Polymerization catalyst, production and use

Claim 2

A transition metal containing catalyst component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent with (A) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbon group, optionally (B) an oxygen containing compound selected from ketones, aldehydes, alcohols, siloxanes or mixtures thereof, (C) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, and (D) a Group IIIa metal hydrocarbyl dihalide with the proviso that if the oxygen containing alcohol, aldehyde, ketone or siloxane is employed the inert solid support material can be treated with (i) the (A) organometallic compound and the (B) oxygen containing compound simultaneously, (ii) the reaction product of the (A) organometallic compound and (B) oxygen containing compound or (iii) the (B) oxygen containing compound followed by treating with the (A) organometallic compound.

Claim 3

The transition metal containing catalyst component of claim 1 wherein the (A) organometallic compound is a dihydrocarbon magnesium compound represented by R 1 MgR 2 wherein R 1 and R 2 which can be the same or different are selected from alkyl groups, aryl groups, cycloalkyl groups, aralkyl groups, alkadienyl groups or alkenyl groups, the (B) oxygen containing compounds are selected from alcohols and ketones represented by the formula R 3 OH and R 4 COR 5 wherein R 3 and each of R 4 and R 5 which may be the same or different can be an alkyl group, aryl group, cycloalkyl group, aralkyl group, alkadienyl group or alkenyl group.

Claim 4

The transition metal containing catalyst component of claim 2 wherein the inert solid support material is one of silica, alumina, magnesia or mixtures thereof.

Claim 5

The transition metal containing catalyst component of claim 2 wherein R 1 , R 2 , R 3 , R 4 and R 5 are alkyl groups having from 1 to 10 carbon atoms.

Claim 6

The transition metal containing catalyst component of claim 2 wherein R 1 and R 2 are different.

Claim 7

The transition metal containing catalyst component of claim 5 wherein R 1 , R 2 and R 3 are alkyl groups having from 1 to 6 carbon atoms.

Claim 8

The transition metal containing catalyst component of claim 6 wherein R 1 is butyl.

Claim 9

The transition metal containing catalyst component of claim 7 wherein R 2 is ethyl.

Claim 10

The transition metal containing catalyst component of claim 6 wherein R 1 , R 2 , R 3 , R 4 and R 5 have 2 to 4 carbon atoms.

Claim 11

The transition metal containing catalyst component of claim 9 wherein the oxygen containing component is an alcohol.

Claim 12

The transition metal containing catalyst component of claim 10 wherein R 3 is butyl.

Claim 13

The transition metal containing catalyst component of claim 2 wherein the transition metal compound or mixtures thereof is represented by the formula TrX' 4-q (OR 7 ) q , TrX' 4-q R q 8 , VOX' 3 or VO(OR 7 ) 3 wherein Tr is a transition metal, R 7 is a hydrocarbyl group having from 1 to 20 carbon atoms, R 8 is an alkyl group, aryl group or aralkyl group having from 1 to 20 carbon atoms or a 1,3-cyclopentadienyl, X' is halogen and q is 0 or a number equal to or less than 4.

Claim 14

The transition metal containing catalyst component of claim 12 wherein Tr is titanium, vanadium or zirconium.

Claim 15

The transition metal containing catalyst component of claim 13 wherein the transition metal compound is TiCl 4 .

Claim 16

The transition metal containing catalyst component of claim 2 wherein the organomagnesium compound and the oxygen containing compound are reacted together prior to contact with the inert support material.

Claim 17

A catalyst system for the polymerization or copolymerization of ethylene and alpha-olefins having from 3 to 12 carbon atoms comprising (a) an organo aluminum compound of the formula AlR" n X" 3-n wherein R" is hydrogen or a hydrocarbon group having from 1 to 20 carbon atoms, X is halogen and n is a number from 1 to 3, and (b) a transition metal containing catalyst component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent with (A) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbyl group, optionally (B) an oxygen containing compound selected from ketones, aldehydes, alcohols, siloxanes or mixtures thereof, (C) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, and (D) a Group IIIa metal hydrocarbyl dihalide and with the proviso that if the oxygen containing alcohol, aldehyde, ketone or siloxane is employed the inert solid support material can be treated with (i) the (A) organometallic compound and the (B) oxygen containing compound simultaneously, (ii) the reaction product of the (A) organometallic compound and (B) oxygen containing compound or (iii) the (B) oxygen containing compound followed by treating with the (A) organometallic compound.

Claim 18

A catalyst system for the polymerization or copolymerization of ethylene and alpha-olefins having from 3 to 12 carbon atoms comprising (a) an organo aluminum compound of the formula AlR" n X" 3-n wherein R" is hydrogen or a hydrocarbon group having from 1 to 20 carbon atoms, X is halogen and n is a number from 1 to 3, and (b) a transition metal containing catalyst component comprising the solid reaction product obtained by treating an inert solid support material in an inert solvent with (A) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbyl group, optionally (B) an oxygen containing compound selected from ketones, aldehydes, alcohols, siloxanes or mixtures thereof, (C) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, and (D) a Group IIIa metal hydrocarbyl dihalide and with the proviso that if the oxygen containing alcohol, aldehyde, ketone or siloxane is employed the inert solid support material can be treated with (i) the (A) organometallic compound and the (B) oxygen containing compound simultaneously, (ii) the reaction product of the (A) organometallic compound and (B) oxygen containing compound or (iii) the (B) oxygen containing compound followed by treating with the (A) organometallic compound.

Claim 19

The catalyst system of claim 16 wherein the (A) organometallic compound is a dihydrocarbon magnesium compound represented by R 1 MgR 2 wherein R 1 and R 2 which can be the same or different are selected from alkyl groups, aryl groups, cycloalkyl groups, aralkyl groups, alkadienyl groups or alkenyl groups, the (B) oxygen containing compounds are selected from alcohols and ketones represented by the formula R 3 OH and R 4 COR 5 wherein R 3 and each of R 4 and R 5 which may be the same or different can be an alkyl group, aryl group, cycloalkyl group, aralkyl group, alkadienyl group or alkenyl group.

Claim 20

The catalyst system of claim 17 wherein the inert solid support material is one of silica, alumina, magnesia or mixtures thereof.

Claim 21

The catalyst system of claim 17 wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are alkyl groups having from 1 to 10 carbon atoms.

Claim 22

The catalyst system of claim 17 wherein R 1 and R 2 are different.

Claim 23

The catalyst system of claim 20 wherein R 1 , R 2 and R 3 are alkyl groups having from 1 to 6 carbon atoms.

Claim 24

The catalyst system of claim 21 wherein R 1 is butyl.

Claim 25

The catalyst system of claim 22 wherein R 2 is ethyl.

Claim 26

The catalyst system of claim 21 wherein R 1 , R 2 , R 3 , R 4 and R 5 have 1 to 4 carbon atoms.

Claim 27

The catalyst system of claim 24 wherein the oxygen containing component is an alcohol.

Claim 28

The catalyst system of claim 25 wherein R 3 is butyl.

Claim 29

The catalyst system of claim 17 wherein the transition metal compound or mixtures thereof is represented by the formula TrX' 4-q (OR 7 ) q , TrX' 4-q R q 8 , VOX' 3 or VO(OR 7 ) 3 wherein Tr is a transition metal, R 7 is a hydrocarbyl group having from 1 to 20 carbon atoms, R 8 is an alkyl group, aryl group or aralkyl group having from 1 to 20 carbon atoms or a 1,3-cyclopentadienyl, X' is halogen and q is 0 or a number equal to or less than 4.

Claim 30

The catalyst system of claim 27 wherein Tr is titanium, vanadium or zirconium.

Claim 31

The catalyst system of claim 28 wherein the transition metal compound is TiCl 4 .

Claim 32

The catalyst system of claim 17 wherein the organomagnesium compound and the oxygen containing compound are reacted together prior to contact with the inert support material.

Claim 33

The catalyst system of claim 30 wherein the oxygen containing compound is an alkyl alcohol having from 1 to 4 carbon atoms and the magnesium containing compound is ethyl-n-butylmagnesium.

Claim 34

The catalyst system of claim 17 wherein the aluminum compound is a trialkyl aluminum wherein the alkyl group has from 1 to 10 carbon atoms.

Claim 35

The catalyst system of claim 32 wherein the aluminum alkyl is tri-n-hexyl aluminum.