Olefine polymerization catalyst

Claim 2

An olefine polymerisation catalyst consisting essentially of 1. one molecular proportion of a solid halide of titanium, vanadium or zirconium wherein the metal has a valency below its maximum, 2. from 0.05 up to 20 molecular proportions of at least one compound selected from the group consisting of Grignard reagents which are substantially ether free, Mg[Al(C 2 H 5 ) 4 ] 2 , Mg(C 6 H 5 ) 2 , lithium aluminium tetraalkyls, aluminium hydrocarbyl halides, aluminium hydrocarbyl sulphates, aluminium hydrocarbyl oxyhydrocarbyls, aluminium trihydrocarbyls and dihydrocarbyl aluminium hydrides, and 3. from 0.01 up to 10 molecular proportions of at least one phosphorus compound of the formula R 3 -n P(Q)(E-Z-G) n wherein R is halogen, hydrocarbyl group, pyridyl, pyrrolyl, pyrrolidyl, piperidyl group, the group --NR' 2 or --OR', E is --O--, --S--, or --NR'--; Z is a bivalent hydrocarbyl group such that E and G are separated by not more than 3 carbon atoms; G is --OR', --SR', --NR' 2 , --PR' 2 , a pyridyl radical, a quinolyl radical, an isoquinolyl radical, a furyl radical or a tetrahydrofuryl radical; R' is a hydrocarbyl group; Q is an oxygen or sulphur atom; and n is 1, 2, or 3, and wherein the amount of component (3) is not greater than the amount of component (2).

Claim 3

The catalyst of claim 1 wherein component (1) is titanium trichloride.

Claim 4

The catalyst of claim 1 wherein component (2) is an aluminium trihydrocarbyl, an aluminium dihydrocarbyl halide or an aluminium dihydrocarbyl hydride.

Claim 5

The catalyst of claim 1 wherein component (1) is titanium trichloride, and component (2) is aluminium triethyl or aluminium diethyl chloride.

Claim 6

The catalyst of claim 1 wherein in component (3) each group R' is a methyl or ethyl group.

Claim 7

The catalyst of claim 1 wherein in component (3) the group R is an alkoxy group or a dialkyl amino group.

Claim 8

The catalyst of claim 1 wherein component (1) has been ground in the dry state.

Claim 9

The catalyst of claim 7 wherein the solid halide which is component (1) has been ground with at least part of component (3) or with triphenyl phosphine oxide in a molar ratio of solid halide to component (3) or triphenyl phosphine oxide of at least 6:1.

Claim 10

The catalyst of claim 8 wherein, in addition to the materials ground with component (1), the catalyst further contains a quantity of at least one compound selected from the group consisting of component (3), pyridine, quinoline, isoquinoline, tetramethylethylenediamine and triphenyl phosphine oxide said quantity being a minor amount sufficient to improve the catalyst activity, stereospecificity or both and the quantity of component (3) being the remainder of component (3).

Claim 11

The catalyst of claim 9 wherein component (1) is not allowed to contact component (3), pyridine, quinoline, isoquinoline, tetramethylethylenediamine or triphenylphosphine oxide in the absence of component (2) of the catalyst other than when the solid halide is ground with component (3), pyridine, quinoline, isoquinoline, tetramethylethylenediamine or triphenylphosphine oxide.

Claim 12

The catalyst of claim 8 wherein the solid halide is titanium trichloride and component (2) is an aluminium trihydrocarbyl, an aluminium dihydrocarbyl halide or an aluminium dihydrocarbyl hydride.

Claim 13

The catalyst of claim 11 further containing a component (4) selected from the group consisting of pyridine, quinoline, isoquinoline, tetramethylethylenediamine and triphenylphosphine oxide, and wherein (a) component (1) is titanium trichloride which has been dry ball-milled with at least one compound selected from the group consisting of component (3), component (4), and mixtures thereof in a molar ratio of component (1) to component (4) of at least 6:1; and b. in addition to said compound dry ball-milled with titanium trichloride, the catalyst contains an additional quantity of component (3), component (4), or mixtures thereof which quantity has not been allowed to contact component (1) in the absence of at least some of component (2), the quantity of component (4) being a minor amount sufficient to improve the catalyst activity, stereospecificity, or both, and the quantity of component (3) being the remainder of component (3).

Claim 14

The catalyst of claim 4 wherein the component (3) is [(CH 3 ) 2 N] 2 P(O)N(CH 3 )CH 2 CH 2 N(CH 3 ) 2 ; (ch 3 ) 2 np(o)[n(ch 3 )ch 2 ch 2 n(ch 3 ) 2 ] 2 ; [(ch 3 ) 2 n] 2 p(o)och 2 ch 2 n(ch 3 ) 2 ; or (CH 3 ) 2 NP(O)[OCH 2 CH 2 N(CH 3 ) 2 ] 2 .

Claim 15

The catalyst of claim 11 wherein component (1) is titanium trichloride which has been ball-milled with [(CH 3 ) 2 N] 2 P(O)N(CH 3 )CH 2 CH 2 N(CH 3 ) 2 wherein the molar ratio of titanium trichloride to [(CH 3 ) 2 N] 2 P(O)N(CH 3 )CH 2 CH 2 N(CH 3 ) 2 is at least 6:1.

Claim 16

In an olefine polymerisation catalyst consisting essentially of 1. a solid halide of titanium, vanadium or zirconium wherein the metal has a valency below its maximum, and 2. at least one compound selected from the group consisting of Grignard reagents which are substantially ether free, Mg[Al(C 2 H 5 ) 4 ] 2 , Mg(C 6 H 5 ) 2 , lithium aluminium tetraalkyls, aluminium hydrocarbyl halides, aluminium hydrocarbyl sulphates, aluminium hydrocarbyl oxyhydrocarbyls, aluminium trihydrocarbyls and dihydrocarbyl aluminium hydrides, the improvement of adding 3. from 0.01 up to 10 molecular proportions for each molecular proportion of the solid halide of at least one phosphorus compound of the formula R 3 -n P(Q)(E-Z-G) n wherein R is halogen, hydrocarbyl group, pyridyl, pyrrolyl, pyrrolidyl, piperidyl group, the group --NR' 2 or --OR'; E is --O--, --S--, or --NR'--; Z is a bivalent hydrocarbyl group such that E and G are separated by not more than 3 carbon atoms; G is --OR', --SR', --NR' 2 , --PR' 2 , a pyridyl radical, a quinolyl radical, an isoquinolyl radical, a furyl radical or a tetrahydrofuryl radical, R' is a hydrocarbyl group; Q is an oxygen or sulphur atom; and n is 1, 2, or 3, and wherein the amount of component (3) is not greater than the amount of component (2).

Claim 17

In an olefine polymerisation catalyst consisting essentially of 1. a solid halide of titanium, vanadium or zirconium wherein the metal has a valency below its maximum, and 2. at least one compound selected from the group consisting of Grignard reagents which are substantially ether free, Mg[Al(C 2 H 5 ) 4 ] 2 , Mg(C 6 H 5 ) 2 , lithium aluminium tetraalkyls, aluminium hydrocarbyl halides, aluminium hydrocarbyl sulphates, aluminium hydrocarbyl oxyhydrocarbyls, aluminium trihydrocarbyls and dihydrocarbyl aluminium hydrides, the improvement of adding 3. from 0.01 up to 10 molecular proportions for each molecular proportion of the solid halide of at least one phosphorus compound of the formula R 3 -n P(Q)(E-Z-G) n wherein R is halogen, hydrocarbyl group, pyridyl, pyrrolyl, pyrrolidyl, piperidyl group, the group --NR' 2 or --OR'; E is --O--, --S--, or --NR'--; Z is a bivalent hydrocarbyl group such that E and G are separated by not more than 3 carbon atoms; G is --OR', --SR', --NR' 2 , --PR' 2 , a pyridyl radical, a quinolyl radical, an isoquinolyl radical, a furyl radical or a tetrahydrofuryl radical, R' is a hydrocarbyl group; Q is an oxygen or sulphur atom; and n is 1, 2, or 3, and wherein the amount of component (3) is not greater than the amount of component (2).

Claim 18

The catalyst of claim 15 wherein component (1) is titanium trichloride.

Claim 19

The catalyst of claim 15 wherein component (2) is an aluminium trihydrocarbyl, an aluminium dihydrocarbyl halide or an aluminium dihydrocarbyl hydride.

Claim 20

The catalyst of claim 15 wherein component (1) is titanium trichloride, and component (2) is aluminium triethyl or aluminium diethyl chloride.

Claim 21

The catalyst of claim 15 wherein in component (3) each group R' is a methyl or ethyl group.

Claim 22

The catalyst of claim 15 wherein in component (3) the group R is an alkoxy group or a dialkyl amino group.

Claim 23

The catalyst of claim 15 wherein component (3) is [(CH 3 ) 2 N] 2 P(O)N(CH 3 )CH 2 CH 2 N(CH 3 ) 2 ; (ch 3 ) 2 np(o)[n(ch 3 )ch 2 ch 2 n(ch 3 ) 2 ] 2 ; [(ch 3 ) 2 n] 2 p(o)och 2 ch 2 n(ch 3 ) 2 ; or (CH 3 ) 2 NP(O)[OCH 2 CH 2 N(CH 3 ) 2 ] 2 .

Claim 24

The catalyst of claim 15 wherein component (1) has been ground in the dry state.

Claim 25

The catalyst of claim 22 wherein the solid halide which is component (1) has been ground with at least part of component (3) or with triphenyl phosphine oxide in a molar ratio of solid halide to component (3) or triphenyl phosphine oxide of at least 6:1.

Claim 26

The catalyst of claim 23 wherein, in addition to the materials ground with component (1), the catalyst further contains a quantity of at least one compound selected from the group consisting of component (3), pyridine, quinoline, isoquinoline, tetramethylethylenediamine and triphenyl phosphine oxide said quantity being a minor amount sufficient to improve the catalyst activity, stereospecificity or both, and the quantity of component (3) being the remainder of component (3).

Claim 27

The catalyst of claim 24 wherein component (1) is not allowed to contact component (3), pyridine, quinoline, isoquinoline, tetramethylethylenediamine or triphenylphosphine oxide in the absence of component (2) of the catalyst other than when the solid halide is ground with component (3), pyridine, quinoline, isoquinoline, tetramethylethylenediamine or triphenylphosphine oxide.

Claim 28

The catalyst of claim 23 wherein the solid halide is titanium trichloride and component (2) is an aluminium trihydrocarbyl, an aluminium dihydrocarbyl halide or an aluminium dihydrocarbyl hydride.

Claim 29

The catalyst of claim 26 further containing a component (4) selected from the group consisting of pyridine, quinoline, isoquinoline, tetramethylethylenediamine and triphenylphosphine oxide, and wherein (a) component (1) is titanium trichloride which has been dry ball-milled with at least one compound selected from the group consisting of component (3), component (4), and mixtures thereof in a molar ratio of component (1) to component (4) of at least 6:1; and b. in addition to said compound dry ball-milled with titanium trichloride, the catalyst contains an additional quantity of component (3), component (4), or mixtures thereof which quantity has not been allowed to contact component (1) in the absence of at least some of component (2), the quantity of component (4) being a minor amount sufficient to improve the catalyst activity, stereospecificity, or both, and the quantity of component (3) being the remainder of component (3).

Claim 30

The catalyst of claim 26 wherein component (1) is titanium trichloride which has been ball-milled with [(CH 3 ) 2 N] 2 P(O)N(CH 3 )CH 2 CH 2 N(CH 3 ) 2 wherein the molar ratio of titanium trichloride to [(CH 3 ) 2 N] 2 P(O)N(CH 3 )CH 2 CH 2 N(CH 3 ) 2 is at least 6:1.