High efficiency catalyst for polymerizing olefins

Claim 1

A process for the polymerization of one or more polymerizable α-olefins under conditions characteristic of Ziegler polymerization wherein the polymerization is conducted in the presence of, as a catalyst for said polymerization, a catalytic reaction product of (A) a tetravalent titanium compound represented by the formula TiX n (OR) 4-n wherein X is a halogen, R is an alkyl or an aryl group having from 1 to 12 carbon atoms and n has a value of 0 to 4; (B) an anhydrous divalent zinc compound represented by the formula R 2 Zn wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; (C) an organomagnesium component selected from (1) an organomagnesium compound or (2) a complex of an organomagnesium compound and an organometallic compound in an amount sufficient to solubilize the organomagnesium compound in a hydrocarbon solvent, said organomagnesium compound and said complex being represented respectively by the following formulas MgR" 2 and MgR" 2 .xMR" y wherein each R" is independently a hydrocarbyl group having from 1 to 20 carbon atoms; M is a metal selected from Al, Zn, Si, Sn, B and P; y is the number of hydrocarbyl groups and corresponds to the valency of M and x is about 0.001 to 10 and (D) a halide source selected from (1) an active non-metallic halide, said non-metallic halide corresponding to the formula R'X wherein R' is hydrogen or a hydrocarbyl group such that the hydrocarbyl halide is at least as active as sec-butyl chloride and does not poison the catalyst and X is halogen or (2) a metallic halide corresponding to the formula MR y-a X a wherein M is a metal of Group IIIA or IVA of Mendeleev's Periodic Table of Elements, R is a monovalent hydrocarbyl radical, X is halogen, y is a number corresponding to the valence of M and a is a number of 1 to y; provided that the proportions of the foregoing components of said catalytic reaction product being such that the atomic ratio of Zn:Mg is from about 0.02:1 to about 25:1, the atomic ratio of Zn:Al is from about 0.02:1 to about 50:1, the atomic ratio of Zn:Ti is from about 0.1:1 to about 200:1, the atomic ratio of excess X:Al is from about 0.0005:1 to about 10:1; and further provided that when the organomagnesium component and/or the halide source provides insufficient quantities of aluminum, there is also present an aluminum compound represented by the formula AlR y' X y" wherein R and X are as defined above and y' and y" each have a value of from zero to three with the sum of y' and y" being three; and wherein the catalyst components are added in the order selected from (a) (C), (D), (B), aluminum compound, if required, and (A); (b) (C), (D), (A), aluminum compound, if required, and (B) and provided that the halide source, (D), is other than a tin compound; and (c) (C), (D), aluminum compound, if required, (A), and (B).