Catalysts prepared from tetrakis (dialkylamide and diarylamide) derivatives of titanium and polymerization of olefins therewith

Claim 2

A supported catalyst which comprises the product resulting from mixing in a suitable inert diluent or solvent the following components A, B, and C: (A) an inorganic support; (B) a metal-containing reducing agent; and (C) a transition metal compound selected from the group consisting of a titanium tetrakis(dialkylamide) or titanium tetrakis(diarylamide) or a combination thereof; the components are employed in quantities which provide an atomic ratio of Ms:Tm of from 2:1 to 160:1; an atomic ratio of Mr:Tm of from 1:1 to 64:1; and wherein Ms represents the metal atoms in the support material, Mr represents the metal atoms in the reducing agent and Tm represents the sum of the transition metal atoms in the transition metal component.

Claim 3

A supported catalyst of Claim 1 wherein the components are employed in quantities which provide an atomic ratio of Ms:Tm of from 8:1 to 80:1 and an atomic ratio of Mr:Tm of from 2:1 to 32:1.

Claim 4

A supported catalyst of Claim 2 wherein the components are employed in quantities which provide an atomic ratio of Ms:Tm of from 11:1 to 40:1 and an atomic ratio of Mr:Tm of from 4:1 to 16:1.

Claim 5

A supported catalyst of any one of the preceding claims wherein (a) component (A) is a magnesium dihalide; (b) component (B) is a compound represented by the formulas Al(R′) 3-m X m and B(R′) 3-m X m wherein each R′ is independently hydrogen or a hydrocarbyl group having from 1 to 20 carbon atoms; X is a halogen; and m has a value of 1 to 2; (c) component (C) is a compound represented by the formula Ti(NR₂)₄ wherein each R is independently an alkyl group having from 1 to 4 carbon atoms, a benzyl group, an alkyl substituted benzyl group wherein each alkyl group has from 1 to 4 carbon atoms, a phenyl group, or an alkyl substituted aryl group having from 7 to 20 carbon atoms, wherein the alkyl groups have from 1 to 4 carbon atoms.

Claim 6

A supported catalyst of Claim 4 wherein (a) component (A) is magnesium dichloride; (b) component (B) is ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, triethylboron, diethylboron chloride, diethylaluminum bromide, ethylaluminum dibromide, triethylaluminum, trimethylaluminum, triisobutylaluminum, lithium aluminum hydride, potassium hydride, sodium hydride, methyllithium or butyllithium or any combination thereof; and (c) component (C) is titanium tetrakis(dimethylamide, titanium tetrakis(diethylamide), titanium tetrakis(di-i-­propylamide), titanium tetrakis(di-n-­ propylamide), titanium tetrakis(di-i-­butylamide), titanium tetrakis(di-n-­butylamide), titanium tetrakis(diphenylamide), titanium tetrakis(dibenzylamide), titanium bis(diethylamide) bis(dimethylamide) or i-­propylamide titanium tris(dimethylamide), or any combination thereof.

Claim 7

A supported catalyst of any one of the preceding claims wherein the transition metal component (C) additionally contains at least one zirconium or hafnium compound selected from a zirconium tetrakis(dialkylamide), a zirconium tetrakis(diarylamide), a hafnium tetrakis(dialkylamide), a hafnium tetrakis(diarylamide), or any combination thereof; wherein the atomic ratio of (Zr+Hf) to (Ti+Zr+Hf) is from >0:1 to 0.9:1.

Claim 8

A supported catalyst of Claim 6 wherein (a) the zirconium compound is represented by the formula Zr(NR₂)₄ wherein each R is independently an alkyl group having from 1 to 4 carbon atoms, a benzyl group, an alkyl substituted benzyl group wherein each alkyl group has from 1 to 4 carbon atoms, a phenyl group, or an alkyl substituted aryl group having from 7 to 20 carbon atoms, wherein the alkyl groups have from 1 to 4 carbon atoms; (b) the hafnium compound is represented by the formula Hf(NR₂)₄ wherein each R is independently an alkyl group having from 1 to 4 carbon atoms, a benzyl group, an alkyl substituted benzyl group wherein each alkyl group has from 1 to 4 carbon atoms, a phenyl group, or an alkyl substituted aryl group having from 7 to 20 carbon atoms, wherein the alkyl groups have from 1 to 4 carbon atoms; and (c) the atomic ratio of (Zr+Hf) to (Ti+Zr+Hf) is from >0:1 to 0.8:1.

Claim 9

A supported catalyst of Claim 7 wherein (a) the zirconium compound is zirconium tetrakis(dimethylamide), zirconium tetrakis(diethylamide), zirconium tetrakis(di-­i-propylamide), zirconium tetrakis(di-n-­propylamide), zirconium tetrakis(di-i-­butylamide), zirconium tetrakis(di-n-­butylamide), zirconium tetrakis(diphenylamide), zirconium bis(diethylamide) bis(dimethylamide) or i-propylamide zirconium tris(dimethylamide), or any combination thereof; (b) the hafnium compound is hafnium tetrakis(dimethylamide), hafnium tetrakis(diethylamide), hafnium tetrakis(di-i-­propylamide), hafnium tetrakis(di-n-­propylamide), hafnium tetrakis(di-i-­butylamide), hafnium tetrakis(di-n-butylamide), hafnium tetrakis(diphenylamide), hafnium tetrakis(dibenzylamide), hafnium bis(diethylamide) bis(dimethylamide) or i-­propylamide hafnium tris(dimethylamide), or any combination thereof; and (c) the atomic ratio of (Zr+Hf) to (Ti+Zr+Hf) is from >0:1 to 0.7:1.

Claim 10

A process for polymerizing one or more α-­olefins or a mixture of one or more α-olefins and one or more polymerizable ethylenically unsaturated monomers which process comprises conducting the polymerization under solution conditions in the presence of (I) a supported catalyst of any one of the preceding claims; and (II) a cocatalyst or activator compound.

Claim 11

A process according to Claim 9 wherein said cocatalyst or activator is diethylaluminum chloride, trimethylaluminum, tri-i-propylaluminum, tri-­i-butylaluminum, triethylaluminum or any combination thereof.

Claim 12

A process of Claim 9 or Claim 10 wherein ethylene or a mixture of ethylene and at least one α-olefin having from 3 to 10 carbon atoms is polymerized.

Claim 13

A process of Claim 11 wherein ethylene or a mixture of ethylene and at least one α-olefin selected from the group consisting of propylene, butene-1, pentene-1, 3-methylbutene-1, 4-methyl-­pentene-1, hexene-1, and octene-1 is polymerized.