Polymerization catalyst, production and use

Claim 2

A transition metal containing solid prepolymerized catalyst component comprising the prepolymerized solid reaction product obtained by treating an inert solid support material in an inert solvent sequentially with (A) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbon group, (B) an oxygen containing compound selected from ketones, aldehydes, alcohols or mixtures thereof, (C) an acyl halide, (D) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal , (E) a Group IIIa metal hydrocarbyl dihalide and prepolymerizing the solid with a minor amount of ethylene with the proviso that the inert solid support material can alternatively 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 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 and the (C) acyl halide is represented by the formula R 8 COX wherein R 8 can be an alkyl group, cycloalkyl group or aryl group having from 1 to 12 carbon atoms and X is halogen and the Group IIIa metal hydrocarbyl dihalide is one of alkyl boron dihalide, alkyl aluminum dihalide or mixtures thereof.

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 and R 2 is ethyl.

Claim 9

The transition metal containing catalyst component of claim 2 wherein the Group IIIa alkyl metal dihalide is one of ethyl boron dichloride or ethyl aluminum dichloride.

Claim 10

The transition metal containing catalyst component of claim 8 wherein the oxygen containing component is an alcohol having from 1 to 4 carbon atoms.

Claim 11

The transition metal containing catalyst component of claim 9 wherein R 3 is butyl.

Claim 12

The transition metal containing catalyst of claim 2 wherien R 8 is an alkyl group having from 1 to 6 carbon atoms or aphenyl having from 7 to 10 carbon atoms and X is chlorine.

Claim 13

The transition metal containing catalyst of claim 11 wherein R 8 is methyl or phenyl.

Claim 14

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 6 ) q , TrX' 4-q R q 7 , VOX' 3 or VO(OR 6 ) 3 wherein Tr is a transition metal, R 6 is a hydrocarbyl group having from 1 to 20 carbon atoms, R 7 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 15

The transition metal containing catalyst component of claim 13 wherein Tr is titanium, vanadium or zirconium.

Claim 16

The transition metal containing catalyst component of claim 14 whrein the transition metal compound is TiCl 4 .

Claim 17

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 18

The transition metal containing catalyst component of claim 16 wherein the oxygen containing compound is an alkyl alcohol having from 1 to 4 carbon atoms and the magnesium containing compound is ethyl-n-butylamgesium.

Claim 19

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" nX" 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 solid prepolymerized catalyst component comprising the prepolymerized solid reaction product obtained by treating an inert solid support material in an inert solvent sequentially with (A) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbyl group, (B) an oxygen containing compound selected from ketones, aldehydes, alochols or mixtures thereof, (C) an acyl halide, (D) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, (E) a Group IIIa metal hydrocarbyl dihalide and prepolymerizing the solid with a minor amount of ethylene with the proviso that the inert solid support material can alternatively be treated with (i) and (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 20

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" nX" 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 solid prepolymerized catalyst component comprising the prepolymerized solid reaction product obtained by treating an inert solid support material in an inert solvent sequentially with (A) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbyl group, (B) an oxygen containing compound selected from ketones, aldehydes, alochols or mixtures thereof, (C) an acyl halide, (D) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, (E) a Group IIIa metal hydrocarbyl dihalide and prepolymerizing the solid with a minor amount of ethylene with the proviso that the inert solid support material can alternatively be treated with (i) and (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 21

The catalyst system of claim 18 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 and the (C) acyl halide is represented by the formula R 8 COX wherein R 8 can be an alkyl group, cycloalkyl group or aryl group having from 1 to 20 carbon atoms and X is halogen and the Group IIIa hydrocarbyl dihalide is one of alkyl boron dihalide, alkyl aluminum dihalide or mixtures thereof.

Claim 22

The catalyst system of claim 19 wherein the inert solid support material is one of silica, alumina, magnesia or mixtures thereof.

Claim 23

The catalyst system of claim 19 wherein R 1 , R 2 , R 3 , R 4 , and R 5 are alkyl groups having from 1 to 10 carbon atoms.

Claim 24

The catalyst system of claim 19 wherein R 1 and R 2 are different.

Claim 25

The catalyst system of claim 22 wherein R 1 , R 2 and R 3 are alkyl groups having from 1 to 6 carbon atoms.

Claim 26

The catalyst system of claim 23 wherein R 1 is butyl and R 2 is ethyl.

Claim 27

The catalyst system of claim 19 wherein the Group IIIa alkyl metal dihalide is one of ethyl boron dichloride or ethyl aluminum dichloride.

Claim 28

The catalyst system of claim 25 wherein the oxygen containing component is an alcohol having from 1-4 carbon atoms.

Claim 29

The catalyst system of claim 26 wherein R 3 is butyl.

Claim 30

The catalyst system of claim 19 wherein R 8 is an alkyl group having from 1 to 6 carbon atoms or a phenyl haivng from 7 to 10 carbon atoms and X is chlorine.

Claim 31

The catalyst system of claim 28 wherein R 8 is methyl or phenyl.

Claim 32

The catalyst system of claim 19 wherein the transition metal compound or mixtures thereof is represented by the formula TrX' 4-q (OR 6 ) q , TrX' 4-q R q 7 , VOX' 3 or VO(OR 6 ) 3 wherein Tr is a transition R 6 is a hydrocarbyl group havin 1 to 20 carbon atoms, R 7 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 33

The catalyst system of claim 30 wherein Tr is titanium, vanadium or zirconium.

Claim 34

The catalyst system of claim 30 wherein the transition metal compound is TiCl 4 .

Claim 35

The catalyst system of claim 19 wherein the organomagnesium compound and the oxygen containing compound are reacted together prior to contact with the inert support material.

Claim 36

The catalyst system of claim 33 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.