Olefine polymerization catalyst
AssigneeImperial Chemical Industries PLC
InventorAnthony David Caunt
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Abstract
An olefine polymerisation catalyst includes a solid compound of a transition metal, e.g. titanium trichloride, an organo-compound of a non-transition metal, e.g. aluminium triethyl or diethyl aluminium chloride and a pentavalent phosphorus compound of the type R.sub.3.sub.-n P(Q)(E--Z--G), e.g. [(CH.sub.3).sub.2 N].sub.2 P(O)N(CH.sub.3)CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 and (CH.sub.3).sub.2 NP(O)[OCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 ].sub.2 The transition metal compound can be ball-milled in the presence of a further compound which can be the specified phosphorus compound or an electron donor compound, e.g., triphenylphosphine oxide. Using catalysts of this type, a combination of high activity and high stereospecificity can be obtained when polymerising an olefine monomer.
Claims28
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.sub.2 H.sub.5).sub.4 ].sub.2, Mg(C.sub.6 H.sub.5).sub.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.sub.3.sub.-n P(Q)(E-Z-G).sub.n
- wherein
- R is halogen, hydrocarbyl group, pyridyl, pyrrolyl, pyrrolidyl, piperidyl group, the group --NR'.sub.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'.sub.2, --PR'.sub.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).
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.sub.2 H.sub.5).sub.4 ].sub.2, Mg(C.sub.6 H.sub.5).sub.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.sub.3.sub.-n P(Q)(E-Z-G).sub.n
- wherein
- R is halogen, hydrocarbyl group, pyridyl, pyrrolyl, pyrrolidyl, piperidyl group, the group --NR'.sub.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'.sub.2, --PR'.sub.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).
Dependencies are inferred from the claim text.