Basf Aktiengesellschaft

Robert Bachl

Guido Funk

Guenther Schweier

Wolfgang Gruber

Hans Frielingsdorf

Volker Warzelhan

Heinz Mueller-Tamm

Erich Kolk

Wolfgang Ball

Roland Saive

Konrad Richter

Rainer Karer

Peter Klaerner

Hans Gropper

Rainer Hemmerich

Gunther Schweier

Martin Laun

Dieter Stein

Peter Hennenberger

Rudolf Mueller-Mall

Leonhard Gonsior

Ehler Ehlers

The homopolymerization and copolymerization of ethene are carried out using a Ziegler catalyst system consisting of

Preparation of homopolymers of ethene and copolymers of ethene with high

A process for the preparation of homopolymers and copolymers of .alpha.-monoolefins by polymerization of the monomer or monomers using a Ziegler catalyst system comprising (1) a transition metal catalyst component and (2) an organoaluminum catalyst component, in which the transition metal catalyst component (1) employed is a solid-phase product (VI) obtained by (1.1) first bringing (1.1.1) a finely divided, porous, inorganic oxidic substance (I) as the carrier, and (1.1.2) a solution (II), as obtained on combining (IIa) an alcohol and (IIb) a transition metal composition, into contact with one another to form a suspension (III), evaporating this suspension to dryness (formation of a solid-phase intermediate (IV)) and (1.2) then (1.2.1) bringing the solid-phase intermediate (IV) obtained from stage (1.1), and (1.2.2) a solution of an organoaluminum compound (V) in an organic solvent, into contact with one another to form a suspension, the resulting suspended solid-phase product (VI) being transition metal catalyst component (1), wherein the transition metal catalyst component (1) employed in a solid-phase product (VI) obtained using a transition metal composition (IIb) comprising (IIb1) a vanadium trihalide, (IIb2) a titanium trihalide and (IIb3) a zirconium tetrahalide.

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

Homopolymerization and copolymerization of ethene are carried out using a Ziegler catalyst system consisting of (1) a transition metal catalyst component prepared by a method in which (1.1) first (1.1.1) an inorganic oxide substance (I) as a carrier and (1.1.2) a solution (II) of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex, (IIb2) a titanium trihalide or titanium trihalide/alcohol complex and, if desired, (IIb3) a zirconium tetrahalide, are combined with formation of a suspension (III), the latter is evaporated down to form a solid-phase intermediate (IV), (1.2) then (1.2.1) the solid-phase intermediate (IV) obtained from (1.1), and (1.2.2) a dissolved organoaluminum compound (V), are combined with formation of a suspension, the resulting suspended substance being a solid-phase product (VI), (2) an organoaluminum catalyst component and (3) an organohalogen catalyst component. In this process, the transition metal catalyst component (1) used is one prepared by a method in which (1.3) in addition (1.3.1) the product (VI) obtained from (1.2) is reacted with (1.3.2) oxygen, the resulting solid-phase end product (VII) being the novel transition metal catalyst component (1).

Preparation of homopolymers of ethene and copolymers of ethene with

A process for the continuous preparation of finely divided homopolymers and copolymers of ethene by catalytic polymerization in a circular tube reactor using a liquid alkane as reaction medium in which the ethene or ethene/comonomer mixture to be polymerized is present in dissolved form and the polymer formed is present in suspended form and running the reaction mixture as a cycle stream to which the feed materials are added by bleeding in and from which the polymer formed is withdrawn by bleeding out reaction mixture, comprising (a) maintaining the mean concentration C.sub.m of polymer in the cycle stream at a value within a certain range and (b) effecting the bleeding out of reaction mixture at a point of the cycle stream at which the concentration of polymer has a value which is lower than the mean concentration C.sub.m by a distinct and definite amount.

Preparation of finely divided homopolymers and copolymers of ethene

Homopolymers and copolymers of ethene are prepared using a Ziegler catalyst system comprising (1) a transition metal catalyst component, (2) an organoaluminum catalyst component and (3) an organohalogen catalyst component, by a method in which the transition metal catalyst component (1) employed is a solid-phase product (VI) obtained by (1.1) first combining (1.1.1) an inorganic oxidic substrate (I), as the carrier, with (1.1.2) a solution (II) consisting of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex, (IIb2) a titanium trihalide or titanium trihalide/alcohol complex and, if required, (IIb3) a zirconium tetrahalide to form a suspension (III), evaporating down this suspension to form a solid-phase intermediate (IV), and (1.2) then (1.2.1) combining the solid-phase intermediate (IV) obtained from (1.1) with (1.2.2) a solution of an organoaluminum compound (V) to form a suspension, the resulting suspended solid-phase product (VI) being the transition metal catalyst component (1).

.alpha.-Monoolefins are polymerized using a Ziegler catalyst system comprising (1) a transition metal catalyst component and (2) an organoaluminum catalyst component, in which (1) is a solid-phase product (VI) obtained by (1.1) first combining (1.1.1) an inorganic oxidic substance (I), as the carrier, with (1.1.2) a solution (II) consisting of (IIa) an organic solvent and (IIb) a transition metal composition to form a suspension (III), evaporating down this suspension to form a solid-phase intermediate (IV), and (1.2) then (1.2.1) combining the solid-phase intermediate (IV), obtained from (1.1), with (1.2.2) a solution of an organoaluminum compound (V) to form a suspension, the resulting suspended solid-phase product (VI) being the transition metal catalyst component (1). The characteristic feature is that (1) is a solid-phase product (VI) obtained using a solution (II) consisting of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex, (IIb2) a titanium trihalide and (IIb3) a zirconium tetrahalide.

Preparation of homopolymers and copolymers of .alpha.-monolefins using a

A transition metal catalyst component (1) for Ziegler catalyst systems is prepared by (1.1) first combining (1.1.1) an inorganic oxidic substance (I), as the carrier, with (1.1.2) a solution (II) consisting of (IIa) an organic solvent and (IIb) a transition metal composition to form a suspension (III), evaporating down this suspension to form a solid-phase intermediate (IV) and (1.2) then combining (1.2.1) the solid-phase intermediate (IV) obtained from (1.1) with (1.2.2) a solution of an organoaluminum compound (V) to form a suspension, the resulting suspended solid-phase products (VI) being the transition metal catalyst component (1). The characteristic feature is that the solution (II) employed in stage (1.1) consists of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex, (IIb2) a titanium trihalide and (IIb3) a zirconium tetrahalide.

Preparation of a transition metal catalyst component for Ziegler

A process for the preparation of homopolymers and copolymers of .alpha.-monoolefins by polymerizing the monomer or monomers with a Ziegler catalyst system comprising (1) a titanium-containing catalyst component and (2) a relevant conventional organo-aluminum compound, (1.1) the catalyst component (1) having been prepared by (1.1.1) milling a titanium compound (I) of the formula TiCl.sub.3.z(AlCl.sub.3) or Cl.sub.m Ti(OB).sub.4-m, where z is from 0 to 0.5, m is from 0 to 3 and B is alkyl, together with (1.1.2) a magnesium alcoholate (II) and, if desired, (1.1.3) a metal chloride (III) of the formula AlCl.sub.3, ZnCl.sub.2 or MnCl.sub.2, to form a milled product (IV), in which polymerization process a catalyst component (1) is employed, in the preparation of which (1.2) the milled product (IV) obtained according to (1.1) is brought together, in an additional step (1.2.1), with (1.2.2) an alkanol (V) and (1.2.3) a liquid alkane (VI), to form a suspension (VII), and thereafter (1.3), in a further additional step (1.3.1), there is added, to the suspension (VII) obtained according to (1.2), (1.3.2) a metal compound (VIII) of a certain type, the metal being aluminum, silicon or titanium, while preserving the suspension state, the product (IX), which results from stage (1.3) and is present as a solid phase in the suspension, constituting the titanium-containing catalyst component (1).

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

A process for the preparation of ethylene homopolymers, and ethylene copolymers with minor amounts of higher .alpha.-monoolefins, by polymerizing the monomer or monomers by means of a supported catalyst (1) containing a chromium-hydrocarbon complex (1.2) on an inorganic oxide carrier (1.1), wherein (1) a supported catalyst is employed which contains (1.2) a chromium-hydrocarbon complex of the formula RCrACrR, where R is a cyclic and/or open-chain hydrocarbon, or hydrocarbon radical, of 2n and 2n+1 carbon atoms respectively and having from 1 to n non-cumulated double bonds, n being from 2 to 10, Cr is chromium and A is cyclooctatetraene, a divalent n-octatetraene radical or alkyl-substituted homologs thereof, on (1.1) a particular inorganic oxide carrier, with or without (2) a co-catalyst chosen from a particular group of alkyl-aluminum compounds. The process gives polymers having a particularly broad molecular weight distribution.

Process for producing ethylene polymers and copolymers by means of a

Manufacture of polymers of .alpha.-monoolefins by polymerization with a Ziegler catalyst system comprising (1) a catalyst component containing titanium and/or vanadium and (2) a particular compound of the metals aluminum, magnesium or zinc. The characteristic feature of the process according to the invention is that the catalyst component (1) containing titanium and/or vanadium is the solid-phase product (VII) contained by first (1.1) bringing a finely divided porous inorganic oxidic material (I), which has the formula Al.sub.2 O.sub.3 or SiO.sub.2.aAl.sub.2 O.sub.3, where a is a number from 0 to 2, into contact with an aluminum compound (II) dissolved in an organic solvent, to form a solid-phase product (III), then (1.2) bringing the solid-phase product (III) obtained in stage (1.1) into contact with a magnesium compound (IV), dissolved in an organic solvent, to form a solid-phase product (V), and finally (1.3) bringing the solid-phase product (V) obtained in stage (1.2) into contact with a compound (VI) of the transition metals titanium and/or vanadium to form a solid-phase product (VII). This process functions better than comparable conventional processes.

Manufacture of olefin polymers

A process for the manufacture of olefin polymers by polymerizing .alpha.-monoolefins at relatively low temperatures and relatively low olefin pressures by means of a catalyst obtained from a silicate carrier (component a), an aluminum compound (component b) and a chromium compound (component c). The catalyst is obtained by (1) in a first stage, initially (1.1) charging a particular silicate carrier (component a) with (1.2) a mixture of (1.2.1) an aluminum salt or a mixture of an aluminum salt with up to 80 mole%, based on the salt mixture, of a nickel-II salt (component b) and (1.2.2) a chromium compound (component c), this compound being chromium trioxide or a compound which is converted to chromium trioxide under the conditions of stage (2), by treatment with a solution of the mixture (1.2), and (2), in a second stage then maintaining the product, obtained from stage (1), for a certain time at a high temperature in an anhydrous oxygen-containing gas stream. The process may be used to produce polymers having a relatively broad molecular weight distribution.

A process for the manufacture of homopolymers and copolymers of .alpha.-monoolefins of 2 to 6 carbon atoms by polymerizing the monomer or monomers by means of a Ziegler catalyst system comprising (1) a catalyst component containing titanium and (2) a particular compound of aluminum, magnesium or zinc, the atomic ratio of titanium from catalyst component (1) to metal (Me) from catalyst component (2) being from 1 : 0.1 to 1 : 500, wherein the titanium-containing catalyst component (1) employed is the solid-phase product (VI) obtained by (1.1) first bringing into contact (1.1.1) a particular finely divided, porous, inorganic oxidic material (I) and (1.1.2) a particular aluminum compound (II) dissolved in an organic solvent, to form a solid-phase product (III) and (1.2) then bringing into contact (1.2.1) the solid-phase product (III) obtained from stage (1.1) and (1.2.2) a solution (IV) which is obtained on bringing together (IVa) 100 parts by weight of a particular alcohol, (IVb) from 0.01 to 6 parts by weight (calculated as titanium) of a titanium trihalide and (IVc) from 0.01 to 4 parts by weight (calculated as magnesium) of a magnesium compound which is soluble in the alcohol (IVa), to form a dispersion (V), and evaporating the dispersion (V) until it has a dry consistency, thus forming the solid-phase product (VI). The new process is particularly advantageous for the manufacture of homopolymers and copolymers having, for example, particularly advantageous morphological properties.

Manufacture of homopolymers and copolymers of .alpha.-monoolefins

A process for the manufacture of homopolymers and copolymers of .alpha.-monoolefins of 2 to 6 carbon atoms by polymerizing the monomer or monomers by means of a Ziegler catalyst system comprising (1) a catalyst component containing titanium and (2) a particular compound of the metals aluminum, magnesium or zinc, the atomic ratio of titanium from catalyst component (1) to metal from catalyst component (2) being from 1:0.1 to 1:500, wherein the titanium-containing catalyst component (1) employed is the solid-phase product (IV) obtained by bringing into contact (1.1) a finely divided, porous, inorganic oxidic material (I) which has the formula SiO.sub.2 . aAl.sub.2 O.sub.3 --, where a is a number from 0 to 2, and (1.2) a solution (II) formed on bringing together (IIa) 100 parts by weight of an alcohol of the general formula Z--OH, where Z is a saturated hydrocarbon radical of 1 to 8 carbon atoms, (IIb) from 0.01 to 6 parts by weight (calculated as titanium) of a titanium trihalide and (IIc) from 0.01 to 4 parts by weight (calculated as magnesium) of a magnesium compound which is soluble in the alcohol (IIa), so as to form a dispersion (III), with the proviso that the weight ratio of inorganic oxidic material (I) to titanium in the titanium trihalide (IIb) is from 1:0.01 to 1:0.2 and the weight ratio of inorganic oxidic material (I) to magnesium in the magnesium compound (IIc) is from 1:0.01 to 1:0.25, and evaporating the dispersion (III) until it has a dry consistency, thus forming the solid-phase product (IV). The new process is particularly advantageous for the manufacture of homopolymers and copolymers having, for example, particularly advantageous morphological properties.

This invention relates to a process for the manufacture of olefin polymers by polymerization of monoolefins with the aid of a silicic xerogel/chromium trioxide catalyst obtained by (1) synthesizing a particulate silicic xerogel, (2) doping this xerogel with chromium trioxide or a chromium compound which converts to chromium trioxide under conditions of stage (3) and (3) maintaining the resulting product at an elevated temperature in a water-free oxygen-containing stream of gas. The characteristic feature of the process of the invention is that the silicic xerogel/chromium trioxide catalyst used is one obtained by (1) synthesizing the silicic xerogel in the first stage as follows: (1.1) taking an aqueous solution of a sodium silicate, (1.2) substituting substantially all of the sodium ions contained in said solution by hydrogen ions by means of an ion exchanger, (1.3) introducing a water-soluble aluminum salt into the resulting aqueous silicic acid solution, (1.4) adjusting the pH of the solution obtained in stage (1.3) to from 0.1 to 3.5, if necessary, (1.5) adjusting the solution obtained in (1.3) or (1.4) to a pH of from 4 to 12 by means of a nitrogen-base compound, (1.6) extracting the product forming the solid phase in stage (1.5) (silicic hydrogel) by means of an alkanol and/or alkanone until the organic liquid absorbs no more water and, finally, (1.7) drying the dehydrated gel saturated with organic liquid resulting from stage (1.6) (xerogel formation). This process makes it possible to obtain polymers having a satisfactory particle size distribution and a favorable melt index.

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Worms, Germany

Robert Bachl