Basf Aktiengesellschaft

James F Jaggard

Heinz Mueller-Tamm

Guenther Schweier

Hans Schick

Peter Klaerner

Johann Nickl

Wolfgang Gruber

Rainer Alexander Werner

Gerhard Staiger

Paul Schneider

Polymers of polypropylene are prepared by means of a Ziegler-Natta catalyst system comprising (1) a titanium component which contains titanium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component, wherein the (1) used is obtained by (1.1) first reacting with one another (1.1.1) in a liquid hydrocarbon, (1.1.2) a finely divided magnesium halide, (1.1.3) an alkanol, (1.1.4) a phthalic acid ester and (1.1.5) titanium tetrachloride under certain conditions, (1.2) then extracting the solid intermediate obtained from (1.1) with titanium tetrachloride until the remaining solid substance has become significantly richer in magnesium, and (1.3) finally washing the solid substance remaining in (1.2) with an alkane in a certain manner.

Preparation of homopolymers and copolymers of propylene by means of a

Polymers of propylene are prepared by means of a Ziegler-Natta catalyst system comprising (1) a titanium component which contains titanium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component, wherein the (1) used is obtained by (1.1) first reacting with one another (1.1.1) in a liquid hydrocarbon, (1.1.2) a finely divided magnesium halide, (1.1.3) an alkanol, (1.1.4) a phthalic acid ester and (1.1.5) titanium tetrachloride under certain conditions, (1.2) then extracting the solid intermediate obtained from (1.1) with a liquid alkylbenzene until the remaining solid substance has become significantly richer in magnesium, and (1.3) finally washing the solid substance remaining in (1.2) with an alkane in a certain manner.

Propylene/ethylene block copolymers are prepared by a process in which, in an agitated bed comprising small polymer particles, first (I) propylene is homopolymerized from the gas phase, in a first polymerization zone, by feeding in a Ziegler-Natta catalyst comprising (1) a titanium(III) component and (2) a dialkyl-aluminum chloride component, with or without (3) a further catalyst component, and then (II) the product obtained in the first polymerization zone is fed into a second polymerization zone, where a mixture of propylene and ethylene is polymerized with the propylene homopolymer present in this product. In this process, the Ziegler-Natta catalyst employed contains a titanium(III) component (1) which is prepared by subjecting (1.1) a titanium-containing compound (a) of the formula TiCl.sub.3. nAlCl.sub.3 and (1.2) an electron donor (b), consisting of (b.sub.1) an ester of a particular class or (b.sub.2) a phosphorus-containing compound of a particular class, to a special milling procedure, the particular features of which are special metering and temperature conditions, suspending the resulting intermediate in a mixture of a liquid hydrocarbon (c) and an oxygen-containing compound (d), comprising (d.sub.1) an ether of a certain class and/or (d.sub.2) an ester of a certain class, and then heating the suspension obtained. The solid remaining in suspension is the titanium(III) component (1) which is to be employed for the polymerization. The polymer obtained has improved morphological properties.

Preparation of propylene/ethylene block copolymers

A process for the preparation of homopolymers and copolymers of .alpha.-monoolefins by means of a Ziegler-Natta catalyst system comprising (1) a titanium-III component, which is prepared by subjecting (1.1) a titanium trichloride/aluminum trichloride compound (a) and (1.2) an ester (b) to a certain type of milling treatment in which (A) a vibratory ball mill providing a relatively high milling acceleration is used, (B) the mill is first charged with the titanium-containing compound (a) and, if appropriate, is run for a certain period, thereafter (C) the ester (b) is added at a certain rate while milling the charge, thereupon (D) the charge is kept at +15.degree. C. or above for a certain period, while continuing the milling, hereupon (E), if appropriate, the product obtained from (D) is milled further for a certain period at +5.degree. C. or below, then (F), if appropriate, but advantageously so, the product obtained from (D) or (E) is kept at +20.degree. C. or above for a certain period, without milling, and thereafter (G), if appropriate, the product obtained from (F) is milled further for a certain period at +5.degree. C. or below, (2) an aluminum-alkyl component containing a chlorine bonded to the aluminum, and (3), if appropriate, a phenolic compound of a certain category, in which process a titanium-III component (1) is employed, in the preparation of which additionally .sup.- (H) a suspension is prepared from (H.sub.1) the product obtained according to (D), (E), (F) or (G), (H.sub.2) a liquid hydrocarbon (c) and (H.sub.3) an oxygen-containing compound (d), consisting of (d.sub.1) an ether of a certain category and/or (d.sub.2) an ester of a certain category, thereafter (I) the suspension obtained according to (H) is kept at an elevated temperature for a certain period, with vigorous agitation, and is then cooled, hereupon (J), if appropriate, the solid is isolated from the suspension obtained according to (I), and, if desired, is washed with a liquid hydrocarbon and dried, the novel titanium-III component (1) being the solid, in suspended form, obtained according to (I) or the solid, in isolated form, obtained according to (J). Using this Ziegler-Natta catalyst system, polymers with relatively high stereo-regularity and advantageous morphological properties can be obtained in relatively high yield.

Preparation of homopolymers and copolymers of .alpha.-mono-olefins by

Alpha-olefins are polymerized with a catalyst containing (1) TiCl.sub.3 /AlCl.sub.3 and (2) aluminum dialkyl chloride wherein (1) is prepared by milling the TiCl.sub.3 /AlCl.sub.3 with a particular phosphorous compound under special conditions and then treating with a liquid hydrocarbon and an ether and/or ester.

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

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 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.

Growing community of inventors

Ludwigshafen, Germany

James F Jaggard