FI64171C - CATALYTIC CONVERTERING FOLDER POLYMERIZATION AV OLFINER - Google Patents

Description

fΓ1 .... ANNOUNCEMENT ίΛΛΊΛ V | £ a <11) UTLÄGGNINGSSKRIFT ° 'Ί C (45) (51) Kv.ik. ^ int.ci.3 C 08 F V78, 4/02, 10/02 FINLAND-FINLAND (21) PMenttlhtkemu * - P »tent» n * öknlng 77 0976 (22) H »k« ml * pllvi - Ansöknlngtdig 29.03 * 77 (23) Alkupilvi— Glltlghetsdag 29-03-77 (41) Has become public - Bllvlt ofFentllg 01 -10 to 77

Patent and Registration Office N »htsvik, ipanon). month-drink ™ date— 30.06.83

Patent and Registration Office of the United States of America and Public Acquisitions (32) (33) (31) Claim Requested — Begird Prlorltet 30-03-76 USA (US) 671937 (71) Union Carbide Corporation, 270 Park Avenue, New York , New York 10017, USA (72) Allen Noshay, East Brunswick, New Jersey, Frederick John Karol,

Bellemead, New Jersey, USA (US) (7 * 0 Oy Borenius & Co Ab (8 * 0 Catalyst mixture and process for the polymerization of olefins) - Catalysts and polymers for the polymerization of olefins

The invention relates to a catalyst mixture for the polymerization of an olefin, to the preparation of this catalyst mixture, and to a process for the polymerization of ethylene alone or with one or more other alpha-olefins using this catalyst mixture.

Ethylene can be homopolymerized or copolymerized at low (* 6.9 MPa) or high (> 6.9 MPa) pressures using catalyst oxides containing transition metal compounds, e.g. chromium oxide, and chromosene compounds placed in inorganic oxide oxide supports, said oxide -aluminium hydroxide, thorium oxide and zirconia. In order for these catalyst mixtures to be used successfully in commercial preparation, it has hitherto been found necessary in these reactions always to first dry the support to remove free moisture and then to activate the supports before or after the transition metal compound is placed at temperatures> are of the order of 300 ° C, suitably 500 ... 800 ° C, for at least 8 days.

2 64171

In some cases, this high temperature activation must also be performed under certain and limited conditions in the gas phase.

Even if the catalysts are prepared under these strictly limited conditions, their use also causes additional disadvantages from a commercial point of view, as it is difficult to control the reproducibility of the catalyst mixture and the activation equipment tends to burn in the long-term high temperature exposure to which it is exposed.

U.S. Patent No. 3,207,699 describes the treatment of dry burnt acidic silica-alumina hydroxide with trimethylsilanes at elevated temperatures to produce improved acid catalysts for a variety of applications. Silica treated in a similar way could not be used for such uses.

U.S. Patent 3,687,920 describes the simple addition of various silane compounds to chromene compounds in a support, wherein the carriers, including silica, are thermally activated at elevated temperatures prior to the placement of the chromosene compound or the use of the silane compound. The addition of a silane compound to catalysts used for the polymerization of ethylene is intended to improve the productivity of the catalysts.

U.S. Patent No. 3,879,368 discloses the treatment of chromosene compounds in a carrier with certain strongly reducing agents and certain silane compounds, wherein the carriers, including silica, are thermally activated prior to placement of the chromosene compound or use of highly reducing agents or silane compounds. Thanks to the use of strongly reducing agents and silane compounds, it is possible to use carriers which are activated at relatively low temperatures. The resulting mixtures are used as catalysts in the polymerization of ethylene, resulting in higher yields of polymers, and the molecular weight distribution of the polymer pathways is relatively wide.

3,641 71

It is an object of the invention to provide a novel commercially useful catalyst mixture in a silica support suitable for the polymerization of ethylene, which is made using chromosene compounds.

It is also an object of the invention to provide a new process for the preparation of commercially useful catalysts suitable for the polymerization of ethylene which contain chromosene compounds placed on silica supports.

It is also an object of the invention to provide a new commercially viable process for the catalytic polymerization of ethylene using a novel catalyst mixture comprising a chromosene compound supported on a silica support.

For the polymerization of the new ethylene according to the invention, ethylene polymers can be prepared by means of a catalyst mixture, the melt flow ratio of which has a relatively melt index value within a relatively narrow range. It can be used to produce ethylene polymer in relatively high yields.

The new catalyst mixture according to the invention is relatively sensitive to the action of hydrogen used as a melt index regulator.

The catalyst mixture of the present invention is characterized in that it comprises a chromosene compound placed in a silica support dried at about 100 to 300 ° C and treated in the presence of a volatile tertiary amine with a hydrosilane compound having a silane or a compound having the structural formula

R - * Si * H

wherein R represents a hydrocarbon group having 1 to 10 carbon atoms and n is an integer from 1 to 3, wherein the catalyst mixture contains about 0.5 to 10% by weight of a chromosene compound.

Silica materials suitable for use as a support in the catalyst compositions of the invention are porous materials having a large surface area, i.e., about 50 to 1000 m 2 / g and a particle size of about 25 to 20 m 2. In a fluidized bed reactor system the particles in the carrier must suitably have the ability to break up, which means the ability of these particles in the carrier to break if used in the fluidized bed as described below, and a polymer growing on them so that these particles can self-expand and form several particles , which rarely contain a catalyst residue derived from a single original support particle.

Any grade of silica support can be used, but microspherical medium density (MSID) silica having a surface area of 350 n \ 2 / g and a pore diameter of about 20 nm (WR Grace G-952 grade) and a medium density (ID) silica with a surface area of 285 m2 / g and a pore diameter of 16.4 nm (WR Grace G-56 grade). Other grades can also be used satisfactorily, such as grade G-986 (W.R. Grace et al.) Having a surface area of 700 m 2 / g and a pore diameter of 5 to 7 nm. Variations in melt index control and polymer productivity can be expected to occur between different types of carriers.

When placed in a large surface area porous silica support as described herein, the chromosene compound forms active sites on the surface and pores of the support. Although the actual mechanism of this process is not fully understood, it is believed that the polymers begin to grow on both the surface and the pores of the catalyst in the support. When the pore-growing polymer becomes sufficiently large in the fusion layer, it breaks the support and thus exposes the fresh catalyst sites in the inner pores of the support. The catalyst in the support can thus be divided several times over its lifetime in the fluidized bed, and thus promotes the formation of polymers containing little catalyst residues, so that the catalyst does not have to be removed from the polymer particles. If the support is too large, it can resist rupture and thus prevent fragmentation, which would lead to the loss of catalyst. In addition, the large carrier can act as a heat concentrator and cause the formation of "hot spots" in the fluidized bed system.

According to the invention, before any treatment with the silane compound, the silica support is heated at about 100 to 300 ° C, preferably at about 150 to 250 ° C, for 1 to 48 hours, which is sufficient to remove water adsorbed on the surface, but not enough to remove silanol groups. significant loss due to condensation.

The silica can also be azeotropically dried by distilling the adsorbed surface water from the support. This can be done azeotropically by distilling the silica support slurry in an azeotropic diluent.

The hydrosilane compound to be used according to the invention may be a silane (S1H4) or a hydrocarbon silane compound having the structural formula ^ n ^ s ^ ^ 4-n in which R represents a hydrocarbon radical C 1 -C 4 q 3a n is an integer from 1 to 3, preferably 1. the hydrocarbon silane compound contains more than one R group, these R groups may be the same or different. R groups include saturated and unsaturated aliphatic and aromatic groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, decyl, phenyl and benzyl groups.

Preferred hydrocarbon silane compounds are methylsilane, dimethylsilane, ethylsilane, diethylsilane, propylsilane, di-propylsilane, butylsilane, dibutylsilane, amylsilane and diamylsilane.

The hydrosilane compounds may be used alone or in combination with each other to treat the carrier. Treatment of the support with the hydrosilane compound is accomplished by contacting the hydrosilane with the support in the presence of a base, suitably at atmospheric pressure and at about 60-80 ° C. Higher pressures 6 64171 and / or higher temperatures can also be used. The contact can be promoted by dissolving the hydrosilane in a hydrocarbon solvent and then immersing the carrier in the solvent and then suitably adding a base.

Suitable solvents for hydrosilane include aliphatic and aromatic hydrocarbon solvents such as n-hexane, heptane, benzene and toluene.

About 0.2 to 2.0, preferably about 0.4 to 0.8 moles of hydrosilane are used per mole of silanol group on the surface of the silica support. This corresponds, depending on the hydrosilane compound used, to about 4 to 20% by weight of the hydrosilane compound, based on the combined weight of the hydrosilane compound and the silane carrier.

The bases used in the preparation of the novel carriers according to the invention are basic, preferably volatile substances, i.e. having a boiling point at atmospheric pressure = 150 ° C. The pH of these substances is in water or other suitable solvent = 7.

The volatile bases are preferably tertiary amines. These include trimethylamine, diethylmethylamine, ethyldimethylamine, triethylamine, n-propyldiethylamine and the like.

About 0.1 to 2.0, preferably about 0.9 to 1.1 moles of base are used per mole of silane compound used. Treatment of a support according to the invention with a hydrosilane compound in the presence of a base causes the hydrosilane compound to chemically bind to the support, simultaneously evolving hydrogen gas, as shown in the following equation (baseh- = Si-QH + H3S1R - ^ (support) · ==== 3 »S iQ-Si + H2

The chromosene compound is also known as bis- (cyclopentadienyl) -chromium-II having the structural formula 1: 64171 7 (R *) n. (R «)" wherein R 'and R "may be the same or different hydrocarbon radicals C1L-C20" 3a n' 3a n "may be the same or different integers 0 ... 5. The R 'and R "hydrocarbon radicals may be saturated or unsaturated and include aliphatic, alicyclic and aromatic radicals such as methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, allyl, phenyl and naphthyl radicals.

The bis- (cyclopentadienyl) chromium (II) compounds used as catalysts in the silica supports of the invention can be prepared as described in U.S. Patent Nos. 2,870,183 and 3,071,605.

The chromosene compounds may be used singly or in combination with each other. The chromosene compounds are suitably placed in their solutions in a silica support. This is conveniently done by immersing the silica support in a solution of the chromosene compound and then evaporating the solvent under air or under reduced pressure. The chromosene compound is placed after the silica support has been treated with the silane compound.

The chromosene compound is used to such an extent that about 0.1 to 3.0% by weight of the chromium of the chromosene compound is incorporated into the support, based on the combined weight of this support and the chromium metal.

After the support is treated with hydrosilane and a chromosene compound, the obtained catalyst mixture can be used as it is without further treatment in the polymerization of ethylene, as described above.

641 71 8

The catalyst mixture consists of powdery free-flowing solid particles.

The catalyst mixture is prepared from the following components, calculated on the total weight of the three main components: - about 80 to 96% by weight of silica support - about 3.5 to 19.5% by weight of the hydrosilane compound, and - about 0.5 to 10% by weight of % chromosene compound.

About 1 x 10 "6 to 1 x 10" 4% by weight of catalyst mixture is used per mole of monomer to be polymerized. The amount of catalyst used may vary depending on the polymerization process used.

Ethylene can be polymerized by the catalyst mixtures according to the invention alone or with one or more other alpha-olefins.

According to the invention, the monomer batch copolymerizable with ethylene may be one or more alpha-olefins having from about 3 to about 12 carbon atoms. The monomers may be monoolefins or unconjugated diolefins.

Among the monoolefins used as mixed monomers, mention should be made of propylene, butene-1, pentene-1,3-methylbutene-1,3-hexene-1,4-methylpentene-1,3-ethylbutene-1, heptene-1, octene-1,1-decene-1,4,4-dimethylpentene-1,4,4-diethylhexene-1,3,4-dimethylhexene-1,4-butyl-1-octene, 5-ethyl-1-decene, 3, 3-dimethylbutene-1 and the like. Suitable diolefins include 1,5-hexadiene, dicyclopentadiene, ethylidene orbornene and the like.

The polymers prepared by the process of the invention are solid materials having densities of about 0.945 to 0.970 and melt indexes of about 0.1 to 100 or greater.

I! 9 64171

Preferred polymers are ethylene homopolymers. The copolymers contain at least 50% by weight, preferably at least about 80% by weight of ethylene.

Once the catalyst mixtures have been formed, the polymerization reaction is carried out by contacting the monomer charge with a catalytic amount of the catalyst mixture at a temperature and pressure sufficient to initiate the polymerization reaction, with virtually no catalyst toxins in the charge. If desired, an inert organic solvent can be used as a diluent and to facilitate handling of the materials.

The polymerization reaction is carried out at temperatures of about 30 ° C to about 200 ° C, depending largely on the operating pressure, the pressure of the whole monomer charge, the catalyst mixture used in each case and its concentration. The operating temperature chosen also depends on the desired melt index of the polymer, as temperature is a factor that can be used to control the molecular weight of the polymer. The temperature is preferably about 30 to 100 ° C using a conventional slurry or particle formation method in an inert organic solvent. The use of higher polymerization temperatures tends to result in polymers having a lower average molecular weight, and thus polymers with a higher melt index, as is the case with more catalyst systems.

The pressure can be any pressure sufficient to polymerize the monomer charge, so the pressure can be less than air without pressure, in which case the inert gas is used as a diluent, or a pressure higher than about 6.9 GPa or more, but preferably without pressure to about 6.9 MPa. Generally, a pressure of 0.14 to 5.6 MPa is suitable.

When an inert organic solvent is used in the process of the invention, the solvent must be inert to all other components and products of the reaction system and stable under the reaction conditions used. However, it is not necessary that the inert organic solvent also act as a solvent for the prepared polymer. Suitable inert organic solvents for use include saturated aliphatic hydrocarbons such as hexane, heptane, pentane, isopentane, isooctane, refined fuel oil, etc., saturated cycloaliphatic hydrocarbons such as cycloentiphane, cyclohexane, cyclohexane, cyclohexane, cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, etc., and chlorinated hydrocarbons such as chlorobenzene, tetrachlorethylene, orthodichlorobenzene, etc. Particularly preferred solvents are cyclohexane, pentane, isopentane, hexane and heptane.

If it is desired to carry out the polymerization to a high concentration of solids as mentioned above, it is of course advantageous for the solvent to be liquid at the reaction temperature. When operated, for example, at a temperature lower than the temperature at which the polymer dissolves in this solvent, the process may be essentially a slurry or suspension polymerization process in which the polymer actually precipitates from the liquid reaction medium and the catalyst is suspended.

This slurry system will, of course, depend on the particular solvent used in the polymerization as well as the temperature at which the polymer dissolves in this solution. Thus, when applying the particle formation method, it is appropriate to operate at a temperature lower than the temperature at which the polymer dissolves in this selected solvent. Thus, the polyethylene produced may have a dissolution temperature in cyclohexane of about 90 ° C, while its dissolution temperature in pentane may be about 110 ° C. Such a particle-formation-polymerization system is characterized in that a high content of polymer solids can be achieved even at low temperatures, using sufficient mixing so that the monomer is properly mixed into the polymerized mass. It appears that although the rate of polymerization may be slightly lower at lower temperatures, the monomer dissolves more readily in the solvent, and thus counteracts the tendency for lower amounts of polymerization and / or low polymer yields.

The slurry process is also characterized in that the monomer also appears to have significant solubility properties in the solid part of the slurry, as long as suitable agitation is used and the polyamide 11 64171 meritation temperature is maintained, so that a wide range of solid particles in the slurry can be varied. Experiments have shown that, according to the sludge technology, a system with a solids content of more than 50% can be obtained, provided that sufficient mixing is obtained. Particularly preferably, the slurry process is applied in the range from 30 to 40% by weight of solid polymer.

In this embodiment, the recovery of the polymer from the solvent is reduced to a simple filtration and / or drying treatment, and no steps are required to purify the polymer and to separate or purify the catalyst. The residual concentration of the catalyst in the polymer is so small that the catalyst can be left in the polymer.

Of course, when using a solvent as the main reaction medium, it is advantageous to keep the solvent substantially anhydrous and free of possible catalyst poisons, such as moisture and oxygen, by redistillation or other purification of the solvent before use. Can be treated with an absorbent material such as large surface area silica, aluminum hydroxide, molecular sieves, and the like to remove residual amounts of contaminants that can reduce the amount of polymerization or poison the catalyst during the polymerization reaction.

By carrying out the polymerization reaction in the presence of hydrogen, apparently acting as a chain transfer agent, the molecular weight of the polymer can be further adjusted.

Experiments have shown that hydrogen can be used in the polymerization reaction in amounts of about 0.001 to 10 moles of hydrogen per mole of olefin monomer. In most polymerization reactions, the full range of molecular weights can be achieved by using about 0.001 to 0.5 moles of hydrogen per mole of monomer.

641 71 12

The homo- or copolymerization of ethylene with the catalysts according to the invention can also be carried out in a reaction process based on the use of a fluidized bed. An example of a fluidized bed reactor and method suitable for this purpose is described in GB Patent 1,253,063.

The following examples illustrate the application of the invention. Examples 1 ... 8

A series of eight catalysts were prepared using and without the use of various silane compounds to illustrate the utility of these compounds in the invention. For comparison, the catalyst of Example 1 was made without any silane or amine compound.

For each catalyst, medium grade silica having a surface area of 300 m 2 / g and an average particle size of 20 μm was used as a support. The support was first heat treated under nitrogen for 18 hours at 200 ° C. Thus, the heated support contained about 2.5 mmol of silanol groups / g. Eight g (20 mmol HSiOH) of this silica was slurried in about 100 mL of n-hexane, and about 1.4 g (16 mmol) of butylsilane was added. The silane compound was thus used in such an amount as to obtain 0.8 moles of the silane compound per mole of the silanol group in the silica support. The other hydrosilane compounds of this invention may likewise be used in such amounts as to give about 0.2 to 2.0 moles of silane per mole of silanol groups in the silica. The slurry was then refluxed at about 75 ° C, and 1.9 g (20 mmol) of triethylamine was slowly added to the boiling system over about one hour. When the amine was used, the amount of (C 2 H 5) 3 N / = SiOH was in the range of 0.1 to 1.0. Thereafter, boiling of the system using reflux was continued overnight, i.e., for about 18 hours. During the treatment, it is believed that the silane compound is chemically bound to the support and at the same time hydrogen is evolved. The system was then cooled, the silica was washed with n-hexane and dried under reduced pressure at 80 ° C anhydrous.

li 13 64171

The following Table I shows the silane compound used in each carrier, and the ratio of the silane compound to the silanol groups is also indicated.

The supported catalyst was then prepared by slurrying 0.4; 0.8 or 1.0 g of the carrier treated as before in about 100 ml of n-hexane and then adding 20 mg of bis- (cyclopentadienyl) chromate to the slurry. The slurry was stirred for about 30 minutes to allow the chromium compound to settle in the support. The amount of support used in each catalyst is also listed in Table I.

Each of the eight catalyst systems prepared as described above was used to homopolymerize ethylene at 60-70 ° C with 500 ml of n-hexane, a H 2 pressure of 173 kPa and an ethylene pressure of 1.2 MPa. The length of each reaction was about 30 minutes. The polymer yield achieved in each experiment is also listed in this Table I, and each experiment resulted in a polymer that was a solid and high density (= 0.95) material. Examination of the figures shown shows that active catalysts are obtained only if the hydrosilane compounds according to the invention are used to modify the catalyst support (Examples 2 to 8). Particularly preferred hydrosilane compounds (Examples 2 and 3) provide supported catalysts that result in polymer formation in relatively high yields.

64171 14

Table I

Pre- Carrier Used SiH / SiOH- Made mark g silane ratio polymer output, g 1 0.4 0 _5 2 1.0 butylsilane 1.0 152 3 1.0 amylsilane 1.0 128 4 1.0 diethylsilane 1.0 73 5 0.4 triethylsilane 1.0 32 6 1.0 triethylsilane 1.0 22 7 0.4 (CH3SiHO ) x * 3.0 17 8 0.8 (CH3S1HO) x * 3.0 21 * polymethylhydroxysiloxane where x is 35

Examples 9 ... 12

A series of four supported catalysts was prepared using a silica-aluminum hydroxide support to illustrate that such a support cannot be used in the present invention. For comparison, the catalysts of Examples 9 and 10 were prepared without any silane or amine compound.

The supports were silica-alumina hydroxide with about 87% by weight silica and about 13% by weight aluminum hydroxide. The surface area of the carrier was about 475 m 2 / g. The carrier was heat-treated under nitrogen for 18 hours. The carrier of Example 9 was treated in this way at 600 ° C, while the carriers of Examples 10 to 12 were treated at 200 ° C. The carriers of Examples 11 and 12 were thus treated with butylsilane and triethylamine as described in Examples 1-8 using a silane / = SiOH ratio of 1.0, and a (C2H5) N / SiOH ratio of 1.0.

|! 15 64171

Table II below lists the activation temperature of the support and the silane compound and amine used in each example.

Catalysts on the support were then prepared as described in Examples 1-8 using 0.4 or 0.8 g of support. The amount of support used for each catalyst is also listed in Table II.

Each of the four catalyst systems prepared as described above was used to homopolymerize ethylene as described in Examples 1-8. The yield of polymer prepared in each experiment is also listed in Table II. The polymer prepared according to Example 9 was a solid, high density (= 0.95) material. Examination of the numerical values in Table II shows that the silica-alumina support cannot be used according to the invention and that it must be thermally activated at relatively high activation temperatures to obtain acceptable results.

Table II

Pre-Carrier Carrier Used Brand made g Activation silane Polymer temperature ° C Yield, g 9 0.4 600 - 70 10 0.4 200 - 0 11 0.4 200 Butyl-0 silane 12 0.8 200 Butyl-0 Silane

Examples 13 and 14

The ethylene polymerization catalyst of the invention was compared to a catalyst prepared according to British Patent GB 1,253,063. The prior art catalyst was prepared by placing 4% by weight of chromosene on a silica support thermally activated under nitrogen for 8 hours at 750 ° C. The surface area of the support was 300 m 2 / g and the average particle size was 20 nm. The chromosene compound was added to the support as described in Examples 1-8, B.

The catalyst of the invention was prepared as described in Examples 1 to 8 using the same support as described above, butylsilane, triethylamine and chromosene. 4% by weight of chromosene was also added to this support. The support was dried for 18 hours at 250 ° C using nitrogen as a shielding gas.

Both catalysts were then used to homopolymerize ethylene in a fluidized bed reactor of the type described in said British patent GB 1,253,063. The reactions were carried out at 100 ° C (3, 2.1 MPa ethylene pressure) to give a yield of 4 to 5 per unit volume and time. The reaction was continued for about 200 hours. Hydrogen was used to adjust the molecular weight. The following Table III shows the average results are shown in numerical values describing the properties of the polymers prepared, which were prepared at about 13.6 to 18 kg per hour, and Table III also lists the main properties of both catalysts.

Examining the results in Table III, it is found that the results obtained using, on the one hand, a catalyst according to the invention prepared using a 250 ° C heat-treated support further treated with butylsilane and, on the other hand, a prior art 750 ° C heat-treated catalyst were: essentially the same.

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In addition to the chromosene compounds described above, other transition metal compounds which can be used as catalysts in the silica supports according to the invention are the bis- (indenyl) and bis- (fluorenyl) chromium (II) compounds having a condensed ring, which are described in U.S. Pat. ., filed on December 29, 1975, the disclosure of which is incorporated herein by reference.

These condensed ring compounds in the support are used in amounts of about 0.001 to 25% by weight or more, based on the total weight of the compound and the silica support. These fused ring compounds can be placed in the silica support of the invention in the same manner as the chromosene compounds described above. The compounds having a fused ring in the support can be used as polymerization catalysts for ethylene.

The structural formula of these fused ring organic chromium compounds is

Ar-Cr (II) -Ar 'wherein Ar and Ar' are the same or different and represent indenyl radicals having the structural formula

(R,) ”(H)?‘ Z

wherein the symbols Ra 'are the same or different carbon-hydrogen radicals C 1 -C 4, m is an integer from 0 to 4, and x is 0, 1, 2 or 3 and fluorenyl radicals having the structural formula 641 71 19 (il) , / (ζ) 2 / (R *) m "in which the symbols Rb 'denote the same or different hydrocarbon radicals C 1 -C 10, m' and m" are the same or different integers 0, 4, Z is H or Rb, and z is 0 or 1. Hydrocarbon radicals Rb may be saturated or unsaturated, and include aliphatic, alicyclic and aromatic radicals such as methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, cyclohexyl, allyl. , phenyl and naphthyl radicals.

Condensed ring compounds which can be used as the silica support according to the invention can be prepared by applying the method described in Advances in Organometallic Chemistry by J.M. Birmingham. F.G.A. Stone and R. West, Eds., Academic Press, New York, 1964, pp. 377-380, the disclosure of which is incorporated herein by reference.

Claims (3)

64171 20 A catalyst mixture for the polymerization of olefins, characterized in that it comprises a chromosene compound placed in a silica support dried at about 100__ to 300 ° C and treated in the presence of a volatile tertiary amine with a hydrosilane resin having a silane or a compound having the structural formula Rn-tSi * -H4_n wherein R represents a hydrocarbon group having 1 to 10 carbon atoms and n is an integer from 1 to 3, wherein the catalyst mixture contains about 0.5 to 10% by weight of a chromosene compound. 2. A process for the polymerization of ethylene alone or with one or more other alpha-olefins, characterized in that the catalyst used is a mixture containing a chromosene compound, the chromosene compound being placed in a silica support dried at about 100 to 300 ° C and treated with a volatile tertiary amine in the presence of a hydrosilane compound having a silane or a compound having the structural formula Rn-eSi * H4_n wherein R represents a hydrocarbon group having 1 to 10 carbon atoms and n is an integer from 1 to 3, wherein the catalyst mixture contains about 0, 5 to 10% by weight of a chromosene compound. 3. A process for preparing a catalyst in a silica support, characterized in that the silica support is dried at about 100-300 ° C long enough to remove water adsorbed on the surface, thereby treating the heat-treated support with a sufficiently large amount of hydrosilane compound in the presence of volatile tertiary amine. the compound reacts with the OH groups of the support in which the hydrosilane compound is a silane or a compound having the structural formula R11-fSifH4_n li 21 64171 wherein R is a hydrocarbon radical C1-C4q and n is an integer from 1 to 3, tertiary amine and treating the hydrosilane-treated support with such an amount of chromocene compound that about 0.1 to 3% by weight of chromium metal is supported on the support, based on the total weight of the catalyst mixture.