Basf Aktiengesellschaft

Basf Aktiengsellschaft

Rainer Konrad

Guido Funk

Roland Saive

Guenther Schweier

Hans-Joachim Mueller

Kaspar Evertz

Martin Lux

Hans-Helmut Goertz

Rudolf Mueller-Mall

Siegfried Weber

Bernhard Rieger

Peter Bauer

Juergen Schmidt-Thuemmes

Hans Gropper

Peter Koelle

Godofredo Follmer

Dieter Lilge

Volker Warzelhan

Bernd Lothar Marczinke

Juergen Kerth

Max Strohmeyer

Rainer Hemmerich

Herbert Morgenstern

Horst Schuch

A process for the preparation of a supported catalyst for the polymerization of .alpha.-olefins, in which

Preparation of a supported catalyst for the polymerization of

A novel Phillips catalyst for the copolymerization of ethylene with .alpha.-olefins, contains, as a catalytically active component, a finely divided, aluminum silicate-supported, phosphorus-containing chromium catalyst. This can be prepared by applying at least one organic phosphorus(III), (IV) and/or (V) compound and at least one chromium(III) compound which does not react with said phosphorus compounds under the reaction conditions used, in succcession in any order or simultaneously, to a finely divided aluminum silicate hydrogel or xerogel with formation of a catalyst intermediate and activating the catalyst intermediate at elevated temperatures in an oxidizing atmosphere, with the result that the chromium catalyst is formed. The novel Phillips catalyst gives ethylene/.alpha.-olefin copolymers in which the comonomers are more uniformly distributed over the copolymer chains than is the case with ethylene/.alpha.-olefin copolymers which have been prepared with the aid of conventional Phillips catalysts. Moldings which have been produced from the ethylene/.alpha.-olefin copolymers obtained in the novel procedure have a particularly high environmental stress cracking resistance and an excellent creep rupture strength.

Phillips catalyst and its use for the preparation of

Low density ethylene copolymers are obtainable by adding an aromatic hydrocarbon solution of a catalyst system, containing, as active components, metallocene complexes of metals of subgroups IV and V of the Periodic Table and oligomeric alumina compounds, to a mixture containing ethylene, comonomers and aliphatic hydrocarbons.

Process for preparing low density ethylene copolymers

Homopolymers of ethylene or copolymers of ethylene with minor amounts of other C.sub.3 -C.sub.12 -alk-1-enes are prepared by catalytic polymerization in a suspension or in the gas phase in the presence of an antistatic agent at from 50 to 120.degree. C. and from 5 to 50 bar by a process in which the antistatic agent used is a mixture of the following substances: a) a metal salt of medialanic acid of the formula (I) ##STR1## b) a metal salt of an anthranilic acid of the general formula (II) ##STR2## where the organic radical R.sup.1 is either

Preparation of homopolymers of ethylene or copolymers of ethylene

A novel Phillips catalyst for the homopolymerization of ethylene and the copolymerization of ethylene with .alpha.-olefins contains, as a catalytically active component, a chromium catalyst supported on a finely divided aluminum silicate gel, modified with a fluoride and activated in an oxidizing atmosphere at elevated temperatures. The finely divided aluminum silicate gel (carrier gel) used here has an alumina content of from 0.5 to 6% by weight, the alumina being concentrated in the surface region of the carrier gel particles. The novel Phillips catalyst has high productivity and gives high molecular weight ethylene homopolymers and copolymers which have excellent low temperature impact strength and do not tend to swell in the blow molding process on emergence from the extruder die.

Phillips catalyst and its use for the preparation of ethylene

A novel Phillips catalyst for the homopolymerization of ethylene and the copolymerization of ethylene with .alpha.-olefins contains as catalytically active components a specific chromium catalyst on an aluminum phosphate support and cocatalysts of the formula I to IV, ##STR1## where M is lithium, sodium and potassium,

Phillips catalyst and its use for preparing ethylene homopolymers and

A process for propene oligomerization catalyzed by transition metal complexes in liquid phase to give propene oligomers with a high content of terminal double bonds, comprises oligomerizing propene in the presence of a catalyst of the formula I

Preparation of propene oligomers

For the production of extrudates of ultra-high molecular weight polyethylene, finely divided polyethylene or polyethylene powder is introduced into the cooled feed zone of a single-screw extruder and compressed therein, melted in a transport zone of the extruder and discharge with shaping of the extrudate and cooling. The polyethylene is processed in the transport zone using a velocity gradient of from 50 to 1,000 sec.sup.-1 in the radial play between the screw and the extruder barrel, heated to 180.degree.-280.degree. C. and then transferred to a screw-free zone in which final shaping of the extrudate is effected.

Production of hardwearing and shock-resistant extrudates of ultra-high

High density ethylene polymers are prepared by polymerizing the monomers in the presence of a Ziegler catalyst system by a process in which the resulting solid ethylene polymer is reacted in the melt with an additive capable of binding acids by esterification. The ester-forming additives are preferably epoxide compounds.

Preparation of ethylene polymers using a Ziegler catalyst system, and

Ethene homopolymers and ethene copolymers with minor amounts of higher .alpha.-monoolefins are prepared by polymerization of the monomer or monomers using a chromium trioxide catalyst which is obtained by a method in which (1) a finely divided, porous, silicate carrier is laden with (2) chromium trioxide or a chromium compound which is converted to chromium trioxide under the conditions of stage (3), and then (3) the intermediate resulting from stage (2) is heated in an oxygen-containing gas stream. In this process, a cocatalyst which consists of a lithiumalkyl used in addition to the chromium trioxide catalyst.

Preparation of homopolymers and copolymers of ethene using a chromium

Ethene polymerization by Phillips catalysis is carried out using (1) a supported catalyst, which is laden with chromium, phosphorus and aluminum, and (2) a cocatalyst, (1) being obtained by a method in which (1.1) a catalyst intermediate laden with chromium, phosphorus and aluminum is prepared from a silicate carrier, a selected chromium compound, a selected phosphorus compound and a selected aluminum compound, and then (1.2) the catalyst intermediate is heated in an oxygen-containing gas stream. In this process, the component (1) used is one which is obtained by a method in which, in each case in a specific manner, (1.1) in a first stage, (1.1.1) first a suspension is prepared from (1.1.1.1) a finely divided silicate carrier and (1.1.1.2) an inert organic solvent, (1.1.2) then, (1.1.2.1) in an inert organic solvent, (1.1.2.2) an organic chromium compound is combined with (1.1.2.3) an aluminum trialkyl, (1.1.3) then (1.1.3.1) the suspension resulting from (1.1.1) is combined with (1.1.3.2) a phosphoric acid or phosphite and (1.1.3.3) the product obtained from (1.1.2), (1.1.4) finally, the suspension obtained in (1.1.3) is evaporated to dryness, and then (1.2) in a second stage, first (1.2.1) the intermediate obtained from (1.1) is treated with a stream of nitrogen, then (1.2.2) the intermediate obtained from (1.2.1) is heated in an oxygen-containing gas stream, and finally (1.2.3) the intermediate obtained from (1.2.2) is treated with a stream of nitrogen, and both a lithiumalkyl and a boronalkyl are used as (2).

Preparation of homopolymers and copolymers of ethene by Phillips

Ethene polymers are prepared by Phillips catalysis using (1) a supported catalyst which is loaded with chromium and titanium and (2) a co-catalyst, (1) having been obtained by preparing (1.1) a chromium- and titanium-loaded catalyst intermediate from (1.1.a) a silicate carrier material, (1.1.b) a selected chromium compound and (1.1.c) a selected titanium compound and then (1.2) heating said catalyst intermediate in an oxygen-containing gas stream, the (1) used having been obtained by, in general terms, (1.1) preparing in the first stage (1.1.1) a suspension from (1.1.1.1) a finely divided silicate carrier material and (1.1.1.2) a liquid alkane, (1.1.2) then (1.1.2.1) combining the suspension resulting from (1.1.1.) with (1.1.2.2.) a finely divided chromium trioxide, (1.1.3) thereupon (1.1.3.1) combining the suspension obtained from (1.1.2) with (1.1.3.2) an alkanol, (1.1.4) thereafter (1.1.4.1) combining the suspension formed in (1.1.3) with (1.1.4.2) a titanium compound of the formula Ti(OR).sub.4, where R is alkyl, aryl or cycloalkyl, and (1.1.5) finally evaporating the suspension obtained in (1.1.4) to dryness, and then (1.2) in the second stage first (1.2.1) treating the catalyst intermediate obtained in the first state (1.1) with a nitrogen stream, thereupon (1.2.2) heating the intermediate obtained in (1.2.1) in an oxygen-containing gas stream, and finally (1.2.3) treating the intermediate obtained in (1.2.2) with a nitrogen stream; and as (2) with an alkyllithium.

Ethane polymers are prepared by Phillips catalysis using (1) a supported catalyst which is laden with chromium, phosphorus and titanium and (2) a cocatalyst, (1) being obtained by a procedure in which (1.1) a catalyst intermediate laden with chromium, phosphorus and titanium is prepared from a silicate carrier, a selected chromium compound, a selected phosphorus compound and a selected titanium compound, and (1.2) the catalyst intermediate is then heated in an oxygen-containing gas stream. In the process, the supported catalyst (1) used is one which is obtained (using specific methods and substances in each case) by a procedure in which (1.1) in a first stage (1.1.1), a suspension is first prepared from (1.1.1.1) a finely divided silicate carrier and (1.1.1.2) an inert organic solvent, (1.1.2) a suspension is then prepared from (1.1.2.1) a finely divided chromium trioxide and (1.1.2.2) an inert organic solvent, (1.1.3) thereafter (1.1.3.1) the suspension resulting from (1.1.2) is combined with (1.1.3.2) a phosphate or phosphite, (1.1.4) then (1.1.4.1) the suspension obtained from (1.1.1) is combined with (1.1.4.2) the reaction product obtained in (1.1.3), (1.1.5) thereafter (1.1.5.1) the suspension formed in (1.1.4) is combined with (1.1.5.2) a titanate, (1.1.6) finally the suspension obtained in (1.1.5) is evaporated to dryness and then (1.2) in a second stage, (1.2.1) the intermediate obtained in (1.1) is first treated with a nitrogen stream, (1.2.2) an intermediate obtained in (1.2.1) is then heated in an oxygen-containing gas stream and finally (1.2.3) the intermediate obtained in (1.2.2) is treated with a nitrogen stream, and a lithiumalkyl is used as (2).

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Rainer Konrad