# US 4,397,763 A · Catalyst and process of polymerization of alpha-monoolefins > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,397,763 A - Document ID: US4397763A - Status: Granted - Kind: A - Application number: 06/348,380 - Filed: 1982-02-12 - Granted: 1983-08-09 - Earliest claimed: 1977-12-13 - Assignees: Phillips Petroleum Company - Inventors: M. Bruce Welch - Web page: https://patentgrep.com/patent/US4397763A ## CPC - C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract Polymerization of alpha-monoolefins employing a catalyst comprising (A) a milled admixture of a titanium halide, anhydrous magnesium or manganous chloride, optionally a Lewis base, and (B) a dihydrocarbylaluminum halide, a dihydrocarbylaluminum hydride, and an ether-alcohol. ## Claims ### Claim 1 A catalyst system consisting essentially of (A) a milled admixture of effective ratios of a titanium halide, anhydrous magnesium or manganous chloride, optionally, with a Lewis base, and (B) effective ratios of at least one dihydrocarbylaluminum halide, at least one dihydrocarbylaluminum hydride, and an ether-alcohol, employing catalytically effective ratios of said (A):(B). ### Claim 2 (depends on 1) The catalyst system according to claim 1 wherein said titanium halide is a di-, tri- or tetrahalide of titanium. ### Claim 3 (depends on 2) The catalyst system according to claim 2 wherein said titanium halide is represented by TiX.sub.4-n R'.sub.n, wherein X is a halogen and is bromine, chlorine, or iodine, R' is an alkyl, cycloalkyl, cycloalkoxy, aryl, aryloxy, or alkoxy radical of 2 to 8 carbon atoms, and n is zero or an integer of 1, 2 or 3. ### Claim 4 (depends on 3) The catalyst system according to claim 3 wherein said titanium halide is titanium tetrachloride, trichloro-n-octyl titanium, dibromodimethyl titanium, iodotriethoxy titanium, trichlorophenoxytitanium, tribromocyclohexyltitanium, trichlorohexyloxytitanium, or mixtures thereof. ### Claim 5 (depends on 2) The catalyst system according to claim 2 wherein said Lewis base is used and is selected from amine, amide, ether, carboxylic acid, ester, ketone, nitrile, or phosphine. ### Claim 6 (depends on 5) The catalyst system according to claim 5 wherein said Lewis base is an aliphatic carboxylic acid, aromatic carboxylic acid, alkylester of aliphatic carboxylic acid, alkylester of aromatic carboxylic acid, aliphatic ether, aromatic ether, aliphatic ketone, aromatic ketone, aliphatic aldehyde, aliphatic alcohol, aromatic alcohol, aliphatic acid halide, aliphatic nitrile, aromatic nitrile, aliphatic amine, aromatic amine, aliphatic phosphine, aromatic phosphine, amide, or a mixture thereof. ### Claim 7 (depends on 6) The catalyst system according to claim 6 wherein said Lewis base is an ester, wherein said ester is an ester of an aliphatic alcohol with an aromatic carboxylic acid represented by the formula: ##STR7## wherein R.sup.3 is an alkyl group of 1 to 4 carbon atoms, R.sup.4 is a para-substituent on the ring and is a monovalent radical selected from --F, --Cl, --Br, --I, --OH, --OR.sup.2, --OOCR.sup.2, --SH, --NH.sub.2, --NHR.sup.2, --NR.sub.2.sup.2, --NHCOR.sup.2, --NR.sup.2 COR.sup.2, NO.sub.2, --CN, --CHO, --COR.sup.2, --COOR.sup.2, --CONH.sub.2, CONR.sub.2.sup.2, --SO.sub.2 R.sup.2, --CX'.sub.3 wherein X'=F, Cl, Br, I or hydrogen and wherein R.sup.2 is a hydrocarbon radical selected from alkyl, cycloalkyl, and aryl of up to 12 carbon atoms. ### Claim 8 (depends on 7) The catalyst system according to claim 7 wherein said Lewis base is triethylamine, triphenylamine, diphenylamine, acetamide, butyramide, acetanilide, acetic acid, benzoic acid, dimethyl ether, diethyl ether, ethyl butylether, diphenyl ether, acetone, methyl n-butyl ketone, acetophenone, acetonitrile, isobutyronitrile, benzonitrile, tributylphosphine propyl-(n-pentyl)phosphine, triphenylphosphine, ethyl benzoate, ethyl anisate (p-methoxybenzoate), ethyl p-dimethylaminobenzoate, ethyl p-fluorobenzoate, ethyl p-cyanobenzoate, methyl benzoate, isopropyl p-diethylaminobenzoate, butyl p-fluorobenzoate, n-propyl p-cyanobenzoate, ethyl p-trifluoromethylbenzoate, methyl p-hydroxybenzoate, ethyl p-methoxycarbonylbenzoate, methyl p-acetylbenzoate, isopropyl p-formylbenzoate, methyl p-nitrobenzoate, ethyl p-carbamoylbenzoate, methyl p-mercaptobenzoate, methyl-p-chlorobenzoate, n-butyl-p-bromobenzoate, isopropyl-p-iodobenzoate, ethyl-p-aminobenzoate, n-propyl-p-methylaminobenzoate, methyl-p-acetamidobenzoate, n-butyl-p-formylbenzoate, dimethyl terephthalate, ethyl-p-(N,N-dimethylcarbamoyl)benzoate, n-propyl-p-(methylsulfonyl)benzoate, methyl-p-trifluoromethylbenzoate, ethyl-p-acetoxybenzoate, or mixtures thereof. ### Claim 9 (depends on 8) The catalyst system according to claim 8 wherein said Lewis base is ethyl anisate or ethylbenzoate. ### Claim 10 (depends on 1) The catalyst system according to claim 1 wherein said (B) dihydrocarbylaluminum compounds are represented by AlR.sup.5.sub.2 X', wherein R.sup.5 is an alkyl radical of 1 to 12 carbon atoms, and X' is fluorine, chlorine, bromine, iodine or hydrogen. ### Claim 11 (depends on 10) The catalyst system according to claim 10 wherein said dihydrocarbylaluminum compounds are selected from the group consisting of dimethylaluminum bromide, diethylaluminum chloride, diisopropylaluminum iodide, diisobutylaluminum hydride, di-(2-ethylhexyl)aluminum chloride, di-n-dodecylaluminum hydride, such that said (B) component includes at least one halide and at least one hydride. ### Claim 12 (depends on 1) The catalyst system according to claim 1 employing a molar ratio of about 0.5:1 to 4:1 titanium halide:Lewis base in said component (A). ### Claim 13 (depends on 1) The catalyst system according to claim 1 wherein said ether-alcohol is a monoalkyl ether of ethylene glycol or diethylene glycol, wherein the alkyl groups each contains 1 to 4 carbon atoms. ### Claim 14 (depends on 13) The catalyst system according to claim 13 wherein said ether-alcohol is 2-methoxyethanol, 2-ethoxyethanol, 2-n-butoxyethanol, 2-(2-methoxyethoxy) ethanol, 2-(2-ethoxyethoxy) ethanol, 2-(2-n-butoxyethoxy)ethanol, and mixtures thereof. ### Claim 15 (depends on 1) The catalyst system according to claim 1 employing an atom ratio of aluminum in the dihydrocarbylaluminum hydride plus the dihydrocarbylaluminum halide to the titanium of about 10:1 to 250:1; and a mole ratio of dihydrocarbylaluminum hydride plus dihydrocarbylaluminum halide to the ether-alcohol of about 0.5:1 to 10:1. ### Claim 16 (depends on 15) The catalyst system according to claim 15 employing an atom ratio of aluminum in the dihydrocarbylaluminum hydride plus the dihydrocarbylaluminum halide to the titanium of about 25:1 to 150:1; and a mole ratio of dihydrocarbylaluminum hydride plus dihydrocarbylaluminum halide to the ether-alcohol of about 1:1 to 5:1. ### Claim 17 (depends on 16) The catalyst system according to claim 16 wherein said ether-alcohol is 2-(2-n-butoxyethoxy)ethanol. ### Claim 18 (depends on 16) The catalyst system according to claim 16 wherein said manganous or magnesium chloride is magnesium chloride, said catalyst includes said Lewis base, said Lewis base is an ester and is ethyl anisate, said titanium halide is titanium tetrachloride, said dihydrocarbylaluminum halide is diethylaluminum chloride, said dihydrocarbylaluminum hydride is diisobutylaluminum hydride, and said ether-alcohol is diethyleneglycolmonobutyl ether. ### Claim 19 (depends on 16) The catalyst system according to claim 16 wherein said manganous or magnesium chloride is magnesium chloride, said catalyst includes said Lewis base and Lewis base is an ester and is ethylbenzoate, and said titanium halide is titanium tetrachloride, said ether-alcohol is diethyleneglycol monobutyl ether, said dihydrocarbyl chloride is diethylaluminum chloride, and said dihydrocarbyl aluminum hydride is diisobutylaluminum hydride. ### Claim 20 (depends on 1) A catalyst according to claim 1 consisting essentially of (A) a milled admixture of titanium tetrachloride, magnesium chloride, and an electron donor selected from ethyl benzoate and ethyl anisate, and (B) diethylaluminum chloride, diisobutylaluminum hydride, and butyl Carbitol.