Polymerization of olefins in the presence of a catalyst containing titanium and zirconium

Claim 1

A process for the polymerization of one or more α-olefins under conditions characteristic of Ziegler polymerization wherein the polymerization is conducted in the presence of, as a catalyst therefor, the reaction product of (A) a trivalent or tetravalent titanium compound; (B) a zirconium compound; (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 and (D) a halide source selected from (1) an active non-metallic halide, said non-metallic halide corresponding to the empirical formula R'X where in R' is hydrogen or an organic group at least as active as sec-butyl and X is halogen or (2) a metallic halide corresponding to the empirical formula MR y-a X a wherein M is a metal of Group IIIA or IVA of Mendeleev's Periodic Table of the Elements, R is a monovalent organic radical, X is halogen, y is a number corresponding to valence of M and a is a number from 1 to y; provided that the proportions of the foregoing components of said catalytic reaction product being such that the atomic ratio of Mg:Zr is from about 1:1 to about 100:1; the atomic ratio of Al:Zr is from about 0.1:1 to about 100:1; the atomic ratio of Zr:Ti is from about 0.1:1 to about 50:1; 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. (E) an aluminum compound represented by the empirical 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 total value of y' plus y" being three; and wherein the components are added in an order selected from: (a) (i) component (C), (ii) component (D), (iii) component (E), if employed, followed by (iv) components (A) and (B) in any order or as a mixture; (b) (i) component (D) if it contains aluminum, (ii) component (C), (iii) components (A) and (B) in any order or as a mixture; and (c) (i) component (D) if aluminum is present, (ii) components (A) and (B) in any order or as a mixture and (iii) component (C).