carried out in the presence of 0.1 to 1 wt. % of an emulsifier relative to the amount of the respective monomers used, and wherein during the polymerisation reaction, during the post-polymerisation and/or after the polymerisation reaction, water or an aqueous alkali solution are added to the reaction mixture for producing the graft copolymer A. ## Claims ### Claim 1 A process for producing a thermoplastic molding compound comprising: (a) providing 10% to 40% by weight of at least one graft copolymer A comprising: 50% to 70% by weight, based on A, of a graft base A1 made of an elastomeric, crosslinked acrylate polymer, and 30% to 50% by weight, based on A, of a graft shell A2 made of a vinylaromatic monomer and of a polar, copolymerizable, ethylenically unsaturated monomer, in a ratio by weight of 80:20 to 65:35, 50% to 90% by weight of a hard matrix B made of one or more copolymers of styrene, α-methylstyrene, acrylonitrile, methyl methacrylate and/or phenylmaleimide, 0% to 40% by weight of at least one further graft copolymer C which differs from the graft copolymer A and which has a weight average particle diameter in the range from 200 to 800 nm, comprising: 50% to 80% by weight, based on C, of an elastomeric crosslinked acrylate polymer C1 which differs from A1, 2.5% to 25% by weight, based on C, of a first graft shell C2 made of a vinylaromatic monomer and of 10% to 45% by weight, based on C, of a second graft shell C3 made of a mixture of a vinylaromatic monomer C31 and of a polar, copolymerizable, ethylenically unsaturated monomer C32 in a weight ratio of C31 to C32 of 90:10 to 60:40; and 0% to 15% by weight of one or more additives D, and then (b) blending the graft copolymer A, the hard matrix B and optionally the graft copolymer C and/or the additives, wherein the sum total of A and B, and optionally C and D, is 100% by weight, and wherein the graft copolymer A, the hard matrix B and the optional graft copolymer C are produced by polymerization reactions, wherein the polymerization reactions for producing the graft copolymer A, the graft base A1, and the graft shell A2, and the polymerization reactions for producing the optional graft copolymer C, the elastomeric crosslinked acrylate polymer C1, the first graft shell C2, and the second graft shell C3, are emulsion polymerization reactions, wherein the reaction for production of the graft copolymer A and the reaction for production of the graft copolymer C is conducted in the presence of 0.01 to 4 times the molar amount of sodium carbonate, based on the total molar amount of initiator used in the production of the graft base and graft shell; and wherein the reaction for production of the graft copolymer A and the reaction for production of the graft copolymer C is conducted in the presence of 0.1% to 1% by weight of an emulsifier based on the amount of the monomers used in each case; and wherein water or an aqueous alkaline solution is added to the reaction mixture for production of the graft copolymer A and the graft copolymer C during the polymerization reaction, during a postpolymerization and/or after the polymerization reaction. ### Claim 2 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein water or an aqueous alkaline solution is added after the addition of monomer has ended. ### Claim 3 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein a product of the polymerization reaction for the production of the graft base A1 and the elastomeric crosslinked acrylate polymer C1 is obtained as an polymer latex L(A1) and L(C1), respectively, and wherein water or an aqueous alkaline solution is added in an amount of 1% to 50% by weight, based on the polymer latex L(A1) or L(C1) obtained from the emulsion polymerization reaction before the next step of the production process is conducted. ### Claim 4 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein the aqueous alkaline solution is an aqueous solution of inorganic carbonates, hydrogencarbonates or hydroxides, and mixtures thereof. ### Claim 5 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein the aqueous alkaline solution is an aqueous solution of Na2CO3, NaHCO3, NaOH and/or KOH having a concentration of 0.01% to 1% by weight. ### Claim 6 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein the emulsifier used is a secondary alkylsulfonate. ### Claim 7 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein the graft base A1 is composed of 55% to 65% by weight, based on A, of acrylate polymer particles having a weight average particle size of 50 to 120 nm and the graft shell A2 is composed of 35% to 45% by weight, based on A, of styrene and acrylonitrile. ### Claim 8 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein the particle size distribution factor Q of the graft base A1 is 0.01 to 0.5. ### Claim 9 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein the weight average particle size of the particles of component A after the graft reaction is in the range from 70 to 150 nm. ### Claim 10 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein the sodium carbonate is used in the production of the graft copolymers A and/or C in an amount of 0.01 to 2.5 mol based on the sum total of the molar amounts of the amount of initiator used in the graft base and graft shell. ### Claim 11 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein the molding compound comprises 1% to 40% by weight of at least one graft copolymer C which differs from the graft copolymer A. ### Claim 12 A process for producing a thermoplastic molding compound comprising: (a) providing 50% to 90% by weight of a hard matrix B made of one or more copolymers of styrene, α-methylstyrene, acrylonitrile, methyl methacrylate and/or phenylmaleimide, 10% to 50% by weight of at least one graft copolymer C with a weight average particle size in the range from 200 to 800 nm, comprising: 50% to 80% by weight, based on C, of an elastomeric crosslinked acrylate polymer C1, 2.5% to 25% by weight, based on C, of a first graft shell C2 made of a vinylaromatic monomer and of 10% to 45% by weight, based on C, of a second graft shell C3 made of a mixture of a vinylaromatic monomer C31 and of a polar, copolymerizable, ethylenically unsaturated monomer C32, where the ratio by weight of C31 to C32 is 90:10 to 60:40; and 0% to 15% by weight of one or more additives D, and then (b) blending the hard matrix B and the graft copolymer C and/or the additives, wherein the sum total of B and C, and optionally D, is 100% by weight, and wherein the hard matrix B and the graft copolymer C are produced by polymerization reactions, wherein the polymerization reactions for producing the graft copolymer C, the elastomeric crosslinked acrylate polymer C1, the first graft shell C2, and the second graft shell C3, are emulsion polymerization reactions, wherein the reaction for production of the graft copolymer C is conducted in the presence of 0.01 to 4 times the molar amount of sodium carbonate, based on the total molar amount of initiator used in the production of the graft base and graft shell; and wherein the reaction for production of the graft copolymer C is conducted in the presence of 0.1%-1% by weight of an emulsifier based on the amount of the monomers used in each case; and wherein water or an aqueous alkaline solution is added to the reaction mixture for production of the graft copolymer C during the polymerization reaction, during a postpolymerization and/or after the polymerization reaction. ### Claim 13 (depends on 12) The process for producing a thermoplastic molding compound as claimed in claim 12, where the coagulate formation of the graft shell of component C is in a range from 0.01% to 0.5% by weight, based on the total weight of the graft copolymer C. ### Claim 14 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein the initiator used in the production of the graft base and graft shell is PPS. ### Claim 15 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein the reaction for production of the graft copolymer A and the reaction for production of the graft copolymer C is conducted in the presence of an alkali metal alkyl sulfonate as emulsifier. ### Claim 16 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein the particle size distribution factor Q of the graft base A1 is 0.1 to 0.4. ### Claim 17 (depends on 1) The process for producing a thermoplastic molding compound as claimed in claim 1, wherein the sodium carbonate is used in the production of the graft copolymers A and/or C in an amount of 0.1 to 2.5 mol, based on the sum total of the molar amounts of the amount of initiator used in the graft base and graft shell. ### Claim 18 (depends on 12) The process for producing a thermoplastic molding compound as claimed in claim 12, where 0.1% to 5% by weight of one or more additives D is added. ### Claim 19 (depends on 12) The process for producing a thermoplastic molding compound as claimed in claim 12, wherein the initiator used in the production of the graft base and graft shell is PPS. ### Claim 20 (depends on 12) The process for producing a thermoplastic molding compound as claimed in claim 12, wherein the reaction for production of the graft copolymer A and the reaction for production of the graft copolymer C is conducted in the presence of an alkali metal alkyl sulfonate as emulsifier.