Basf Aktiengesellschaft

Hans Schick

Heinz Mueller-Tamm

Johann Nickl

James F Jaggard

Erich Kolk

Peter Hennenberger

Guenther Schweier

Friedrich Urban

Karl-Heinz Fauth

Heinrich Mohr

Paul Schneider

Rudolf Herbeck

The conversion is increased in the preparation of polyisobutylene by polymerization of isobutylene in a polymerization zone at from 0.degree. to -130.degree. C. in the presence of from 0.01 to 1.0% by weight of a boron trifluoride catalyst, from 0.001 to 1.0% by weight of a molecular weight regulator and from 30 to 90% by weight of a low-boiling solvent which is inert under the reaction conditions, by a process in which the content of but-1-ene in the monomeric isobutylene is kept constant at from 1.9 to 2.1, in particular 2.0, % by weight.

Polymerization of isobutylene

A process for the manufacture of a titanium-containing component of a catalyst for the Ziegler-Natta polymerization of .alpha.-monoolefins, by (a) milling a titanium-containing compound of the general formula TiCl.sub.3.nAlCl.sub.3 (where n is a number from 0.01 to 1) with (b) an ether of a particular type or an ester of a particular type, wherein (1) a vibratory ball mill giving a relatively high milling acceleration is used, (2) the mill is first charged with the titanium-containing compound (a), after which it may or may not be run for a certain period, thereafter (3) while milling, the amount of the ether or ester (b) which corresponds to a particular molar ratio of aluminum in the titanium-containing compound (a) to ether or ester (b) is added continuously or in small portions, then (4) the batch is milled for a certain period, after which (5) the product obtained from stage (4) may or may not be washed with a hydrocarbon and dried, and following which (6) the product obtained from stage (4) or (5) may or may not be milled for a certain period at a low temperature, next (7) the product obtained from stage (4), (5) or (6) is brought together with a liquid silicon compound of a particular type or a liquid tin compound of a particular type (these compounds acting as promoters) and the batch is left for a certain period and is then separated into a solid-phase product and into a liquid-phase product, and thereafter (8) the solid-phase product obtained from stage (7) is washed with a hydrocarbon or with one of the promoters mentioned under (7) and is dried, following which (9) the product obtained from stage (8) may or may not be milled for a certain period at a low temperature. Using the titanium-containing catalyst components thus obtainable makes it possible to produce polymers, having a high stereoregularity, in high specific yields.

Manufacture of a titanium-containing component for catalysts of the

A process for the manufacture of a titanium-containing component of a catalyst for the polymerization of monoolefins by the Ziegler-Natta method by milling (a) a particular titanium-containing compound, viz. a titanium trichloride/aluminum trichloride complex and (b) a particular ester with one another, in which process (1) a vibratory ball mill producing a particular milling acceleration is used, (2) the mill is first charged with the titanium-containing compound (a) and may or may not then be run for some time in the absence of diluents, (3) while milling, the ester (b) is added at a particular rate, continuously or in small portions, and in the absence of diluents, thereafter (4) the grist is brought to an elevated temperature, while milling, and is kept at this temperature until from 5 to 85% of the aluminum trichloride originally present in a bonded form in the titanium-containing compound (a) have been eliminated from the said compound (a), after which (5) if appropriate, the product obtained in accordance with (4) is washed with a hydrocarbon and dried, and then (6) the product obtained in accordance with (4) or in accordance with (5) is milled for a certain length of time at a low temperature in the absence of a diluent. Polyolefins of high stereoregularity can be obtained in a high specific yield by means of the catalyst component manufactured according to the invention.

A process for the manufacture of a titanium-containing component of a catalyst for the polymerization of monoolefins by the Ziegler-Natta method by milling (a) a particular titanium-containing compound, viz. a titanium trichloride/aluminum trichloride complex and (b) a particular ether with one another, in which process (1) a vibratory ball mill producing a particular milling acceleration is used, (2) the mill is first charged with the titanium-containing compound (a) and may or may not then be run for some time in the absence of diluents, (3) while milling, the ether (b) is added at a particular rate, continuously or in small portions, and in the absence of diluents, thereafter (4) the grist is brought to an elevated temperature, while milling, and is kept at this temperature until from 6 to 85% of the aluminum trichloride originally present in a bonded form in the titanium-containing compound (a) have been eliminated from the said compound (a), after which (5) the product obtained according to (4) is washed with a hydrocarbon and then (6) the product obtained in accordance with (5) is dried and milled for a certain length of time at a low temperature in the absence of a diluent. Polyolefins of high stereoregularity can be obtained in a high specific yield by means of the catalyst component manufactured according to the invention.

A process for the manufacture of a titanium-containing component of a catalyst for the polymerization of monoolefins by the Ziegler-Natta method by milling (a) a titanium trichloride/aluminum trichloride complex and (b) a particular ether with one another, in which process (1) a vibratory ball mill producing a particular milling acceleration is used, (2) until from 6 to 85% of the aluminum trichloride originally present in a bonded form in the titanium-containing compound (a) have been eliminated from the said compound (a). Polyolefins of high stereoregularity can be obtained in a high specific yield by means of the catalyst component manufactured according to the invention.

A process for the manufacture of a modified titanium-containing component of a catalyst for the polymerization of a .alpha.-monoolefins by the Ziegler-Natta method wherein (a) a compound containing titanium and (b) a compound containing phosphorus are ground dry in a vibratory ball mill. It is characteristic of the process that (1) a mill of relatively large useful volume is employed, (2) the mill is first charged with the compound (a) containing titanium, (3) while grinding the material at a low temperature, the compound (b) containing phosphorus is added gradually, thereafter (4) the material is gradually brought to a higher temperature, while continuing the grinding, and is kept at about this temperature for a prolonged period, then (5) a finely particulate 1-alkene polymer having a particular glass transition temperature and a particular intrinsic viscosity is added to the material and finally (6) the material is kept at a low temperature for a prolonged period, while continuing the grinding.

Manufacture of a modified titanium component for catalysts of the

A process for the manufacture of a modified titanium-containing component of a Ziegler-Natta catalyst for the polymerization of C.sub.3-6 .alpha.-monoolefins, wherein a specific titanium-containing compound and a specific phosphorus-containing compound are dry-milled at a specific grinding acceleration in a vibratory ball mill. The characteristic feature of the process of the invention is that a mill is used which has a specific useful volume and the mill is initially charged with a specific amount of the titanium-containing compound, which is milled at a low temperature while the phosphorus-containing compound is gradually added, whereupon milling is continued while the temperature of the process material is gradually raised to a specific value and maintained at said value for a specific period of time, whereupon, if desired, milling is again continued at a lower temperature for a specific period of time. In this manner, modified titanium-containing components are obtained which in the polymerization process produce highly reproducible yields of polymer.

Manufacture of a modified titanium component for Ziegler-Natta catalysts

Copolymers of 4-methylpentene-1 are prepared by copolymerization of 4-methylpentene-1 with one or more other C.sub.2-18 .alpha.-alkenes at a temperature above room temperature and in the presence of hydrogen using a Ziegler/Natta catalyst system. The polymerization is carried out at a relatively very high temperature and in the presence of an inert gas with the proviso that the partial pressures of the inert gas and of the hydrogen and the sum of the partial pressures of the inert gas, hydrogen and 4-methylpentene-1 have specific values. In this way, copolymers having large crystalline fractions are obtained in a high yield per unit of catalyst system per unit time.

Manufacture of copolymers of 4-methylpentene-1

Homopolymers of 4-methylpentene-1 are prepared by homopolymerization of 4-methylpentene-1 at a temperature above room temperature, in the presence of hydrogen and in contact with a Ziegler/Natta catalyst system. The polymerization is carried out at a relatively very high temperature and in the presence of an inert gas, the polymerization system being under a specific total pressure, while the partial pressures of the inert gas and the hydrogen have specific values. In this way, homopolymers having large crystalline fractions are obtained in high yields per unit of catalyst system per unit time.

Manufacture of homopolymers of 4-methylpentene-1

Particulate polymers of ethylene are prepared by polymerization of ethylene or ethylene/.alpha. -monoalkene mixtures in a dry agitated bed (B) of the particulate polymer by means of a Ziegler/Natta catalyst system consisting of (1) a titanium-containing component and (2) an aluminum-containing component, the said components (1) and (2) being separately fed to the bed (B). Component (1) is a particulate reaction product (U) (of) (1.1) a substance of the formula TiCl.sub.3 . (AlCl.sub.3).sub.n where n is a number equal to from 0 to 0.34, and (1.2) a reaction product (R) of phosgene and a substnace (S) obtained from a substance of the formula Mg.sub.6 . Al.sub.2 . (OH).sub.16 . CO.sub.3 . (H.sub.2 O).sub.4 by calcination (heating), provided that (R) has a chlorine content of from 10 to 76% by weight and (U) has been obtained by milling (1.1) and (1.2) together.

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Mannheim, Germany

Hans Schick