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 sequentially with optionally (A) Cl 2 , Br 2 , interhalogen or mixtures thereof, (B) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbon group, (C) an oxygen containing compound selected from ketones, aldehydes, alcohols or mixtures thereof, (D) an acyl halide, (E) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, and optionally (F) Cl 2 , Br 2 , an interhalogen or mixtures thereof with the proviso that the inert solid support material can alternatively be treated with (i) the (B) organometallic compound and the (C) oxygen containing compound simultaneously, (ii) the reaction product of the (B) organometallic compound and (C) oxygen containing compound or (iii) the (C) oxygen containing compound followed by treating with the (B) organometallic compound and at least one of (A) and (F) treatment is performed.

Claim 3

The transition metal containing catalyst component of claim 1 wherein the (B) 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 (C) 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 (D) 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 halogen of (A) and/or (F) is Cl 2 .

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 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 wherein R 8 is an alkyl group having from 1 to 6 carbon atoms, aryl group 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 wherein 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-butylmagnesium.

Claim 19

The transition metal catalyst of claim 2 wherein the (F) Cl 2 treat is performed.

Claim 20

The transition metal catalyst of claim 2 wherein the (A) Cl 2 treat is performed.

Claim 21

The transition metal catalyst of claim 2 wherein the (A) and (F) Cl 2 treat is performed.

Claim 22

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 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 sequentially with optionally (A) Cl 2 , Br 2 , an interhalogen or mixtures thereof, (B) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbyl group, (C) an oxygen containing compound selected from ketones, aldehydes, alcohols or mixtures thereof, (D) an acyl halide, (E) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, and optionally (F) Cl 2 , Br 2 , an interhalogen or mixtures thereof with the proviso that the inert solid support material can alternatively be treated with (i) the (B) organometallic compound and the (C) oxygen containing compound simultaneously, (ii) the reaction product of the (B) organometallic compound and (C) oxygen containing compound or (iii) the (C) oxygen containing compound followed by treating with the (B) organometallic compound and at least one of (A) and (F) treatment is performed.

Claim 23

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 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 sequentially with optionally (A) Cl 2 , Br 2 , an interhalogen or mixtures thereof, (B) an organometallic compound of a Group IIa, IIb or IIIa metal wherein all the metal valencies are satisfied with a hydrocarbyl group, (C) an oxygen containing compound selected from ketones, aldehydes, alcohols or mixtures thereof, (D) an acyl halide, (E) at least one transition metal compound of a Group IVb, Vb, VIb or VIII metal, and optionally (F) Cl 2 , Br 2 , an interhalogen or mixtures thereof with the proviso that the inert solid support material can alternatively be treated with (i) the (B) organometallic compound and the (C) oxygen containing compound simultaneously, (ii) the reaction product of the (B) organometallic compound and (C) oxygen containing compound or (iii) the (C) oxygen containing compound followed by treating with the (B) organometallic compound and at least one of (A) and (F) treatment is performed.

Claim 24

The catalyst system of claim 21 wherein the (B) 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 (C) 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 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 halogen of (A) and/or (F) is Cl 2 .

Claim 25

The catalyst system of claim 22 wherein the inert solid support material is one of silica, alumina, magnesia or mixtures thereof.

Claim 26

The catalyst system of claim 22 wherein R 1 , R 2 , R 3 , R 4 , and R 5 are alkyl groups having from 1 to 10 carbon atoms.

Claim 27

The catalyst system of claim 22 wherein R 1 and R 2 are different.

Claim 28

The catalyst system of claim 25 wherein R 1 , R 2 and R 3 are alkyl groups having from 1 to 6 carbon atoms.

Claim 29

The catalyst system of claim 26 wherein R 1 is butyl.

Claim 30

The catalyst system of claim 27 wherein R 2 is ethyl.

Claim 31

The catalyst system of claim 28 wherein the oxygen containing component is an alcohol having from 1-4 carbon atoms..

Claim 32

The catalyst system of claim 29 wherein R 3 is butyl.

Claim 33

The catalyst system of claim 22 wherein R 8 is an alkyl group having from 1 to 6 carbon atoms, an aryl group having from 7 to 10 carbon atoms and X is chlorine.

Claim 34

The catalyst system of claim 31 wherein R 8 is acetyl or phenyl.

Claim 35

The catalyst system of claim 22 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 36

The catalyst system of claim 33 wherein Tr is titanium, vanadium or zirconium.

Claim 37

The catalyst system of claim 34 wherein the transition metal compound is TiCl 4 .

Claim 38

The catalyst system of claim 22 wherein the organomagnesium compound and the oxygen containing compound are reacted together prior to contact with the inert support material.

Claim 39

The catalyst system of claim 36 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 40

The catalyst system of claim 22 wherein the (F) Cl 2 treat is performed.

Claim 41

The catalyst system of claim 22 wherein the (A) Cl 2 treat is performed.

Claim 42

The catalyst system of claim 22 wherein the (A) and (F) Cl 2 treat is performed.

Claim 43

The transition metal containing catalyst component of claim 2 wherein the inert solid support material is silica, the (B) and (C) compounds are added as the reaction product of n-butylethyl magnesium with butanol, (D) is benzoyl chloride, and (E) is TiCl 4 . IVb, Vb, VIb VIIb