GB1234738A - Process for producing sulphur curable amorphous copolymers - Google Patents

Abstract

1,234,738. Amorphous copolymers. SUMITOMO CHEMICAL CO. Ltd. 12 Feb., 1939 [16 Feb., 1968], No. 7663/69. Heading C3P. Amorphous, linear, olefinic copolymers are prepared by contacting ethylene, and at least one C 3-20 α-olefin and optionally a polyene, with a catalyst system comprising (A) a reaction product of a vanadium compound containing at least one of alkoxy, halogen or acetyacetonyl with at least one phosphoric acid, phosphoric anhydride or ester of the formula (R<SP>1</SP>O) m PO(OH) 3-m wherein R<SP>1</SP> is C 1-20 hydrocarbon and m is 1 or 2 and (B) an aluminium hydride or organoaluminium compound of the formula AlR n X 3-n wherein R is C 1-20 hydrocarbon, X is -halogen or hydrogen and n is a positive number of not more than 3. The α- olefine may be propylene, butene-1, pentene-1, 3 - methyl - butene - 1, hexene - 1, 3 - methylpentene - 1, 4 - methyl - pentene - 1, heptene - 1, decene - 1 or vinylcyclopentane. The polyene may be 5 - methyl - 2,5 - norbornadiene, 5- methylene-, 5 - ethylidene-, 5 - isopropylidene-, 5 - isopropenyl-, 5 - (11 - butenyl)-, or 5 - (2<SP>1</SP>- butenyl) - norbornene, cyclooctadiene, vinylcyclohexane, 1,5,9 -cyclododecatriene, 6- methyl - 4,7,8,9 - tetrahydroindene, 2,21- dicyclopentenyl, trans - 1,2 - divinylcyclobutane, 1,4 - hexadiene, 1,6 - octadiene and 6 - methyl - 1,5 - heptadiene. Optionally amines, cyclic N compounds, acid amides, ethers, esters, ketones, aldehydes, compounds of phosphorous, arsenic, antimony or bismuth, chelating agents, halogen, sulphur, metal halides, oxygen, nitro compounds, nitroso compounds, P-oxide compounds, azo compounds, organic sulphides, disulphides, quinones, acid halides or hydrogen may be added as third component to the catalyst. In the examples: (1) ethylene and propylene or butene - 1 are polymerized in n-heptane in the presence of hydrogen using as catalyst ethylaluminium sesquichloride and the reaction produce of tri-n-amyl orthovanadate ester and di-n-butyl phosphate ester; (2) a terpolymer of ethylene, propylene and isoprene is prepared in n-heptane using as catalyst diethylaluminium chloride and the reaction product of tri-n-butylorthovanadate ester and phosphoric acid; (3) a terpolymer of ethylene, propylene and 1,4-hexadiene is prepared in n-heptane using the catalyst system in (1) above; (4) a terpolymer of ethylene, propylene and 5-ethylidene norbornene is prepared (a) in the presence of tetrachloroethylene, trihexyl aluminium and the reaction product of n-amyloxyvanadyl dichloride and di - n - butyl phosphate ester.; (b) in n-heptane in the presence-of ethylaluminium sesquichloride and the reaction product of VOCl 3 and di-n-butyl phosphate ester; and (c) in heptane in the presence of ethylaluminium sesquichloride and the reaction product of oxyvanadium diacetylacetonate and dibutyl phosphate ester.