DE2015592A1 - Polymerization catalyst - Google Patents

Description

PATENT LAWYERS

OR. MOLLER-BORe DR, MANITZ. DR DEUFEL

DIPL-ING. DARK FOREST. DIPL-JNG. GRÄMKOW 7 O 1 5 59

β MONKS 22nd ROBERT-KOCH-STO. 1 w

TELEPHONE 225110.

Munich, April 1, 1970 Lo / Or - J IO31

THE INTEEtEfA'l'IONAI · SYKl ¹ EETXO RCTBER COMPAiTY LIHX = XED Brunswick House, Brunswick Place, Southampton, Hampshire} Sngland ■

Polymerization catalyst

Priorities: Great Britain of April 1, 1969, No. 17025/69 Great Britain of Feb. 24, 197 ⁰ Y Hr. 8816/70

The invention relates to the polymerization of olefins, inclusive Polyenes, and the catalysts used for them »

In one embodiment of the invention, a Iräger deposited catalyst supplied as Kata ^ lyeator includes:.

(A) one or more compounds of a transition metal the group. IVA to VIII of the periodic table and

(B) one or more compounds of a metal from group IA ₁ .1IA ₇ IIB, TIIB ₅ IVB or VB of the Periodic Table, the compounds having one or more bonds from the metal to hydrogen "- and / or carbon

009Ö51 / 1793

possess material atoms,

and wherein the catalyst int in intimate contact with a particulate solid "support E-SORT + ie metal compound as defined below v / ith _s umfassb which, when a solubility in water of less than I O ₅ g / .l 20 0, and which is a metal salt or oxide or a mixture and / or a complex of 2 or more of these.

According to another embodiment of the invention, a method for preparing a catalyst located on a substrate is provided which comprises intimate Tn '. <Ontact-Eringen a particulate Meta.Uvei bindur ^k) g, as defined below and a solubility in water of less than 1.0 g / l at 2.0 ° 0 and a metal salt or oxide or a mixture and'Or is a complex of two or more of these. with (B'i) one or more compounds of a metal of the group ΪΑ _Τ IJA or λϊϋ of the periodic table, soft have one or more bonds from the metal to hydrogen and / or carbon atoms, the subsequent admixing of component (A), the one or more compounds of a transition metal of groups IVA to VIII of the periodic table, and optionally the subsequent addition (B2) of one or more compounds of a metal of group IA, HA, HB, IHB, IVB or VB of the periodic table, these compounds being or have multiple bonds from the metal to hydrogen and / or carbon atoms, uafasst.

According to a further embodiment of the invention, a process for the production of an olefin polymer is provided, which the polymerization of at least one olefin in gaseous or liquid phase in the presence of one on a Supported catalyst, as defined above, or one prepared according to the method defined above, -comprises catalyst located on a carrier.

C 0 9 8 5 1/1 7 9 9 bad

The component (A) consists of one or more compounds a transition metal of groups IVA to VIII of the periodic table, z. B. titanium, zirconium, hafnium, vanadium, chromium, Tungsten, manganese, iron, cobalt or nickel. Compounds of metals from groups IVA, VA, VIA or from cobalt.-or Nickel are particularly preferred. Pine typj: before component

(A) is a transition metal compound which is well known in dsn Ziegler-Natta type catalysts are active. Preferably the transition metal is in the compound in its highest oxidation »? state or in one at one or two lower states than the maximum. At least one ligand should be bound to it - the one with your Hydrogen or hydrocarbon on component (B) exchangeable is, preferably at least two such ligands. In the description, information relates to the component

(B) also to components (B1) uno. (£ 2) like them above if this is possible due to the context. Preferred idgands are chlorine, bromine, iodine and alkoxy radicals. Transition metal compounds, which are in hydrocarbon or mixtures of hydrocarbons are soluble are particular suitable. Examples of compounds suitable for use as component (A) and titanium tetrachloride, zirconium tetrachloride, Vanaclium oxytrichloride and chromyl or molybdenum halide p or oxyhalides «mixtures of titanium compounds grains can be used. Titanium tetrachloride is particularly effective.

Component (B) consists of one or more compounds of a metal from group IA, IIA, HiJ, IIIB, IVB or VB des Periodic table, the compounds containing metal-hydrogen or metal-carbon bonds. Particularly suitable compounds are compounds of potassium, sodium, lithium, Calcium, magnesium, zinc, aluminum, silicon, tin and antimony and especially compounds of magnesium. Examples of suitable compounds are Grignard reagents. z. B. phenyl,

009851/1799

Methyl or ethyl magnesium bromide, metal hydrocarbon · ¹ compounds, ζ. B. alkyls, aryls and aralkyls such as lithium butyl, lithium phenyl and kagnesium diphenyl, complex hydrides such as lithium aluminum hydride and the substitution products derived therefrom by replacing one or more hydrogen atoms with ethyl glycol dimethyl ether radicals and sodium borohydride and aluminum compounds of the general formula: H. ¹ H ¹¹ R ¹¹¹ Al or E ¹ R ¹¹ AlX, where RSR "and R ¹ ", which can be the same or different. Are hydrogen or hydrocarbon radicals, such as alkyl, aryl, aralkyl? Alkenyl. Alkynyl, cycloalkyl or cycloalkenyl and X is a halogen atom, an alkoxy group, an aryloxy group or the best of a secondary amine or amide, morphaptan, biophenol, carbonic acid or sulfonic acid. Alkyl, alkenyl, alkynyl or alkoxy groups advantageously have 1-8, in particular 1-6; Cycloalkenyl and alkenyl radicals suitably 3-8, especially 4-6 and aralkyl radicals suitably 7-10, especially 7-9 carbon atoms. Arylreete and Arylosryreste are two-dimensional - one - or sveikernig, especially '* phenoxy or phenoxy. Less preferred aluminum compounds of the general formula R ^{1 AlX 1} X ''', where R ^{1 has} the meaning given above and I ¹ and X ", which may be the same or different, are halogen atoms, alkoxy or aryloxy groups, kotinen in conjunction with activators therefor may be used as described, inter alia, in British patents 920 512, 937 557 and 901 035. Such suitable aluminum compounds are fully described in British patents 799 392 and 799 823b and the statements made there also apply to the present invention. thus, the component (B), for example Aluminiumtriäthy1 be Aluminiumäthyleesquichlorid (Al ^ Cl ^ AET), Diäthylaliuniniumchlorid or Diieobutylaluminiuahydrid. Preferably Organoa3iuniniumhalogenide ₅ are laben which ßtöichiometrisch less than two Ualogenatotoe per aluminum atom, or organoaluminum compounds containing no halogen can be used. the Lewis acid activity of such compounds can, if ge wishes by adding a Lewis acid free of tlbargangsmetall, z. B. aluminum halide can be changed. Grignard reagents are particularly effective.

Preferably eats; the compound forming component (B) in a IiJSgiuigisroijj ^; «! or a Mi. »cJjung von L5ßungeiaittelJT _M

U098F.1 / 179Θ

in particular organic solvents, especially hydrocarbons or ethers, soluble, so that a solution without Decomposition of the compound can be established. However, the compound can form a complex with the solvent, 2 »B. a JLtherat; form.

The particulate solid which forms the carrier should desirably have a maximum particle diameter of e.g. B. have 1 mm. It is preferably a powder having a maximum particle diameter of 0.1 ranu Suitably, mindesteno 95 wt.% Of the particles have a Teilchendurchmeeser from below 20 microns, z. From 0.1 to 20 microns.

The particulate metal compound which forms the carrier can be a metal oxide, including a mixed oxide, or a metal salt or a mixture of two or more such compounds. Metal salts of particular importance are the halides, including mixed halides and complex halides, silicates, including complex silicates, and the carbonates including basic carbonates. Sine suitable "Hasse of mixed oxides eind spinels, single 'Finally, the inverse spinels" Examples of such mixed oxides are Γ-Alundniu & oxide and spinel itself. A preferred class of metal salts ^ are dio fluorides, including mixed fluoride and complex fluorides such. B. Magnesium fluoride, a mixture of magnesium fluoride / calcium fluoride and cryolite. Other examples of suitable compounds are qi-aluminum oxide, fluorinated aluminum oxide / silica-aluminum oxide, calcium carbonate, magnesium carbonate, magnesium silicate, aluminum silicates and sodalite. Borates, phosphates, e.g. B. boron phosphate, and sulfates, such as barium sulfate, are also valuable.

Preferred compounds for use as carriers are those of metals from> Group IIA of the Periodic Table and of zinc and aluminum. The term "metal compound" such as it is used here with regard to the carrier, is so EU

009851/1799 ^ _0RIGINAL

stand that it includes compounds of the elements insofar as the element in question has metallic properties. Borphoaphut is included herein, but other compounds of e.g. B. boron, which is a semimetal, does not necessarily fall under this definition.

It is desirable to ensure that the wearer is practical free of water, including water of hydration, and others harmful substances, ζ "Β * absorbed gases. This can suitably be achieved by operating in vacuum or under an inert atmosphere, ζ. B. dry nitrogen, except for one Temperature below its melting point, e.g. B. 200 ° to 400 ° C, for example, is heated by drying in the oven or calcination. In this way, any loss of activity is reduced or excluded.

The molar ratio of component (A) to component (B) should preferably be such that (B) is present in molar excess, particularly preferably such that the molar ratio from (B) to (A) is at least 10: 1.

The amount of (B) in contact with the carrier can be within further limits vary, e.g. B. from 1 to 50 wt.%, In general from 1 to 20% by weight based on the carrier, the The weight and type of support used are such that there is a large surface area for the other catalyst components is.

In a preferred embodiment of the invention, the Catalyst prepared by placing the support under dry, acid-free conditions, e.g. B, in vacuum or in one Inert gas, with component (B), optionally in the presence a suitable diluent which is a solvent can be for this component, »is mixed together. Mixing can be carried out, for example, by adding the dry carrier to the component which, if solid, in a suitable solvent, ζ. B. ether, is dissolved,

009851/1799 - 6 -

is ground or rubbed in, the solvent subsequently ficjid is removed, generally by heating. Alternatively, the carrier can be made into a paste with a diluent, z. B. liquid paraffin, are mixed before this Component (B) is added, the diluent likewise being removed by means of a rush ".i essend, for example by Er heat. Particularly preferably, the carrier is brought into contact with the component (B), and then the component (A) added in order to obtain a large surface for the reaction. Nevertheless, the addition can be done in the reverse order result in a useful catalyst.

There is a particularly effective way of working for mixing therein, the component (B) as a fine dispersion or solution Add carrier under fluidized bed conditions and then remove any solvent which may be present. Of course, the rate of addition of component (B) should be such that the fluid properties of the bed do not pass through excessive wetting will be lost. At this stage it can turn out to be favorable, the material in an intermediate stage to be heated, again preferably under fluid bed conditions. The fluidizing gas can e.g. B. nitrogen, hydrogen or argon eain. The treated carrier can then heat treated or, if desired, ground to a fine powder.

The catching principle obtained by bringing the component into contact (B) was obtained with the carrier, is with the transition metal compound, of component (A), optionally in Missing presence of a solvent or a liquid diluent. When component (A) is volatile is e.g. B. in the case of titanium tetrachloride, the mixing ir suitably be carried out as a gas pesticide process, r ,. B. in which the steam of component (A) in one

00985171799. .

Diluent gas, ζ. B. nitrogen, diirch a bed of the "initial product sent v / ircu On the other hand, solid-solid- or liquid-solids procedures can be used.

The amount of component (A) used can be less or more,

which are the required amount for stoichiometric FeaSrbiai ale, to the amount of component (E) already used for contacting the carrier, e.g. B. 0.1 to 10, preferably 0.25 to k Atol of the transition metal in component (A) per equivalent (calculated on the metal-carbon or metal-carbon bonds) of component (B).

It was found that yields of polymer were reduced can be achieved by preparing a supported catalyst in the following particularly preferred manner can.

The catalyst support is first in intimate contact with (B1) one or more specific compounds in accordance with the definition of component (B) given above, in particular compounds of an element of group IA, IIA, or HB of the periodic table, which are metal-hydrogen or metal1- Has carbon bonds, brought. Then component (A), as defined above, is then mixed in. Optionally thereafter (B2) is one or more compounds added to the arbitrarily · »those compounds which _t falls under the above given definition of component (B) can no.

Examples of component (BI) are Grignard reagents which are a metal] ΊβΓ group IA ₁ IXA. IIB "Jl6ß Periodic Table, z. B. phenylmagneaium bromide, methylmagneaium bromide, metal alkyls, aryls and aralkyls, e.g. B. Lithivmbutyl, Lithiumphenyl and Magnesiumdiplienylf kciuplexo hydrides, z. B. lithium aluminum hydride, di-3 removed from this by replacing one or more hydrogen atoms with ethylene glycol dicethyl ether residues.

■■ - 8 -

009851/1799 ^ ₀ original

headed products, and sodium borohydride. Preferably -is the Compound in a solvent or mixture of Solvents, soluble, especially organic solvents, especially hydrocarbons, or in Äblisin, . so that a solution is made without decomposing the compound can be »However, the connection can also be a complex with the solvent, e.g. B, form an etherate.

Component (B2) can be identical to component (BI) or different from «a. Examples of suitable compounds, which are not included in the definition of component (B1) are those in which the metal antimony or Aluminum icü, z. B. any of those described in detail above Aluminum compounds (accompanied if appropriate of e.g. activators or transition omeball-free Lewis acids, As already mentioned). It has been found to use of the aluminum compounds as component (B2) is of particular value. '

Bringing the carrier into contact with component (B1) can be done by any of the suggested above Working methods for bringing him into contact with the Component (B) is applied using the fluidized bed process again is particularly effective. The amount of (B1) used in contacting with the carrier can also be within further limits vary, e.g. B. from 1 to 50 wt.%, Im generally from 1 to 20% by weight based on the carrier "

• The working methods for adding component (A) can be as follows as already described, and again the applied quantities can be as -3 a j as already discharged »

The product from mixing component (A) with the with the component '(BI.) treated carrier can be used as such Polymerization of olefins can be used. However, whether often useful, still a lot of component (B2) “like

00983171799

stated above, to be added. It is desirable to have a molar excess of (B1) + (B2) with regard to (A) to have, and is particularly desirable; it, at least auoroichend (B2) to be present, so that this as a catcher serves and removes reactive contaminants that may be present. Quantities of (B2) in excess of those which are required for interception act as cocatalysts and are preferred.

This additional addition is suitably made by using a Solution of component (B2) in an organic solvent, eg "hexane, carried out,

As already mentioned, the product of the admixture of the treated carrier and the transition material component (A) is useful for the polymerization and copolymerization of olefins, including diolefins, cyclo-olefins and activated vinyl compounds, e.g. B. styrene, especially ethylene and propylene, active either in the gaseous or in the liquid phase. Such polymerizations are usually carried out at temperatures from -20 ° C to + 250 ° C, preferably at 20 ° 0 or more, and at pressures of subatmospheric pressure, e.g. B. _V 50 µm to, for example, 100 ata, preferably 1 to 50 ata, and desirably under conditions free of moisture Child free of molecular oxygen / BiS ^ f can be achieved by the presence of compounds in controlled amounts, e.g. B. hydrogen, water or alcohols., Are modified, which are known per se in order to reduce the molecular weight of the end product and / or to increase the yield.

At each stage in the preparation of the catalyst product, the mixture or the reaction product obtained by mixing the component or the solid components can be used self-treated to increase or decrease the surface area by grinding or pelletizing. One

/ 1799

Increased activity can be achieved by applying ultrasonic vibrations to some or all of the catalyst components, preferably at a frequency of a. E.g. 10 * to 10 Hz, e.g. B, 2 χ - 2 χ 10 ^ Hz in a strength voxi 10 - 100 W or more, for example at 30 kHz. w && 4-0 -W intensity. in the presence of an inert, organic dispersion medium such as hexane, cyclohexane or diethyl ether. These can be retained or removed as desired, but with the restriction that, when using ethers, they are preferably removed before the addition of the catalyst components (A), since otherwise the catalyst can be deactivated.

The catalysts according to the invention which are deposited on the support are heterogeneous and can easily be removed after the polymerization by-ζ. B. Centrifugation or Filtration * be removed »However, the high polymer yields that are available with these catalysts allow that only very small amounts in the product of the polymerization reaction are present. Because their chemical ester activity is low. can these small amounts of catalyst almost always in the final polymer can be maintained without any deleterious effect 'so that lengthy washing or libbing steps are unnecessary be made. =. Another benefit is that there is little or no loss of transparency, if the residue remains, since the refractive index of the catalyst deposited on the support is the same as that of the Polymerisates is or is approaching this.

In addition, the catalyst composition of the invention stored under dry, oxygen-free conditions and, when desired, used in polymerizations -.will. As a result - "no loss of activity is observed after a comparatively long storage period" - "· .- ■ - ■ .... *

- 11- - ■

0-9-8 5 17 17 9 9

BADORlQINAt

JISL

2016592

The polymers obtained by means of the supported catalyst according to the invention can be used for any applications for which conventional polymers are used. For example, molded articles or panels, films or fibers which are at least partially composed of the polymers produced by means of the catalysts of the invention can be formed. Other components can of course also be incorporated. ? -. B. fillers, plasticizers, antioxidants and, where appropriate, such as under the general name EPDM-Polymerisste, ie Terpoiyaerisate from ethylene, propylene and non-conjugated diene, known polymers, Vulkan! Sations «constituents.

The following examples illustrate embodiments of the invention:

example 1

5 g of synthetic cryolite * is put into a hard glass tube of 15 weeks using dry nitrogen . Inside diameter, which is provided with a sintered glass plate, fluidized. The bed is heated to 500 ° C, then cooled to ambient temperature. A solution of magnesium phenyl bromide in dry ether is added dropwise to the top of the bed until a total of 10 mol of the organometallic compound has been added. The bed is heated to 200 ° C., then cooled to ambient temperature. A solution of titanium tetrachloride in dry Kexane is then added dropwise to the bed until a total of 1 mKol TiCl4 has been added. The nitrogen flow is exchanged for a flow of dry, oxygen-free ethylene, which is passed through in sufficient quantities to keep the bed in a tufted condition. After 20 minutes the ethylene flow is switched off and the bed is extracted with boiling decalin, with 2 to 4 g of crystalline polyols being obtained.

T71799

BATH ORIGINAL

Example 2

The catalyst is prepared as in Example 1, and O ₅ 2 g are transferred into a pressure bomb which contains 300% of dry cyclohexane. The bomb is purged with dry, pure ethylene, then pressurized to 35.2 kg / cm (500 psig) with the same gas. The bomb is heated slowly and ethylene is added to keep the pressure at 35 »2 kg / cm (500 rsig). The final temperature is 140.degree. C. On cooling, the product is removed from the bomb and freed from solvents. 61 g of crystalline polyethylene are obtained.

Example 3 . .

Ammonium alum, SH ^ A1 (SO ^) ₂ «12H ₂ O, is heated to 1000 ° G until no further vapors are released. The product, ^ -AlpO _5. , Is sieved through a 152 micron mesh (100 mesh. BS) screen. The procedure of the example is repeated using 5 g of this oxide in place of the cryolite. It will be 0,? g crystalline polyethylene obtained, i

Example 4,

20 g calcium carbonate (whiting chalk) with an average particle size of less than 1 ji were dried at 300 ° 0 and transferred to a steel ball mill with a capacity of 1.14 l (1 quart), which was flushed with dry nitrogen; 200 ml of a dry medicinal paraffin wax was added and milling was started. A solution of 4 g of phenylmagnesium bromide, calculated on the active base, in 50 ml of diet bottle was added to the compartment for 4 hours. Milling was continued while dry nitrogen was bubbled through, and the mill was heated, first to 50 ° 0 and finally to 100 ° 0, until all the ether was removed. Ditio took about 6 hours.

OÖ9I5I / 1799

2015 & 92

The mill was then allowed to cool to about 15 ° G, then 4 g of TiGl ^ in hexane were added, the grinding was again started and continued for 1 hour.

The prepared catalyst was tested for polymer ablation activity as follows examined ':

i is a 1-1-stirred autoclave was purged MIB dry nitrogen, then filled with 500 ml dry hexane and heated to 50 ° 0th Ethylene was introduced to a pressure of 2.11 kg / cm * "(30 psig), 0.25 mmol of aluminum tributyl was added, followed by 10 mg of catalyst. The pressure was increased to 703 kg / cm (100 psig). increased and maintained for 1 hour . 53 ß of polyethylene were produced.

Example ^

5 g of heavy magnesium oxide were heated to 300 ° C in a small Reaction vessel heated and fluidized with dry nitrogen. The reaction vessel was cooled to 30 ° G, then was added 0.5 g of methyl magnesium bromide in 3 al ither dropwise and the bed was mechanically agitated, if necessary, to maintain its fluidity. Awake 5 mia were 0.2 g TiOl / j. in 2 ml of JSexane was added and it became nitrogen passed until the hexane was removed.

The prepared catalyst was transferred to a sealed bottle containing 100 ml of hexane and by means of Ultrasound dispersed.

It was investigated as described in the first example, but with 0.5 mmol of aluminum triisobutyl and 4.0 mg of catalyst were used. The yield of polyethylene was 43 g.

This catalyst was also used for copolymerization activities examined. 1 g were in 500 ml of hexane, which approximately

~ 14 .009851 / 1799

45 χ 201 && 92

1 mmol aluminum triethyl contained ■, dispersed. Ee were. Ethylene and propylene under atmoephär-ischsiri Brück for 5 hours initiated. 40 g of soluble copolykerissate Mt approximately insoluble material generated. During the course of the reaction, the temperature was allowed to rise from 20 to 30 ° C.

Example 6

A 4.55 liter stirred autoclave was flushed with dry nitrogen, filled with 4 liters of dry hexane and heated to 90.degree. The autoclave was purged with hydrogen by increasing the pressure to 7.03 kg / cm ^? "(100 psig) and vented to 2.11 kg / cm ² (30 psig). This operation was carried out twice before the addition of 10 milliliters of triobutyl aluminum followed by 100 milligrams of catalyst" prepared as described in Example 4 The pressure was increased to 5 »2 kg / cm (75 psig) with hydrogen and then increased to 8.44 kg / cm (120 psig) by bubbling in ethylene, the latter pressure being maintained for a period of 2 hours Further addition of ethylene was maintained, 104 g of polyethylene were formed, which possessed a melt index of 2.5 under a weight of 21 * 6 kg for 10 minutes

Examples 7 to 9

Example 1 was repeated, the same, already being ~ method was used, but with changes in the catalyst components and the catalyst carrier. the Katalyeatörkooponenten and, the carrier and the yields of the obtained polyethylene are as follows:

Example Component A Component B Carrier Yield

Titanium tetrachloride lithium aluminum fluorinated 1.9

hydrated aluminum oxide

■ - 1-5 0-0986-1 / "1-7 99 BAD ORlQlNAl.

201S592

Example component A component B ! Carrier yield

Titanium tetra-lithium-butyl-aluminum-2,6 chloride oxide

"Cyclopenta-Magnesium- 1.0

dienylEiagne- d siuaibromide

009851/1799

Claims (32)

P at en ta η s ρ rüch e 1.) Catalyst deposited on a carrier, thereby .ge-, indicates that he is a catalyst includes: (A) one or more compounds of a transition metal of groups IVi to VIII of the periodic table and (B) one or more compounds of a metal from groups IA, HA, HB, IHB, IVB or VB des Periodic table, where the compounds contain one or more compounds from metal to hydrogen and / or carbon atoms, wherein the catalyst is in intimate contact with a particulate Solid-state carrier that has a metal connector Binding with a solubility in water of less than 1.0 g / l at 20 ° C, in the form of a metal salt or oxide or a mixture and / or a complex of two or includes several of these and wherein to metal compounds also include compounds of the elements, provided that they have metallic properties. 2.) Catalyst according to claim 1, characterized geke η η - % eich η et ι that the transition metal in component (A) is in the maximum oxidation state or in a state one or two units below the rnaxä.- - times oxidation state. 3 «) catalyst according to claim 1 or 2, characterized in that the transition metal bound at least two ligands in component (A) contains which nit the hydrogen and / or the group '-17 - ■' V ^: ■,. ^{; :} . 009851/1799 or the groups linked to the base materials in component (B) via carbon atoms. 4.) Catalyst according to one of the preceding claims, characterized in that the Component (A) in hydrocarbons or in one Mixture of hydrocarbons is soluble. · 5) A catalyst according to any one of the preceding claims, characterized 6 ^θ k ^{hen Ά G} i ^c h η et - in that the component (A) Chromylhalogenide, Chromyloxyhalogenide, molybdenum halides or Holybdänoxyhalogenide is. 6.) Catalyst according to one of claims 1 to 4-, characterized indicated that component (A) Titanium tetrachloride or vanadium imoxy trichloride. 7.) Catalyst according to one of the preceding claims, characterized in that the metal of the compound of component (B) is potassium, sodium, Lithium, magnesium, calcium or aluminum. 8.) Catalyst according to one of claims 1 to 6, characterized characterized in that the metal of the compound of component (B) is zinc or antimony. 9.) Catalyst according to «Lnem of the preceding claims, characterized by the fact that component (B) is soluble in organic solvents, 10.) Catalyst according to one of the preceding claims, characterized in that component (B) is a magnesium compound. - 18.- 2015532 11) The catalyst according to claim 10, characterized GEK η s η is characterized in that the component (B) is a Grignard "reagent is. · 12.) Catalyst according to claim 11, characterized in that daa Grignä-ci reagent phenylmagnesium bromide, Methylmagnesium bromide or Ethylmagnesiusl - is bromide. 13.) Catalyst according to one of the preceding claims, characterized geke r. η ζ it η β t that the particulate solid support is or contains a compound of a metal from group HA of the periodic table or of Sink or aluminum. 14-.) Catalyst according to one of the preceding claims, characterized in that the carrier is a metal halide, silicate or carbonate, or this contains *, 15.) Catalyst according to claim 14, characterized in that g s k e η η is characterized that the halide is a fluoride 16) The catalyst according to claim 14, characterized GEK "η η - characterized in that the support is calcium carbonate or Magneeiuxncärbonat or contains this. 17 ·) Catalyst according to one of the preceding claims, characterized in that the carrier is or contains a metal oxide. 18.) Catalyst according to claim 17, characterized in that g β k β η η -. ζ ei chne t * that the Trägex a spinel, QC-Alu- or magnesium oxide is or contains this. - 19 -009851/1799 ι V 20 * 6 * 92 • ~ i 19 ·) Catalyst according to one of the previous claims, characterized in that the particles of the carrier have a maximum diameter of 1 mm own. 20.) Catalyst according to claim 191, characterized in that the particles have a diameter from 0.1 to 20 microns. 21.) Catalyst according to one of the preceding claim ©, characterized characterized in that from 0.1 to 10 atoles of a transition metal in the component (A) p * o equivalent of component (B), calculated on the metal-hydrogen or the metal-carbon bonds, available. 22.) Catalyst according to claim 21, characterized in that from 0.25 to M atom of the transition metal in component (A) per equivalent of component (B) are present. 23 ·) Catalyst according to one of the preceding claims, characterized in that the component (B) is present in molar excess with respect to the components (A). 24.) Catalyst according to one of the preceding claims, characterized in that di · Henge d * r component (B) in Xontakt «dt de» carrier from 1 to 50% by weight of the carrier. 25 «) Process for the production of a catalyst according to a« of the preceding claims, whereby g e k β η η be net that the component (B) is brought into contact with the solid * question before the component (A) is set. 009 851/1799 20rt & 592 26.) The method according to claim 25, characterized in: g β ke nm? - indicates that the carrier yfö ^ epQ \ u§ & tnr contact-bringing. is kept in the form of a fluidized bed with at least defa * KompoiieTitä '(Ä). 27.) The method according to claim 25 or 26, characterized in that the component "(A) and / or component (B) is used in solution in an organic solvent / who? the. 28.) The method according to claim 25, 26 or 27, characterized in that a component (B) whose metal is an element of group IA, HA, or IIB of the periodic table. 29 ·) Method according to claim 28, characterized in that 9Is component (B) is a Grignard reagent is used" 30) The method of claim 25, 28 or 29 "characterized g e indicates that the addition of the component (A) following one or more compounds dee of metals of Group ΪΑ, HA, HB, IHB, IVB or VB period systems is added wherein the compounds contain one or more bonds from the metal to hydrogen and / or carbon atoms. 31.) Use of the catalyst according to one of claims Λ to 24 or of a catalyst prepared by the process of claims 25 to 30 for the polymerization of one or more olefins. 32.) Use according to “Claim 35 for the polymerization of ethylene and / or propylene. 33 ·) olefin polymer obtained using the catalyst according to claim 31 or 32. I 799