# US 10,370,472 B2 · Ethylene copolymerisates having improved low-temperature properties and good oil resistance, vulcanizable mixtures made therefrom and vulcanizates > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,370,472 B2 - Document ID: US10370472B2 - Status: Granted - Kind: B2 - Application number: 15/568,837 - Filed: 2016-04-19 - Published: 2018-04-26 - Granted: 2019-08-06 - Earliest claimed: 2015-04-30 - Assignees: Arlanxeo Deutschland GmbH - Applicants: Arlanxeo Deutschland GmbH - Inventors: Susanna Lieber; Olaf Isenberg-Schulz; Ulrich Frenzel; Rainer Kalkofen - Web page: https://patentgrep.com/patent/US10370472B2 ## CPC - C08F 218/08: Vinyl acetate - C08F 210/02: Ethene - C08F 220/286: {and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate} - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract The present invention relates to copolymers of ethylene, vinyl esters of an alkyl carboxylic acid and other specific unsaturated carboxylic esters which have lower glass transition temperature than copolymers of ethylene and vinyl esters of an alkyl carboxylic acid, and also to production and use of these, to vulcanizable mixtures comprising the copolymers of the invention, to crosslinking of these and to vulcanizates and moldings obtainable therefrom. ## Claims ### Claim 1 Ethylene copolymers comprising: i) 10 to 69% by weight of copolymerized ethylene, ii) 30 to 84% by weight of copolymerized units of at least one vinyl ester of an alkyl carboxylic acid, and iii) 1 to 50% by weight of repeating units derived from at least one monomer of the general formula (I) CH2═C(R1)(COO(R2O)nR3) (I) in which R1 is hydrogen or methyl, R2 is respectively mutually independently a linear or branched C2 to C6-alkylene group, R3 is hydrogen, unsubstituted phenyl or phenyl having one or more C1-C3 alkyl substituents, a linear or branched C1-C8 alkyl group or —C(═O)R4, R4 is hydrogen or a linear or branched C1-C8 alkyl group, and n is a number from 2 to 30, where the quantities are based on the entirety of the monomers i) to iii). ### Claim 2 (depends on 1) The ethylene copolymers according to claim 1, where the vinyl esters of an alkyl carboxylic acid derived from an alkyl carboxylic acid group having from 2 to 13 C atoms and also from a vinyl alcohol group having from 2 to 5 C atoms. ### Claim 3 (depends on 1) The ethylene copolymers according to claim 1, comprising from 2 to 40% by weight. ### Claim 4 (depends on 1) The ethylene copolymers according to claim 1, where the moieties R2 are selected mutually independently from the group comprising ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-1,3-diyl, pentane-1,3-diyl, pentane-1,4-diyl, pentane-1,5-diyl, and 2-methylbutane-1,4-diyl. ### Claim 5 (depends on 1) The ethylene copolymers according to claim 1, where the moieties R3 are selected from the group consisting of H, CH3, CH2CH3, CH2CH2CH3, CH2CH2CH2CH3, CHO, COCH3, COCH2CH3, COCH2CH2CH3 and COCH2CH2CH2CH3. ### Claim 6 (depends on 1) The ethylene copolymers according to claim 1, wherein the copolymers comprise a total quantity of less than 25% by weight of one or more other copolymerized monomers (iv). ### Claim 7 (depends on 6) The ethylene copolymers according to claim 6, wherein the other monomers (iv) are selected from C1-C8-alkyl acrylates, C1-C8-alkyl methacrylates, acrylates containing epoxy groups, methacrylates containing epoxy groups, vinyl ketones, vinylaromatic compounds, conjugated dienes, α-monoolefins, vinyl monomers having a hydroxy group, chlorovinyl acetate, vinylidene fluoride, hexafluoropropene, vinylidene chloride, tetrafluoroethylene, tetrachloroethylene, vinyl chloride, unsaturated amide monomers and carbon monoxide. ### Claim 8 (depends on 1) A process for the production of the ethylene copolymers according to claim 1, the process comprising subjecting ethylene, the vinyl esters of an alkyl carboxylic acid, the monomers of the general formula (I), and optionally one or more other monomers (iv) to free-radical polymerization. ### Claim 9 (depends on 8) The process according to claim 8, wherein, after the polymerization reaction has been initiated, the monomers of the general formula (I) are added. ### Claim 10 (depends on 8) The process according to claim 8, wherein, after the polymerization reaction has been initiated, the monomers of the general formula (I) are added in the form of a mixture with the vinyl ester and/or with a solvent. ### Claim 11 (depends on 1) Vulcanizable mixtures comprising the ethylene copolymers according to claim 1. ### Claim 12 (depends on 11) A process for the production of vulcanizates made of vulcanizable mixtures according to claim 11, the process comprising crosslinking the ethylene copolymers by means of diamines, polyacids, anhydrides of a polyacid, compounds comprising peroxide groups and/or high-energy radiation. ### Claim 13 (depends on 11) Vulcanizates obtained from the vulcanizable mixtures according to claim 11. ### Claim 14 (depends on 11) Articles of manufacture comprising the vulcanizable mixtures according to claim 11, wherein the articles of manufacture comprise unfoamed or foamed mouldings, cable conduction layers, cable sheathing, gaskets, transport belts, bellows, hoses, cylinder-head-cover gaskets and O-rings. ### Claim 15 (depends on 1) Plastics or rubbers comprising the ethylene copolymers according to claim 1 as a blend component. ### Claim 16 (depends on 1) Non-volatile plasticizer and/or impact modifier for plastics comprising the ethylene copolymers according to claim 1. ### Claim 17 (depends on 1) The ethylene copolymers according to claim 1, wherein the copolymers comprise: 15 to 59% by weight, of the copolymerized ethylene, 2 to 40% by weight of repeating units derived from the monomers of the general formula (I), and 35 to 80% by weight, of the copolymerized units of the at least one vinyl ester of an alkyl carboxylic acid wherein the amounts are each based on the entirety of the monomers i) to iii). ### Claim 18 (depends on 17) The ethylene copolymers according to claim 17, wherein the copolymers comprise 6 to 20% by weight, of repeating units derived from monomers of the general formula (I), based on the entirety of the monomers i) to iii).