CA1163617A - Catalyst for polymerization of olefins and polymerization process employing such catalyst - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A catalyst useful for polymerizing olefins which comprises a solid catalyst component [A] and an organometallic component [B], the solid catalyst component [A] being obtained by reacting (1) a solid inorganic oxide, (2) a hydrocarbon-soluble organomagnesium component of the general formula M.alpha.Mg.beta.R?R?XrYs wherein .alpha., p, q, r and s each independently is 0 or a number greater than 0, .beta. is a number greater than 0, p + q + r + s = m.alpha. + 2.beta., m is the valence of M, M is a metal of the 1st and 3rd groups of the Periodic Table.
R1 and R2 each independently is a hydrocarbon group having 1 to 20 carbon atoms, X and Y each independently is an OR3, OSiR4R5R6. NR7R? or 5R9 group wherein R3, R4, R5, R6, R7 and R9 each independently is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and R9 is a hydrocarbon group having 1 to 20 carbon atoms, or of the reaction produc? of M.alpha.Mg.beta.R?R?XrYs with at least one electron donor selected from the group consisting of ethers, thoiethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols and amines and (3) a chlorosilane compound having a Si-H bond and of the formula HaSiC?bR??(a+b) wherein R10 is a hydrocarbon group having 1 to 20 carbon atoms, 0 < a ? 2 b > 0 and a + b ? 4, separating a reaction product from the reaction mixture and washing the separated reaction product with an inert hydrocarbon and reacting the washed reaction product with (4) a titanium compound having at least one halogen atom and/or a vanadium compound having at least one halogen atom, and a polymerization process employing such a catalyst.

Description

11~3~17 B~C~GROUND OF ~IE I~NTION
_ielc of the Invention This invention relates to a highly acti~le catalyst îo{ producing pol~olefins having a good particle diameter distribution and to a polymer-ization process e~ploying such a catalyst.
Description of the Prior Art There have been developed and proposed many catalyst systems for lo~-pressure processes of producing polyolefins which comprise a transiticn metal compound of a metal of Groups IV to ~I A of the periodic Table and an organometallic compound of a metal of Groups I to III of the Periodic Table since the Dr. Ziegler's discovery. Most of the catalyst systems, ho~ever, are not sufficient with the catalyst activity and require the step of re-moving catalyst residue from the polymer formed and accordingly, the cost of producing polymers are hi8h. Recently, development of highly active catalysts capable of eliminating the step of removing catalyst residue from the polymer formed and simplifying the process to reduce the cost of producing polymers is extensively carried out and there has been proposed a group of catalysts employing the reaction products of inorganic magnesium compounds or organomagnesium compounds and titanium compounds or vanadium compounds.
It ~ould be highly desired that the catalyst activity per transi-tion metal atom in the catalyst is increased and at the sa~e ti~e ail the characteristic features required for industrial catalysts, such as the particle diameter distribution of polymers, the bulk density of polymers and the stability of catalysts, are improved. At the present, a further increase in the ca~alvst activity in order to eliminate the catalyst residue re~oval step a~d at the same time a stable operation of slurry polymeriza-tio,n process continuously for a long period of time, and an improvement on the particle performances such as unificaticn of the part,cle dia~.eter of the po'ymer formed and incr2ase in the bulk density of the poly~:er formed

- 2 -are considered very important from the industrial view point.
As one means for preparing catalysts having a high catalyst activity ?er transition metal atom, it is known to employ a solid catalyst component obtained by reacting a solid inorganic oxide with a transition metal.
Japanese Patent Application (OPI) No. 2258/1971 describes a process for poiymerizing olefins by employing a solid catalyst component obtained by firstly reacting silica with an alkylmagnesium halide and secondly reacting the resulting reaction product with a titanium compound. Japanese Patent Application (OPI) No. 92879/1975 describes a method of preparing a carrier catalyst by heating silica and a magnesium halide and adding a transition metal compound thereto. Further, Japanese Patent Application (OPI) No.
47990/1976 describes a method of preparing a solid catalyst component by firstly reacting a silicon compound synthesized by the high temperature process with an organomagnesium compound and secondly reacting the resulting reaction product with a titanium compound. Furthermore, Japanese Patent Application (OPI) No. 95790/1977 describes a method of obtaining a solid catalyst component by firstly contacting silica with an alcohol-soluble magnesium compound and a solution of a titanium halide and secondly vapor-izing the alcohol to concentrate the reaction mixture solution. Still further, Japanese Patent Application (OPI) No. 148093/1979 describes a method of preparing a catalyst by dissolving a titanium compound and a magnesium compound in an electron donor and impregnating a porous carrier in the resulting solution. Also, Japanese Patent Application (OPI) No. 115405/1980 describes a method of preparing a catalyst comprising a solid inorganic oxide, an organomagnesium compound, a Lewis base compound and titanium tetrachloride.
According to these catalysts, the catalyst activity per transi-tion metal atom is considerably high but the cataly5t activity per unit weight of the solid catalyst component is not satisfactory. Thus, further lmproVementS on the catalyst productivity of polymers and at the same time on the particle diameter distribution and the bulk density of the polymers formed are demanded.

tl63617 As a result oF the study on solid inorganic oxides, various organo-magnesium compounds and various reagents in order to improve the above-described points, it has now been discovered that the solid substance obtained by reacting an inorganic oxide carrier substance, an inert hydro-carbon-soluble organomagnesium and a chlorosilane compound having a Si-~bond, separating and washing the reaction product with an inert hydrocarbon and reacting the reaction product with a transition metal compound, in combination with an organometallic compound, is a highly active catalyst for producing polyolefins having a good particle dia~eter.
SUMMARY OF THE INVENTION
According to this invention there is provided a catalyst useful for polymerizing olefins which comprises a solid catalyst component [A] and an organometallic component ~B], the solid catalyst component [A] being obtained by reacting (1) a solid inorganic oxide, (2) a hydrocarbon-soluble organomagnesium component of the general formula Mc~M~Rpxrys wherein ~, p, q, r and s each independently is O or a number greater than 0, ~ is a number greater than 0, p + q + r + s = m~ + 2~, m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, Rl and R2 each independently is a hydrocarbon group having 1 to 20 carbon atoms, X and Y each indeper..dently is an oR3, oSiR~R5R6, NR7R3 or SR9 group wherein R3, R~, R5, R6, R7 and R8 each independently is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and R9 is a hydrocarbon group having 1 to 20 carbon atoms, or of the reaction product of M~lg~RpRq~rYs with at least one electron donor selected from the group consisting of ethers, thioethers, ketones, aldehydes, hydrocarbyl carboxylic acids or derivatives thereof, alcohols, thioalcohols and amines and (3) a chlorosilane compound having a Si-~ bond and of the formula HaSiC~bR4-(a~h) wherein Rl is a hydrocarbon group having 1 to 20 carbon atoms, 0 C a _ 2 b > 0 and a + b _ 4, separating a reaction product from the reaction mixture and washing the separated reaction product with an inert hydrocarbon and reacting the washed reaction product with (4) a titanium compound having at least one halogen atom and/or a vanadium compound having at least one halogen atom.
Also, according to this invention there is provided a process for polymerizing olefins by employing such a catalyst.
One of the characteristic features of this invention is a high catalyst efficiency per unit weight of the solid catalyst component [A]
and moreover, a very high catalyst efficiency per chlorine atom in the solid catalyst component [A]. According to Japanese Patent Application (OPI) No.
40696/1978 there has been proposed a catalyst for polymerizing olefins which comprises (a) a solid catalyst component obtained by reacting a solid reaction product of a hydrocarbon-soluble organomagnesium component and a chlorosilane compound with a titanium or vanadium component and (b) an organometallic compound. The catalytic activity of this catalyst per transition metal atom and per unit weight of the solid catalyst component is high, but the catalyst efficiency per chlorine atom of the present invention is higher than that of Japanese Patent Application (OPI) No. 40696/1978 since the amount of chlorine atom contained in the solid catalyst component of this _ 5 _ 1 ~63~ 17 Ja?anese Patellt Application is higher than that of the present invention.
~hen the amount of chlorine atom remaining in the polymer is great, corrosion is caused on the metallic surface of molding apparatus. Thus it is preferred that the amount of chlorine atom is reduced as much as possible. In this respect the catalyst of the present invention is superior to the known catalysts.
Another characteristic feature of this invention is a high catalyst efficiency per transition metal atom.
Still another characteristic feature of this invention is that there can be obtained polymer powder having an excellent particle distribu-tion and a high bulk density.
A further characteristic feature of this invention is that there can be produced polymers having a broad molecular weight distribution.
DETAILED DESCRIPTION OF THE INVENTION
Each of the component materials and the reaction conditions which can be employed for the preparation of the catalyst of this invention will now be described hereinafter in detail.
The solid inorganic oxide (1) which can be employed for the pre-paration of the solid catalyst component [A] is a carrier selected from silica, alumina and a composite containing silica and alumina. It is preferred to employ a carrier prepared especially for the use of a catalyst carrler, for example, the catalyst carrier suitable for the polymerization of ethylene by the known Philips method. It is also possible to employ any type of alumina which can be used as a catalyst carrier and preferably y-alumina.
It is preferred that the carrier containing silica or alumina or both silica and alumina has a particle diameter of about 1-1000~, a BET
surface area of about 50-1000 m2/g and a pore volume of about 0.3-3.5 mQ/g.
A more preferred is silica having an average particle diameter of about 20-300~, a BET surface area of about 150-1000 m2/g and a pore volume of about 0.5-2.0 mQ/g.

1163~17 It is preferred that the inorganic oxide carrier is substantially dry and does not contain physically-adsorbed water. Thus it is preferred that the inorganic oxide carrier is heat-treated at about 300C or higher temperatures for a given period of time under reduced pressure.
The organomagnesium component (2) which can be used in preparing the solid catalyst component [A] is represented by the general formula Mo~Mg~3RpRqxrys wherein M, R1, R2, X, Y, ~, ~, p, q, r and s are the same as defined above, and includes dihydrocarbyl magnesium R2~1g ~herein R is a hydrocarbon group and complexes of the dihydrocarbyl magnesium with other organometallic compounds.
In this formula R1 and R2 each independently is a hydrocarbon group having l to 20 carbon atoms. Exemplary hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, amyl, hexyl and decyl groups; cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group; and aralkyl groups such as benzyl group. Of these groups, alkyl groups are preferred. M is a metal of the 1st to 3rd groups of the Periodic Table. Exemplary metals represented by M include lithium, sodium, potassium, beryllium, calcium, barium, zinc, boron and aluminum. Of these metals, beryllium, boron, aluminum and zinc are preferred due to their ease of making hydrocarbon-soluble organomagnesium complexes. The atomic ratio of Mg to M, i.e., ~/~ may be widely varied but it is preferred to employ the hydrocarbon-soluble organomagnesium complex in which the ~/a ratio is O.Ol to lO. It is more preferred to employ the hydrocarbon-soluble organo-magnesium complex in which a~O and the ~/a ratio is l to lO. X and Y each independently is an oR3, osiR4RsR6, NR7R8 or SR9 group where in R3, R4, R5, R6, R7 and R8 each independently is a hydrogen atom or a hydrocarbon group having l to 20 carbon atoms and R9 is a hydrocarbon group having l to 20 carbon atoms. Exemplary hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, amyl, hexyl and decyl groups; cycloalkyl groups ~ 1636 17 such as cvclohe~yl group; aryl groups such as phenyl group; and aralkyl groups such as benzyl group. ~, p~ q, r and s each independently is 0 o.
a number greater than 0 and ~ is a number greater than Q and the relationship of p + q + r + s = m~ + 2~ wherein m is the valence of M is satisfied. This relationship shows stoichiometry between the valence of M plus Mg and the substitutents. A preferred range of 0 ~ (r + s)/(~ + ~) < 1.0 designates that a total number of X and Y per total number of M and Mg is 0 to less than 1Ø I~ is more preferred to employ the range of 0 < (r + s)/(~ + ~) < 0.8.
The organomagnesium compounds or complexes can be prepared by reacting an organomagnesium compound of RlMgQ or R2Mg wherein Rl is the same as defined above and Q is a halogen atom, with an organometallic compound of MR2 or MR2 lH wherein M, R~ and m are the same as defined above, in an inert hydrocarbon medium such as hexane, heptane, cyclohexane, benzene and toluene at a temperature of about 0C to about 150C, and, if necessary or if desired, further reacting the resulting reaction product with an alcohol, water, a siloxane, an amine, an imine, a thiol or a dithio compound.
Furthermore, the organomagnesium compounds or complexes can be prepared by reacting a compound of MgX2 or RlMgX with a compound of MRm or MRm lH or by reacting a compound of RlMgX or RlMg with a compound of R2MX or Y MX wherein M, R1, R2, X, Y and m are the same as defined above and n is a number of 0 to m.
In general, organomagnesium compounds are insoluble in an inert hydrocarbon medium but organomagnesium complexes with ~ > 0 are soluble in an iner~ hydrocarbon medium.
Also organomagnesium compounds with ~ = 0 such as (sec-C4Hg)2Mg, (C2Hs)Mg(n-C4Hg) and (n-C6Hl2)2Mg are soluble in an inert hydrocarbon and accordingly, can be used in this invention with good results. Details will now be given of such organomagnesium compounds with ~ = 0.

~163617 The hydrocal-bon-soluble organomagnesium compound of the formula Mg~Rp ~ ~rYS is one of the compounds shown in the follo~ing three catego~ies:
(a) ~t least one of Rl and R2 is a secondary or tertiary alkyl group having 4 to 6 carbon atoms;
(b) Rl and R2 are alkyl groups having a different number of carbon atoms; and (c) At least one of Rl and R2 is a hydrocarbon group having 6 or more carbon atoms.
Preferred Rl and R2 are one of the following three combinations:
(a') Rl and R2 both are hydrocarbon groups having 4 to 6 carbon atoms and at least one of Rl and R2 is a secondary or tertiary alkyl group;
(b') Rl is an alkyl group having 1 to 3 carbon atoms and R2 is an alkyl group having 4 or more carbon atoms; and (c') Rl and R2 both are alkyl groups having 6 or more carbon atoms.
In the above described category of (a) and (a'), exemplary groups of the secondary or tertiary alkyl groups having 4 to 6 carbon atoms include sec-C4Hg, tert-C4Hg, -CH(CH3)(C3H7), -CH(C2Hs)2~ -C(C2Hs)(CH3)2, -CH(CH3)(C4Hg), -CH(C2Hs)(C3H7), -C(CH3)2(C3H7) and -c(CH3)(C2Hs)2~ Of these groups, secondary alkyl groups are preferred and sec-C4Hg is more preferred.
In the category of (b) and (b'), ethyl and propyl are preferred alkyl groups having 1 to 3 carbon atoms and ethyl is more preferred.
Exemplary alkyl groups having 4 or more carbon atoms include butyl, amyl, hexyl and octyl. Of these alkyl groups butyl and hexyl are preferred.
In the category of (c) and ~c'), exemplary hydrocarbon groups having 6 or more carbon atoms include hexyl, octyl, decyl and phenyl. Of these hydrocarbon groups, alkyl groups are preferred and hexyl is more pre-ferred.
Thus, exemplary hydrocarbon-soluble magnesi-mm compounds of the formula MgRpRq includes (sec-C4Hg)2Mg, (tert-C4Hg)2Mg, (n-C4Hg)Mg(C2Hs), _ 9 _ li636 17 (n-C.,~ 1g(sec-C4~1s), (n-C~H~)~1g(tert-C4Hs), (n-C6Hl3)~g(C2~s), (n-CgHl7)~1g(C2~s), (n-C6Hl3)2~1g, (n-C8Hl7)2~1g and (n-CloH2l)~1g.
In this invention it is essential that the organomagnesium com-pounds are soluble in an inert hydrocarbon medium.
Since with increased numbers of carbon atoms of the alkyl groups the organomagnesium component (2) becomes easily soluble in an inert hydro-carbon medium but the viscosity of the solution obtained tends to increase.
Thus it is not advantageous from the viewpoint of ease of handling to employ unnecessarily long carbon chain alkyl groups.
The above described organomagnesium compounds can be used in the form of a solution and this solution may contain a small amount of a complex-ing agent such as an ether, an ester or an amine.
As ~he organomagnesium component (2), the above described compounds can be employed and it is preferred to react these compounds with an electron donor in the liquid phase.
The electron donors which can be employed in this invention in-clude ethers, thioethers, ketones, aldehydes, hydrocarbyl carboxylic acids or derivatives thereof, alcohols, thioalcohols and amines which are well known compounds as the electron donor.
The ethers are represented by the general formula Rl2oRl3 ~herein Rl 2 and Rl3 each is an aliphatic, aromatic or alicyclic hydrocarbon group having l to about 20 carbon atoms. Exemplary groups are methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, octyl, dodecyl, cyclohexyl, phenyl and benzyl groups.
The thioethers are represented by the general formula Rl4SRls wherein Rl 4 and Rls each is an aliphatic, aromatic or alicyclic hydrocarbon group having l to about 20 carbon atoms. Exemplary groups are methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl and phenyl groups.
The ketones are represented by the general formula Rl6CoRl7 wherein Rls and Rl7 each is an aliphatic, aromatic or alicyclic hydrocarbon group 1~63~17 having 1 to about 20 carbon atoms. Ex~mplary groups are methyl, ethyl, propyl, butyl, ~Iyl, hexyl, cyclohecyl and phenyl groups, and dimethyl ketone and diethyl ketone are especially preferred.
The aldehydes are represented by the general formula Rl BcHo wherein Rl 8 iS an aliphatic, aromatic or alicyclic hydrocarbon group having 1 to about 20 carbon atoms. Exemplary groups are methyl, ethyl, propyl, butyl, hexyl, cyclohexyl and phenyl groups.
The hydrocarbyl carboxylic acids or derivatives thereof are aliphatic, alicyclic or aromatic, saturated or unsaturated carboxylic acids where the number of carbon atoms of the carboxylic acids can vary widely and is preferably 1 to about 20, their acid anhydrides, their esters, their acid halides and their acid amides. Exemplary hydrocarbyl carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, maleic acid, acrylic acid, benzoic acid, toluic acid and terephthalic acid. Exemplary hydrocarbyl carboxylic acid anhydrides include acetic anhydride, propionic anhydride, n-butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride and phthalic anhydride. Among the hydrocarbyl carboxylic acid esters, it is preferred that the alcohol of the ester group has 1 to about 20 carbon atoms.
Exemplary hydrocarbyl carboxylic acid esters include methyl or ethyl formate, methyl, ethyl or propyl acetate, methyl, ethyl, propyl or butyl propionate, ethyl butyrate, ethyl valerate, ethyl caproate, ethyl n-heptanoate, dibutyl oxalate, ethyl succinate, ethyl malonate, dibutyl maleate, methyl or ethyl acrylate, methyl methacrylate, methyl, ethyl, propyl or butyl benzoate, methyl, ethyl, propyl, butyl or amyl toluate, methyl, or ethyl p-ethylbenzoate, methyl, ethyl, propyl or butyl anisate and methyl or ethyl p-ethoxybenzoate.
The hydrocarbyl carboxylic halides are preferably the carboxylic chlorides including, for example, acetyl chloride, propionyl chloride, butyryl chloride, succinoyl chloride, benzoyl chloride and toluyl chloride. Exemplary hydro-carbyl carboxylic acid amides include dimethyl formamide, dimethyl acetamide 1~6361~

and dimethvl propionamide.
The alcohols are aliphatic, aromatic or alicyclic alcohols having 1 to about 20 carbon atoms. Exemplary alcohols include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol~ hexyl alcohol, phenol and cresol. It is preferred to use sec- or tert-alcohols or aromatic alcohols including sec-propyl alcohol, sec-butyl alcohol, tert-butyl alcohol, sec-amyl alcohol, tert-amyl alcohol, sec-hexyl alcohol, phenol and o-, m- or p-cresol.
The thioalcohols are aliphatic, aromatic or alicyclic alcohols having 1 to about 20 carbon atoms. Exemplary thioalcohols include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, amyl mercap,an, hexyl mercaptan and phenyl mercaptan. It is preferred to use sec-, tert- or aromatic thioalcohols.
The amines are aliphatic, alicyclic or aromatic amines having 1 to about 20 carbon atoms. It is preferred to use sec- or tert-amines including trialkylamines, triphenylamine and pyridine.
The reaction between the hydrocarbon-soluble organomagnesium com-ponent (2) and the electron donor is conducted in an inert reaction medium such as aliphatic hydrocarbons including hexane and heptane; aromatic hydro-carbons including benzene, toluene and xylene; alicyclic hydrocarbons includ-ing cyclohexane and methylcyclohexane; ethers; and any mixtures thereof.
The reaction order of these compounds is optional. For example, the electron donor is added to the organomagnesium component (2), or vice versa, or both components are simultaneously added to a reaction zone.
In these reactions, the amount of the electron donor is not particularly limited, but preferably is at most about 1 mol, more preferably in the range of about 0.01 to about 0.8 mol, most preferably about 0.05 to about 0.5 mol per mol of the organomagnesium component (2).
Details will no~ be given of the chlorosilane compound (3) having a Si-H bond and of the formula 1 163~ 17 HasicQbR~-(a+b) wherein a, b and Ri are the same as defined above.
The hydrocarbon groups represented by Rl 3 have 1 to 20 carbon atoms and include aliphatic, alicyclic or aromatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl and phenyl. Preferred hydrocarbon groups are alkyl groups having l to 10 carbon atoms, and lower alkyl groups such as methyl, ethyl, propyl are more preferred. The range of a and b is typically O<a~2, b>0 and a+b-4. A preferred range of a is O<a<2.
Exemplary chlorosilane compounds include HSiC~3, HSiCQ2 (CH3 ), HSiC~2(C2Hs), HSiCQ2(n-C3H7), HSiC~2(i-C3H7), HSiC~2(n-C4Hg~, HSiC~2(C6Hs), HSiC~2 (4-CQ-C6H4), HSiC~2 (CH=CH2), HSiC~2 (CH2C6Hs), HSiCQ2 (l-Cl oH7), HSiC~2(CH2CH=CH2), H2SiCQ(CH3), H2SiCQ(CzHs) ~ HSiCQ(CH3)2, HSiCQ(CH3) (i-C3H7), HSiC~(CH3)(C6Hs), HSiCQ(C~Hs)2 and HSiCQ(C6Hs)2. This compound alone, a mixture of these compounds or a mixture partially containing any of these compounds may be used. Preferred chlorosilane compounds are trichlorosilane, monome~hyldichlorosilane, dimethylchlorosilane and ethyldichlorosilane.
More preferred chlorosilane compounds are trichlorosilane and monomethyl-dichlorosilane.
Further details will now be provided of (4) the titanium compound having at least one halogen atom and/or a vanadium compound having at least one halogen atom.
Exemplary tltanium compounds and vanadium compounds include halides, oxyhalides and alkoxyhalides of titanium or vanadium such as titanium tetra-chloride, titanium tetrabromide, titanium tetraiodide, ethoxytitanium tri-chloride, propoxytitanium trichloride, butoxytitanium trichloride, dipropoxy-titanium dichloride, dibutoxytitanium dichloride, tripropoxytitanium monochloride, tributoxytitanium monochloride, vanadium tetrachloride, vanadyl trichloride, monobutoxyvanadyl dichloride, dibutoxyvanadyl monochloride and dibutoxy-vanadyl dichloride and mixtures thereof. Preferred titanium compounds and î lS3~ 1~

vanadium con)pounds are those having at least three halogen atoms, and titanium tetrahalides are more preferred.
Details will now be given to the preparation of the solid catal~st component [A~.
The reaction of the solid inorganic oxide (l), the hydrocarbon-soluble organomagnesium component (2) and the chlorosilane compound (3) is conducted in an inert reaction medium such as aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as ben~ene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane;
ethers such as ether and tetrahydrofuran; and mixtures thereof. Of these inert reaction media, aliphatic hydrocarbons are preferred from the viewpoint of catalyst performance.
As to the manner of the reaction, it can involve (i) reac~ing the component (2) and the component (3) in the presence of the component (1) Lmethod (i)]; (ii) firstly reacting the component (1) with the component (2) to give a reaction product and then reacting the reaction product with the component (3) ~method (ii)]; (iii) firstly reacting the component (1) with the component (3) to give a reaction product and then reacting the reaction product with the component (2) [method (iii)3. Of these methods, the two methods (i) and (ii) can provide better results.
According to the method (i), it is preferred that the solid in-organic oxide (1) is firstly suspended in an inert reaction medium to form a suspension and then the hydrocarbon-soluble organomagnesium component (2) and the chlorosilane compound (3) are simultaneously added into the suspen-sion. The reaction ratio of the three components (1), (2) and (3) are not particularly limited but it is preferred that the mol ratio of the component ~ magnesium atom in the component (2) : the component (3) is l : about 0.01-100 : about 0.01-100. A more preferred mol ratio of the component (1) :
ma~nesium 2tom in the component (2) : the component t3) is 1 : about 0.1-10 : about 0.1-10. The reaction temperature is not particularly limited il63~7 and typicaLly ranges fron~ about -?5C to about 100C. A preferred reaction temperature ranges from about 10C to about 60C.
According to the method (ii), the reaction between the component (1) and the component (2) may be conducted by simultaneously introducing the two components (1) and (2) into a reaction æone; suspending the component (1) in an inert reaction medium and adding the component (2) to the resulting suspension; or adding the component (1) to the component (2). The former two methods can provide better results. The reaction ratio of the two components (1) and (2) is not particularly limited but it is preferred to employ about 0.01-100 mols, more preferably about 0.1-10 mols of the hydro-carbon-soluble organomagnesium component (2) per mol of the solid inorganic oxide (1). The reaction temperature is not particularly limited and typical-ly ranges from about -25C to about 100C. A preferred reaction temperature ranges from about 10C to about 60C.
It is preferred that the reaction product of the component (1) and the component (2) is separated, washed with an inert hydrocarbon and then reacted with the component (3)~ The reaction between the reaction product and the component (3) may be conducted by simultaneously introducing the reaction product and the component (3) into a reaction zone or suspending the reaction product in an inert reaction medium and then adding the component

(3) to the resulting suspension. The reaction ratio of the reaction product and the component (3) is not particularly limited but it is preferred to employ about 0.1-1000 mols, more preferably about 1-100 mols of the component (3) per mol of magnesium atom in the reaction product. The reaction temperature is not particularly limited but from the viewpoint of reaction rate the reaction is preferably carried out at a temperature of from about 40C to about 100C.
According to the method (iii), the reaction bet~een the component (1~ and the component (3) may be conducted by simultaneously introducing the two components (1) and (3) into a reaction zone; suspending the component (1) in an inert reaction medium and adding the component (3) to the resulting suspension; or adding the component (1~ to the component (3). Any of these three methods can provide good results. The reaction ratio of the two components (1) and (3) is not particularly limited but it is preferred to employ about 0.01-100 mols, more preferably about 0~1-10 mols of the component (3) per mol of the component (1). The reaction temperature is not particularly limited but it is preferred to conduct the reaction at a temperature of from about 40C to about 100C.
It is preferred that the reaction product of the component (1) and the component (3) is separated, washed with an inert hydrocarbon and then reacted with the component (2). The reaction between the reaction product and the component (2) may be conducted by simultaneously introducing the reaction product and the component (2) into a reaction zone or suspending the reaction product in an inert reaction medium and then adding the component (2) to the resulting suspension. The reaction ratio of the reaction product and the component (2) is not particularly limited but it is preferred to employ about 0.1-1000 mols, more preferably about 1-100 mols of the component (2) per mol of chlorine atom in the reaction product. The reaction temperature i5 not particularly limited and typically ranges from about 0C to about 100C.
Now details will be given of the reaction between the reaction product of the solid inorganic oxlde (1), the hydrocarbon-soluble organo-magnesium component (2) and the chlorosilane compound (3) and a titanium compound having at least one halogen atom and/or a vanadium compound having at least one halogen atom ~4).
It is preferred that the reaction product of the three components (1), (2) and (3) is separated, washed with an inert hydrocarbon and then reacted with the component (4). The reaction may be conducted by employing an inert reaction medium or by employing the undiluted titanium compound and/or vanadium compound (4) as such as the reaction medium without using llS3~17 an inert reaction medium. The inert reaction media which can be emploved in this reaction include alipihatic hydrocarbons such as he~ane and heptane;
aromatic hydrocarbons such benzene, toluene and xylene; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, Of these inert reaction media, aliphatic hydrocarbons are preferred. The reaction temperature employed is not particularly limited but it is preferred to employ a temperature of from about 40C to about 100C. The concentration of the titanium compound and/or the vanadium compound (4) is not particularly limited but it is preEerred that the concentration of the titanium compound and/or tne vanadium compound (4) is at least about 4 mols per liter of the inert reaction medium. More preferably, undiluted titanium compound and/or vanadium compound (4) as such is employed as the reaction medium~ As to the reaction ratio of the reaction product of the components (1), (2) and (3) and the component (4), good results can be obtained when the reaction is conducted in the presence of the titanium compound and/or the vanadium compound (4) in a sufficiently excess amount based on the magnesium atom in the reaction product of the components (1), (2) and (3).
The composition and the structure of the solid catalyst component [A~ obtained by the above described reaction may vary depending upon the kinds of the starting materials and the reaction conditions and as a result of the composition analysis, it has been found that the solid catalyst com-ponent ~A~ contains about 0.3-10% by weight of titanium and/or vanadium and has a large surface area.
The organometallic compounds [B] which is employed with the solid catalyst component [A~ are compounds of metals of the 1st to 3rd groups of the Periodic Table and include organoaluminum compounds, organomagnesium compounds and organozinc compounds. Of these organometallic compounds, organoaluminum compounds are preferred. As the organoaluminum compounds, those represented by the formula AQRtlZ3-t 1~63~17 wherein Rll is a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrogen atom~ a halogen atom, an alkoxy group, an aryloxy group or a silo~J group and t is 2 to 3, can be used individually or as a mixture. In the above described formula, the hydrocarbon groups having 1 to 20 carbon atoms represented by Rll include aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons.
Exemplary organoaluminum compounds include trialkylaluminums such as triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, trihexadecylaluminum; dialkylaluminum hydrides such as diethylaluminum hydride, diisobutylaluminum hydride; di-alkylaluminum alkoxides such as diethylaluminum ethoxide, diisobutylaluminum ethoxide, dioctylaluminum butoxide, diisobutylaluminum octyloxide; dialkyl-aluminum halides such as diethylaluminum chloride, diisobutylaluminum chloride; dialkylaluminum siloxides such as dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethyldimethylsiloxyaluminum diethyl; aluminum isoprenyl and mixtures thereof.
A combination of these organoaluminum compounds with the above described solid catalyst component [A] provides a hi~hly active catalyst, and especially trialkylaluminums and dialkylaluminum hydrides are preferred because they show the highest activity.
The solid catalyst component [A~ and the organometallic component [B~ may be added to the polymerization system under the polymerization conditions or may be mixed prior to the polymerization.
The amount of the organometallic compound [B] typically ranges from about one millimol to about 3000 millimols per gram of the solid catalyst component [A].
The electron donor which can be employed as the catalyst component 1 1~361 7 [C~ may be the same as the one which can be emploved for the reaction with the hydrocarbon-soluble organomagnesium component (2). Of the ethers, thioethers, ketones, aldehydes, hydrocarbyl carboxylic acids or derivatives thereof, alcohols, thioalcohols and amines, preferred electron donors are the hydrocarbyl carboxylic acids or derivatives thereof. The amount of the electron donor typically ranges from about 0.01 mol to about 10 mols, pre-ferably ranges from about 0.1 mol to about 1 mol per mol of the organometallic compound [B].
The olefins which can be polymerized by using the present catalyst may be ~-olefins, especially ethylene. Tlle present catalysts may be employed for stereospecific polymerization of propylene by using a combination of the organometallic compound with the electron donor. Also the present catalysts may be employed for polymerizing ethylene or propylene in the presence of other monoolefins such as propylene, butene-1 and hexene-1 and dienes such as butadiene and isoprene and moreover for polymerizing dienes.
As for the polymerization method, there may be employed the usual suspension-, solution- and gas phase-polymerizations. In the cases of suspension- and solution-polymerizations, the catalyst is introduced into a reactor together with a polymerization medium, e.g., aliphatic hydrocarbon such as hexane, or heptane; aromatic hydrocarbon such as benzene, toluene or xylene; or alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, and, ethylene or propylene is added under a pressure of 1 to 20 Kg/cm- in an inert atmosphere and allowed to polymerize at a temperature from about room temperature to about 200C. Polymerization of propylene can also be conducted in liquid propylene.
~ or gas phase-polymerization, it is possible to carry our polymer-ization under an ethylene or propylene pressure of 1 to 50 Kg/cm2 and a temperature from about room temperature to about 120C, using a fluidized bed, moving bed or mixing with a stirrer to provide better contact between the ethylene or propylene and catalyst.

1 163~ 17 There May be employed single stage polymeri~ation or multistage polymeri~ation .
The present catalyst makes it po~sible to prepare a polymer whose molecular weight distribution is considerably broad even in one stage polymer-ization. Furthermore, when multiple stage polymerization is effected in at least two pol~erization zones having different polymerization conditions, by USillg the present catalyst it is possible to prepare a polymer whose molecular weight distribution is much broader. Such a polymer is very suitable for the production of articles by blow molding or film making.
In order to control the molecular weight of the polymer, it is also possible to add hydrogen, a halogenated hydrocarbon or an organo-metallic compound which can easily cause chain transfer.
The following examples of preferred embodiments further illustrate the principle and practice of the invention:
In the following examples, MI is the melt index measured according to ASTM ~-1238, wherein the temperature and the load employed are 190C
and 2.16 Kg, respectively;
FR is the quotient of the melt high-load index measured at a temperature of 190C and a load of 21.6 Kg divided by MI; the larger the quotient, the broader is the molecular weight distribution;
Mesh is the one measured according to JIS Z8801-1966; and Boiling n-heptane extraction residue is the residue obtained by extracting a polymer with boiling n-heptane for 6 hours.
Example 1 (1) Treat~ent of Inorganic Oxide Carrier Silica containing 99.5 percent by weight of SiO2 and having a B~T surface area of 365 m /g, a pore volume of 1.7 mQ/g and an average particle diameter of 65 ~ was heated at 350C for 2 hours under reduced pressur2 and then cooled to room temperature and kept in a nitrogen atmosphere.
(2) Synthesis of Hydrocarbon-soluble Organomagnesium Component ~2) In a 500 m~ flask having been purged with nitrogen were charged 27.6 g of di-n-butylmagnesium and 3.80 g of triethylaluminum together with 200 mQ of n-heytane, and the mixture was reacted at 80C for 2 hours to give an organomagnesium complex solution. As a result of analysis, the composition of this complex was AQ~lg6.0(C2Hs)3.o(n-c4Hg)l2.o and the concentration of the organometal was 1.10 mol per liter of n-heptane.
(3) Synthesis of Solid Catalyst Component [A]
In a 200 mQ flask equipped with a dropping funnel and a water-cooled reflux condenser from which oxygen and moisture had been removed by replacement with dry nitrogen, there were charged 5.0 g of the above-described heat-treated dry silica as obtained in (1) and then 20.8 cc of n-hexane to form a suspension with stirring. To the suspension formed were added dropwise 20.8 mmols of the above-described organomagnesium complex solution as obtained in (2) and 20.8 cc of a n-hexane solution containing one mol of trichlorosilane per liter of n-hexane at the same time over one hour with stirring while the internal temperature of the flask was controlled at room temperature. The mixture was reacted at room temperature further for one hour. The solid formed was separated by filtration, sufficiently washed with n-hexane and dried.
In an autoclave having been purged with nitrogen were charged 2.0 g of the solid as obtained above and 30 mQ of titanium tetrachloride, and the mixture was reacted at 130C for 2 hours with stirring. The solid formed was separated by filtration, sufficiently washed with n-hexane and dried to give a solid catalyst component [A]. As a result of analysis, the solid catalyst component [A] contained 1.9 % by weight of Ti and 15.6 by weight of CQ.

~ 163617 ~4) Polymerization o~ Ethylene In a 1.5 ~ autoclave having been evacuated al~d purged with nitrogen were charged 20 mg of the solid catalyst componerlt [A] as prepared in t3) and 0.4 ~ ol of triisobutylaluminum together with 0.8 Q of dehydrated and deaerated n-hexane. While the internal temperature of the autoclave was maintained at 80C, hydrogen and ethylene were pressured to 1.6 Kg/cm2 and 2.4 Kg/cm2~ respectively, and the total guage pressure was adjusted to

4.4 Kg/cm2. Polymerization of ethylene was carried out for one hour while the total gauge pressure of 4.4 Kg/cm2 was maintained by supplying additional ethylene. The yield of polymer was 95 g and the catalyst efficiency was 104,000 g/g-Ti-hour-ethylene pressure. The polymer powder obtained showed a MI of 0.45, a FR of 81 and a bulk density of 0.430 g/cm3.
The particle distribution was as follows;
Mesh Weight %
< 14 6.5 28 26.8 22.6 48 6.1 Examples 2 to 10 Solid catalyst components ~A] were prepared by using the same heat-treated dry silica as in Example 1. chlorosilane compounds, titanium compounds and/or vanadium compounds as described in Table in the same manner as in Example 1.
Polymerization of ethylene was carried out by using the solid catalyst components [A] under the same polymerization conditions as in Example l. The results are shown in Table.
Comparative Example 1 A solid catalyst component [A] was prepared in the same manner as in Example 1 except that ethylaluminum dichloride was employed instead of the trichlorosilane, and polymerization of ethylene was carried out by using the solid catalyst component [A~ under the same conditions as in Example 1. The results are shown in Table.

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~ - ~5 -~1~3617 E~ample 11 In a 1.5 R autoclave havin& been purged with nitrogen were charged 10 mg of the same solidcatalyst component [A] as prepared in Example 1 and 0.4 mmol of triethylaluminum as the organometallic component ~3 together with 0.8 Q of dehydrated and deaerated n-hexane. While the internal temperature of the autoclave was maintained at 80C, hydrogen and ethylene were pressured to 3.8 Kg/cm2 and 5.8 Kg/cm2, respectively, and the total guage pressure was adjusted to 10.0 Kg/cm2. Polymerization of ethylene was carried out for 2 hours while the total guage pressure of 10 ~g/cm2 was maintained by supplying additional ethylene. The yield of polymer was 217 g. The amounts of Ti and CQ remaining in the polymer as the catalyst residue were 0.9 ppm and 7.2 ppm and thus the residual amount of CQ was especially small. The particle distribution of the polymer powder obtained was as follows;
Mesh Weight %
< 14 41.0 22.8 28 25.7 8.5 The bulk density of the polymer powder was 0.415 g/cm3 and the dry flow property of the powder was very good.
Example 12 Gamma-alumina having a BET surface area of 315 m2/g, a pore volume of 1.45 mQ/g and a particle of 20 to 110 ~ was dried at 350~C for 2 hours under reduced pressure in the same manner as in Example 1.
A solid catalyst component [A] was prepared by using 5.0 g of the above obtained gamma-alumina, 20.8 mmols of AQMgO(C2Hs)3(n-c4Hg)l2~ 20.8 mmols of HSiCQ3 and 30 mQ of TiCQ4 under the same reaction conditions as in Example 1. As a result of analysis, the solid catalyst component [A]
contain~d 1.7 % by weight of Ti.

1 i63~17 Pol~merization of ethylene was carried out by using the solid catalyst component [A~ under the same polymerization conditions as in Example l. The yield of polymer was 65 g and the catalyst erficiency was 79,700 g/
g-Ti-hour-ethylene pressure. The polymer showed a MI of 0.29 and a FR of 76.
Example 13 Silica having a BET surface area of 600 m~/g, a pore volume of 1.0 mQ/g and an average particle diameter of 58 ~ was dried at 350C for 2 hours under reduced pressure in the same manner as in Esample 1.
In a 200 mQ flask equipped with a dropping funnel and a water-cooled reflux condenser from which oxyten and moisture had been removed by replacement with dry nitrogen there were charged 5.0 g of the abo~e-described heat-treated dry silica and then 20.8 cc of n-hexane to form a suspension with stirring. To the suspension formed was added dropwise 20.8 mmols of the same organomagnesium component as obtained in Example 1 over one hour with stirring while the internal temperature of the flask was controlled at room temperature. The mixture was reacted at room temperature further for one hour. The solid formed was separated by filtration, washed with n-hexane and dried.
In an autoclave having been purged with nitrogen were charged the solid as obtained above and 20.8 cc of n-hexane to form a suspension with stirring. To the suspension was added dropwise 20.8 cc of a n-hexane solution contalning one mol of trichlorosilane per liter of n-hexane at 60C
over one hour with stirring, and the mixture was reacted at 60C further ::
for one hour. The solid formed was separated by filtration, sufficiently ; ~ washed with n-hexane and dried.
In an autoclave having been purged with nitrogen were charged 2.0 g of the above-described solid and 30 m~ of titanium tetrachloride, and the mixture was reacted at 130C for 2 hours with stirring. The solid formed was separated by filtration to obtain a solid catalyst component [A].

AS 2 result of analysis,the solid catalyst component ~A] contained 2.0 %
by ~eight of Ti~
Polymerization of ethylene was carried out by using the solid catalyst component [A] under the same polymeri~ation conditions as in Example 1. The yield of polymer was 82 g and the catalyst efficiency was 85,400 g/g-Ti-hour-ethylene pressure. The polymer showed a ~II of 0~51 and a FR of 80~
Example 14 Polymerization of a mixed gas of ethylene and butene-l containing 3 mol % of butene-l instead of ethylene was carried out by using the same catalyst as in Example 1 under the same polymerization conditions as in Example l~ The yield of polymer was 86 g and the polymer obtained showed a MI of 0~28 and a FR of 91~
Example 15 In a 1~5 Q autoclave having been evacuated, dried and filled with nitrogen were charged 30 mg of the same solid catalyst component ~A] as pre-pared in Example 1, 2~4 mmols of triethylaluminum and 0~8 mmol of ethyl benzoate together with 0~8 Q of dehydrated and deaerated n-hexane~ While the internal temperature of the autoclave was maintained at 60C, propylene was pressured to 5.0 Kg/cm2~ Polymeri~ation of propylene was carried out for 2 hours while the total pressure was maintained at a gauge pressure of 4~8 Kg/cm~ As a result, 131 g of a n-hexane insoluble polymer and 9~5 g of a n-hexane soluble polymer were obtained~ The catalyst efficiency was 23,000 g/g-Ti-hour-propylene pressure and the boiling n-heptane extraction residue of the n-hexane insoluble polymer was 88.1 %.
Example 16 In a 1 Q autoclave having been evacuated were charged 10 mg of the same solid catalyst component ~A¦ as prepared in Example l and 0.1 mmol of tri-n-octylaluminum together with 0.6 Q of dehydrated and deaerated n-octane. After 10 mmols of hydrogen was charged in the autoclave, t ~6~6 ~7 ethylene wax pressured into the autoclave at a pressure of 40 Kg/cm~ while the temperature of the autoclave was maintained at 150C. Polymerization of ethylene was carried out for 30 ~inutes while the total pressure was maintained constant by supplying additional ethylene. The yield of polymer was 88 g.
xample 17 Gas phase polymerization was conducted by using a 50 Q stainless steel fluidized bed type autoclave. Into the autoclave whose temperature was kept at 80C and whose gauge pressure was adjusted to 10 Kg~cm2 were charged lO0 mg of the same solid catalyst component [A] and 200 mmols of AQ(n-C6HI3)3 and polymerization was carried out for one hour by introducing a mixed gas of ethylene, butene-l and hydrogen at a mol ratio of l : 0~03 : 0.15 into the autoclave at a space velocity of 15 cm/second. As a result, there was obtained 953 g of a powder polymer having a bulk density of 0.423 g/cm3, a true specific gravity of 0.934 g/cm3, a Ml of l.S and a FR of 35.
Example 18 In a flask from which oxygen and moisture had been evacuated and purged with dry nitrogen was charged 30 mmols of the same organomagnesium complex solution as in Example l, and then 8 cc of a n-hexane solution containing one mol of ethyl benzoate per liter of n-hexane was added thereto at room temperature with stirring and the mixture was reacted at room temperature for one hour. In a flask was chraged 5 g of the same heat-treated dry silica as in Example l, and then 20.8 cc of n-hexane was added thereto with stirring to form a suspension. To the suspension were added dropwise 20 cc of the above-described organomagnesium reaction solution and 20 cc of a n-hexane solution containing one mol of trichlorosilane per liter of n-hexane at the same time over one hour with stirring while the internal temperature of the flask was controlled at room temperature, and then the mixture was reacted at room temperature further for one hour. The solid formed was separated, washed with n-hexane, dried and reacted with titanium ~163~17 tetrachloride under t~e s~me reactioll condicions a~ in E~ample l to vive a solid catalyst component [~]. As a result of analysis, this solid catalyst component [A] contained 1.6 % by weight of Ti and 14.2 % by weight of C~.
Polymerization of propylene was carried out by using 30 mg of the above-described solid catalyst component [A], 2.4 mmols of triethylaluminum and 0.8 mmol of ethyl p-toluate under the same polymerization conditions as in E~ample 15. The yields of a n-hexane insoluble polymer and a n-he~ane soluble polymer were 126 g and 4.1 g, respectively. The catalyst efficiency was 26,300 g/g-Ti-hour-propylene pressure and the boiling n-heptane extraction residue of the n-hexane insoluble polymer was 93.1 %. The particle distribution was as follows;
~esh Weight %
< 14 9.6 28.1 28 35.0 27.3 The bulk density of the polymer powder obtained showed 0.435 g/cm3 and the dry flow property of the powder was very good.
Example l9 In a 1.5 Q autoclave having been purged with nitrogen and dried under vacuum was charged 350 g of liquid propylene. While the internal temperature of the autoclave was maintained at 60C, polymerization of propylene was carried out for 2 hours at 60C by adding 10 mg of the same solid catalyst component [A] as prepared in Example 18, 1.5 m ls Gf triethylaluminum and 0.6 mmol of ethyl benzoate. The yield of polymer was 138 g. The catalyst efficiency was 6900 g-polypropylene/g-solid catalyst component-hour~ The amounts of Ti and CQ remaining in the polymer as the catalyst residue were 1.2 ppm and 10.3 ppm and thus the residual amount of CQ was especially small. The boiling n-heptane extraction residue of the polypropylene obtained was g2.1 % and the bulk density of the polymer 1 1~3617 powder W.IS 0.440 g/cm3 and the dry flow propertv of the powder was very good.
It ~ill be appreciated that instant specification and e~amples are set forth by wav of illustration and not limitation, and tha~ various modifications and cihanges may be made without departing from the spirit ~nd scope of the present invention.

Claims (16)

WHAT IS CLAIMED IS :

1. A catalyst useful for polymerizing olefins which comprises a solid catalyst component [A] and an organometallic component [B], the solid catalyst component [A] being obtained by reacting (1) a solid inorganic oxide, (2) a hydrocarbon-soluble organomagnesium component of the general formula M.alpha.Mg.beta.R?R?XrYs wherein .alpha., p, q, r and s each independently is 0 or a number greater than 0, .beta. is a number greater than 0, p + q + r + s = m.alpha. + 2.beta., m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R1 and R2 each independently is a hydrocarbon group having 1 to 20 carbon atoms, X and Y each independently is an OR3, OSiR4R5R6, NR7R8 or SR9 group wherein R3, R4, R5, R6, R7 and R8 each independently is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and R9 is a hydrocarbon group having 1 to 20 carbon atoms, or of the reaction product of M.alpha.Mg.beta.R?R?XrYs with at least one electron donor selected from the group consisting of ethers, thioethers, ketones, aldehydes, hydrocarbyl carboxylic acids or derivatives thereof, alcohols, thioalcohols and amines and (3) a chlorosilane compound having a Si-H bond and of the formula HaSiC?bR??(a+b) wherein R10 is a hydrocarbon group having 1 to 20 carbon atoms, 0 < a ? 2 b > 0 and a + b ? 4, separating a reaction product from the reaction mixture and washing the separated reaction product with an inert hydrocarbon and reacting the washed reaction product with (4) a titanium compound having at least one halogen atom and/or a vanadium compound having at least one halogen atom.

2. The catalyst of claim 1, wherein the reaction between (2) the hydrocarbon-soluble organomagnesium component or the reaction product of the hydrocarbon-soluble organomagnesium component with the electron donor and (3) the chlorosilane compound is carried out in the presence of (1) the solid inorganic oxide.

3. The catalyst of claim 1, wherein (1) the solid inorganic oxide is reacted with (2) the hydrocarbon-soluble organomagnesium component or the reaction product of the hydrocarbon-soluble organomagnesium component with the electron donor and the reaction product is separated from the reaction mixture, washed with an inert hydrocarbon and subsequently reacted with (3) the chlorosilane compound.

4. The catalyst of any one of claims 1 to 3, wherein (1) the solid inorganic oxide is an inorganic oxide carrier selected from the group consisting of silica, alumina and a composite containing silica and alumina.

5. The catalyst of claim 1, 2 or 3, wherein the solid inorganic oxide is silica having an average particle diameter of 1 to 1000 µ, a BET surface area of 50 to 100 m2/g and a pore volume of 0.3 to 3.5 m?/g.

6. The catalyst of claim 1, wherein M in the hydrocarbon-soluble organomagnesium component (2) is beryllium, boron, aluminum or zinc metal.

7. The catalyst of claim 6, wherein M in the hydrocarbon-soluble organomagnesium component (2) is aluminum metal.

8. The catalyst of claim 1, wherein .beta./.alpha. in the hydrocarbon-soluble organomagnesium component (2) is 1 to 10.

9. The catalyst of claim 1, wherein in the hydrocarbon-soluble organomagnesium component (2) .alpha. is zero and (a) R1 and R2 both are alkyl groups having 4 to 6 carbon atoms and at least one of R1 and R2 is a secondary or tertiary alkyl group or (b) R1 is an alkyl group having 1 to 3 carbon atoms and R2 is an alkyl group having at least 4 carbon atoms or (c) R1 and R2 both are hydrocarbon groups having at least 6 carbon atoms.

10. The catalyst of claim 1, wherein in the hydrocarbon-soluble organomagnesium component (2) at least one of r and s is a number greater than zero.

11. The catalyst of claim 1, wherein a in the chlorosilane compound is 0 < a < 2.

12. The catalyst of claim 1, wherein the titanium compound (4) is titanium tetrachloride.

13. The catalyst of claim 1, wherein the organometallic component [B]
is an organoaluminum compound of the formula A?R?1Z3-t wherein R11 is a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group or a siloxy group and t is 2 to 3.

14. The catalyst of claim 1 which additionally comprises an electron donor [C].

15. A process for polymerizing an .alpha.-olefin which comprises contacting the .alpha.-olefin with a catalyst of claim 1.

16. A process for polymerizing an a-olefin which comprises contacting the .alpha.-olefin with a catalyst of claim 14.