Verfahren zur Herstellung von Olefinpolymerisaten

摘要

A catalyst composition for polymerizing hydrocarbons consists of at least one from each of the classes A, B and C, where (A) is a halide of aluminium, (B) a complex hydride MM1Hx, where M is an alkali metal, M1 is aluminium, gallium, indium, or thallium, and x is the sum of the valences of M and M1, and (C) a salt of a monobasic organic acid and titanium or a complex salt of a dibasic organic acid and titanium and alkali metals or ammonia, or a titanium derivative of formula XnTi(OR)m or Tia[(OCH2CH2)aNH(3-a)]b, where X is a halogen, b the valence of titanium, a is 1, 2 or 3, n is 0 or integral, M at least 1 and m+n=b, while R is either R1 or R2, R1 being alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl or combinations of these and R2 being a halogen-substituted R1 or R1 radicals which contain oxygen in the form of an ether linkage and are halogen-substituted, and R contains from 1-20 carbon atoms, the compound containing up to 50 carbon atoms. Specified (A)'s are the trichloride (preferred), tribromide, trifluoride and triiodide, specified (B)'s are lithium, sodium, potassium, caesium or rubidium aluminium hydride, sodium or lithium gallium hydride, lithium thallium hydride and lithium indium hydride, while specified (C)'s are titanium acetate, and butyrate, sodium titanium malonate, potassium titanium oxalate, titanium butoxide, tetra - sic. - butyl-, tetra - isopropyl-, tetra - 2 - ethylbutyl -, tetra - 2 - ethylhexyl -, tetrasteryl-, tetraethyl-, tetra-(chloroethyl)-, tetra - m - tolyl -, tetraallyl -, tetracyclohexenyl -, tetracyclopentyl -, dichlorodiethyl - and monochlorotriethyl-, titanates and mono-, di- and tri-ethanolamine titanates.ALSO:Polymerizable hydrocarbons are polymerized using as catalyst at least one from each of the classes A, B and C, where (A) is a halide of aluminium, (B) a complex hydride MM1Hx, where M is an alkali metal, M1 is aluminium, gallium, indium or thallium and x is the sum of the valences of M and M1, and (C) a salt of a mono-basic organic acid and titanium or a complex salt of a dibasic organic acid and titanium and alkali metals or ammonia or a titanium derivative of formula where X is a halogen, b the valence of titanium, a is 1, 2 or 3, n is O or integral, m at least 1 and m/sNn=b, while R is either R1 or R2, R1 being alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl or combinations of these, and R2 being a halogen-substituted R1, or R1 radicals which contain oxygen in the form of an ether linkage and are halogen-substituted, and R contains from 1 to 20 carbon atoms, the compound containing up to 50 carbon atoms. Specified (A)'s are the trichloride (preferred), tribromide, trifluoride and triiodide; specified (B)'s are lithium, sodium, potassium, caesium, or rubidium aluminium hydride, sodium or lithium gallium hydride, lithium thallium hydride, and lithium indium hydride while specified (C)'s are titanium acetate, and butyrate, sodium titanium malonate, potassium titanium oxalate, titanium butoxide, tetra - sec. - butyl -, tetraisopropyl -, tetra - 2 - ethylbutyl -, tetra - 2 - ethylhexyl, tetrasteryl-, tetraethyl-, tetra-(chloroethyl)-, tetra-m-tolyl-, tetra-alkyl-, tetracyclohexenyl-, tetracyclopentyl-, dichlorodiethyl-, and mono-chlorotriethyl-, titanate, and mono-, di-, and tri-ethanolamine titanates. Specified polymers are ethylene, propylene, 1-butene, 1-hexene 1-octene, isobutylene, butene-2, pentene-2, hexene-2, heptene-3, 2-methyl-butene-1, 2-methyl hexene-1, 2-ethyl-heptene-1, 1,5-hexadiene, 1,4-pentadiene, 1,4,7-octatriene, cyclohexene, styrene and alkyl-substituted styrenes and copolymers of ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, propylene and 1-butene and propylene and a pentene. The polymerization may take place in the gaseous phase without a diluent or preferably, in liquid phase in the presence of an inert organic hydrocarbon diluent, e.g. propane, butane, pentane, iso-octane, cyclohexane, methylcyclohexane, benzene, toluene, and halogenated hydrocarbons and by batch or continuous process methods. Contaminants such as carbon dioxide, oxygen and water are kept out of the polymerization zone and the product removed and washed with an alcohol.