Polymerization of olefins from catalysts prepared from organo zirconium-chromium compounds

Claim 2

A process for polymerizing one or more α-olefins which comprises conducting polymerization under Ziegler polymerization conditions in the presence of a catalyst which comprises (A) the reaction product of (1) at least one zirconium compound represented by the empirical formula (RO) m ZrX 4-m wherein R is a monovalent hydrocarbyl group having from 1 to about 20 carbon atoms, X is chlorine or bromine and m has a value from 0 to 4; and (2) an inorganic oxygen-containing chromium compound in a mole ratio of component (2) to component (1) of from about 0.05:1 to about 6:1; (B) a solid catalyst support containing magnesium; (C) a tetrahydrocarbyloxy titanium or titanium halide compound; and (D) an organometallic activating agent; wherein the Mg:Cr atomic ratio is from about 1:1 to about 200:1, the Al:Cr atomic ratio is from about 1:1 to about 250:1; the Cr:Ti atomic ratio is from about 0.1:1 to about 50:1; and the excess X:Al atomic ratio is from about 0.005 to about 10:1.

Claim 3

The process of claim 1 wherein said zirconium compound is represented by the empirical formula (RO) m ZrX 4-m wherein R is a monovalent hydrocarbyl group having from 1 to about 20 carbon atoms, X is chlorine or bromine and m has a value from 0 to 4; (i) said oxygen containing chromium compound is represented by the empirical formulae CrO 3 or CrO 2 X 2 , wherein X are as defined above; (ii) the molar ratio of component (A2) to component (A1) is from about 0.1:1 to about 2:1; (iii) said Mg containing support, component (B), is prepared by reacting (a) a compound represented by the empirical formula MgR" 2 .xA1R" 3 wherein each R" is independently a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms and x has a value from about zero to about 10 with (b) a halide source selected from non-metallic halides and metallic halides; (iv) component (C) is a tetrahydrocarbyloxy titanium compound having from 1 to about 10 carbon atoms in each hydrocarbyloxy group; (v) said organometallic activating agent, component (D), is a trialkyl aluminum or a dialkyl aluminum halide wherein each alkyl group independently has from 1 to about 12 carbon atoms and (vi) the Mg:Cr atomic ratio is from about 10:1 to about 150:1, the Al:Cr atomic ratio is from about 10:1 to about 200:1, the Cr:Ti atomic ratio is from about 0.2:1 to about 3:1 and the excess X:Al atomic ratio is from about 0.002:1 to about 2:1.

Claim 4

The process composition of claim 2 wherein (i) in said zirconium compound and said oxygen-containing chromium compound each R is independently an alkyl group having from 1 to about 10 carbon atoms; (ii) the molar ratio of component (A2) to component (A1) is from about 0.2:1 to about 1:1; (iii) in component (B) the R groups are independently selected from an alkyl group having from 1 to about 10 carbon atoms and x has a value from about 0.15 to about 2.5; (iv) component (D) is a trialkyl aluminum compound and (v) the Mg:Cr atomic ratio is from about 20:1 to about 100:1, the Al:Cr atomic ratio is from about 25:1 to about 150:1, the Cr:Ti atomic ratio is from about 0.3:1 to about 1.5:1, and the atomic ratio of excess X:Al is from about 0.01:1 to about 1:1.

Claim 5

The process of claim 3 wherein the zirconium compound is Zr(OnPr) 4 , Zr(OiPr) 4 or mixture thereof and the oxygen-containing chromium compound is CrO 3 , CrO 2 Cl 2 or mixture thereof.

Claim 6

The process of claims 1, 2, 3 or 4 wherein ethylene is polymerized.

Claim 7

The process of claims 1, 2, 3 or 4 wherein a mixture of ethylene and one or more α-olefins having from 3 to about 10 carbon atoms are polymerized.

Claim 8

The process of claim 6 wherein a mixture of ethylene and one or more α-olefins having from 4 to about 8 hydrocarbons are polymerized.

Claim 9

The process of claim 7 wherein a mixture of ethylene and one or more of butene-1, hexene-1 or octene-1 are polymerized.

Claim 10

The process of claims 1, 2, 3 or 4 wherein solution polymerization conditions are employed.

Claim 11

The process of claim 5 wherein solution polymerization conditions are employed.

Claim 12

The process of claim 6 wherein solution polymerization conditions are employed.

Claim 13

The process of claim 7 wherein solution polymerization conditions are employed.

Claim 14

The process of claim 8 wherein solution polymerization conditions are employed.