Patent GB-832083-A (GB)
Title: Process and catalyst for polymerization of polymerizable hydrocarbons
IPC: C08F4/12
Filed: 1956-12-28
Abstract: Polymerizable hydrocarbons are polymerized using a catalyst comprising (1) a halide of titanium, zirconium, hafnium or germanium, (2) a peroxide of formula R1OOR1, where R1 is hydrogen or an alkyl, aralkyl, cycloalkyl, acyl, alkyne or aryl radical, and (3) a component which is (a) an organometal halide of formula RxMXy, where R is an alkyl, cycloalkyl, or aryl radical, M is aluminium, gallium, indium, thallium or beryllium, X is a halogen, and the sum of x and y is equal to the valency of the metal M, or (b) a mixture of an organic halide and elemental sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, zinc, cadmium, mercury, aluminium, gallium, indium or thallium, or (c) a complex hydride of formula M1M11Hm, where M1 is an alkali metal, M11 is aluminium, gallium, indium or thallium, and m is equal to the sum of the valencies of M1 and M11. The metal halide may be titanium di-, tri- or tetra-, -chloride, -bromide, -iodide or -fluoride, and similar compounds of zirconium, hafnium and germanium.  The peroxide may be hydrogen peroxide, methyl hydroperoxide, isopropyl hydroperoxide, tert. - butyl hydroperoxide, cyclohexyl hydroperoxide, a ,a -dimethyl-p-isopropylbenzyl hydroperoxide, dimethyl peroxide, di-n-propyl peroxide, di-tert.-butyl peroxide, methyl ethyl peroxide, 3-methyl-3-hydroperoxy-1-butyne, 2-methyl-3-butynyl hydroperoxide, bis-(2-methyl-3-butynyl) peroxide, dibenzoyl peroxide, diacetyl peroxide, dipropionyl peroxide, a ,a -dinaphthyl peroxide, peroxyformic acid, peroxyacetic acid, peroxybutyric acid, peroxybenzoic acid, peroxycinnamic acid or diperoxyterephthalic acid. The organometal halide may be CH3AlCl2, (CH3)2-AlCl, C2H5AlCl2, (C2H5)2AlCl, (C4H9)2AlBr, C8H17AlI2, (C3H7)2GaF, dicyclohexyl gallium chloride, phenyl gallium dibromide, C20H41-GaBr2, (C14H29)2GaF, diphenyl indium chloride, C8H17InF2, cyclohexyl indium dibromide, C17H35BeI, CH3BeBr, 3-methylcyclohexylaluminium dichloride, 2-cyclohexylethyl gallium dichloride, p-tolyl beryllium iodide, di-(3-phenyl-1-methylpropyl) indium fluoride, or 2-(3-isopropylcyclohexyl)-ethyl thallium dibromide.  The organic halide may be ethyl bromide, propyl chloride, butyl iodide, pentyl fluoride, 1,2-dibromoethane, 1,3-dibromopropane, 1,2,3-tribromopropane, 1,2,3-trichloropropane, 1,1-difluoroethane, 1,4-diiodobutane, 1,3-dichlorocyclohexane, benzyl chloride, 1,4-dichlorobenzene, 1-bromodecane, 1-chloro-dodecane, 2-chloro-octane, 2-chloro-4-methyloctane, cyclopentyl chloride, 1-chloro-3-phenylpropane, 1-bromo - 3 - phenylhexane, cyclohexyl chloride, phenyl chloride, allyl bromide, or propargyl chloride.  The hydride may be lithium aluminium hydride, potassium aluminium hydride, sodium aluminium hydride, caesium aluminium hydride, sodium gallium hydride, lithium thallium hydride, lithium indium hydride, lithium gallium hydride or rubidium aluminium hydride.  The catalyst may be used to polymerize ethylene, propylene, 1-butene, 1-hexene, 1-octene, isobutylene, butene-2, pentene-2, hexene - 2, heptene - 2, 2 - methylbutene - 1, 2-methylhexene-1, 2-ethylheptene-1, 1,5-hexadiene, 1,4-pentadiene, 1,4,7-octatriene, cyclohexene, styrene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3 - dimethyl - 1,3 - butadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-methyl-3-ethyl-1,3-pentadiene, and 2-phenyl butadiene.  The polymerization is carried out at -250 DEG  to 500 DEG  F., and at a pressure from atmospheric to 1000 p.s.i.g. in the presence of an inert organic liquid diluent.  In examples, polyethylene of molecular weights of 38,575 and 35,964 are obtained using as catalysts titanium tetrachloride benzoyl peroxide, and a mixture of diethylaluminium chloride and ethylaluminium dichloride.ALSO:Polymerizable hydrocarbons are polymerized using a catalyst comprising (1) a halide of titanium, zirconium, hafnium or germanium, (2) a peroxide of formula R1OOR1, where R1 is hydrogen or an alkyl, aralkyl, cycloalkyl, acyl, alkyne or aryl radical, and (3) a component which is (a) an organometal halide of formula RxMXy, where R is an alkyl, cycloalkyl, or aryl radical, M is aluminium, gallium, indium, thallium or beryllium, X is a halogen, and the sum of x and y is equal to the valency of the metal M, or (b) a mixture of an organic halide and elemental sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, zinc, cadmium, mercury, aluminium, gallium, indium or thallium, or (c) a complex hydride of formula M1M11Hm, where M1 is an alkali metal, M11 is aluminium, gallium, indium or thallium, and m is equal to the sum of the valencies of M1 and M11. The metal halide may be titanium di-, tri- or tetra-, -chloride, -bromide, -iodide or -fluoride, and similar compounds of zirconium, hafnium and germanium.  The peroxide may be hydrogen peroxide, methyl hydroperoxide, isopropyl hydroperoxide, tert.-butyl hydroperoxide, cyclohexyl hydroperoxide, a ,a -dimethyl-p - isopropylbenzyl hydroperoxide, dimethyl peroxide, di-n-propyl peroxide, di-tert.-butyl peroxide, methyl ethyl peroxide, 3-methyl-3-hydroperoxy - 1 - butyne, 2 - methyl - 3 - butynyl hydroperoxide, bis-(2-methyl-3-butynyl) peroxide, dibenzoyl peroxide, diacetyl peroxide, dipropionyl peroxide, a ,a -dinaphthyl peroxide, peroxyformic acid, peroxyacetic acid, peroxybutyric acid, peroxybenzoic acid, peroxycinnamic acid or diperoxyterephthalic acid. The organometal halide may be CH3AlCl2, (CH3)2AlCl, C2H5AlCl2, (C2H5)2AlCl, (C4H9)2AlBr, C8H17AlI2, (C3H7)2GaF, dicyclohexyl gallium chloride, phenyl gallium dibromide, C20H41GaBr2, (C14H29)2GaF, diphenyl indium chloride, C8H17InF2, cyclohexyl indium dibromide, C17H35BeI, CH3BeBr, 3-methylcyclohexylaluminium dichloride, 2-cyclohexylethyl gallium dichloride, p-tolyl beryllium iodide, di - (3 - phenyl - 1 - methylpropyl) - indium fluoride, or 2-(3-isopropylcyclohexyl)-ethyl thallium dibromide. The organic halide may be ethyl bromide, propyl chloride, butyl iodide, pentyl fluoride, 1,2-dibromoethane, 1,3-dibromopropane, 1,2,3-tribromopropane, 1,2,3-trichloropropane, 1,1-difluoroethane, 1,4-diiodobutane, 1,3-dichlorocyclohexane, benzyl chloride, 1,4-dichlorobenzene, 1-bromodecane, 1-chlorododecane, 2-chloro-octane, 2-chloro-4-methyloctane, cyclopentyl chloride, 1-chloro-3-phenylpropane, 1-bromo-3-phenylhexane, cyclohexyl chloride, phenyl chloride, allyl bromide, or propargyl chloride. The hydride may be lithium aluminium hydride, potassium aluminium hydride, sodium aluminium hydride, caesium aluminium hydride, sodium gallium hydride, lithium thallium hydride, lithium indium hydride, lithium gallium hydride or rubidium aluminium hydride. The catalyst may be used to polymerize ethylene, propylene, 1-butene, 1-hexene, 1-octene, isobutylene, butene-2, pentene-2, hexene-2, heptene-2, 2-methylbutene-1, 2-methylhexene-1, 2-ethylheptene-1, 1,5-hexadiene, 1,4-pentadiene, 1,4,7-octatriene, cyclohexene, styrene, 1,3-butadiene 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3 - pentadiene, 2 - methyl - 3 - ethyl - 1,3 - pentadiene, and 2-phenyl butadiene.  The polymerization is carried out at -250 DEG  to 500 DEG  F., and at a pressure from atmospheric to 1000 p.s.i.g. in the presence of an inert organic liquid diluent.  In examples, polyethylene of molecular weights of 38,575 and 35,964 are obtained using as catalysts titanium tetrachloride benzoyl peroxide, and a mixture of diethylaluminium chloride and ethylaluminium dichloride.