Basf Aktiengesellschaft

Badische Anilin- & Soda-fabrik Aktiengesellschaft

Gerhard Staiger

Klaus Bronstert

Peter Klaerner

Heinz Mueller-Tamm

Peter Hennenberger

Hannes Schick

Wolfgang Gruber

James F Jaggard

Paul Schneider

.alpha.-Monoolefins are polymerized using a catalyst system which comprises (1) a titanium component obtained by first (1.a) preparing an intermediate from (1.a.1) titanium tetrachloride, (1.a.2) a modifier and (1.a.3) a magnesium alcoholate, and the (1.b) preparing the titanium component from (1.b.1) titanium tetrachloride, (1.b.2) the intermediate from (1.a) and, if required, (1.b.3) a further modifier, (2) an alkylaluminum and (3) a cocatalyst. In this process, (i) the titanium component (1) used is obtained by first (1.1) preparing a first intermediate from (1.1.1) titanium tetrachloride, (1.1.2) a modifier obtained from (1.1.2.1) a titanate and (1.1.2.2) a phthaloyl dichloride, and (1.1.3) a magnesium alcoholate, then (1.2) preparing a second intermediate from (1.2.1) titanium tetrachloride, (1.2.2) the intermediate from (1.1) and, if required, (1.2.3) a phthaloyl dichloride as a further modifier, and finally (1.3) preparing the titanium component from (1.3.1) titanium tetrachloride and (1.3.2) the intermediate from (1.2), and (ii) the cocatalyst (3) used is a trialkoxysilane.

Preparation of homopolymers and copolymers of .alpha.-monoolefins using

A process for the preparation of homopolymers and copolymers of .alpha.-monoolefins by means of a Ziegler-Natta catalyst system comprising (1) a halide of trivalent titanium, (2) an oxygen compound (ester) having a specific formula and (3) an aluminum-alkyl, the titanium halide (1) and the oxygen compound (2) being milled together before use, wherein the catalyst system employed contains, as a further component, (4) a phenolic compound of the formula ##STR1## where R.sup.3 is C.sub.1 -C.sub.6 -alkyl, R.sup.4 is hydrogen or C.sub.1 -C.sub.6 -alkyl, p is an integer from 0 to 5 and q is an integer from 1 to 5.

Preparation of .alpha.-monoolefin homopolymers and copolymers

A process for the manufacture of poly-.alpha.-olefins by polymerizing .alpha.-olefins by means of a catalyst system comprising (1) a titanium-containing component obtained from (1.1) a compound of the formula TiCl.sub.3.1/3AlCl.sub.3 and (1.2) an organic electron donor, containing phosphorus, nitrogen and/or oxygen atoms, which has been milled with the compound of the formula TiCl.sub.3.1/3AlCl.sub.3 (1.1), in order to form a complex compound, the milling being carried out without assistants or additives in a vibratory ball mill under specific acceleration conditions and at a temperature which is from 4.degree. to 10.degree. C. below the temperature at which the particles of the material being ground begin to agglomerate, and (2) an aluminum-containing component, in which process the titanium-containing component (1) of the catalyst system used is one which has been treated, after milling and before polymerization, with (i) titanium tetrachloride and (ii) an ether and/or an ester.

Manufacture of poly-.alpha.-olefins

A process for the manufacture of homopolymers and copolymers of .alpha.-monoolefins by polymerizing the monomer or monomers at relatively low temperatures under relatively low pressures by means of a Ziegler-Natta catalyst comprising (I) a titanium chloride component and (II) an aluminumalkyl component, wherein the titanium chloride component (I) employed is obtained by exposing a conventional catalyst component consisting, or substantially consisting, of titanium trichloride or titanium tetrachloride, to a carbon dioxide atmosphere under specific conditions. Catalysts obtained from titanium chloride components (I) which have been treated in this way exhibit a relatively long induction period.

Manufacture of homopolymers and copolymers of .alpha.-monoolefins

A process for the preparation of homopolymers and copolymers of .alpha.-monoolefins by means of a Ziegler-Natta catalyst system comprising (1) a titanium halide of the formula

Process for the preparation of homopolymers and copolymers of

A special process for the preparation of a titanium component for polymerization catalysts of the Ziegler-Natta type, wherein (1) in a first stage (1.1) an alcoholate of the formula Mg(OR).sub.2, where R is lower alkyl, and (1.2) benzoyl chloride are milled together in a particular molar ratio in a vibratory ball mill under particular milling conditions, especially a relatively low temperature, in the absence of a diluent, thereafter (2) in a second stage (2.1) the material resulting from stage (1) is brought together with (2.2) titanium tetrachloride in a particular ratio, the batch is kept at an elevated temperature for some time, with constant mixing, and the resulting solid is isolated, excess titanium tetrachloride being removed, and finally (3) in a third stage (3.1) the solid resulting from stage (2) is again brought together with (3.2) titanium tetrachloride in a particular ratio, the batch is again kept at an elevated temperature for some time, with constant mixing, and the resulting solid, constituting the novel titanium component, is isolated, excess titanium tetrachloride being removed. The novel titanium component permits the preparation of .alpha.-monoolefin polymers in high yield and with high isotacticity.

Preparation of a component for polymerization catalysts

A special process for the preparation of a titanium component for polymerization catalysts of the Ziegler-Natta type, wherein (1) in a first stage (1.1) an alcoholate of the formula Mr(OR).sub.2, where R is lower alkyl and (1.2) a chlorotoluene of the formula ##STR1## where X is chlorine or hydrogen, are milled together in a particular molar ratio in a vibratory ball mill under particular milling conditions, especially a relatively low temperature, in the absence of a diluent, thereafter (2) in a second stage (2.1) the material resulting from stage (1) is brought together with (2.2) titanium tetrachloride in a particular ratio, the batch is kept for some time at an elevated temperature, with constant mixing, and the resulting solid is isolated, excess titanium tetrachloride being separated off, and finally (3) in a third stage (3.1) the solid resulting from stage (2) is again brought together with (3.2) titanium tetrachloride in a particular ratio, the batch is again kept for some time at an elevated temperature, with constant mixing, and the resulting solid, constituting the novel titanium component, is isolated, excess titanium tetrachloride being removed. The novel titanium compound permits the production of polymers of .alpha.-monoolefins not only in high yield but also with high isotacticity.

Preparation of a titanium component for polymerization catalysts of the

A process for the manufacture of homopolymers and copolymers of .alpha.-monoolefins by polymerizing the monomer or monomers at relatively low temperatures under relatively low pressures by means of a Ziegler-Natta catalyst comprising (I) a titanium trichloride component and (II) an aluminum-alkyl component, wherein the titanium trichloride component (I) employed is obtained by exposing a conventional catalyst component consisting, or substantially consisting, of titanium trichloride, to a carbon monoxide atmosphere under specific conditions. Catalysts obtained from titanium trichloride components (I) which have been treated in this way exhibit a relatively long induction period.

A process for the manufacture of homopolymers and copolymers of .alpha.-monoolefins by polymerizing the monomer or monomers by means of a Ziegler-Natta catalyst comprising (I) a titanium trichloride component and (II) an aluminum-alkyl component, wherein the titanium trichloride component (I) employed is obtained by (1) in a first stage moistening a suitable conventional catalyst component, consisting entirely or substantially of titanium trichloride, with a hydrocarbon mixture comprising a liquid alkane hydrocarbon and a liquid benzene hydrocarbon and (2) in a second stage drying the catalyst component, moistened with the hydrocarbon mixture, under an inert gas, with constant mechanical mixing, within a certain period, at a temperature which is from 5.degree. to 50.degree. C. above the boiling point of the highest-boiling hydrocarbon present in the hydrocarbon mixture which has been used to moisten the component. Homopolymers and copolymers having particularly advantageous morphological properties can be manufactured by the process of the invention.

A process for the manufacture of a modified titanium component for catalysts of the Ziegler/Natta type by milling a mixture of a titanium compound of the formula TiCl.sub.3 .13AlCl.sub.3 and an organic electron donor containing phosphorus and/or nitrogen atoms. The characterizing feature is that the mixture is first milled wet in a liquid inert hydrocarbon medium under specific conditions, then separated from the hydrocarbon medium and finally milled dry under specific conditions. Such modified titanium components give catalysts which provide particularly well reproducible results in the polymerization of .alpha.-olefins.

Manufacture of a modified titanium component for catalysts of the

A process for the manufacture of poly(.alpha.-olefins) by polymerization of .alpha.-olefins using a catalyst system comprising (1) a titanium-containing component of (1.1) a substance of the formula TiCl.sub.3 . 1/3 AlCl.sub.3 and (1.2) an organic electron donor containing phosphorus atoms and/or nitrogen atoms, ground together with said substance (1.1), and (2) an aluminum-containing component of a substance of formula Al(C.sub.n H.sub.2 ..sub.n.sub.+1).sub.3 or Al(C.sub.n H.sub.2..sub.n.sub.+1).sub.2 Cl, where n is an integer of from 2 to 6. The characteristic feature is that the catalyst system used is one in which the component (1.1) has been ground with component (1.2) without the use of auxiliaries or additives in a vibratory ball mill using specific steel balls and a specific grinding acceleration over a specific period of time at a temperature which is just below that at which the particles in the ground material begin to agglomerate. The advantage of this process is that the efficiency of the catalyst system is very high and/or poly(.alpha.-olefins) are obtained which have a particularly large fraction which is insoluble in boiling n-heptane.

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Bobenheim-Roxheim, Germany

Gerhard Staiger