Catalysts for polymerization of olefins

Abstract: A catalytic ingredient for use in the polymerization of olefins comprises a carrier comprising a magnesium compound precipitated from solution and a catalytic component supported on the carrier and which is a titanium halide, vanadyl halide or vanadium halide, the catalyst being obtained by a process which comprises the steps of: (A) mixing (a) one or more magnesium compounds of the formulae Mg(OR¹) n (OR²) 2-n and/or MgR 3 / m(OR) 2-m (in which R¹, R², R³ and R⁴ are the same or are different and each is a C₁-C₂₀ alkyl group, an allyl group, a C₃-C₂₀ cycloalkyl group or a C₅-C₂₀ aromatic group; and m and n are the same or are different and each has a value of from 0 to 2), with (c) a saturated or unsaturated monohydric alcohol of the general formula, R⁵OH (in which R⁵ is a C₁-C₂₀ alkyl group, allyl group, a C₃-C₂₀ cycloalkyl group, or a C₅-C₂₀ aromatic group), or a polyhydric alcohol having from 1 to 20 carbon atoms, for reaction in solution in the presence of (b) carbon dioxide in an inert hydrocarbon solvent, to obtain component (A); (B) subjecting component (A) to mixing and reaction with (d) a titanium halide of the formula TiX p (OR⁶) 4-p and/or a vanadyl halide of the formula VOX q (OR⁷) 3-q and/or a vanadium halide of the formula VX r (OR⁸) 4-r and/or a silane halide of the formula SiX s (OR⁹) 4-s (in which X is Cℓ or Br; each of R⁶, R⁷, R⁸ and R⁹ is a C₁-C₂₀ alkyl group, an allyl group or C₃-C₂₀ cycloalkyl group; each of p, r and s is an integer of from 1 to 4; and q is an integer of from 1 to 3); together with (e) a siloxane compound having an -Si-O-Si- bond alone or in admixture with a silane compound of the formula SiR 10 / t (OR¹¹) 3-t (in which R¹⁰ and R¹¹ are each a C₁-C₂₀ alkyl group, or allyl group, a C₃-C₂₀ cycloalkyl group or a C₅-C₂₀ aromatic group; and t has a value of from 0 to 3), thereby giving solid product (I); (C) reacting solid product (I) with (f) a saturated or unsaturated monohydric alcohol of the formula R¹²OH (in which R¹² is a C₁-C₂₀ alkyl group, allyl group, a C₃-C₂₀ cycloalkyl group or C₅-C₂₀ aromatic group) or a polyhydric alcohol having up to 20 carbon atoms and (g) a cyclic ether thereby causing dissolution and re-precipitation to give solid product (II); and (D) subjecting solid product (II) to further reaction with (g) component (B) consisting of a titanium halide and/or a vanadyl halide and/or a vanadium halide as defined for (d) above, thereby to give solid product (III): followed by further reaction with a mixture of component (B) and (h) an electron donor thereby obtaining solid product (IV) for use as the catalytic component.

Description: BACKGROUND OF THE INVENTION Field of the Invention This invention relates to catalysts useful for polymerization of alpha-olefins and more particularly, to a titanium halide catalytic component supported on magnesium compounds and a catalyst system comprising such a supported catalytic component. Description of the Prior Art Catalysts on magnesium-containing carriers which have high catalytic activity and good stereospecificity have been developed and are known to be suitable for vapor phase polymerization of alpha-olefins because of their advantages that the treatment of the catalyst residue in produced polymer is easy and that removal of App components is not necessary. In order to ensure good operability, the catalysts for the vapor phase polymerization of alpha-olefins are further required to have a good shape of particles with a narrow distribution of particle size, a good shatter resistance and a high bulk density. One of techniques for obtaining a controlled shape of catalyst particles is described in Japanese Laid-open Patent Application No. 63-54,405 wherein magnesium compounds are dissolved in an alcohol in the presence of carbon dioxide and treated with a mixture of a titanium halide and an organosilane to cause precipitation, to which a cyclic ether compound is added for re-dissolution and recrystallization, thereby obtaining a carrier with a good shape, and the carrier is activated to provide a catalyst. In the vapor phase polymerization of alpha-olefins wherein secondarily produced rubber components are not extracted in solvent as is different from the suspension polymerization, there are produced a number of copolymers. For the production of adhesive polymers having high rubber contents, it is necessary to keep good fluidity of polymer powder, which in turn requires the polymer powder having a large size. Accordingly, catalytic ingredients having a large particle size are required as bringing about such a large-sized powder. In general, catalyst particles prepared from a solution by a precipitation method involve the inevitable drawback that although particles of the carrier are uniform with a sharp distribution of particle size, part of the particles is broken in a subsequent activation step. In addition, particles of a larger size are more liable to break. In Japanese Laid-open Patent Application No. 63-54,405, there is the problem that when the particle size is as large as 30 µ (1µ = 1 µm), the particles are broken in large amounts during the activation treatment such as with titanium halides, so that fine powder increases in amount. In Japanese Laid-open Patent Application No. 63-54,405, there is described a method for preparing a catalytic component with a good shape wherein alkaline earth metal alcoholates are dissolved as an alcohol solution by the use of carbon dioxide and a silicone compound is used for the formation of a catalytic component, followed by complexing the alkaline earth metal such as magnesium by the use of tetrahydrofuran. Many methods using silicon compounds for the formation of catalytic components have been attempted, but use of a boron compound instead of the silicon compound has never been disclosed up to now. In Japanese Laid-open Patent Application No. 63-277,204, use of a boron compound in combination with a silicon compound is set forth but the effect of the boron compound is not explained. We heve found a process for preparing a large-sized catalyst of the supported type wherein a specific type of silane compound, i.e. an alkylsilane alkoxide, is used as a shape-controlling agent at the time of precipitation from solution and an alcohol is added to a recrystallization system to which a cyclic ether compound has been added, by which a catalytic ingredient is prepared and particularly, a large-sized catalyst is prepared without any breakage thereof during treatment with titanium halides or with the particles being broken only in small amounts, if any. It is an object of the invention to provide a large-sized catalyst of the supported type which is obtained by a process wherein the catalyst particles can be controlled in size while keeping high catalytic activity and good polymerization capability in high steric regularity, thereby giving the large-sized particles with an improved shape and size distribution. The above objects can be achieved, according to the invention, by a catalytic ingredient for polymerization of olefins which comprises a carrier made primarily of a Mg compound precipitated from its solution and a titanium halide, vanadyl halide or vanadium halide supported on the carrier and which consists essentially of a solid product (IV) obtained by a process which comprises: (A) mixing (a) a magnesium compound of the general formula, Mg(OR 1 ) n (OR 2 ) 2-n or MgR 3 m (OR 4 ) 2-m , or a mixture of the magnesiun compounds, wherein R 1 , R 2 , R 3 and R 4 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group, a cycloalkyl group having from 3 to 20 carbon atoms or an aromatic group having from 5 to 20 carbon atoms, and m and n are independently a value of from 0 to 2, with (c) a saturated or unsaturated monohydric alcohol of the general formula, R 5 OH, or polyhydric alcohol and each having from 1 to 20 carbon atoms in the presence of (b) carbon dioxide in an inert hydrocarbon solvent for reaction in dissolved state, thereby obtaining ingredient A; (B) mixing the ingredient A for reaction with (d) a titanium halide of the general formula TiX p (OR 6 ) 4-p wherein X represents Cl or Br, R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, and p is a value of from 1 to 4, and/or a vanadyl halide of the general formula, VOX q (OR 7 ) 3-q , and/or a vanadium halide of the general formula, VOX r (OR 8 ) 4-r , wherein X represents Cl or Br, R 7 and R 8 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is a value of from 1 to 3 and r is a value of from 1 to 4 and/or a halogenated silane of the general formula, SiX s (OR 9 ) 4-s . wherein X represents Cl or Br, R 9 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, and s is a value of from 1 to 4, and (e) a siloxane compound having the Si-O-Si bond or a mixture of the siloxane compound and a silane compound of the general formula, R 10 t Si(OR 11 ) 4-t , wherein R 10 arid R 11 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, and t is a value of from 0 to 4, thereby obtaining solid product (I); (C) reacting the solid product (I) with (f) a saturated or unsaturated, monohydric alcohol of the general formula, R 12 OH, or polyhydric alcohol and each having from 1 to 20 carbon atoms and (g) a cyclic ether wherein the product (I) is dissolved in and re-precipitated from a mixture of the alcohol and the cyclic ether, thereby obtaining solid product (II); and (D) subjecting the solid product (II) to reaction with (h) an ingredient B consisting of a titanium halide of the general formula, TiX p (OR 6 ) 4-p wherein X represents Cl or Br, R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, and p is a value of from 1 to 4, and/or a vanadyl halide of the general formula, VOX q (OR 7 ) 3-q , and/or a vanadium halide of the general formula, VOX r (OR 8 ) 4-r , wherein X represents Cl or Br, R 7 and R 8 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is a value of from 1 to 3 and r is a value of from 1 to 4, to obtain solid product (III), followed by further reaction with a mixture of (i) the ingredient B and (j) an electron donative material, thereby obtaining solid product (IV). The alcohol used in the step (C) should preferably be a linear alcohol having from 2 to 10 carbon atoms. Moreover, The catalytic ingredient defined above may be used in combination with an organometallic compound with or without further combination with an electron donative compound used as a third ingredient whereby such combinations are particularly suitable for use as a catalyst for polymerization of alpha-olefins. BRIEF DESCRIPTION OF THE DRAWING The drawing is a flow chart illustrating process for preparing a catalytic ingredient according to the invention. The catalytic ingredient or system according to the invention is obtained by the procedure described above. This procedure is described in detail according to the steps involved therein. In the step A, a magnesium compound of the general formula Mg(OR 1 ) n (OR 2 ) 2-n or MgR 3 m (OR 4 ) 2-m , or a mixture of the magnesium compounds, wherein R 1 ,R 2 , R 3 and R 4 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group, a cycloalkyl group having from 3 to 20 carbon atoms or an aromatic group having from 5 to 20 carbon atoms, and m and n are independently a value of from 0 to 2, are mixed and reacted, in dissolved state, with (c) a saturated or unsaturated, monohydric alcohol of the general formula, R 5 OH, or polyhydric alcohol and each having from 1 to 20 carbon atoms in the presence of (b) carbon dioxide in an inert hydrocarbon solvent, thereby obtaining ingredient A. The reaction is carried out at a temperature of from 10 to 200°C. preferably from 20 to 150°C, for a time of from 10 minutes to 24 hours. Preferably, the starting materials are charged at room temperature ranging from 10 to 30°C and then heated to 40 to 150°C in order to facilitate dissolution of the magnesium compound or compounds. The magnesium alcoholates useful in the present invention include, for example, Mg(OCH 3 ) 2 , Mg(OC 2 H 5 ) 2 , Mg(OC 3 H 7 ) 2 , Mg(OC 4 H 9 ) 2 , Mg(OCH(CH 3 )C 2 H 5 ) 2 , 2Mg(OC 8 H 17 ) 2 , Mg(OCH 2 CH(C 2 H 5 )C 4 H 9 ) 2 , Mg(OCH 2 CHCH 2 ) 2 , Mg(OC 6 H 5 ) 2 , Mg(OC 6 H 11 ) 2 , Mg(OC 6 H 4 CH 3 ) 2 , Mg(OC 10 H 7 ) 2 , Mg(OC 10 H 6 CH 3 ) 2 , Mg(OC 10 H 17 ) 2 , Mg(OC 10 H 16 CH 3 ) 2 , Mg(OCH 3 )(OC 2 H 5 ), Mg(OC 2 H 5 )(OC 6 H 13 ), Mg(OC 2 H 5 )(OC 8 H 17 ), and Mg(OC 3 H 7 )(OC 6 H 5 ). Examples of th alkyl magnesium include Mg(CH 3 ) 2 , Mg(C 2 H 5 ) 2 , Mg(C 3 H 7 ) 2 , Mg(C 4 H 9 ) 2 , Mg(C 6 H 13 ) 2 , Mg(C 8 H 17 ) 2 , Mg(CHCHC 2 H 5 ) 2 , Mg(C 6 H 5 ) 2 , Mg(C 6 H 4 CH 3 ) 2 , Mg(C 6 H 11 ) 2 , Mg(C 10 H 7 ) 2 , Mg(CH 3 )(C 2 H 5 ), Mg(C 2 H 5 )(C 6 H 11 ), and Mg(C 3 H 7 )(C 6 H 5 ). These compounds may be used singly or in combination. In addition, Mg(OC 2 H 5 )(C 4 H 9 ) and Mg(OC 3 H 7 )(C 6 H 5 ) may also be used. The alcohols used as the ingredient (c) may be aliphatic saturated and unsaturated alcohols. Examples of the alcohol include methanol, ethanol, propanol, iso-propanol, iso-butanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol, dodecanol, propenyl alcohol, butenyl alcohol, ethylene glycol, and trimethylene glycol. Of these, aliphatic alcohols having from 2 to 10 carbon atoms are preferred. In the step B, the ingredient A is reacted, in the presence of (e) a siloxane compound having the Si-O-Si bond or a mixture of the siloxane compound and a silane compound of the general formula, R 10 t Si(OR 11 ) 4-t , wherein R 10 and R 11 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, and t is a value of from 0 to 4, with (d) a titanium halide of the general formula, TiX p (OR 6 ) 4-p wherein X represents Cl or Br, R 6 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, and p is a value of from 1 to 4, and/or a vanadyl halide of the general formula, VOX q (OR 7 ) 3-q , and/or a vanadium halide of the general formula, VOX r (OR 8 ) 4-r , wherein X represents Cl or Br, R 7 and R 8 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is a value of from 1 to 3 and r is a value of from 1 to 4 and/or a halogenated silane of the general formula, SiX s (OR 9 ) 4-s , wherein X represents Cl or Br, R 9 represents an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, and s is a value of from 1 to 4, thereby obtaining solid product (I). The above reaction should preferably be carried out in an aromatic or aliphatic inert hydrocarbon solvent used in appropriate amounts. Although the mixing order for the reaction may be such that the ingredient A and the siloxane compound or its mixture with the silane compound are first mixed, with which there is mixed the titanium halide and/or vanadyl halide and/or vanadium halide, it is preferred that the siloxane compound is mixed with the titanium halide and/or vanadyl halide and/or vanadium halide, to which the ingredient A is added. The temperature during the mixing may be in the range of from -40°C to 100°C and is preferably in the range of from -10°C to 50°C. Examples of the siloxane compound (e) include linear polysiloxanes of the general formula, R 3 Si-(OSiR 2 ) n -OSiR 3 , wherein R represents an alkyl group having from 1 to 20 carbon atoms, an aryl group, a cycloalkyl group or an aromatic group, and n is a value of from 1 to 10 3 , such as hexamethyldisiloxane, hexaethyldisiloxane, hexabutyrodisiloxane, octamethyltrisiloxane, and octaethyltrisiloxane, polyalkylalkoxysiloxanes having an alkoxy group or groups at part thereof such as hexamethyl-1,5-diethoxytrisiloxane, and hexaethyl-1,5-dimethoxytrisiloxane, polyalkoxyalkylsiloxanes of the general formula, R(RO) 2 Si-(OSi(OR) 2 ) n -OSi(OR) 2 R, wherein R and n have, respectively, the same meanings as defined above, such as hexaethoxy-1,5-dimethyltrisiloxane, and octaethoxy-1,5-dimethyltrisiloxane, and cyclic polysiloxanes of the general formula, (OSiR 2 ) n , wherein R and n have, respectively, the same meanings as defined above, such as hexamethylcyclotrisiloxane, and octaethylcyclotetrasiloxane. Examples of the silane compound used by mixing with the above-mentioned siloxane compounds include trimethylmonoethoxysilane, trimethylmonopropoxysilane, trimethylmonobutoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonobutoxysilane, tripropylmonoethoxysilane, tributylmonomethoxysilane, tributylmonoethoxysilane, trihexylmonoethoxysilane, cyclohexyldimethylmonoethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane. dimethyldibutoxysilane, diethyldimethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, cyclohexylmethyldiethoxysilane. methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltributoxysilane, propyltriethoxysilane, butyltrimethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane. The molar ratio of Si/Mg in the siloxane compound or its mixture with the silane compound and the ingredient A used in the step B is generally in the range of 1 to 2.0:1, preferably 0.3:1 to 1:1. The titanium halides (d) of the general formula, TiX p (OR 6 ) 4-p , include, for example, titanium tetrachloride, titanium tetrabromide, titanium trichloride methoxide, titanium trichloride ethoxide, titanium trichloride propoxide, titanium trichloride butoxide, titanium trichloride hexoxide, titanium trichloride octoxide, titanium trichloride cyclohexoxide, titanium trichloride phenoxide, titanium dichloride diethoxide, titanium dichloride dipropoxide, titanium dichloride dibutoxide, titanium dichloride dioctoxide, titanium dichloride diphenoxide, titanium dichloride dicyclohexoxide, titanium dibromide diethoxide, titanium dibromide dibutoxide, titanium chloride tributoxide, titanium chloride triphenoxide, titanium bromide triethoxide, and titanium bromide triphenoxide. The titanium halides other than titanium tetrachloride and titanium tetrabromide can be prepared by reaction between titanium tetrahalides and orthotitanic acid esters. In place of those products obtained by the above reaction, mixtures of titanium tetrahalides and ortho-titanic acid esters may be used in the practice of the invention. Of these, titanium tetrachloride is most preferred. Examples of the vanadyl halides and vanadium halides, respectively, represented by the general formulas, VOX q (OR 7 ) 3-q , and VOX r (OR 8 ) 4-r , include vanadyl trichloride, vanadyl tribromide, vanadyl dichloride ethoxide, vanadyl dibromide methoxide, vanadyl dichloride ethoxide, vanadyl dichloride butoxide, vanadyl trichloride phenoxide, vanadyl dibromide methoxide, vanadyl dibromide propoxide, vanadyl dibromide cyclohexoxide, vanadyl chloride dimethoxide, vanadyl chloride diethoxide, vanadyl chloride dicyclohexoxide, vanadyl bromide dipropoxide, vanadyl bromide dibutoxide, vanadium tetrachloride, vanadium tetrabromide, vanadium trichloride methoxide, vanadium trichloride ethoxide, vanadium trichloride butoxide, vanadium tribromide cyclohexoxide, vanadium trichloride phenoxide, vanadium dichloride diethoxide, vanadium dibromide dibutoxide, vanadium dichloride diphenoxide, vanadium chloride trimethoxide, vanadium bromide triethoxide, vanadium chloride tripropoxide, vanadium bromide tributoxide, and vanadium chloride triphenoxide. Examples of the halogenated silanes (d) of the general formula, SiX s (OR 9 ) 4-s , include silicon tetrachloride, silicon tetrabromide, silicon tribromide methoxide, silicon trichloride ethoxide, silicon tribromide propoxide, silicon trichloride butoxide, silicon trichloride cyclohexoxide, silicon dichloride dimethoxide, silicon dibromide diethoxide, silicon dichloride dipropoxide, silicon dibromide dibutoxide, silicon dichloride diphenoxide, silicon bromide trimethoxide, silicon chloride triethoxide, silicon bromide tripropoxide, and silicon chloride tributoxide. These may be used singly or in combination. The molar ratio of the metals in total in the titanium halide or/and vanadyl halide or/and vanadium halide or/and halogenated silane and Mg in the ingredient A used in the step B is generally in the range of 1:0.3 to 20:1, preferably 1:0.5 to 5:1. In the step C, the solid product (I) obtained in the step B is dissolved in a solvent containing the cyclic ether (g) and re-precipitated to obtain solid product (II). Part or all of the solid product is dissolved and re-precipitated to obtain a carrier (solid product (II)) having uniform particle shape and size. In the mother liquor for the precipitation in the step C. the siloxane compound (e) contained in the mother liquor of the step B exists. The alcohol (f) may be added to the suspension containing the solid product (I), after which the cyclic ether (g) is added. Alternatively, the alcohol and cyclic ether are added at the same time. As a result, there can be obtained the carrier particles (solid product (II)) with a large size. The temperature at which the alcohol (f) and cyclic ether (g) are added is in the range of from -40 to 100°C, preferably from -10 to 50°C. After the addition, the temperature is raised to 50 to 150°C in 1 minute to 10 hours, preferably 5 minutes to 5 hours, at which the reaction system is kept for 1 minute to 6 hours, preferably from 5 minutes to 3 hours, thereby completing the precipitation. Examples of the cyclic ether (g) include tetrahydrofuran, tetrahydropyran, methyltetrahydrofuran, dimethyltetrahydropyran, tetramethyltetrahydrofuran, dioxane, dioxorane, trioxane, pyran, benzopyran and dihydrobenzofuran. Of these, tetrahydrofuran is most preferred. Examples of the alcohol include linear alkyl alcohols such as methanol, ethanol, n-propanol, iso-propanol, butanol, iso-butanol, tertiary butanol, pentanol, hexanol, 2-ethylhexanol, and octanol, cyclic alkyl alcohols such as cyclopentanol, and cyclohexanol, diols such as 1,2-propanediol, and 1,4-butanediol, ethylene glycol, trimethylene glycol, propenyl alcohol, and butenyl alcohol. Of these, a linear alkyl alcohol having from 2 to 10 carbon atoms, such as ethanol, propanol, butanol, or 2-ethylhexanol is most preferred. In the step D, the solid product (II) the solid product (II) is reacted with (h) the ingredient B including the titanium halide of the general formula, TiX p (OR 6 ) 4-p , and/or the vanadyl halide of the general formula, VOX q (OR 7 ) 3-q , and/or the vanadium halide of the general formula, VOX r (OR 8 ) 4-r , wherein each X represents Cl or Br, R 6 , R 7 and R 8 independently represent an alkyl group having from 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having from 3 to 20 carbon atoms, q is a value of from 1 to 3 and p and r are, respectively, a value of from 1 to 4 and further reacted with a mixture of the ingredient B (i) and an electron donative material or compound (j) to obtain solid product (IV). The ingredient B can be selected from the titanium halide, vanadyl halide and vanadium halide described with respect to the step B. The mixing of the solid products (II) and (III) and the ingredient B may be effected by adding the ingredient B to the solid products (II) and (III) or by adding the solid products (II) and (III) to the ingredient B. The treating temperatures of the solid products (II) and (III) in the step D may be in the range of from 40 to 200°C, preferably from 50 to 150°C for each case. The reaction time for both products is in the range of from 5 minutes to 6 hours, preferably from 10 minutes to 5 hours. After completion of the reaction, the resultant solid product is separated by filtration or decantation, after which it is washed with an inert hydrocarbon solvent to remove unreacted compounds or side products therefrom. The washing effect may be further facilitated by washing the product with an aromatic solvent such as toluene, benzene, xylene or the like prior to the washing with the inert hydrocarbon solvent. The electron donative compounds suitable for the above treatment include aromatic mono- and polycarboxylic acid esters. Examples of the polycarboxylic acid esters include benzene polycarboxylic acid esters, and naphthalene polycarboxylic acid esters. Specific examples include benzene polycarboxylic acid esters such as monomethyl phthalate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-tert-butyl phthalate, di-n-hexyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diphenyl phthalate, dibenzyl phthalate and aromatic monocarboxylic acid esters such as benzoates with or without a substituent, e.g. methyl benzoate, ethyl benzoate, butyl benzoate, iso-butyl benzoate, cyclohexyl benzoate, methyl p-toluate, ethyl p-toluate, methyl p-anisate, butyl p-anisate, ethyl chlorobenzoate, methyl bromobenzoate. The electron donative compounds used in the step D is used in an amount of 0.0001 to 1.0 mole, preferably from 0.005 to 0.8 moles, per gram atom of titanium or vanadium. The diluents useful in the present invention are, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, halogenated aromatic hydrocarbons such as chlorobenzene, and dibromobenzene, alkanes such as hexane, heptane, octane, nonane, decane, undecane, cyclohexane, and methylcyclohexane, halogenated alkanes such as 1,2-dichloroethane, 1,1,2-trichloroethane, and carbon tetrachloride, iso-paraffin hydrocarbons, and kerosine. The catalytic ingredient is prepared in an atmosphere of an inert gas such as nitrogen or argon gas or an alpha-olefin under conditions where catalyst poisons such as water, and oxygen-carbon oxide are eliminated. The diluent and the starting materials used should favorably be purified in order to remove catalyst poisons from the preparation system for the catalyst. According to the invention, the solid product (IV) which is suitable for use as the catalytic ingredient can thus be obtained. In this manner, the catalyst in the form of particles which have a large size suitable for use in polymerization of olefins can be obtained while keeping a good crystal shape without breakage of the particles into finer powder during the production process or with a very reduced degree of the breakage, if any. Thus, a large-sized catalyst having a sharp size distribution can be obtained. The large-sized catalyst with a sharp size distribution is advantageous in that the catalyst particles are kept as a replica for polymer particles produced by the polymerization. As is well known in the art, when the particles of polymer which are adhesive in nature are large in size, the flowability is drastically improved over that in the case where small-sized catalyst particles are used. Thus, the large-sized catalyst particles are very useful in preparing copolymers having a high content of rubber component by vapor phase polymerization in a high operation efficiency. It will be noted that the reaction steps (A) through (D) described hereinabove are summarized in the accompanying drawing wherein the respective starting compounds are particularly shown. The catalyst according to the invention is useful for use in polymerization of alpha-olefins such as ethylene and propylene and is most useful in the stereospecific polymerization of alpha-olefins having three or more carbon atoms such as, for example, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and mixtures thereof with or without ethylene. When the catalytic component according to the invention is used, polyalpha-olefins having high crystallinity can be prepared by contacting at least one alpha-olefin with the catalytic component under polymerizing conditions. Such conditions include polymerization temperature and time, a pressure of monomer, the manner of removing contaminants for the catalyst, the proper selection of a medium for polymerization in the slurry step, the type of additive for controlling the molecular weight of polymer and other conditions well known in the art. The polymerization may be effected by suspension, bulk and vapor phase polymerization processes. The amount of the catalyst may vary depending on the polymerization process, the size of reactor, the type of monomer to be polymerized and other factors known in the art and can be determined with reference to examples described hereinafter. Typically, the catalyst of the invention is used in an amount of from 0.2 to 0.02 mg per g of produced polymer. Irrespective of an adopted polymerization process, the polymerization is carried out at a high temperature sufficient to ensure a reasonable polymerization rate and to avoid an unduly long residence time in the reactor but at a temperature which is not so high as to bring about the production of a product with a low level of stereoirregularity caused by too high a polymerization rate. The polymerization temperature is generally in the range of from 0°C to 120°C and is preferably in the range of from 20°C to 95°C from the standpoint of good of catalytic properties and high production rates. More preferably, the polymerization is carried out at a temperature ranging from 50°C to 80°C. The polymerization of alpha-olefins according to the invention is effected at an atmospheric pressure or at a monomer pressure higher than the atmospheric pressure. In general, the pressure of monomer is in the range of > 0.54 bar G, 0.550 kg/cm 2 G (1 kg/cm 2 = 0.981 bar). It will be noted that in the vapor phase polymerization, the monomer pressure must not be less than a vapor pressure of an alpha-olefin to be polymerized at the polymerization temperature. The polymerization time is generally in the range of from 0.5 to several hours in a batch process. THis time corresponds to an average residence time in continuous processes. The polymerization time of from 1 hour to 4 hours is general for the reaction in an autoclave. In the slurry process, the polymerization time can be controlled as desired. The polymerization time of from 0.5 to several hours is generally in the continuous slurry process. The diluents suitable for use in the slurry polymerization process include alkanes and cycloalkanes such as pentane, hexane, heptane, n-octane, iso-octane, cyclohexane and methylcyclohexane, alkylaromatic compounds toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethylbenzene and mono and di-alkylnaphthalenes, halogenated and hydrogenated aromatic compounds such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene, tetrahydronaphthalene, and decahydronaphthalene, high molecular weight paraffins and mixtures thereof, and other known diluents. It is often desirable that prior to use, the medium for the polymerization is purified, for example, through distillation, percolation through a molecular sieve, contact with a compound capable of removing trace impurities such as an alkylaluminium compound or other means. The vapor phase polymerization process which is useful for application of the catalyst of the invention includes both an agitated bed reactor system and a fluidized bed reactor system and is described, for example, in United States Patent Nos. 3,957,448, 3,965,083, 3,971,768, 3,970,611, 4,129,701, 4,101,289, 3,652,527 and 4,003,712. These references are cited in the afore-indicated Japanese Laid-open Patent Application No. 63-54,405. A typical vapor phase olefin polymerization reaction system is comprised of a reaction vessel wherein an olefin monomer and the catalytic component are added and which includes an agitated bed for polymer particles to be formed. Typically, catalytic components are supplied at the same time or separately through one or more valve-controlled ports of the reaction vessel. The olefin monomer is typically fed into the reactor through a circulation gas system wherein the monomer withdrawn as an off-gas and a fresh starting monomer are mixed and fed into the reaction vessel. A quenching liquid which may be a liquid monomer may be added to an olefin being polymerized through the circulation gas system in order to control the temperature. Irrespective of the manner of polymerization, the polymerization should be effected under such conditions that oxygen, water and other substances capable of acting as a catalyst poison are eliminated. According to the polymerization process of the invention, the polymerization can be carried out by the use of an additive which is able to control the molecular weight of polymer. For this purpose, hydrogen may be used as is well known in the art. Although not essentially required, the catalyst may be contacted with water, an alcohol, acetone or other catalyst deactivators by a procedure known in the art at the time of completing or stopping the polymerization or at the time of deactivating the catalyst. The product prepared according to the process of the invention is usually solid in nature and is mainly composed of an isotactic polyalpha-olefin. The yield of the polymer is high relative to the amount of catalyst and can be obtained without separation of the catalytic residue. The level of a stereoregular side product is significantly low and a useful product is obtained without isolation. The polymer product prepared in the presence of the catalyst according to the invention can be processed into useful articles by extrusion molding, injection molding and other ordinary techniques. As will be apparent from the foregoing, the catalyst particles useful for polymerization of olefins are prepared under varying conditions for small and large sizes without breakage of the particles during the production process, or even if the particles are broken, the breakage can be significantly suppressed in a much smaller degree than the case using silane compounds as a shape control agent. Especially, it becomes possible to make a large-sized catalyst having a sharp size distribution. The large-sized catalyst with a sharp size distribution is kept as a replica for the polymer produced by the polymerization, so that when the polymer is formed as adhesive polymer particles, the fluidity of the polymer particles is drastically improved over the case where smaller polymer particles are produced. This is well known to one skilled in the art. This is why the catalyst of the invention is very useful in preparing copolymers having a high content of rubber component by vapor phase polymerization at high operation efficiencies. The present invention is more particularly described by way of examples, which should not be construed as limiting the invention. Comparative examples are also shown. Example 1 Step A: formation of a magnesium carbonate solution 230 g of magnesium ethoxide, 415 ml of 2-ethyl-1-hexanol and 1650 ml of toluene were charged into a 3 liter autoclave equipped with an agitator, a pressure gage and a thermometer and purged with highly pure nitrogen. The mixture was heated at 90°C for 3 hours while agitating at 500 r.p.m. in the presence of carbon dioxide. The resultant solution was cooled and the carbon dioxide gas was purged, followed by handling substantially at an atmospheric pressure. The solution contained 0.1 g/ml of magnesium ethoxide. Step B: formation of solid particles 300 ml of toluene, 19 ml of TiCl 4 and 25 ml of hexamethyldisiloxane were charged into a 1500 ml baffled flat bottom flask (baffling rate of 0.15) equipped with an agitator, a thermometer, a condenser and a sealing line for nitrogen and mixed at room temperature at 300 r.p.m. for 5 minutes. Thereafter, 150 ml of the solution obtained in Step A was charged in 10 minutes. Immediately after the charging, solid particles (I) were precipitated. Step C: re-precipitation of solid particles To the solution were added 3 ml of ethanol and 50 ml of tetrahydrofuran (THF) by the use of a syringe. The mixture was heated to 60°C within 15 minutes while agitating at 300 r.p.m. The precipitated particles started to be dissolved in the THF solution and then started to be re-precipitated within 15 minutes. Formation of the solid was completed within 10 minutes. After continuing the agitation at 60°C for 45 minutes, the agitation was stopped to cause the resultant solid (II) to be settled down. The supernatant liquid was removed by decantation and the remaining solid (II) was washed twice with 200 ml of toluene. Step D: treatment with titanium (IV) compound To the solid (II) obtained in Step D were added 200 ml of toluene and 100 ml of TiCl 4 . While agitating at 600 r.p.m. the mixture was heated to 135°C within 20 minutes, at which it was kept for 1 hour. The agitation was stopped to cause solid (III) to be precipitated, followed by removal of a supernatant liquid by decantation. 100 m of TiCl 4 , 250 ml of toluene and 2.1 ml of diisobutyl phthalate were added to the solid (III), and the mixture was agitated at 600 r.p.m. at 135°C for 1.5 hours. The supernatant liquid was removed by decantation. 200 ml of TiCl 4 was added to the residue and heated under reflux for 10 minutes while agitating at 600 r.p.m. The supernatant liquid was removed by decantation and the residue was washed three times with 200 ml of toluene and then four times with 200 ml of hexane. As a result, there was collected 11.6 g in total of solid product (IV). The solid product (IV) had an average size of 37.2 µ with a fine powder having a size not larger than 5 µ being contained in an amount of 0.2%. The results of analysis revealed that the product had 17.3% of magnesium, 2.3% of titanium, 55.6% of chlorine and 8.6% of di-n-butyl phthalate. Vapor Phase Polymerization 2 mmols of triethyl aluminium, 0.3 mmols of diphenyldimethoxysilane, 16.0 mg of the solid product (IV) and 0.8 litres of hydrogen were charged into a stainless steel reactor which was purged with nitrogen, had an inner capacity of 3 liters and had a multi-stage agitator. Thereafter, propylene was continuously introduced at 70°C so that a total pressure was kept at 22 kg/cm 2 G and polymerized for 2 hours. Subsequently, unreacted propylene was discharged to obtain 382 g of powdery polypropylene. Most polypropylene particles were made of inclined hexagonal columnar shaped crystals. The extraction residue of the polymer with boiling n-hexane for 6 hours was 0.8% and the polymer had a bulk density of 0.48 g/cm 3 . Example 2 The general procedure of Example 1 was repeated except that 150 ml of the solution obtained in Step A of Example 1 was used, 100 ml of toluene, 100 ml of chlorobenzene and 32 ml of hexamethylcyclotrisiloxane were used in Step B, 40 ml of THF was used in Step C, and for the third treatment with TiCl 4 in Step D, 200 ml of TiCl 4 was used as the solvent and the mixture was kept at 125°C for 1 hour, thereby obtaining 12.7 g of solid product (IV). The solid product had an average size of 30.5 µ and the content of particles with a size not larger than 5 µ was 0.7%. Example 3 The general procedure of Example 1 was repeated except that a 1 liter autoclave was used for the reactions of Step B and the subsequent steps, 170 ml of the solution obtained in Step A of Example 1 was used in Step B along with 200 ml of toluene, 28 ml of hexamethyl-1,5-diethoxytrisiloxane, 70 ml of THF was used in Step C and the procedure ranging from Step B to Step C was effected under agitation at 400 r.p.m. at a controlled pressure of carbon dioxide of 1 kg/cm 2 G, and for the second treatment with TiCl 4 in Step D, 2.1 ml of diisobutyl phthalate was used instead of the di-n-butyl phthalate, thereby obtaining 21.0 g of solid product (IV). The product had an average size of 33.2 µ and the content of particles with a size of not larger than 5 µ was 1.8%. The results of analysis for the solid product revealed that the product contained 18.3% of Mg, 2.5% of Ti, 55.9% of Cl and 7.8% of diisobutyl phthalate. Example 4 The general procedure of Example 1 was repeated except that 150 ml of the solution obtained in Step A of Example 1 was used, 150 ml of toluene, 50 ml of chlorobenzene and 36 ml of octaethoxy-1,5-dimethyltetrasiloxane were used in Step B, and 60 ml of THF was used in Step C, thereby obtaining solid product (IV). This product had an average size of 25.3 µ and the content of particles with a size not larger than 5 µ was 0.2%. Example 5 The general procedure of Example 1 was repeated except that 114 ml of the solution obtained in Step A was used in Step B of Example 1 along with 140 ml of toluene, 60 ml of iso-paraffin (Isober G), 14 ml of TiCl 4 and 22 ml of hexamethyldisiloxane, 27 ml of THF was used in Step C, and the treatment with TiCl 4 was effected by two stages in Step D where the third washing with TiCl 4 was not performed, thereby obtaining 10.6 g of solid product (IV). The solid product (IV) had an average size of 22.8 µ and the content of particles having a size of not larger than 5 µ was 0.5%. Example 6 The general procedure of Example 1 was repeated except that 286 g of magnesium propoxide was used instead of magnesium ethoxide and 283 ml of 2-ethyl-1-hexanol was used in Step A, thereby obtaining 12.2 g of solid product (IV). The solid product (IV) had an average size of 27.5 µ and the content of particles having a size of not larger than 5 µ was 1.2%. Example 7 One liter of toluene, 200 ml of hexamethyldisiloxane and 100 ml of TiCl 4 were charged into a 5 liter reactor having an agitator, a thermometer, a condenser, a sealing line for nitrogen and a feed line for starting materials along with a heating jacket and four flat baffles provided therein (baffling rate of 0.15), and agitated at room temperature at 120 r.p.m. for 5 minutes, followed by charging 500 ml of the solution obtained in Step A of Example 1 in 30 minutes. Thereafter, 250 ml of THF was charged into the mixture and the agitation speed was raised to 180 r.p.m., followed by heating to 60°C within 15 minutes and keeping the temperature for 45 minutes. The slurry obtained after the reaction was transferred, under nitrogen-sealing conditions, into a five liter filter equipped with an agitator, a condenser, a thermometer, a sealing line for nitrogen and a heating jacket and having a filter unit, followed by filtration and washing twice with 500 ml of toluene. 500 ml of TiCl 4 and 500 ml of toluene were added to the solid product (II) in the filter and kept at 135°C at 180 r.p.m. for 1 hour. The mixture was filtered, after which 500 ml of TiCl 4 , 10.5 ml of di-n-butyl phthalate and 1000 ml of toluene were added and kept at 135°C at 180 r.p.m. for 1.5 hours, after which it was filtered. 1000 ml of TiCl 4 was added to the resultant solid product (IV) and refluxed under heating conditions for 10 minutes, followed by washing three times with 500 ml of toluene and then four times with 500 ml of hexane. The solid product (IV) left in the filter was dried by passing a hot nitrogen stream of approximately 60°C to obtain 82.2 g of the catalyst. The results of analysis revealed that the solid product (IV) contained 18.7% of Mg, 2.6% of Ti, 56.2% of Cl and 6.2% of di-n-butyl phthalate. The solid product (IV) had an average size of 45.1 µ and the content of the particles having a size of not larger than 5 µ was 0.4%. Comparative Example 1 The general procedure of Example 1 was repeated except that any alcohol was not used in Step B of Example 1, thereby obtaining 11.7 g of solid product (IV). In this case, a long time was required for precipitation after which decantation had to be effected over Steps C to D, resulting in a loss of part of fine particles. The content of fine particles with a size of not larger than 5 µ in the resultant solid product (IV) was as high as 4.5%. In the same manner as in Example 1 using the above solid product (IV), vapor phase polymerization of propylene was performed. Comparative Example 2 The general procedure of Example 1 was repeated except that any alcohol and any siloxane compound were not used in Step B of Example 1, thereby obtaining 12.3 g of solid product (IV). The content of particles having a size of not larger than 5 µ in the solid product (IV) was 39.2%. In the same manner as in Example 1 using the above solid product (IV), vapor phase polymerization of propylene was performed. The results on the size distribution of the polymers obtained in Example 1 and Comparative Example 1 are shown in Table 1 Comparative Example 3 The general procedure of Example 4 was repeated except that in Step B of Example 4, 20 ml of trimethylchlorosilane was used instead of the siloxane compound. Evaluation on Vapor Phase Polymerization The solid products (IV) obtained in Examples 2 to 7 and Comparative examples 1 to 3 were used to carry out vapor phase polymerization in the same manner as in Example 1. The results are shown in Table 2. Example 8 The general procedure of Example 1 was repeated except that in Step B of Example 1, 10 ml of dimethyldiethoxysilane was used along with 20 m of hexamethyldisiloxane, thereby obtaining 12.9 g of solid product (IV). The solid product (IV) had an average size of 35.2 µ and the content of particles having a size of not larger than 5 µ was 2.0%. Example 9 The general procedure of Example 1 was repeated except that in Step C of Examples 1, 60 ml of tetrahydropyran was used instead of 50 ml of THF, thereby obtaining 10.9 g of solid product (IV). The solid product (IV) had an average size of 21.9 µ and the content of particles having a size of not larger than 5 µ was 6.3%. Example 10 The general procedure of Example 1 was repeated except that in Step C of Example 1, 32 ml of dimethylpolysiloxane having a viscosity of 10 cps was used instead of 25 ml of hexamethyldisiloxane and 60 ml of 2-methyltetrahydrofuran was used instead of 50 ml of THF, thereby obtaining 13.1 g of solid product (IV). The solid product (IV) had an average size of 29.8 µ and the content of particles having a size of not larger than 5 µ was 2.7%. Comparative Example 4 The general procedure of Example 9 was repeated except that hexamethyldisiloxane and any alcohol were not used in Step B of Example 9, thereby obtaining 10.5 g of solid product (IV). The solid product (IV) contained a large quantity of fine particles and the content of fine particles with a size of not larger than 5 µ was 29.7%. Comparative Example 5 The general procedure of Example 10 was repeated except that any siloxane compound was not used in Step B of Example 10, thereby obtaining 13.6 g of solid product (IV). The solid product (IV) contained a large quantity of fine particles and the content of fine particles with a size of not larger than 5 µ was 11.3%. Evaluation on Slurry Polymerization The catalysts (solid products (IV)) obtained in Examples 8 to 10 and Comparative Examples 4 and 5 were used to carry out the hexane slurry polymerization of propylene. 100 ml of hexane was charged into a 1.5 liter autoclave, to which 2 mmols of TEA, 0.2 mmols of diphenyldimethoxysilane and from 15 to 17 mg of each catalyst were added, followed by introduction of 60 ml of hydrogen and polymerization of propylene at 70°C for 2 hours while keeping the pressure of propylene at 7 kg/cm 2 G. After completion of the reaction, the monomer gas was purged and 50 g of methanol was added to the reaction system and agitated at 70°C for 10 minutes, followed by separation by filtration to obtain the polymer. The polymer was dried and its yield per the amount of the catalyst used was calculated. The polymer dissolved in the hexane was collected from the filtrate. The results are shown in Table 3. Example 11 The catalyst obtained in Example 2 was used for bulk polymerization. 2 mmols of TEA, 0.3 mmols of phenyltriethoxysilane, 9 ml of the catalyst and 300 ml of hydrogen were charged into a one liter bulk polymerization vessel along with 500 g of propylene, followed by polymerization at 70°C for 30 minutes at a pressure of 35 kg/cm 2 G. Unreacted propylene monomer were purged to obtain 227 g of a dried powder. The yield of the polymer per g of the catalyst was 25,300 g. The percent extraction determined by refluxing with hexane for 6 hours was 0.8% and the apparent bulk density of the polymer was 0.49 g/cm 3 . Example 12 10 mg of the catalyst obtained in Examples 7 was used for bulk polymerization for 20 minutes in the same manner as in Example 11, after which unreacted propylene was purged. Thereafter, a mixed gas of propylene/ethylene = 2/1 and 150 ml of hydrogen gas were introduced for carrying out vapor phase polymerization at 70°C for 30 minutes at a pressure of 18 kg/cm 2 G. The yield of the polymer was 187 g and the ethylene content in the polymer was 11.5%. Example 13 15 mg of the catalyst obtained in Example 7, 2 mmols of TEA, 0.2 mmols of diphenyldimethoxysilane and 150 ml of hydrogen were charged into a polymerization vessel as used in Example 1, into which a mixed gas of propylene/ethylene = 4/1 was introduced, followed by copolymerization of propylene-ethylene at 70°C for 1 hour at a pressure of 22 kg/cm 2 G. The yield of the polymer was 169 g and the ethylene content in the polymer was 48%. Size Distribution of Polymers Obtained By Vapor Phase Polymerization Example 1 Comp. Ex. 1 Comp. Ex. 2 Powder Size (%) (%) (%) 2000 µ < 0.0 0.0 0.0 1400-2000 µ 12.6 0.3 0.0 1000-1400 µ 67.5 8.7 3.5 710-1000 µ 18.0 37.4 11.9 500-710 µ 1.6 36.5 13.8 355-500 µ 0.2 11.7 9.4 250-355 µ 0.2 3.0 6.7 180-250 µ 0.1 0.7 14.4 106-180 µ 0 1.0 15.2 <106 µ 0 0.7 25.1 Average Size ( µ ) 1162 686 225 Example No. Results of Vapor Phase Polymerization Catalytic Activity (g-PP/g-Cat) Extraction Residue with C 7 (%) MFR (g/10 min.) Apparent Bulk Density of Polymer (g/cm 3 ) Ex. 2 23600 99.0 3.5 0.46 3 24000 98.8 3.3 0.47 4 21700 99.3 4.8 0.47 5 22000 98.1 4.2 0.46 6 22900 98.6 3.1 0.47 7 24100 99.1 3.9 0.49 Comp.Ex. 1 21700 98.4 4.2 0.45 2 16800 97.6 5.3 0.39 3 22300 98.7 3.6 0.38 Example No. Results of Vapor Phase Polymerization Catalytic Activity (g-PP/g-Cat) Dissolution Rate in n C 6 (%) Extraction Residue with C 7 (%) MFR (g/10 min.) Apparent Bulk Density of Polymer (g/cm 3 ) Ex. 8 11200 0.32 99.13 3.6 0.48 9 8500 0.87 99.22 3.7 0.46 10 8300 0.72 98.61 3.2 0.45 Comp.Ex. 4 8100 0.40 98.87 4.3 0.41 5 8700 1.67 96.84 5.7 0.43

Claims: A catalytic ingredient for use in the polymerization of olefins which comprises a carrier comprising a magnesium compound precipitated from solution and a catalytic component supported on the carrier and which is a titanium halide, vanadyl halide or vanadium halide, the catalyst being obtained by a process which comprises the steps of: (A) mixing (a) one or more magnesium compounds of the formulae Mg(OR 1 ) n (OR 2 ) 2-n and/or MgR 3 / m(OR) 2-m (in which R 1 , R 2 , R 3 and R 4 are the same or are different and each is a C 1 -C 20 alkyl group, an allyl group, a C 3 -C 20 cycloalkyl group or a C 5 -C 20 aromatic group; and m and n are the same or are different and each has a value of from 0 to 2), with (c) a saturated or unsaturated monohydric alcohol of the general formula, R 5 OH (in which R 5 is a C 1 -C 20 alkyl group, allyl group, a C 3 -C 20 cycloalkyl group, or a C 5 -C 20 aromatic group), or a polyhydric alcohol having from 1 to 20 carbon atoms, for reaction in solution in the presence of (b) carbon dioxide in an inert hydrocarbon solvent, to obtain component (A); (B) subjecting component (A) to mixing and reaction with (d) a titanium halide of the formula TiX p (OR 6 ) 4-p and/or a vanadyl halide of the formula VOX q (OR 7 ) 3-q and/or a vanadium halide of the formula VX r (OR 8 ) 4-r and/or a silane halide of the formula SiX s (OR 9 ) 4-s (in which X is Cℓ or Br; each of R 6 , R 7 , R 8 and R 9 is a C 1 -C 20 alkyl group, an allyl group or C 3 -C 20 cycloalkyl group; each of p, r and s is an integer of from 1 to 4; and q is an integer of from 1 to 3); together with (e) a siloxane compound having an -Si-O-Si- bond alone or in admixture with a silane compound of the formula SiR 10 / t (OR 11 ) 3-t (in which R 10 and R 11 are each a C 1 -C 20 alkyl group, or allyl group, a C 3 -C 20 cycloalkyl group or a C 5 -C 20 aromatic group; and t has a value of from 0 to 3), thereby giving solid product (I); (C) reacting solid product (I) with (f) a saturated or unsaturated monohydric alcohol of the formula R 12 OH (in which R 12 is a C 1 -C 20 alkyl group, allyl group, a C 3 -C 20 cycloalkyl group or C 5 -C 20 aromatic group) or a polyhydric alcohol having up to 20 carbon atoms and (g) a cyclic ether thereby causing dissolution and re-precipitation to give solid product (II); and (D) subjecting solid product (II) to further reaction with (g) component (B) consisting of a titanium halide and/or a vanadyl halide and/or a vanadium halide as defined for (d) above, thereby to give solid product defined for (d) above, thereby to give solid product (III): followed by further reaction with a mixture of component (B) and (h) an electron donor thereby obtaining solid product (IV) for use as the catalytic component. A catalytic ingredient according to claim 1 wherein the molar ratio of Si in the siloxane compound or the mixture of the siloxane compound and the silane compound used in Step B to Mg in ingredient A is from 0.1:1 to 2.0:1. A catalytic ingredient according to claim 1 wherein the molar ratio of the total metals in the titanium halide and/or vanadyl halide and/or vanadium halide and/or halogenated silane used in Step B to Mg in ingredient A is from 1:0.3 to 20:1. A catalytic ingredient according to any one of the preceding in which the alcohol used in Step C is a C 2 -C 20 linear alcohol. A catalytic ingredient according to any one of the preceding claims wherein the cyclic either used in step (C) is tetrahydrofuran. The catalytic ingredient according to any one of the preceding claims wherein the electron donor is an aromatic mono or polycarboxylic acid ester. A catalytic ingredient according to any one of the preceding claims wherein the electron donor material is used in an amount of 0.0001 to 1.0 mole per gram atom of titanium or vanadium contained in solid product (III). A catalyst for the polyvinyl of olefins comprising a catalytic component as claimed in any one of the preceding claims together with an organometallic compound. A catalyst as claimed in claim 8 further comprising an electron donor.

Inventors: HAYASIDA TERUAKI, MATUKAWA TETUYA, TACHIBANA MASAMI, UWAI TOSHIHIRO, HAYASIDA, TERUAKI, MATUKAWA, TETUYA, TACHIBANA, MASAMI, UWAI, TOSHIHIRO
Applicants: CHISSO CORP, CHISSO CORPORATION
Application year: 1990
Main classification: C08F10
IPC codes: C08F4, C08F10