Basf Aktiengesellschaft

Wolfgang Gruber

Hans Frielingsdorf

Heinz Mueller-Tamm

Guenther Schweier

Robert Bachl

Erich Kolk

Rainer Alexander Werner

James F Jaggard

Leonhard Gonsior

Juergen Kerth

Oskar Buechner

Gunther Schweier

Peter Hennenberger

Gerhard Staiger

Rudolf Mueller-Mall

Ralf Zolk

Norbert Scholz

Klaus-Dieter Ruempler

Werner Georg Metzger

Georg Friedrich Vock

Kurt Erdmann

Guenther John

Propylene/ethylene polymers are prepared by a process in which, in each case in the presence of hydrogen and by means of gas phase polymerization, first (A), in a first polymerization zone, propylene is homopolymerized, and the resulting propylene homopolymer is introduced into (B) a second polymerization zone, where a mixture of propylene and ethylene is then polymerized with the reaction product obtained in (A). In this process, ethylene is homopolymerized in a further polymerization zone (C), likewise by gas phase polymerization, with certain provisos, and the resulting reaction product is likewise fed to the second polymerization zone (B).

Preparation of propylene/ethylene polymers

Propylene/ethylene block copolymers are prepared by a continuous process in which, in each case in an agitated fixed bed of finely divided polymer from the gas phase, first (I) in a first polymerization zone, propylene is homopolymerized by feeding in a Ziegler-Natta catalyst system consisting of (1) a titanium component which contains titanium, magnesium, chlorine and a phthalic acid derivative, (2) an aluminumalkyl component and (3) a silane component, and (II) in a second polymerization zone, a mixture of propylene and ethylene is polymerized with the propylene homopolymer present in the reaction mixture obtained in the first polymerization zone by feeding in the said reaction mixture. In the process, (A) a titanium component (1) is used which is obtained by a method in which (1.1) first, (1.1.1) in a liquid hydrocarbon, (1.1.2) a finely divided magnesium halide, (1.1.3) an alkanol, (1.1.4) a certain phthalic acid derivative and (1.1.5) titanium tetrachloride are reacted with one another under certain conditions, (1.2) the solid intermediate obtained from (1.1) is extracted with titanium tetrachloride or a liquid alkylbenzene until the remaining solid substance has become substantially richer in magnesium, and (1.3) finally, the solid substance remaining in (1.2) is washed with an alkane in a certain manner, (B) a specific silane is used as (3), and (C) specifically selected polymerization parameters are employed, with relationships between the first and second polymerization zones.

Preparation of propylene/ethylene polymers of the toughened

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.

.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

Propylene/ethylene block copolymers are prepared by a process in which, in an agitated fixed bed comprising small polymer particles and in each case in the presence of hydrogen, first (I) propylene is homopolymerized from the gas phase, in a first polymerization zone, by feeding in a Ziegler-Natta catalyst, 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 the product from the first polymerization zone. The process has the following features: (a) in the first polymerization zone, polymerization is carried out at a particular total pressure and at a particular temperature, with the proviso that the ratio of the partial pressure of propylene to that of hydrogen (P/H-I) has a specific value, (b) in the second polymerization zone, polymerization is carried out at a particular total pressure and at a particular temperature, with the provisos that (i) the ratio of the partial pressure of propylene to that of ethylene and (ii) the ratio of the partial pressure of propylene to that of hydrogen (P/H-II) have specific values, (c) the total pressure in the first polymerization zone is kept substantially higher than that in the second polymerization zone, (d) the temperature in the second polymerization zone is chosen to be substantially lower than that in the first polymerization zone, and (e) the ratio of P/H-I to P/H-II has a specific value. Polymers having high impact strength and good morphological properties are obtained.

Preparation of propylene/ethylene block copolymers

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.

A process for the manufacture of olefin polymers by polymerizing .alpha.-monoolefins of 2 to 8 carbon atoms by means of a catalyst which is obtained from a silicate carrier (component a), an organo-metallic compound containing alkoxide groups (component b) and a chromium compound (component c), wherein the catalyst employed is obtained by (1) first charging (1.1) a finely divided porous xerogel (component a) of the formula SiO.sub.2 . m Al.sub.2 O.sub.3, where m is a number from 0 to 2, with (1.2) a particular aluminum compound containing alkoxide groups (component b), (2) then charging (2.1) the product obtained from stage (1) with (2.2) a particular chromium compound (component c) by treatment with a solution of the chromium compound, with intimate mixing and evaporation of the solvent and (3) finally heating the product, obtained from stage (2), in an anhydrous stream of gas containing oxygen. This process makes it possible to influence the essential properties of the polymers in relatively diverse ways, in the desired direction, by relatively slight modifications of the catalyst.

A process for the manufacture of olefin polymers by polymerizing .alpha.-monoolefins of 2 to 8 carbon atoms by means of a catalyst which is obtained from a silicon-containing material (component a), an organo-metallic compound containing alkyl groups (component b) and a chromium compound (component c), wherein the catalyst employed is obtained by (1) first bringing into contact (1.1) an alkogel (component a) of the empirical formula SiO.sub.2 .multidot. m Al.sub.2 O.sub.3 .multidot. n ROH, where m is a number from 0 to 2, n is a number such that the content of ROH in the alkogel is from 1 to 85 per cent by weight and R is alkyl of 3 to 8 carbon atoms, and (1.2) an aluminum compound containing certain alkyl groups (component b), with intimate mixing, to form a solid-phase reaction product, (2) then bringing into contact (2.1) the solid-phase reaction product obtained from stage (1) and (2.2) a solution of a particular chromium compound (component c), with intimate mixing and evaporation of the solvent, and (3) finally heating the product, obtained from stage (2), in an anhydrous stream of gas containing oxygen, with the proviso that the product obtained from stage (1) or from stage (2) is dried and comminuted before it is used further in the next stage. This process makes it possible to influence the essential properties of the polymers in relatively diverse ways, in the desired direction, by relatively slight modifications of the catalyst.

A process for the manufacture of olefin polymers by polymerization of monoolefins using a silicic xerogel/chromium trioxide catalyst obtained by (1) synthesizing a particulate silicic xerogel, (2) doping said xerogel with chromium trioxide or a chromium compound capable of converting to chromium trioxide under the conditions of stage (3) and (3) heating the resulting product in a gas stream containing oxygen. The silicic xerogel/chromium trioxide catalyst used is one which has been obtained by (1) synthesizing the silicic xerogel in the first stage by (1.1) starting with a silicic hydrogel having a relatively high solids content, (1.2) extracting water from said hydrogel by means of an alkanol and/or alkanone until the organic liquid absorbs no further water, (1.3) extracting the organic liquid used in stage (1.2) from the resulting dehydrated gel saturated with said organic liquid by means of a hydrocarbon or oxohydrocarbon until said hydrocarbon or oxohydrocarbon absorbs no further organic liquid from stage (1.2), and (1.4) drying the resulting dehydrated gel saturated with hydrocarbon or oxohydrocarbon (xerogel formation), and (2) doping said xerogel in the second stage with the desired amount of chromium from a solution of chromium trioxide in an alkanone or solution of a chromium compound capable of converting to chromium trioxide under the conditions of stage (3) in an alkanol or alkanone with evaporation of the solvent.

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.

A process for the manufacture of olefin polymers by polymerization of .alpha.-monoolefins by means of a silicic acid xerogel/chromium trioxide catalyst, which is obtained by a method wherein (1) a finely divided silicic acid xerogel is first manufactured by (1.1) employing a silicic acid hydrogel of relatively high solids content, (1.2) extracting at least 60% of the water contained in the hydrogel from the latter by means of a particular organic liquid, (1.3) drying the gel thus obtained until there is no further loss in weight (xerogel formation) and (1.4) reducing the xerogel thus obtained to particles of diameter from 20 to 2,000 .mu.m,

Growing community of inventors

Frankenthal, Germany

Wolfgang Gruber