GB916132A - Polymerization and copolymerization of ª--monoolefins and diolefins - Google Patents

Abstract

Olefins may be polymerized by contacting with a catalyst formed by mixing a compound of formula TOaXb-a where T is a metal of Group IVa, Va, VIa, VIIa or VIII of the periodic system, X is a halogen, a is 0, 1 or 2, b is 1 to 7 and b-a is at least 1, with a catalyst component formed by reacting at 0 DEG to 150 DEG C. an anhydrous, particulate, finely divided, inorganic solid having hydroxyl groups chemically bonded to atoms forming part of the surface thereof with a compound of formula AlM1vXnRy-n where M1 is a metal of Group I, v is 0 or 1, X is a halogen, n is 0, 1 or 2, R is a monovalent hydrocarbon radical or hydride radical, y is 2, 3 or 4 and y-n is at least 2. The aluminium compound may be contacted with the inorganic solid in the liquid state, as a solution or in the vapour state, e.g. by passing the vapour alone or mixed with an inert carrier gas through the solid in a fixed, moving or fluidized bed reactor. Polymerization may be effected batchwise or continuously in the gas phase or preferably in the presence of an inert liquid reaction medium, e.g. aliphatic, cycloaliphatic and aromatic hydrocarbons, many suitable compounds being listed. Polymerization may be effected in the presence of a chain transfer agent, e.g. hydrogen, and the olefin feed and reaction medium may be purified before the polymerization by treatment with a metal alkyl. Many suitable monomers, solvents, inorganic solids, aluminium compounds and metal halides are listed and the examples describe processes using (1) ethylene, isooctane, silica, triisobutyl aluminium and titanium tetrachloride; (3) ethylene, isooctane, titania, triisobutyl aluminium and titanium tetrachloride; (4) propylene, benzene, magnesia, triethyl aluminium and zirconium tetrachloride; (5) ethylene and propylene, xylene, thoria, dihexyl aluminium chloride and zirconium tetrachloride; (6) butadiene and butene-1 isooctane, titania, diisobutyl aluminium hydride and manganese dichloride; (7) styrene, benzene, ferric oxide, trimethyl aluminium and ferric bromide; (8) butene-1, isooctane, zirconia, triisobutyl aluminium and vanadium trichloride; (9) butadiene, hexane, corundum, potassium trioctyl aluminium fluoride and vanadium oxytrichloride; (10) propylene, benzene, alumina, triethyl aluminium and zirconium tetrachloride; (11) ethylene and propylene, benzene, silica, dihexyl aluminium bromide and zirconium tetrachloride; (12) styrene, isooctane, alumina, potassium trioctyl aluminium fluoride and titanium tetraiodide; (13) butadiene, isoprene and ethylene, carbon black, trimethyl aluminium and titanium tetrachloride; and (14) ethylene, hydrogen, isooctane, titania, triisobutyl aluminium and titanium tetrachloride. The products may be extruded, milled, cast and converted to sponges or latices. They may be halogenated, dehalogenated, sulphohalogenated, sulphonated and crosslinked. They may be compounded with antioxidants, stabilizers, fillers, e.g. silica and carbon black, extenders, plasticizers, pigments, insecticides and fungicides. They may be compounded with hydrocarbon oils and waxes, and used as additives for lubricating oils and gelling agents for hydrocarbon oils.