GB1586267A - Catalyst for polymerizing olefins and process for the polymerization of olefins - Google Patents

Description

(54) CATALYST FOR POLYMERIZING OLEFINS AND PROCESS FOR THE POLYMERIZATION OF OLEFINS (71) We, ASAHI KASEI KOGYO KABUSHIKI KAISHA, of 2-6 Dojimahama 1-chome, (formerly 25-1 Dojimahamadori-1-chome), Kita-ku, Osaka, Japan, a Japanese body corporate, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to a novel highly-active catalyst for polymerizing olefins which provides polyolefins having excellent grain size and to a method for polymerizing olefins in which said novel polymerization catalyst is used. More particularly this invention relates to a highly-active catalyst for polymerizing olefins which provides polymers having excellent grain size, and formed by combining A) a solid component obtained by the reaction of a specified organomagnesium component and a chlorosilane compound containing Si-H bond and a titanium compound or a vanadium compound and (B) an organometallic compound and (C) as an optional component a carboxylic acid or its derivative.

For low pressure production methods of polyolefins in which a catalyst comprising a transition metal of the 4th to 6th A group of the Periodic Table, and an organometallic compound of the 1st to 3rd group of the Periodic Table is used, a great number of catalysts have been proposed and developed since the discovery thereof made by Karl Ziegler.

However, most of the catalytic systems require the step of removing catalyst residue from formed polymer due to insufficiency of activity, which makes the production cost of the polymer higher.

In this connection, the development of a higher activity catalyst which enables the omission the catalyst removal step to simplify the process, has been pursued with the object of reduction of cost.

Catalytic systems in which a reaction product of an inorganic- or organo-magnesium compound and a titanium or vanadium compound have been proposed.

However, the necessity of cost reduction for polymer production is steadily rising.

On this account, a further improvement of catalysts has become extremely important problem. In other words improvement and advancement over not only the activity of a catalyst per g transition metal, but also grain size, bulk density, stability of catalyst and all the characteristic properties required as an industrial catalyst are being pursued. Accordingly, it is the present status of this industry that long range continued stable operation of slurry polymerization process as well as the improvement of properties of particles such as uniformity of grain size of formed polymer, increase of bulk density in view of the efficiency of the process have now become very important together with the necessity of higher activation for the skipping of catalyst removal step.

A method for producing polyolefin under a lower pressure using a catalyst obtained by reacting an organomagnesium compound, preferably a solution of an organomagnesium complex soluble in an inert hydrocarbon medium with an organoaluminum halide to produce a solid material of halogen-containing magnesium compound which is further reacted with a transition metal compound such as titanium and the like has been known by Japanese patent publication No. 11672 of 1976. This catalyst has a considerably high activity per g transition metal but it is necessary to increase the activity further for completely omitting a catalyst removal step in the polyethylene production process. Further since an organoaluminum halide is used as a reaction agent, the performance of the catalyst was insufficient due to poor grain size distribution and poor bulk density of polymer.

Although a system comprising (1) a reaction product of an inorganic or organomagnesium compound and a titanium or vanadium compound and (2) an organoaluminum compound shows notable activity to propylene polymerization, the use of it as a commercial stereospecific polymerization catalyst for olefin such as propylene is difficult because a boiling heptane soluble portion relative to the total formed polymer i.e. proportion of non-crystalline polymer is extremely large (e.g. Japanese laid open patent application No.9342 of 1972, and Japanese patent publication No.13050 of 1968).

As a method for overcoming the above-mentioned problem, there have been proposed the methods described in Japanese laid open patent applications Nos 16986 of 1973; 16987 of 1973 and 16988 of 1973. These methods are the catalytic system comprising a solid component obtained by grinding together a complex compound of a titanium halide and an electron donor with anhydrous magnesium halide, and an additional reaction product of a trialkylaluminum with an electron donor. However, even by using any of these methods, the proportion of boiling heptane insoluble portion in the formed polymer is not yet satisfactorily high and particularly, yield of polymer per g solid component is insufficient, and the content of halogen in polymers, which brings about the corrosion of equipments of production process and molding machines, and physical properties of obtained product are not fully satisfactory.

According to the present invention there is provided a catalyst for polymerizing olefins comprising (A) a solid catalyst component comprising (1) a magnesium solid component (2) a titanium and/or a vanadium compound having at least one halogen atom, and optionally (3) carboxylic acid or derivative thereof, wherein the magnesium solid component (1) is obtained by reacting (i) an organomagnesium component having the general formula M MgssR 1pRq2XrYs wherein a is 0 or a number greater than Q; p and p are each numbers greater than 0; q, r and s are each 0 or a number greater than 0, having the relationship p + q + r + 5= my + 2p; M is a metal of Groups I, II or III of the Periodic Table, m is a valency of M; R l and R2 are the same or different hydrocarbon groups having 1 to 20 carbon atoms; X and Y are the same or different groups selected from halogen, OR3, OSiR4R5R6, NR7RB or SR9, and R3, R4, R5, R6 R7 and R are each hydrogen or a hydrocarbon radical, and R9 is a hydrocarbon group, with ii) a chlorosilane containing at least one Si-H bond and having the general formula HaSiClbR4-(a+b) wherein a and b are numbers greater than 0 having the relationship a +buzz and a m2 and R is hydrocarbon or chlorophenyl group, (B) an organo-metallic compound containing a metal of groups I, II, or III of the Periodic Table, and optionally (C) a carboxylic acid or derivative thereof.

The first feature of the present invention is a provision of an extremely high catalyst efficiency per g transition metal. As evidence from the specific Examples herein after described, the catalyst efficiency can reach a value more than 100,000 g polymer per g transition metal per hour per ethylene pressure (1 kg/cm2) in case of ethylene polymerization. The complete omission of a catalyst removal step is possible.

The second feature of the present invention is the attainment of production of polymer powder having excellent grain size and high bulk density.

The third feature of the present invention is the extremely good colour tone of molded articles when the polymer prepared by using the present catalyst is used in molding.

The fourth feature of the present invention is the capability of producing polymer having a wide range of molecular weight distribuiton from broader molecular weight distribution to narrower molecular weight distribution by way of the catalyst of the present invention. This can be put into practice by the treatment of the solid catalyst component (A) with an inorganic-or organo-aluminum, tin and silicon compound. The control of the molecular weight distribution can be also made by the catalyst synthesis condition.

The fifth feature of the present invention is the capability of controlling die swell of formed polymer in case of the production of polyethylene and increase of polymerization activity in case of production of polypropylene, polybutene, etc. by using a mechanical grinding and contacting means such as a ball mill and the like at the time of preparation of the solid catalyst component (A).

The sixth feature of the present invention is the attainment of higher stereoregularity in addition to the above-mentioned higher activity in case where a carboxylic acid or its derivative is simultaneously used e.g. in the production of polypropylene and polybutene. For example, a value of boiling heptane insoluble portion reaches up to 95.8%.

Although the essential cause of the above mentioned remarkable performance of the catalyst of the present invention is not yet certain, important function leading to the essential cause is conceivably attributed to the fact that the highly active halogenated magnesium solid camponent (A) has a large surface area and in the preferred forms, contains an alkyl group possessing reducing power.

The effect of the present invention is based upon the solid material of the above-mentioned specified active magnesium halide and cannot be expected when compounds such as magnesium chloride are used as evidence also from the Comparative Examples. The difference between the above mentioned solid catalyst component (A) and solid catalysts prepared by using magnesium chloride is evident also from the attached drawings. Fig. 1 shows the X-ray diffraction spectrum of the solid catalyst component obtained in Example 130, and Fig. 2 shows that of the solid catalyst synthesized according to Example 2 of Japanese patent application laid-open No. 48-16986 (1973), where the abscissa (28) shows twice the diffraction angle and the ordinate shows the relative ratio of strength. In case of ethylene polymerization, as evidence from the comparison of specific Example 1 and Comparative Examples 1 and 2, compared with the case of the use of an organoaluminum halide as a reacting agent as in Japanese patent publication No. 11672 of 1976, the case of the use of a chlorosilane compound provides notable increase of catalyst performance such as higher catalyst efficiency, uniform grain size of polymer, higher bulk density and broader molecular weight distribution. In this regard the latter case is very advantageous in commercial production.

Moreover it provides a more active catalyst for highly stereospecific polymerization also in the case of propylene polymerization.

Description will now be given with regard to organomagnesium component (i) which is used in the synthesis of the solid catalyst component (A).

Component (i) is shown in the form of a complex compound of an organomagnesium but includes so-called Grignard compound RMgX, R2Mg and all the complex of these compounds with other metallic (M) compounds. The hydrocarbon groups represented by R1-R9 in the above-mentioned formula, include alkyl, cycloalkyl, and aryl group, for example, methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, cyclohexyl and phenyl groups.

It is particularly preferable that Rl is an alkyl group. It does not matter even if R3 to R8 are hydrogen atoms. As halogen, chlorine, fluorine, bromine and iodine are used but chlorine is particularly preferable.

As metal atom M, any metal element of the first to the third group of the Periodic Table can be used, for example, sodium, potassium, calcium, beryllium, lithium, zinc, barium, boron and aluminum.

Preferably B/ α # 0,1, more preferably # 0.5, and (r+s)/(α+ss) is in the range of 0-2.0.

As catalyst components to be used in the present invention, organomagnesium complexes or compounds soluble in an inert hydrocarbon medium are preferable. As such organomagnesium complexes, those complexes in which M is aluminum, zinc, boron or beryllium, the ratio of magnesium to metal atom M, p/a, is equal to or greater than 0.5, preferably 1 - 10, the ratio of the sum of the groups X+Y to the sum of metal atom, 13(r+s)/(a +ss)30, preferably 0.83(r+s)/(a+ss)30, and X and Y are groups other than halogen in the above-mentioned general formula are used.

As organomagnesium compounds, those dialkylmagnesium compounds of the abovementioned general formula, in which a =0, r +s=0, R l, R2 are alkyl groups, and alkoxy and siloxymagnesium compounds in which a = 0, (r + s)/ ss = 1, and X, Y are OR3 or OSiR4R5R6 are preferably used.

As such compounds, (sec.-C4H9)2Mg, (tert.-C4H9)2Mg, n-C4H9MgC2H5, n-C4H9Mg sec.-C4H9, n-C4H9Mg-tert.-C4H9, n-C6H13MgC2H5, n-C8H17MgC2H5, (n-C6H13)2Mg, (n C8Hl,)2Mg, (n-C10H21)2Mg, n-C4H9Mg(OC3H7), n-C4H9Mg(OC4H9), n-C4H9 M(OC5H1 i), n-C4H9Mg(OC6H 13), n-C4H9Mg(OC8H17), C5H1 1Mg(OC4H9), C6Hl3Mg(OC3H7), n-C4H9Mg(OSiH.CH3 .C4H9), and n-C4HgMg(OSi H C6H5 C4Hg) are mentioned.

As compounds of this kind, a complex compound of alkylmagnesium halide or dialkylmag nesium with a Lewis base such as ether, ketone, amine or a solution of these compounds in ether is also useful.

Among the above-mentioned organomagnesium components (i), those which are particularly preferable are complexes represented by the general formula described above and consisting of compounds of two metals of M and Mg which are soluble in an inert hydrocarbon.

These organomagnesium compounds or organomagnesium complexes are synthesized by reacting an organomagnesium compound represented by the general formula, RlMgQ or R2Mg (wherein R' has the same meaning as defined above and Q is halogen) with an organometallic compound represented by the general formula MR2m or MR,n IH wherein M, Rand m have the same meaning as defined above, in an inert hydrocarbon medium such as hexane, heptane, cyclohexane, benzene or toluene at a temperature in the range from room temperature to 1 500C and if necessary further reacting the resulting reaction product with an alcohol, water, siloxane, amine, imine, mercaptan or a dithiocompound.

Further the organomagnesium compound or organomagnesium complex can be synthesized by reacting MgX2 or R 1MgX with MR2m, or MR2m-lH or by reacting R 1MgX or MgR21 with R2rlMXm n or by reacting R'MgX or MgR2 with YnMXm.n wherein M, Rl, R2, X, Y have the above-mentioned meaning and include the case of X and Y are halogen, and n is a number of 0 to m.

Description will now be given with regard to the chlorosilane compounds (ii).

The hydrocarbon groups represented by R in the formula given above include alkyl, cycloalkyl, aryl, for example, methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl and phenyl groups. Preferably the hydrocarbon group is alkyl containing 1 - 10 carbon atoms and a lower alkyl group such as methyl, ethyl or propyl is particularly preferable. The range of the value of a and b is defined by b > 0, a+b < 4, and 0 < a < 2. R may also be a chloro phenyl group.

As such compounds HSiCl@ CH@SiHCl@ C@H@SiHCl@ @@C@H@SiHCl@ i@C@H@SiHCl@ n-C4H9SiHC12, i-C4H9SiHC12, C6H5SiHC12, 4-CIC6H4SiHC12, CH2 = CHSiHC12, C6H5CH2SiHCl2, CloH7SiHCl2 CH2 = CHCH2SiHCl2, CH3SiH2Cl, C2H5SiH2Cl, (CH3)2SiHCl, (CH3)(i-C4H9)SiHCl, (CH3)(C6H5SiHCl, (C2H5)2SiHCl, (C6H5)2SiHCI alone or a mixture of these compounds or a mixture partially containing any of these compounds are preferable. As particularly preferable chlorosilane compounds, trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane and ethyldichlorosilane, can be mentioned.

The reaction between organomagnesium compound or organomagnesium complex (i) and the chlorosilane compound (ii) can be carried out in an inert reaction medium e.g. an aliphatic hydrocarbon such as hexane, heptane, an aromatic hydrocarbon such as benzene, toluene, xylene, an alicyclic hydrocarbon such as cyclohexane, methylcyclohexane or an ether type medium such as ether, tetrahydrofuran or a mixture of these compounds.

From the point of catalyst performance, an aliphatic hydrocarbon medium is preferable.

With regard to the reaction temperature, there is no particular limitation but from the point of the reasonable rate of reaction, the reaction is preferably carried out at a temperature of 40"C or higher. With regard to the reaction ratio, there is no particular limitation but it is recommended to use preferably the range of 0.01 mol to 100 mol chlorosilane component and most preferably 0.1 mol to 10 mol relative to one mol of the organomagnesium component.

Preferable results can be obtained in case of polymerization of propylene if an excess of the chlorosilane component is used relative to the organomagnesium component.

With regard to the reaction method, the following methods may be used: a simultaneous addition method in which the two components are introduced at the same time into a reaction zone (method a); a method in which the chlorosilane component is charged to the reaction zone in advance and thereafter the organomagnesium complex component is introduced in the reaction zone (method b), or a method in which the organomagnesium complex component is charged to the reaction zone in advance, and then the chlorosilane component is added (method c). Any of these methods provides good result but particularly method (b) gives preferable result in case of polymerization of propylene. When the organomagnesium compound is insoluble, it is possible also to use the chlorosilane compound as a reaction reagent in the reaction medium in the form of heterogeneous treatment reaction. Also in such an occasion, the above-mentioned conditions of temperature and mol reaction ratio are preferable.

The structure and composition of the component (1) obtained according to the abovementioned reaction, may vary according to the kinds of starting raw materials, and reaction condition, but it is assumed from the analytical value of preferred compositions that their structure is halogenated magnesium compound having approximately 0.1 - 2.5 millimol of alkyl groups with Mg-C bonds per g solid material. This solid material has an extremely large specific surface area showing a value as high as 100 - 300 m2/ according to the measurement by B.E.T. method. The halogenated magnesium component 1) used in the present invention has an extremely high surface area compared with the conventional magnesium halide solid and it is a preferred feature that said component (1) is an active magnesium halide containing alkyl group possessing reduction power.

Description will now be made with regard to the titanium compound containing at least one halogen which may be used as component (2).

As a tetravalent titanium compound (2-1), a halide or alkoxyhalogenide or titanium such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxytitanium trich bride, propoxytitanium trichloride, butoxytitanium trichloride, dibutoxytitanium dichloride, tributoxytitanium monochloride, may used solely or in the form of mixture. Preferable compounds are compounds containing 3 or 4 halogen atoms per molecule, particularly preferable is titanium tetrachloride. As halides of trivalent titanium (2-2) titanium trichloride, titanium tribromide, titanium triiodide can be mentioned. A solid solution containing one component of these compounds may also be used. As solid solutions, a solid solution of titanium trichloride and aluminum trichloride, a solid solution of titanium tribromide and aluminum tribromide,-a solid solution of titanium trichloride and vanadium trichloride, a solid solution of titanium trichloride and ferric trichloride, and a solid solution of titanium trichloride and zirconium trichloride can be mentioned. Among these, preferable are titanium trichloride, and a solid solution of titanium trichloride and aluminum trichloride (TiCe3 1/ 3AeCe3).

As vanadium compounds containing at least one halogen atom which may also be used as component (2), vanadium tetrachloride, vanadyl trichloride, monobutoxyvanadyl dichloride or dibutoxyvanadyl dichloride, may be used singly, or they may be used as a mixture with halide, hydroxyhalogenide or alkoxyhalogenide of titanium.

As an optional component (3), a carboxylic acid or a derivative thereof may be used in production of the solid catalyst component (A). The carboxylic acid or a derivative thereof includes aliphatic, alicyclic and aromatic, saturated and unsaturated, mono and polycarboxylic acids and acyl halides, acid anhydrides and esters thereof.

As the carboxylic acid, for example, formic acid, acetic acid, propionic acid, butyric acid. oleic acid, palmitic acid, stearic acid, pentanoic acid, oxalic acid, malonic acid, succinic acid, maleic acid, acrylic acid, benzoic acid, hydroxybenzoic acid, amino benzoic acid, anisic acid, toluic acid, phthalic acid, terephthalic acid, and naphthalene carboxylic acid may be mentioned. Among them, benzoic acid and toluic acid are preferable.

As the acyl halide, for example, acetyl chloride, propionyl chloride, n-butyryl chloride, isobutyryl chloride, succinyl chloride, benzoyl chloride, toluyl chloride can be mentioned.

Among them aromatic carboxylic acid halide such as benzoyl chloride, toluyl chloride are particularly preferable.

As carboxylic acid anhydride, for example, acetic anhydride, propionic anhydride, n-butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, toluic anhydride, phthalic anhydride are mentioned. Among them, benzoic anhydride is preferred.

As carboxylic acid ester, for example, ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, ethyl propionate, ethyl n-butyrate, ethyl valerate, ethyl capronate, ethyl heptanoate, di-n-butyl oxalate, monoethyl succinate, diethyl succinate, ethyl malonate, di-n-butyl malate, methyl acrylate, ethyl acrylate, methyl methacrylate, methyl benzoate, ethyl benzoate, n- and isopropyl benzoate, n-, i-, sec.- and tert. butyl benzoate, methyl p-toluate, ethyl p-toluate, i-propyl p-toluate, n, and i-amyl toluate, ethyl o-toluate, ethyl m-toluate, methyl p-ethylbenzoate, ethyl p-ethylbenzoate, methyl anisate, ethyl anisate, i-propyl anisate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, and methyl terephthalate. Among them, esters of aromatic carboxylic acid are preferable, particularly, methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate are preferable.

Description will now be given for obtaining a solid catalyst component (A) by subiecting the solid component (1) obtained by the reaction between the organomagnesium component (i) and the chlorosilane compound (ii), to reaction and/or grinding with titanium and/or vanadium compound component (2). The contact of the component (1) with a titanium or vanadium compound can be any of the following methods: a method in which a titanium or vanadium compound is subjected to contact reaction in liquid phase, a method in which a titanium or vanadium compound is used in a solid phase and brought into intimate contact by way of mechanical grinding means such as a ball mill, and the simultaneous use of these methods When the contact reaction is carried out by using a titanium or vanadium compound in a liquid phase, the reaction may be carried out using an inert reaction medium or using an undiluted titanium or vanadium compound per se as a reaction medium without using an inert reaction medium. As an inert reaction medium, for example, there may be mentioned aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, among which aliphatic hydrocarbons are preferred. The reaction temperature and the concentration of the titanium or vanadium compound, though not specifically limited, are preferably in the range of 100"C or higher and 4 mol/e of a titanium or vanadium compound concentration or higher, respectively. Still more preferably, undiluted titanium or vanadium compound per se is used for carrying out reaction as a reaction medium. With regard to a reaction mole ratio, a favorable result is obtained by conducting the reaction in the presence of a sufficiently excessive amount of a titanium or vanadium compound relative to the magnesium compound in the solid component (1).

On the other hand, when a titanium or vanadium compound is used in a solid phase, it is possible to use, as a method for subjecting it to intimate contact with a solid material, a known mechanical grinding procedure such as a revolving ball mill, a vibration ball mill. Although there is no limitation with respect to the condition of grinding-contacting, it is referable to reduce the amount of titanium or vanadium compound in view of catalyst efficiency per g transition metal.

In the production of the catalyst of the present invention, it does not matter even if the above-mentioned various kinds of contacting means are used singly, or sequentially or simultaneously. For example, it is possible to adopt a method in which a solid catalyst component (A) is obtained by subjecting a titanium compound to contact reaction in liquid phase is also ground in a ball mill with or without a solid titanium compound. If these procedures are used simultaneously or sequentially for contacting in the production of the catalyst of the present invention, it is very effective because the die swell of formed polymer can be controlled.

The composition and structure of the solid catalyst component (A) obtained by the various kinds of above-mentioned contact reaction vary according to the kinds of starting raw materials and synthesis condition, but it has been revealed from the analytical values of using a titanium compound as component (2) that component (A) contains approximately 0.5 10% by weight of titanium and has a high surface area in the range of 30 - 300 m /g.

It is possible to vary the molecular weight distribution of polyethylene and the control of properties of grain size by treating the solid catalyst component (A) further with an inorganic or organo-component of aluminum, tin or silicon.

Next, description will will be given with respect to the preparation of the solid catalyst component (A) by reacting and/or by grinding a titanium compound (2) and a carboxylic acid or its derivative thereof (3) with the solid material (1) obtained by the reaction between the organomagnesium component (i) and the chlorosilane compound (ii).

The titanium compounds containing at least one halogen atom used in the production of solid catalyst component (A) are tetravalent titanium compounds containing at least one halogen atom and/or halides of trivalent titanium.

For the reaction of the above mentioned solid material, the titanium compound and the carboxylic acid or a derivative thereof, any of the methods can be adopted such as [1] a method in which a titanium compound and a carboxylic acid or its derivative thereof are reacted in a liquid or gas phase, [2] a method in which a liquid or gas phase reaction and are combined with or followed by, grinding. First, description will be given for the order of the reaction and/or grinding of the solid material, the titanium compound, and the carboxylic acid or its derivative thereof.

The method [1] includes a process of simultaneous reaction of the solid material, titanium compound and carboxylic acid or its derivative thereof (method O), a process of reacting the solid material and a titanium compound followed by the reaction with a carboxylic acid or a derivative thereof (method 0), and a processj of firstly reacting the solid material and the carboxylic acid or a derivative thereof followed by the reaction with a titanium compound (method (G)). Although either of these methods may be employed, the latter two methods, especially method (2), are preferable. carboxylic acid or a derivative thereof but especially following three methods give favorable results; namely a method wherein the three components are ground together (synthesis O), a method wherein the solid component and the carboxylic acid or a derivative thereof are firstly contacted and then mechanical grinding is carried out after the addition of the halogenated trivalent titanium (synthesis 02), and a method wherein the solid component and the halogenated trivalent titanium compound are mechanically ground and contacted and followed by the treatment with a carboxylic acid or a derivative thereof (synthesis O).

In the case of (III), a method wherein the above-mentioned solid component (1), a tetravalent titanium compound (2-1), a trivalent titanium compound (2-2), and a carboxylic acid or a derivative thereof (3 are simultaneously ground (synthesis Q), a method wherein solid obtained by reacting (1 and (2-1) is treated with (3) followed by grinding thereof together with (2-2) (synthesis O), a method wherein solid obtained by reacting (1) and (3) is treated with (2-1) followed by grinding thereof together with (2-2) (synthesis (!)), a method wherein solid obtained by reacting 1 and (2-1), is ground after addition of (2-2) and (3) (synthesis Q)), may be mentioned. Among them, synthesis 2) is preferred.

Further by treating the solid catalyst component (A) prepared by the method [1] and [2] described above with a tetravelent titanium compound (4) containing at least one halogen atom, further increase of catalyst efficiency, i.e. the first feature of the present invention, is attained. One of the tetravalent titanium compounds (2-1) mentioned above may be employed as the tetravalent titanium compound (4), and titanium tetrahalide, especially titanium tetrachloride is preferred.

Firstly, among the methods wherein solid catalyst component (A) synthesized by the method [1] is further treated with the above mentioned halogenated tetravalent titanium, there are included a method of reacting simultaneously said solid material, titanium compound and carboxylic acid or its derivative thereof, followed by further treatment with a halogenated tetravalent titanium compound (synthesis Q), a method of reacting the abovementioned solid material and the titanium compound followed by the reaction with a carboxylic acid or a derivative thereof and further by the treatment with a tetravalent titanium halide (synthesis Q)), and a method of reacting the above-mentioned solid material and a carboxylic acid or a derivative thereof followed by the reaction with a titanium compound and further by the treatment with a tetravalent titanium halide (synthesis O.

Next, with regard to the method wherein the solid catalyst synthesized according to method [2] is further treated with a tetravalent titanium halide, explanation will be given for (I), (II) and (III) In the case of (I), there are three possible methods wherein the solid catalysts synthesized according to [2]-(I)-0, [2]-(I)-0 and [2]-(I)q are respectively treated with a tetravalent titanium halide, but the latter two methods are preferred.

In the case of (it), there are four possible methods wherein the solid catalyst synthesized according to the methods [2]-(II)-0, [2]-(II)-0, [2]-(II)-0 and [2]-(II) 4) are respectively treated with a tetravalent titanium halide.

In the case of (III), there may be mentioned a method wherein a solid material (1), a tetravalent titanium compound (2-1), a trivalent titanium compound (2-2), and a carboxylic acid or a derivative thereof (3) are simultaneously ground, followed by the treatment with a tetravalent titanium halide synthesis O), a method wherein the solid obtained by reacting solid (1) and compound (2-1) is treated with acid or a derivative thereof (3), ground together with compound (2-2) and treated with a tetravalent titanium halide (synthesis O), a method wherein the solid obtained by reacting (1) and (3) is treated with (2-1), ground together with (2-2), and further treated with a tetravalent titanium halide (synthesis (G)), a method wherein the solid obtained by reacting (1) and (2-1) is ground together after addition of (2-2) and (3) and further treated with a tetravalent titanium halide (synthesis (i)), a method wherein the solid obtained by reacting (1) and (2-2) is treated with (3), ground together with (2-2) and further treated with a tetravalent titanium halide (synthesis O. Among them the methods 0 ( ) and 0 are preferred.

Next, the operation of reacting and/or grinding the above-mentioned solid material, titanium compound, and carboxylic acid or its derivative will be explained.

The reaction between a solid material (1) (obtained by reacting the organomagnesium component (i) and a chlorosilane compound (ii) or a reaction product of this solid material and a carboxylic acid or a derivative thereof) and a titanium compound (2) is carried out as already described.

The reaction with a carboxylic acid or a derivative thereof (3) is carried out using an inert reaction medium. As a reaction medium, any of the above mentioned aliphatic, aromatic or alicyclic hydrocarbons may be used. The reaction temperature, though not specifically limited, preferably ranges from room temperature to 1000C. When the solid material and the carboxylic acid or a derivative thereof are reacted, the ratio of the two components of the reaction is not specifically limited. However, it is recommended that carboxylic acid or a derivative thereof ranges 0.001 mol - 50 mol, preferably 0.005 mol - 10 mol relative to one mol of alkyl group contained in the organomagnesium solid component. When the reaction product of the solid material and the titanium compound is reacted with the carboxylic acid or a derivative thereof, the ratio of the two components of the reaction ranging 0.01 mol - 100 mol, preferably 0.1 mol - 10 mol of the amount of carboxylic acid or a derivative thereof relative to one mol of titanium atom in the organomagnesium solid material is recommended.

As a grinding means, well known mechanical grinding means such as a rotary ball mill, a vibration ball mill, an impact ball mill, and the like may be employed. Grinding time is in the range of 0.5 - 100 hours, preferably 1 - 30 hours, and grinding temperature is in the range 0 - 200 C, preferably 10 - 1500C.

Further treatment of the solid component (A) with a tetravalent titanium halide is carried out using an inert reaction medium or utilizing the titanium compound itself as a reaction medium. As an inert reaction medium, there may be mentioned, for example, aliphatic hydrocarbons such as hexane or heptane, aromatic hydrocarbons such as benzene or toluene, and alicyclic hydrocarbons such as cyclohexane or methylcyclohexane, but aliphatic hyd rocarbons are preferred. The concentration of the titanium compound is preferably 2 mol/e or higher, especially preferred is the use of the titanium compound itself as a reaction medium. Although reaction temperature is not specifically limited, preferable results are obtained when reaction is conducted at a temperature of 80"C or higher.

Although the composition and the structure of the solid catalyst components (A) obtained according to the above mentioned reactions vary depending on starting materials and reaction conditions, it was found from the analysis of preferred compositions that the solid catalyst component (A) contains approximately 1 - 10 percent by weight of titanium and has a surface area of 30 - 300 m2/g.

Organometallic compounds used as component [B] are organic compounds of metals of I III group in the Periodic Table and especially an organoaluminum compound and complexes containing an organomagnesium are preferred. As organoaluminum compounds, those represented by the general formula AtRl Z3.. (wherein R is a hydrocarbon group having 1 20 carbon atoms (inclusive), Z is a member selected from hydrogen, halogen, alkoxy, aryloxy and siloxy, and t is a number of 2 - 3 (inclusive)) are used solely or as a mixture. In the above formula, the hydrocarbon group having 1 - 20 carbon atoms (inclusive) which is represented by Rl includes aliphatic hydrocarbon, aromatic hydrocarbon and alicyclic hydrocarbon groups.

Specifically, compounds, for example, triethylaluminum, tri-n-propylaluminium, triisop ropylaluminium, tri-n-butylaluminium, triisobutylaluminium, trihexylaluminium, trioc tylaluminium, tridecylaluminium, tridodecylaluminium, trihexadecylaluminium, dieth ylaluminium hydride, diisobutylaluminium hydride, diethylaluminium ethoxide, diisobutylaluminium ethoxide, dioctylaluminium butoxide, diisobutylaluminium octyloxide, diethylaluminium chloride, diisobutylaluminium chloride, dimethylhydroxyaluminium dimethyl, ethylmethylhydroxyaluminium diethyl, ethyldimethylsiloxyaluminium diethyl and aluminium isoprenyl, and mixtures thereof are recommended.

A combination of these alkylaluminium compounds with the above mentioned solid catalyst component (A) provides highly active catalysts, and especially trialkylaluminium and dialkylaluminium hydride are preferable because it enables to attain the highest activity.

The complexes which contain an organomagnesium are thos hydrocarbon soluble organomagnesium complexes represented by the general formula MMgR 1qR2qXrY (wherein a and p are numbers greater than 0 with the proviso that p/a is 0.1 - 10, p is a number greater than 0; q, r, and s are each 0 or a number greater than 0, having the relationship of p+q+r+s=mdx+2 and 0 < (r+s)/(a+P) < 1.0, M is aluminium zinc, boron or beryllium; m is the valency of M, R' and R are the same or different hydrocarbon groups having 1 - 10 carbon atoms, X and Y are same or different groups indicating OR3, OSiR4R5R6, NR7Rs, or SR9 wherein R3, R4, R5, R6, R7 and R8 are hydrogen or a hydrocar bon group having 1 - 10 carbon atoms and R9 is a hydrocarbon group having 1 - 10 carbon atoms), and especially complexes wherein M is aluminum are preferred.

In the case of polymerization of propylene and the like olefins, the carboxylic acid or a derivative thereof to be added to an organometallic compound may be the carboxylic acid or a derivative thereof used for preparation of the solid catalyst component, and it may be same with or different from the compound prepared by the solid catalyst component.

As to the manner of addition, the two components may be mixed prior to the polymeriza tion or they may be added to the polymerization system, separately. Especially preferred is to add separately the previously prepared reaction product of an organometallic compound and a carboxylic acid or a derivative thereof and an organometallic compound to the polymeriza tion system. The the two componets may be combined in the range from 0 mol to 10 mol, preferably 0 to 1 mol, of carboxylic acid or its derivative relative to a mol of the organometallic compound.

The catalyst of the present invention comprising the solid catalyst component (A) and the - component (G) of an organometallic compound incorporated with or without (C) a carbox ylic acid or a derivative thereof may be added to the polymerization system under the polymerization condition or it may be blended prior to the polymerization. The ratio of the component of an organometallic compound with or without a carboxylic acid or a derivative thereof relative to 1 gram of the solid catalyst component preferably ranges from 1 millimol to 3000 millimol on the basis of the amount of the organometallic compound.

Olefins which can be polymerized by using the catalyst of the present invention include a-olefins, monoolefins such as ethylene, propylene, butene-1 and hexane-1, and dienes such as butadiene and isoprene.

Especially, the catalyst of the present invention is also suitable for polymerizing stereospec ifically propylene, butene-1, pentene-1, 4-methylpentene-1 and 3-methylpentene-1. It is also possible to add hydrogen, a halogenated hydrocarbon or an organometallic compound which is liable to cause chain transfer in order to regulate the molecular weight of the polymer.

As to the manner of polymerization, a usual suspension polymerization, a solution polymerization, a bulk polymerization in liquid monomer, or a gas phase polymerization can be employed. Suspension or solution polymerization may be carried out at from room temperature to 1500C by introducing the catalyst together with a polymerization solvent e.g. an aliphatic hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as benzene, toluene or xylene, or an alicyclic hydrocarbon such as cyclohexane or methylcyc lohexane, and introducing an olefin such as ethylene or'propylene to a pressure of 1 - 20 kg/cm2 under inert atmosphere. Bulk polymerization of olefins may be carried out under the condition of an olefin such as propylene, etc. being in the liquid state using a catalyst and the liquid olefin as a polymerization solvent. For example, propylene can be polymerized in propyiene itself under a pressure of 10 - 45 kg/cm2 at a temperature of from room tempera ture to 900 C. On the other hand, gas phase polymerization can be carried out under the condition of an olefin such as propylene being in gaseous state, e.g. under a pressure of 1 - 50 kg/cm2 and at a temperature ranging from room temperature to 1200C in the absence of a solvent, by means of a fluidized bed, a movable bed or mechanical stirrer so that the olefin such as propylene and the catalyst can be well contacted.

The polymerization may be conducted either as single zone polymerization or as the so called multiple zone polymerization.

Hereinafter the present invention will be illustrated by Examples. In these Examples MI indicates melt index and is measured at a temperature of 190C and a load of 2.16 kg according to ASTM D-1238. FR indicates a quotient obtained by dividing the MI value obtained at a temperature of 1900C and at a load of 21.6 kg by MI. FR is a measure of molecular weight distribution and the greater the value, the broader the distribution of molecular weight. SR shows the weight (g) of total 10 cm of molten polymer strand which has flown out of a melt-indexer under a high load of 21.6 kg and is one of a measure of relative swell ratio.

Additionally, residue from n-heptane extraction used in the exmaples means residue formed by six hour extraction of the polymer with boiling n-heptane, and inherent viscosity was measured in tetralin at 135 C. Catalyst efficiency is indicated by polymer yield (g) per transition metal component (g) per hour per olefin pressure of 1 kg/cm Example I (I) Synthesis of component (i) (hydrocarbon soluble organomagnesium comples) Di-n-butyl magnesium (13.80 g) and triethylaluminum (1.90 g) were charged into a 200 ml volume flask having been purged with nitrogen together with heptane (100 ml) and reacted at 80"C for two hours to obtain a solution of an organomagnesium complex. Analysis showed that the complex had a composition of AlMg6.0(C2H52.s(n-C4H9)l2.l and the concentration of the organometal was 1.16 mol/e.

(II) Preparation of component (1) (solid material) Oxygen and moisture in a 200 ml volume flask fitted with a dropping funnel and a water cooled reflux condenser were purged with nitrogen, and under a nitrogen atmosphere, 50 mmol of trichlorosilane (HSiC13) solution in heptane (1 mol/e) was charged in the flask and heated to 50"C. Next, 50 mmol of the solution of said organomagnesium complex was measured and taken up into the dropping funnel, added thereto dropwise with stirring over one hour at 500C, and further reacted therewith at this temperature for one hour. Resulting hydrocarbon insoluble white precipitate was isolated, washed with hexane, and dried to obtain a white solid material. Analysis showed that 1 g of this solid contained 9.20 mmol of Mg, 19.20 mmol of Cl, 1.70 mmol of Si and 0.94 mmol of alkyl group, and specific surface area measured by B.E.T. method was 270 m2/g.

(III) Preparation of solid catalyst component (A) To a pressure proof ampoule having been purged with nitrogen charged 2.0 g of the above mentioned solid material and 30 ml of titanium tetrachloride. After reaction was conducted with stirring at 1300C for two hours, solid portion was isolated by filtration, washed thoroughly with hexane, and dried, and a pale red-violet solid catalyst was obtained. Analysis of this solid catalyst showed that it contained 2.5% by weight of Ti and that the specific surface area measured by B.E.T. method was 210 m2/g.

(IV) Polymerization The solid catalyst component (A) prepared according to procedure of in (III) (10 mg) and triisobutylaluminium (0.4 m.mol) together with dehydrated and deaerated hexane (0.8 e) were charged into a 1.5 e volume autoclave which had been deaerated to vacuum and purged with nitrogen. While keeping the temperature inside the autoclave at 800 C, hydrogen pressure and ethylene pressure were increased to 1.6 kg/cm2 and 2.4 kg/cm2, respectively, and adjusting the total pressure at a pressure of 4.4 kg/cm2 (gauge). While keeping the total pressure at 4.4 kg/cm2 (gauge) by supplying ethylene, polymerization was conducted for one hour to obtain 75g of a polymer. The efficiency of the catalyst was 125,000 g/g-titanium component.hour.ethylene pressure, MI was 0.30, FR was 68 and SR was 0.59. The resulting polymer had a bulk density of 0.343 g/cm3, powder of 35 - 150 mesh particle size occupied 93% by weight and showed excellent particle characteristics.

Comparative Example I According to the prior art patent literature using ethylaluminium dichloride as a reaction reagent (Japanese Patent Publication No. 51 (1976) - 11672, Example 5), catalyst synthesis was conducted as follows.

Namely, a solution of organomagnesium complex which was same as described in above Example 1 of the present invention and ethylaluminium dichloride were reacted in the molar ratio of 1: 4 at 40"C for two hours to prepare a solid material. To this reactant slurry, titanium tetrachloride was added so as to give a molar ratio of Ti: Mg of 1: 6.6, and the reaction was carried out at 400C for one hour to synthesize a catalyst slurry. Using 0.01 m.mol Ti equivalent of thus synthesized catalyst slurry and 1.6 m.mol of triisobutylaluminium, polymerization was conducted in the same manner as Example 1 to obtain 57 g of a polymer.

The efficiency of the catalyst was as low as 49,500, MI was 0.52, and FR was only 41. The bulk density of the resulting polymer was as small as 0.237 g/cm3, the proportion of 35 - 150 mesh size powder was as small as 57%, and particle characteristics were poor. Additionally, isolation and analysis of the solid component of this catalyst showed its Ti content of 2.0 % by weight and its specific surface area of as small as 53 m /g.

Comparative Example 2 According to Example 1 except for using as a reaction re-agent ethylaluminium dichloride in place of trichlorosilane, catalyst preparation as well as polymerization were conducted.

Analysis of the solid component of this catalyst showed its Ti content of 17.3 % by weight and its specific surface area of 46 m2/g. The yield of polymer was as little as 13 g, the catalyst efficiency was as low as 3,100 MI was 0.27 and FR was 52. The bulk density of the polymer was 0.205 g/cm3, the proportion of 35 - 150 mesh size powder was 28%, aggregation of powder and adhesion to the polymerization reactor were drastic and particle characteristics were poor.

Example 2 - 16 Following the procedure of Example 1, catalyst preparation and polymerization were conducted and the results shown in Table 1 were obtained. Further catalyst synthesis and polymerization were conducted using the compounds and conditions shown in Table 1.

Table I Catalyst Solid catalyst component Molar Temper- Ti or V Tempera- Ti+V Specific Silane ratio ture ( C) compound ture ( C) % by surface Example Organomagnesium compound compound Mg/Si x hour (conc.) x hour weight area (m2/g) TiCl6 2 AlMg6.0Et2.9n-Bu12.1 HSiCl3 1/4 40 x 2 (neat) 130 x 2 2.5 203 TiCl4 3 AlMg6.0Et2.0n-Bu9.5(OBu)3.5 HSiCl3 5/1 50 x 2 (neat) 120 x 3 2.2 220 TiCl4 4 AlMg6.0Et2.9n-Bu12.1 HSiCl2Me 1/1 50 x 2 (4mol/l 130 x 2 5.1 21.5 TiCl4 5 ZnMg2.0Et2.0n-Bu3.9 HSiCl3 2/1 80 x 2 (neat) 110 x 4 2.3 176 equivalent mol mixture of TiCl4 and VCl4 6 AlMg4.0Et2.9(n-Hexyl)8.0 HSiCl3 1/3 50 x 2 (neat) 130 x 2 1.5 207 BeMg4.0Et0.7n-Pr6.3- TiCl4 7 [N-(n-Bu)2]3.0 HSiClEt2 1/1 80 x 5 (neat) 130 x 2 2.8 194 equivalent mol mixture of TiCl4 and VOCl3 8 BeMgEt2.8n-Pr1.5(SEt)0.7* HSiCl3 1/1 50 x 5 (neat) 130 x 2 6.2 172 Table I (continued) Catalyst Solid catalyst component Molar Temper- Ti or V Tempera- Ti+V Specific Silane ratio ture ( C) compound ture ( C) % by surface Example Organomagnesium compound compound Mg/Si x hour (conc.) x hour weight area (m2/g)

* m oo N m o H N H N (s - (s 9 Me HSiC3 2/1 's x 5 (4 mol/) oo. x 2 2.9 224 TiC4 (s AMg6.oEt2.tnBu & 6OBu4.3 HSiCt2Me 1/1 60 x H (neat) 110 x 3 3.1 195 X X K K X K H (OSi n Bu)3.5 TiC4 II Me llSiC3 2/1 70x1 (neat) 120x2 3.2 218 TiC4 12 Sec.-Bu2Mg HSiC2Me 1/2 50 x 2 (neat) 130 x 1 2.8 212 'jc uS Yg i=1 S 9 E- n.BuMg(On-Octyl) HSiC(Me)2 1/3 50 x ~ E- ~ E- ~ E Me u: ~ ~ es (s c9 X K K X X K O H HSiC3 O 50x2 O O O m \0 b -} V} 1 e S S U U i) U U U c5 . m m' t-O-S m = = S m, a ~ a O o E e oe o ~ es e t TiCl4 15 n-C4H9MgC2H5 HSiCl3 1/2 60 x 2 (neat) 130 x 1 2.3 198 TiCl4 16 (n-C6H13)2Mg HSiCl3 1/2 60 x 2 (neat) 130 x 1 2.1 176 Table I (continued) Catalyst Result of polymerization Catalyst Particle characteristics efficiency

g/g Ti, bulk Organometallic compound Yield #hr@ethylene,# density 35-150 mesh Example (m mole) (g) g/cm2 MI FR SR (g/cc) powder (%) 2 AliBu3 (1.6) 66 110,000 0.12 67 0.61 0.323 92 3 AlEt3 (0.4) 82 156,000 1.42 28 0.63 0.342 93 4 AliBu2H (0.4) 187 153,000 0.33 61 0.58 0.338 94 5 AliBu3 (0.4) 65 118,000 0.23 70 - 0.310 93 6 AlEt2.5(OEt)0.5(1.6) 45 118,000 0.75 60 - 0.296 85 7 AliBu3 (3.2) 62 92,000 0.62 63 - 0.311 83 8 AlEt2.5Cl0.5 (1.6) 146 98,000 0.28 71 0.64 0.301 82 9 AlMg6.0Et2.9-n-Bu@2.1 (0.8) 78 112,000 1.03 38 - 0.334 90 10 AlEt3 (1.6) 85 114,000 2.11 28 - 0.312 94 11 AlEt3 (1.6) 88 115,000 1.75 26 - 0.311 92 12 AliBu3 (0.4) 57 85,000 0.19 91 0.64 0.315 93 13 AlEt3 (0.4) 64 83,000 0.95 31 - 0.306 96 14 Al(hexyl)3 (1.6) 54 78,000 0.23 75 0.59 0.343 88 15 AliBu3 (1.6) 56 101,000 0.35 62 - 0.311 90 16 AliBu2 (1.6) 52 103,000 0.21 65 - 0.325 92 Example 17 Two grams of solid catalyst component (A) synthesized in the same manner as in Example 1 and 30 ml of 0.1 mol/ e solution of ethylaluminum dichloride in heptane were charged into a 100 ml ampoule and reacted at 900C for one hour to obtain a solid catalyst. The Ti content in the solid was 2.2%by weight, the specific surface area of the solid was 225 m2/g. In the same manner as in Example 1 except for the use of this solid catalyst, polymerization was conducted resulting in 74 g of a polymer. The catalyst efficiency was 140,000, MI was 0.29 and FR was 78. The bulk density was 0.355 and the proportion of the 35 - 150 mesh size powder was 98%.

Example 18 Using diethylaluminum chloride in place of ethylaluminium dichloride, the reaction was conducted according to Example 17 resulting in a solid catalyst. The content of Ti in the solid was 2.3% by weight, and the specific surface area was 185 m2/g. Polymerization was conducted in the same manner as Example 1 except for using this solid catalyst instead of 85 g of a polymer was obtained. Catalyst efficiency, 154,000; MI, 0.79; FR, 39; bulk density, 0.353; and proportion of 35 - 150 mesh powder, 96%.

Example 19 Except for using a solution of n-butyl-magnesiumchloride- 1.8 dibutylether complex in heptane in place of the solution of organomagnesium complex in heptane used in Example 1, solid catalyst component synthesis and polymerization were carried out according to Example 1. The content of Ti in the solid catalyst component was 2.9% by weight and the specific surface area was 165 m2/g. Yield of polymer, 45 g; catalyst efficiency, 65,000; MI, 0.27; FR, 72; bulk density 0.306; proportion of 35-150 mesh powder, 87%.

Example 20 (i) Synthesis of organomagnesium compound (component (i)) A 500 ml volume flask fitted with a dropping funnel and a water cooled reflux condenser was purged with dry nitrogen, and 20.0 g of 100 - 200 mesh metallic magnesium powder and 300 ml of n-heptane were charged thereto. The flask was heated to 900C. Then 0.81 mole of n-butyl chloride was measured and taken up in the dropping funnel, and it was dropped with stirring at 90"C over one hour. After the initiation of the reaction, stirring was further continued for additional two hours at 90 - 95"C. Then solid was filtered off, washed with hexane and dried. Analysis of the solid showed its composition to Mgn-Buo.sCll l.

(ii) Synthesis of solid material (component (1)) Into an autoclave having been purged with nitrogen, were charged 50 m mol on magnesium basis of the above mentioned organomagnesium compound and 100 ml of 1 mol/e trichlorosilane solution in heptane. After reacting them with stirring at 600C for two hours, solid portion was filtered off and washed with hexane resulting in a solid material.

(iii) Synthesis of solid catalyst component (A) and polymerization Polymerization was conducted in the same manner as Example 1 except for using the above-mentioned synthesis of the solid catalyst component. The content of Ti in the solid catalyst component was 3.7% by weight and the specific surface area of the solid catalyst component was 107 m2/g. The results of the polymerization were as follows: Polymer yield, 46 g; catalyst efficiency, 52,000; MI, 0.46; FR, 65; bulk density, 0.305; proportion of 35 150 mesh powder, 67%.

Example 21 Except for t kg/cm2 (gauge) by supplying ethylene, polymerization was conducted for one hour and 55 g of a polymer was obtained. Catalyst efficiency, 74,000; MI, 0.19; FR, 88; SR, 0.77.

Example 23 Into an autoclave having been purged with nitrogen, were charged 5.0 g of solid material prepared according to the same manner as in Example 22 and 50 ml of titanium tetrachloride.

After they were subjected to reaction with stirring at 1300C for two hours, solid part was isolated by filtration, washed thoroughly with hexane and dried resulting in a pale red-violet already supported solid. Four g of this supported solid was charged into a ball mill described in Example 22 and milled solely for 5 hours to obtain a solid catalyst component. The analysis of this solid catalyst component showed its Ti content of 2.5% by weight. Using this solid catalyst component, polymerization was conducted in the same manner as in Example 22.

Polymer yield, 49 g; catalyst efficiency, 82,000; MI, 0.25; FR, 75; SR, 0.70.

Example 24 The solid material (3.5 g) prepared in Example 2 and titanium trichloride (Stauffer Co. AA grade) (0.5 g) were charged into a ball mill described in Example 22, and they were ground together for 5 hours resulting in a solid catalyst componet. The analysis of this solid catalyst component showed its Ti content of 5.5% by weight. Using this solid catalyst component, polymerization was conducted in the same manner as in Example 22. Polymer yield, 94 g; catalyst efficiency, 71,000; MI, 0.20; FR, 90; SR, 0.80.

Example 25 Using 3.5 g of solid material prepared in the same manner as in Example 20 and 0.5 g of titanium trichloride (Stauffer Co. AA grade), a solid catalyst component was obtained by grinding them together in the same manner as in Example 22. The analysis of the solid catalyst component showed its Ti content of 3.0% by weight. Using this solid catalyst componet, polymerization was conducted in the same manner as in Example 22. Polymer yield, 43 g; catalyst efficiency, 60,000; MI, 0.18; FR, 82; SR, 072.

Example 26 Using AlMg.oEt2.o n-Bus.s OBu3 s as an organomagnesium compound in an amount of 250 mmol, using HSiCl2(CH3) as a chlorosilane compound and using diisobutylaluminum hydride as an organometallic compound in polymerization, and using all other conditions same as in Example 22, solid material synthesis, solid catalyst component synthesis by way of milling together the solid material and titanium trichloride, and polymerization were conducted. The Ti content in the solid catalyst component was 3.1 %by weight and the results of polymerization were as follows: Polymer yield, 51 g; catalyst efficiency, 69,000; MI, 0.28; FR, 75; SR, 0.72.

Example 27 Except for using ZnMgz.oEtz.on-Bu.s as an organomagnesium compound and equimolecular mixture of HSiCl3 and SiCl4 as the chlorosilane compound, a solid material was synthesized in the same manner as in Example 22. Next, using this solid material supporting reaction was conducted according to Example 23 to synthesize a supported solid. Next, this supported solid, and titanium trichloride were milled together in the same manner as in Example 24 to synthesize a solid catalyst component. Except for using this solid catalyst component and organomagnesium complex A1Mgs.oEt2.9n-Bul2.1 as an organometallic compound during the polymerization, polymerization was conducted in the same manner as Example 22. The Ti content in the solid catalyst component was 4.8%by weight and the results of polymerization were as follows: Polymer yield 71 g; catalyst efficiency, 62,000; MI, 0.20; Fr, 85; SR, 0.79.

Example 28 Using BeMg4.oEto.7n-Pr6.3[N(n-Bu)z] .o as an organomagnesium compound, HSiClEt2 as a chlorosilane compound in an amount of 100 mmol, using the solid material synthesis time of 5 hours (4 hours for dropping and additional one hour after dropwise addition), and other conditions same as in Example 22, a solid material was prepared. This solid material (3.74 g) titanium trichloride (Stauffer Co. AA grade) (0.21 g) and vanadium trichloride (0.05 g) were charged into a ball mill of Example 22 in the same manner, and they were milled together to prepare a solid catalyst component. Except for using this solid catalyst component and diethylaluminum ethoxide as an organometallic compound in the polymerization in an amount of 1.6 mmol, polymerization was conducted in the same manner as in Example 22.

The Ti content in the solid catalyst component was 1.4% by weight and the results of polymerization were as follows: Polymer yield, 20 g; catalyst efficiency, 60,000; MI, 0.31; FR, 74; SR, 0.72.

Example 29 Using B Mg1.oEt2.s(n-C6Hl3)l.s (SEt)0.7 as an organomagnesium compound and employing a solid material synthesis time of 5 hours (four hours for dropwise addition and additional one hour after the dropwise addition) and according to Example 22 except for the conditions above, a solid material was synthesized. Using this solid material, supporting reaction according to Example 23 was carried out to prepare a supported solid, which was milled solely in a ball mill to produce a solid catalyst component. Except for using this solid catalyst component and tri-n-hexylaluminum as an organometallic compound in the polymerization and in an amount of 3.2 mmol of the latter, polymerization was conducted in the same manner as Example 22. The Ti content in the solid catalyst component was 4.5 % by weight and the results of polymerization were as follows: Polymer yield, 63 g; catalyst efficiency, 58,000; MI, 0.20; FR, 75; SR, 0.70.

Example 30 Except for using

as an organomagnesium compound, a solid material was synthesized in the same manner as in Example 22. This solid material (3.74 g), titanium trichloride (Stauffer Co. AA grade) (0.21 g) and titanium tetrachloride (0.03 ml) were charged into a ball mill described in Example 22 in the same manner and they were milled to gether to prepare a solid catalyst component.

Using this solid catalyst component, polymerization was conducted in the same manner as in Example 22. The Ti content in the solid catalyst component was 1.8% by weight, and the results of polymerization was as follows: Polymer yield, 34 g; catalyst efficiency, 79,000; MI, 0.33; FR, 78; SR, 0.81.

Example 31 The solid catalyst component synthesized in Example 22 was further treated with ethylaluminum dichloride (condition of treatment: Ti of solid catalyst component/AlEtCl2 = 1/5 (molar ratio), 80"C, one hour), filtered, washed with hexane, and dried, and polymerization was carried out in the same manner as Example 22. The Ti content of-the treated solid catalyst was 3.0% by weight, and the results of polymerization were as follows: Polymer yield, 50 g; catalyst efficiency, 70,000; MI, 0.15; FR, 88; SR, 0.75.

Example 32 The already supported solid synthesized as in Example 23 (not yet subjected to milling) was treated with diethylaluminum chloride (condition of treatment: Ti of the supported solid/AlEt2Cl = 1/5 (molar ratio), 80"C, one hour), filtered, washed with hexane, and dried to obtain treated supported solid. This solid was milled singly in a ball mill in the same manner as in Example 23 to prepare a solid catalyst. Using this solid catalyst, polymerization was conducted according to Example 22. The content of Ti in the solid catalyst was 3.0% by weight and the result of polymerization were as follows: Polymer yield, 49 g; catalyst efficiency, 68,000; MI, 0.20; FR, 83; SR, 0.72.

Example 33 Polymerization conducted employing the same catalyst and the same condition as in Example 22 except for using a gaseous mixture of ethylene-butene- 1 containing 1% of butene-1, in place of ethylene. The results of polymerization were as follows: Polymer yield, 48 g; catalyst efficiency, 65,000; MI, 0.38; FR, 73; SR, 0.75.

Example 34 (i) The procedures of Example 1 were followed for synthesis of hydrocarbon soluble organomagnesium complex, and Preparation of a solid material by the reaction with a chlorosilane compound.

(iii) Preparation of solid catalyst component.

To an autoclave having been purged with nitrogen was charged 2.0 g of the above mentioned solid material 30 ml of titanium tetrachloride. After reaction was conducted with stirring at 1300C for two hours, solid portion was isolated by filtration, washed thoroughly with hexane, and dried, and a pale red-violet solid was obtained. Analysis of this solid showed that it contains 2.5% by weight of Ti and that the specific surface area measured by B.E.T. method was 210 m2/g.

Hexane (100 ml) was placed in an autoclave having been purged with nitrogen and the solid catalyst component obtained above and ethyl benzoate were fed to give a molar ratio of titanium in the solid to ethyl benzoate of 1: 0.2. The mixture was reacted with stirring at 800C for one hour. Thereafter, the solid portion was filtered, washed with hexane, and dried to obtain a final solid catalyst component (a Ti content of 2.3 wt.%).

(iv) Slurry polymerization of propylene.

The final solid catalyst component (100 mg) obtained in (iii), above, and 1.6 mmol of triethylaluminum were charged together with 0.8 liter of hexane into a 1.5-liter autoclave, the inside of which had been purged with nitrogen and deaerated to vacuum. While the temperature inside the autoclave was being maintained at 600C, hydrogen and propylene were presurized to 0.1 kg/cm2 and 5.0 kg/cm2, respectively, so that a total gauge pressure of 4.8 kg/cm2 can be achieved. Polymerization was allowed to proceed for one hour by supplying propylene, while maintaining a total gauge pressure of 4.8 kg/cm2. There were obtained 20 g of a hexane-insoluble polymer and 2.4 g of a hexane-soluble polymer.

The catalyst yield was 1,750 g-pp/g of Ti component-hour-propylene pressure. After the hexane-insoluble polymer was extracted with boiling heptane, the remaining portion was 86.5%.

Example 35 (i) The procedures of Example 1 were followed for Synthesis of a hydrocarbon-soluble organomagnesium complex, and (ii) Synthesis of a solid material by the reaction with a chlorosilane compound.

(iii) Synthesis of a solid catalyst component.

To an autoclave having been purged with nitrogen were added 5.0 g of the solid material synthesized in (ii), above, and 50 ml of titanium tetrachloride. The mixture was reacted with stirring at 1300C for 2 hours. The solid portion was filtered off, isolated, washed fully with hexane, and dried to obtain a supported solid of a light reddish purple color.

The supported solid (4.0 g) and 63 mg of ethyl benzoate were fed under nitrogen atmosphere to a 100-cm3 stainless steel ball mill containing twenty five 9-mm stainless steel balls. The ball mill was vibrated at a speed of 1,000 vib/min or higher for 5 hours, to obtain a ground solid catalyst component. The catalyst had a Ti content of 2.3 wit. %.

(iv) Polymerization of propylene The solid catalyst component (100 mg) synthesized in (iii), above, and 1.6 mmol of triethylaluminum were charged together with 0.8 liter of dehydrated and deaerated hexane into a 1.5-liter autoclave, the inside of which had been purged with nitrogen and deaerated to vacuum. While the temperature inside the autoclave was being maintained at 600C, hydrogen and propylene were pressurized to 0.1 kg/cm2 and 5.0 kg/cm2, respectively, so that a total gauge pressure of 4.8 kg/cm2 could be achieved. Polymerization was allowed to proceed for one hour by supplying propylene, while maintaining a total gauge pressure of 4.8 kg/cm2.

There were obtained 32 g of a hexane-insoluble polymer and 4.2 g of a hexane-soluble portion. The catalyst yield was 2,780 g-PP/g of Ti component-hour-propylene pressure.

After the hexane-insoluble polymer was extracted with boiling heptane, the remaining portion was 84.5%.

Example 36 The same procedures as in Example 1 were followed for (i) synthesis of a hydrocarbonsoluble organomagnesium complex and (ii) synthesis of a solid material by the reaction with a chlorosilane compound.

(iii) Synthesis of a solid catalyst component.

To an autoclave having been purged with nitrogen were fed 2.0 g of the above solid material and 30 ml of titanium tetrachloride. The mixture was reacted with stirring at 130"C for 2 hours. The solid portion was separated by filtration, washed fully with hexane, and dried to obtain a light pink solid. The solid (1.9 g) was taken up in a 200-ml flask having been purged with nitrogen, which was fitted with a waterpcooled reflux condenser. Sixty ml of hexane was added, followed by addition of 1.5 mmol of ethyl benzoate in hexane (0.5 mol/ e).

The mixture was heated to reflux, and the reaction proceeded with stirring for one hour.

After the reaction mixture was left to cool to room temperature, the solid portion was filtered, washed fully with hexane, and dried to obtain a solid catalyst component of a light purple color (S-36). Analysis of the solid catalyst showed that it contains 2.1 wt.% of titanium. The specific surface area measured by the B.E.T. method was 215 m2/g.

(iv) Polymerization of propylene in a solvent The solid catalyst component (200 mg) synthesized in (iii), above, 3.2 mmol of triethylaluminum and 1.2 mmol of ethyl benzoate were charged, together with 0.8 liter of dehydrated and deaerated hexane, into a 1.5-liter autoclave, the inside of which had been purged with nitrogen and deaerated to vacuum. Propylene was pressurized up to a pressure of 5.0 kg/cm so as tq keep the total pressure at 4.8 kg/cm2 gauge, while maintaining the temperature inside the autoclave at 60"C. Polymerization was allowed to proceed for 2 hours, maintaining the above gauge pressure. There were obtained 115 g of a hexaneinsoluble polymer and 4.0 g of a hexane-soluble portion. The catalyst yield was 288 g of PP/g of solid catalyst-hour or 2,740 g of PP/g of Ti component-hour-propylene pressure. The hexane-insoluble polymer was extracted with boiling n-heptane, whereby the remaining portion was 95.6%. The hexane-insoluble polymer had an inherent viscosity of 5.8 dl/g. The characteristics of particles were excellent, showing a bulk density of 0.327 g/cm3 and a proportion of 35 - 150 mesh powder was as good as 92%.

Example 37 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 200 mg of the solid catalyst component synthesized in part (iii) of Example 36 and 3.2 mmol of triethylaluminum. There was obtained 156 g of a hexane-insoluble polymer and 17.6 g of hexane-soluble portion. After the hexane-insoluble polymer was extracted with n-heptane, the remaining portion was 86.1%. The catalyst yield was 390 g of PP/g of solid catalyst component hour or 3,720 g of PP/g of Ti component-hour-propylene pressure.

Example 38 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using a preformed mixture of 1.6 mmol of triethylaluminum in hexane (1 mol/ and 0.8 mmol of ethyl benzoate in hexane (1 mol/e); and 1.6 mmol of triethylaluminum and 200 mg of the solid catalyst component (S-36) prepared in Example 36. There were obtained 152 g of a hexane-insoluble polymer and 5.5 g of a hexane-soluble portion. The catalyst yield was 3,620 g of PP/g of Ti component-hour-propylene pressure. After the hexane-insoluble polymer was extracted with n-heptane, the remaining portion was 94.3%.

Example 39 Liquid propylene (350 g) was charged into a 1.5-liter autoclave, the inside of which had been purged with nitrogen and deaerated to vacuum. The inside temperature was elevated until 60"C. The solid catalyst component (50 mg) synthesized in part (iii) of Example 36, 2.8 mmol of triethylaluminum and 1.0 mmol of ethyl benzoate were then added to the autoclave.

While maintaining the inside temperature at 600C, the polymerization was allowed to proceed for 2 hours, to obtain 101 g of a polymer. The catalyst yield was 1,010 g of PP/g of solid catalyst-component-hour or 48,100 g of PP/g of Ti component-hour. After the polymer was extracted with boiling n-heptane, the remaining portion was 92.5%.

Comparative Example 3 A solid catalyst component was prepared in the same manner as in part (iii), Example 36, using magnesium chloride instead of the solid material prepared in Example 34 by reacting an organomagnesium complex with a chlorosilane compound. The solid catalyst component was synthesized by reacting 2.0 g of anhydrous MgCl2 with 30 ml of titanium tetrachloride at 1300C for 2 hours, filtering, washing and drying the solid portion, then reacting with ethyl benzoate for one hour. The solid catalyst component contained 0.07 wt.% of titanium.

Polymerization was carried out in hexane as a solvent in the same manner as in part (iv), Example 36, using 1.0 g of the solid catalyst component, 3.2 mmol of triethylaluminum, and 1.2 mmol of ethyl benzoate. There were obtained 38 g of a hexane-insoluble polymer and 12 g of a hexane-soluble portion. After the hexane-insoluble polymer was extracted with boiling n-heptane, the remaining portion was 76.5%. The catalyst yield was 19 g of PP/g of solid catalyst component-hour or 5,420 g of PP/g of Ti component-hour-propylene pressure.

Comparative Example 4 In the reaction of an organomagnesium complex with chlorosilane described in part (ii) of Example 1, there was used methyl trichlorosilicon, SiCl3 CH3, instead of HSiCl3. To a 500-ml flask equipped with a dropping funnel and a water-cooled reflux condenser, there was charged under nitrogen atmosphere 100 mmol of SiCl3CH3 in heptane (1 mol/e). The flask was heated to 50"C. Thereafter, 100 mmol of an organomagnesium complex solution synthesized as in part (i) of Example 1 was weighed and taken up into the dropping funnel, and added to the flask dropwise with stirring at 500C over one hour. The mixture was further reacted for one hour at this temperature to form a white precipitate. The precipitate was isolated, washed with hexane and dried to obtain 0.42 g of a white solid substance. Yield of the solid substance was 1/20 as small as in part (ii) of Example 1.

The solid material thus obtained was then reacted with titanium tetrachloride and ethyl benzoate in the same manner as in part (iii), Example 36, to obtain a solid catalyst component. Analysis of this catalyst component showed that it contained 5.6 wt.% of titanium.

Using 200 mg of the solid catalyst component, 3.2 mmol of treithylaluminum and 1.2 mmol of ethyl benzoate, polymerization was carried out in a hexane solvent in the same manner as in part (iv), Example 36. There were obtained 43 g of a hexane-insoluble polymer and 7.3 g of a hexane-soluble portion. After the hexane-insoluble polymer was extracted with nrheptane, the remaining portion was 72.2%. The catalyst yield was 108 g of PP/g of solid catalystcomponent-hour or 380 g of PP/g of Ti component-hour-propylene pressure. The polymer had a bulk density of 0.23 g/cm Example 40 A solid material (1.9 g) synthesized by reacting an organomagnesium complex with trichlorosilane (HSiCl3) as described in part (ii) of Example 1, was placed in a 200-ml flask having been purged with nitrogen and fitted with a water-cooled reflux condenser. Thereto were added 60 ml of hexane and 6 ml (40 mmol) of ethyl benzoate. The mixture was heated to reflux, and the reaction was allowed to proceed with stirring for one hour. The solid portion was filtered off, washed fully with hexane; and dried. The solid is then taken up in an autoclave having been purged with nitrogen and 40 ml of a solution (4 mol TiCl4/liter) of titanium tetrachloride in hexane. The mixture was reacted with stirring at 1300C for 2 hours.

The solid portion was filtered off, washed fully with hexane and dried to obtain a light yellowish white solid catalyst component. Analysis of this catalyst component showed that it contained 2.2 wt. O/o titanium. The specific surface area measured by the B.E.T. method was 207 m2/g.

Using this solid catalyst component (200 mg), 3.2 mmol of triethylaluminum and 1.2 mmol of ethyl benzoate, polymerization was allowed to proceed in the hexane solvent at 600C and at a total gauge pressure of 4.8 kg/cm2 for 2 hours in the same manner as in part (iv), Example 36. There were obtained 122 g of a hexane-insoluble polymer and 4.3 g of a hexane-soluble portion. After the hexane-insoluble polymer was extracted with n-heptane, the remaining portion was 95.3 %. The catalyst yield was 305 g of PP/g of solid catalyst-component-hour or 2,780 g of PP/g of Ti component-hour-propylene pressure. The hexane-insoluble polymer had an inherent viscosity of 5.4 dl/g and a bulk density of 0.334 g/cm3.

Example 41 - 50 Following the procedure of Example 36, but using instead of AlMg6.0(CgH5)2.s(n-C4Hg) 12.1 in part (i), Example 36, the organomagnesium complexes given in Table 2, there were reacted the organomagnesium complex, trichlorosilane (HSiCl3), titanium tetrachloride, and ethyl benzoate to obtain respective solid catalyst components. Using 200 mg of a solid catalyst component, 3.2 mmol of triethylaluminum, and 1.2 mmol of ethyl benzoate, polymerization was allowed to proceed in the hexane solvent in the same manner as in Example 36. Conditions for catalyst synthesis and the results of polymerization are as given in Table 2.

Table 2 Synthesis of solid catalyst component Conditions for the reaction with HSiCI3 Analytical values Organomagnesium compounds Mol ratio Temperature Ti Specific Mg/Si ( C) x (wt.%) surface Time (hour) area Example (m2/g) 41 AeMg6.0Et2.0n-Bus.so-Bu3.s 5/1 50 x 2 2.1 217

H AtMgs.oEt2.0 n-Bu9.1(Oi-Et)3.5 42 Me 2/1 50 x 5 2.6 228 43 AeMg4.oEt2.9(n-C6Hl3)s.o 1/3 50 x 2 1.6 205 44 ZnMg2.oEt2.o n-Bu3.s 1/1 80 x 2 1.8 185 45 BeMg4.oEt o.7n-Pr6.3[N(n-Bu)z]3.0 1/1 80 x 5 2.8 195 46 B Mgl.oEt2.sn-Prl.s(SEt)0.7 1/1 50 x 5 5.5 170 47 n-BuMgCe (Butyl ether solution) 1/1 50 x 2 2.6 183 48 sec-Bu2Mg 1/1 50 x 2 2.7 198 49 n-C4H9MgC2H5 1/1 50 x 2 2.4 182 50 (n-C6H,3)2Mg 1/1 50 x 2 2.5 160 Table 2 (continued) Polymerization results Example Polymer yield Hexane-soluble Residue of Catalyst yield Bulk (g) portion n-heptane- g-PP/g-Ti component- density (g) extraction hour-propylene (g/cm3) of polymer (So) pressure 41 133 9.7 92.2 3160 0.332 42 107 3.8 95.9 2060 0.329 43 97 7.2 92.3 3040 0.279 44 123 11.0 90.7 3420 0.317 45 73 2.3 96.4 1300 0.301 46 83 4.1 94.5 760 0.291 47 90 4.4 95.3 1730 0.302 48 99 3.8 95.6 1830 0.321 49 120 11.7 94.8 2500 0.322 50 112 9.3 95.1 2240 0.331 Example 51 i) Synthesis of a hydrocarbon-soluble organomagnesium complex Di-n-butyl-magnesium (138.0 g) and 19.0 g of triethylaluminum were taken up in a flask having been purged with nitrogen together with l liter of n-heptane. The mixture was reacted with stirring at 800C for 2 hours to obtain an organomagnesium complex solution. Analysis of this complex revealed that it had composition of AlMg6.o(C2H5)2.s(n-C4H9)l2.l and an organometal concentration of 1.16 mol/e.

(ii) Synthesis of a solid material by the reaction with a chlorosilane compound To a 2-liter flask fitted with a dropping funnel and a cooler, having been fully purged with nitrogen, there was charged 200 mmol of a solution of monomethyl dichlorosilane (HSiCl2CH3) in n-heptane (2 mol/ under the stream of nitrogen. While the flask was maintained at 65"C, 100 mmol of the abovementioned solution of an organomagnesium complex was added dropwise over one hour through the dropping funnel. Thereafter, the mixture was reacted at650Cforonehour.Awhite solid material thusformedwasfiltered off, washed with n-hexane and dried to obtain 8.5 g of a white solid (A-51). Analysis of this solid showed that it contained 9.25 mmol Mg, 17.9 mmol Cl, 1.64 mmol Si, and 0.53 mmol alkyl groups per gram of the solid. The specific surface area measured by the B.E.T. method was 281 m /g.

(iii) Synthesis of a solid catalyst component The above white solid (A-51, 5.0 g) was taken up in a flask having been fully purged with nitrogen. Thereto were added 60 ml of n-hexane and 6.0 mmol of a solution of 0.1 mol of ethyl benzoate in one liter of hexane. The mixture was reacted with stirring at 800C for one hour. The solid portion was filtered off, washed fully with n-hexane and dried to obtain white powder (B-S 1).

The above white solid (B-51, 4.5 g) and 60 ml of titanium tetrachloride were charged into an autoclave having been purged with nitrogen. The mixture was reacted with stirring at 100"C for 2 hours. The solid portion was then filtered off, washed with n-hexane and dried to obtain a solid catalyst component of a light yellow color (S-51). Analysis of this catalyst component showed that it had a Ti content of 2.50 wt.%.

(iv) Slurry polymerization of propylene The slurry polymerization of propylene was carried out in the same manner as in Example 36, using the solid catalyst component (S-51,50 mg) synthesized in (iii), above, and 3.2 mmol of triethylaluminum:There were obtained 145 g of hexane-insoluble polymer and 15.7 g of a hexane-soluble portion. After the hexane-insoluble polymer was extracted with n-heptane, the remaining portion was 86.8%. The catalyst yield was 1,450 g of PP/g of solid catalystcomponent-hour or 11,600 g of PP/g of Ti component-hour-propylene pressure.

Example 52 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 40 mg of the solid catalyst component (S-51) synthesized in part (iii), Example 51, 3.2 mmol of triethylaluminum, and 1.2 mmol of ethyl benzoate. There were obtained 107 g of a n-hexane-insolbule polymer and 3.7 g of a n-hexane-soluble portion. The catalyst yield was 8,560 g of PP/g of Ti component-hour-propylene pressure. After the n-hexane-insoluble polymer was extracted with n-heptane, the remaining portion was 96.15'o. The polymer had an inherent viscosity of 5.1 dl/g and a bulk density of 0.335 g/cm3.

Example 53 The slurry polymerization of propylene was carried out in the same manner as in Example 36, using the preformed mixture of 1.6 mmol of a triethylaluminum solution in hexane (1 mol/e) and 0.8 mmol of ethyl benzoate solution in hexane (1 mol/e), 50 mg of the solid catalyst (S-51) synthesized in Example 51, and 0.8 mmol of triethylaluminum. There were obtained 148 g of a hexane-insoluble polymer and 4.8 g of a hexane-soluble portion. After the hexane-insoluble polymer was extracted with n-heptane, the remaining portion was 95.0%. The catalyst yield was 11,800 g of PP/g of Ti component-hour-propylene pressure.

Example 54 Liquefied propylene (350 g) was introduced into a 1.5-liter autoclave having been purged fully with nitrogen and dried in vacuo. While the temperature inside the autoclave was being kept at 60"C, 20 mg of the solid catalyst component (S-51) synthesized in Example 51, 1.6 mmol of triethylaluminum, and 0.6 mmol of ethyl benzoate were added into the autoclave.

Polymerization was carried out with stirring at 60"C for 2 hours, to obtain 130 g of a polymer.

The catalyst yield was 130,000 g of P catalyst component (S-56) thus obtained had a Ti content of 1.87 wt.%.

(v) Propylene polymerization in a solvent The catalyst solid component (100 mg) synthesized in (iv), above, 3.2 mmol of triethylaluminum, and 0.8 liter of dehydrated and deaerated hexane were introduced into a 1.5-liter autoclave, the inside of which had been purged with nitrogen and deaerated in vacuo. While the temperature inside the autoclave was being maintained at 600C, polymerization was carried out for 2 hours by supplying propylene at a pressure of 5.0 kg/cm2 so as to keep a total gauge pressure of 4.8 kg/cm . Results of this polymerization were as given in Table 3.

Example 57 Polymerization was carried out in the hexane solvent in the same manner as in Example 36, using 100 mg of the solid catalyst component synthesized in part (iv), Example 56,1.2 mmol of ethyl benzoate, and 3.2 mmol of triethylaluminum. Results of this polymerization were as given in Table 3.

Example 58 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using a preformed mixture of 1.6 mmol of triethylaluminum in hexane (1 mol/ and 0.8 mmol of ethyl benzoate in hexane (1 mol/f), 100 mg of the solid catalyst component (S-56) synthesized in Example 56, and 0.8 mmol of triethylaluminum. Results of the polymerization were as given in Table 3.

Example 59 Liquid propylene (350 g) was introduced into a 1.5-liter autoclave, the inside of which had been purged with nitrogen and deaerated in vacuo. The inside temperature was elevated up to 60"C. Thereafter, 25 mg of the solid catalyst component synthesized in Example 56, 2.4 mmol of triethylaluminum, and 0.8 mmol of ethyl benzoate were added. Polymerization was carried out for 2 hours, while maintaining the inside temperature at 600C to obtain 112 g of a polymer. The catalyst yield was 2,230 g of PP/g of solid catalyst- component-hour or 119,000 g of PP/g of Ti component-hour. After the polymer was extracted with boiling n-heptane, the remaining portion was 92.8%.

Comparative Example S A solid catalyst component was synthesized in the same manner as in Example 56, using magnesium chloride in place of a solid material prepared by reacting an organomagnesium complex compound with monomethyl-dichlorosilane as described in Example 56. The catalyst had a Ti content of 1.61 wt.%.

Polymerization was carried out in the hexane solvent in the same manner as in Example 36, using 400 mg of the solid catalyst component, 3.2 mmol of triethylaluminum and 1.2 mmol of ethyl benzoate. Results obtained are given in Table 3.

Example 60 A magnesium-containing solid (3.85 g) synthesized as in part (ii), Example 34, 0.23 g of ethyl benzoate and 0.30 g of titanium trichloride (TiCl3.1/3AlCl3 of a AA grade, prepared by Toyo Stauffer Company) were ground under nitrogen atmosphere in a vibrating ball mill for 5 hours. The solid catalyst component obtained had a Ti content of 1.66 wt.%.

Polymerization was carried out in the hexane solvent in the same manner as in Example 36, using 100 mg of the solid catalyst component, 3.2 mmol of triethylaluminum and 1.2 mmol of ethyl benzoate. Results obtained are given in Table 3.

Example 61 A magnesium-containing solid material (3.80 g) synthesized as in part (ii), Example 34, and 0.30 g of titanium trichloride (grade AA, prepared by Toyo Stauffer Company) were ground under nitrogen atmosphere in a vibrating ball mill for 5 hours. A solid catalyst component was obtained by reacting the solid material obtained with ethyl benzoate in the same manner as Example 36. The solid catalyst component thus obtained had a Ti content of 1.71 wt.%.

Polymerization was carried out in a hexane solvent in the same manner as in Example 36, using 100 mg of the solid catalyst component, 3.2 mmoloftriethylaluminum and 1.2 mmolof ethyl benzoate. Results obtained are given in Table 3.

Table 3 Example Yield of Hexane- Residue of Catalyst yield hexane- soluble n-heptane g-PP/g-Ti component insoluble portion extraction hour-propylene polymer (g) of polymer pressure (g) (to) 56 138 11.6 85.8 7380 57 116 4.6 95.4 6200 58 160 6.9 94.3 8560 59 112 - 92.8 (119,000) 60 84 3.7 94.4 5060 61 105 4.4 94.9 6140 Comparat. example 73 6.4 76.5 1130 Example 62 (i) Synthesis of a hydrocarbon soluble organomagnesium complesx Di-n-butylmagnesium (138.0 g), 19.0 g of triethylaluminum and 1 liter of n-heptane were charged into a flask having been purged with nitrogen. The mixture was reacted with stirring at 80"C for 2 hours to obtain a solution of an organomagnesium complex. Analysis of this complex showed that it had composition of AlMg6.0(C2H5)2.s(n-C4Hg) 12.1 and an organometal concentration of 1.16 mol/e.

(ii) Synthesis of a solid material by the reaction with a chlorosilane compound To a 2-liter flask having been fully purged with nitrogen and fitted with a dropping funnel and a cooler, there was charged under nitrogen stream 1 mol of trichlorosilane (HSiC13) in 1 e of n-heptane. The flask was heated to 650C, and 500 mmol of the above organomagnesium complex solution was added dropwise over 1 hour. Reaction was allowed to proceed for additional 1 hour, while maintaining 65"C. A white solid thus formed was filtered off, washed with n-hexane and dried to give 42.4 g of a white solid (A-62). Analysis of this solid showed that it contained 9.21 mmol Mg, 19.15 mmol C1, 1.73 mmol Si, and 0.55 mmol alkyl groups per gram of the solid. The specific surface area measured by the B.E.T. method was 273 m2/g.

(iii) Synthesis of a solid catalyst component.

The above white solid (5.7 g) was introduced into a flask having been fully purged with nitrogen and 60 ml of n-hexane and 4.5 mmol of ethyl benzoate in hexane (0.25 mol/e) were added. The mixture was reacted with stirring at 800C for 1 hour. The solid was then filtered off, washed fully with n-hexane and dried to obtain white powder (B-62).

The above white powder (B-62, 5.0 g) and 40 ml of titanium tetrachloride were charged into an autoclave having been purged with nitrogen. The mixture was reacted with stirring at 1300C for 2 hours. The solid was then filtered off, washed with n-hexane and dried to obtain a yellowish white solid (C-62).

Thereafter, 4.0 g of the solid (C-62) was transferred into a stainless steel mill of 95 mm in diameter and 100 mm long, together with twenty five steel balls having 10 mm in diameter.

The mill was operated at a rate of 1,000 vib/min or higher for 5 hours to give a solid catalyst component (S-62). Analysis of this catalyst showed its Ti content of 2.1 wt.%.

(iv) Slurry polymerization of propylene The solid catalyst component (S-62, 40 mg) synthesized in (iii), above, 2.4 mmol of triethylaluminum and 0.8 liter of fully dehydrated and deaerated n-hexane were charged into a 1.5-liter autoclave, the inside of which had been fully purged with nitrogen and dried in vacuo. While inner temperature was being maintained at 60 C, polymerization was carried out with stirring for 2 hours by supplying propylene at a pressure of 5.0 kg/cm2 so as to keep a total gauge pressure of 4.8 kg/ cm . There were obtained 153 g of a n-hexane-insoluble polymer and 12.3 g of a n-hexane-soluble portion. The catalyst yield was 15,300 g of PP/g of Ti component-hour-propylene pressure. After the n-hexane-insoluble polymer was extracted with n-heptane, the remaining portion was 87.1%.

Example 63 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using the solid catalyst component (S-62, 40 mg) synthesized in part (iii), Example 62, 2.4 mmol of triethylaluminum and 0.8 mmol of ethyl benzoate. There were obtained 124 g of a n-hexane-insoluble polymer and 4.1 g of a n-hexane-soluble portion. The catalyst yield was 12,4000 g of PP/g of Ti component-hour-propylene pressure. After the n-hexane-insoluble polymer was extracted with n-heptane, the remaining portion was 95.8%. The polymer had an inherent viscosity of 5.9 dl/g. As for particle characteristics, the polymer had a bulk density of 0.35 g/cm3 and particles of 35 - 150 mesh occupied as high as 92%.

Example 64 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using a preformed mixture of 1.6 mmol of triethylaluminum in hexane (1 mol/e) and 0.8 mmol of ethyl benzoate in hexane (1 mol/e), 40 mg of the solid catalyst component (S-62) synthesized in Example 62, and 1.6 mmol of triethylaluminum. There were obtained 1 3 g of a hexane-insoluble polymer and 5.8 g of a hexane-soluble portion. After the hexaneinsoluble polymer was extracted with n-heptane, the remaining portion was 94.7%. The catalyst yield was 17,100 g of PP/g of Ti component-hour-propylene pressure Example 65 Liquefied propylene (350 g) was introduced into a 1.5-liter autoclave, the inside of which had been fully purged with nitrogen and dried in vacuo. While the temperature inside the autoclave was maintained at 60"C, there were added 10 mg of the solid catalyst component (S-62) synthesized in Example 62, 1.6 mmol of triethylaluminum, and 0.6 mmol of ethyl benzoate. Polymerization was carried out with stirring at 600C for 2 hours to obtain 108 g of a polymer. The catalyst yield was 257,000 g of PP/g of Ti component-hour. After the polymer was extracted with n-heptane, the remaining portion was 94.5%.

Comparative Example 6 A solid catalyst component was synthesized by using magnesium chloride in place of the solid material obtained in Example 62 by the reaction an organomagnesium complex with a chlorosilane compound. Anhydrous magnesium chloride (5.7 g) was reacted with 4.5 mmol of'an ethyl benzoate solution in the same manner as in Example 62. Resultant product was further reacted with 30 ml of titanium tetrachloride at 1300C for 2 hours and then ground to obtain a solid catalyst component. Analysis of this catalyst showed a Ti content of 0.54 wt.%.

Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 400 mg of the solid catalyst component, 3.2 mmol of triethylaluminum, and 1.2 mmol of ethyl benzoate. There were obtained 38 g of a hexane-insoluble polymer and 15.3 g of a hexane-soluble portion. After the hexane-insoluble polymer was extracted with boiling n-heptane, the remaining portion was 75.8%. The catalyst yield was 47.5 g of PP/g of solid catalyst-component-hour or 1,760 g of PP/g of Ti component-hour-propylene pressure.

Comparative Example 7 In the reaction of an organomagnesium complex with a chlorosilane described in Example 62, there was used 100 ml of a solution of methyltrichlorosilane (CH3Si C13) in 1 mol/e n-heptane in place of TiC13. The temperature was elevated up to 650C. Thereafter, 100 mmol of an organomagnesium complex solution, prepared as in part (i), Example 34, was added dropwise through the dropping funnel at 650C with stirring for 1 hour. The mixture was further reacted for one hour. The solid portion is then filtered off, washed with n-hexane and dried to obtain 0.46 g of a white solid. The yield of solid material was about 1/20 times as small as in part (ii), Example 62.

This solid material was used to synthesize a solid catalyst component in the same manner as in part (iii), Example 62. Analysis of the solid catalyst component showed a Ti content of 5.0 wt.%.

Slurry polymerization of propylene was carried out in the same manner as in Example 36. using 200 mg of the above solid catalyst component, 3.2 mmol of triethylaluminum and 1.2 mmol of ethyl benzoate. There were obtained 51 g of a hexane-insoluble polymer and 8.9 g of a hexane-soluble portion. After the hexane-insoluble polymer was extracted with boiling n-heptane the remaining portion was 72.5%. The catalyst yield was 128 g of PP/g of solid catalyst component-hour or 512 g of PP/g of Ti component-hour-propylene pressure. The hexane-insoluble polymer had a bulk density of 0.24 g/cm3.

Example 66 A solution of an organomagnesium complex (3 mol) synthesized in the same manner as in part (i) Example 62, was introduced into a 2-liter flask. While maintaining the temperature at 65"C. there was added dropwise 1.5 mol of dichloromethylsilane over 1 hour to carry out the reaction with stirring. After the addition is complete, reaction was further allowed to proceed at 650C with stirring for 1 hour. A white solid thus formed was filtered off, washed fully with n-hexane and dried. This solid (4.0 g) was then reacted with ethyl benzoate in the same manner as in Example 62 to synthesize a solid (B-66). which was then reacted with titanium tetrachloride to form a solid (C-66). A solid catalyst component (S-66) was obtained by grinding the solid (C-66) in the same manner as in Example 62. Analysis of the solid catalyst component showed its Ti content of 2.3 wt.%.

Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 40 mg of this solid catalyst component and 2.4 mmol of triethylaluminum. Results obtained were as given in Table 4.

*Example 67 Slurry polymerization of propylene was carried out in the same manner as in Example 36, except that 40 mg of the solid catalyst component synthesized in Example 66, 2.4 mmol of triethyl aluminum and 0.8 mmol of ethyl benzoate were used. Results obtained are given in Table 4.

Example 68 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using a preformed mixture of 1.6 mmol of triethylaluminum in hexane (1 mol/e) and 0.8 mmol of ethyl benzoate in hexane (1 mol/f), 40 mg of the solid catalyst component (S-66) synthesized in Example 66, and 0.8 mmol of triethylaluminum. Results obtained are given in Table 4.

Example 69 To an autoclave having been fully purged with nitrogen, there was charged 3.8 g of a solid material which was synthesized by the reaction of an organomagnesium complex compound with trichlorosilane (HSiCl3) as in part (ii), Example 34. Thereto was added 80 ml of a solution (4.0 mol TiCl4/liter) of titanium tetrachloride in n-hepatane. The mixture was reacted with stirring at 1300C for 2 hours. Thereafter, the solid portion was filtered off, washed fully with n-hexane and dried to obtain a solid (A-69). The solid (1.9 g) was charged into a 200-ml autoclave having been fully purged with nitrogen. Sixty ml of n-hexane and 6 ml of ethyl benzoate were added, and the mixture was heated to a temperature of refluxing.

After the reaction proceeded for 1 hour with stirring, a solid (B-69) was filtered off, washed fully with n-hexane and dried. This solid was ground in the same manner as in Example 62 to obtain a solid catalyst component (S-69). Analysis of this catalyst component showed its Ti content of 2.8 wt.%.

Slurry polymerization of propylene was carried out in the same manner as in Exmaple 36, using 40 mg of the solid catalyst component, and 2.4 mmol of triethylaluminum. Results obtained are given in Table 4.

Example 70 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 40 mg of the solid catalyst component (S-69) synthesized in Example 69, 2.4 mmol of triethylaluminum and 0.8 mmol of ethyl benzoate. Results obtained are given in Table 4.

Table 4 Example Yield of Hexane Residue of Catalyst yield

hexane- soluble n-heptane / g-PP/g-To compo insoluble portion extraction nent-hour-propylene polymer (g) of polymer pressure (g) ( So) 66 145 11.2 86.6 15,800 67 118 3.7 96.0 12,800 68 163 5.3 94.7 17,700 69 140 12.3 85.9 12,500 70 114 4.7 94.4 10,200 Example 71 (i) Synthesis of a hydrocarbon-soluble organomagnesium complex Di-n-butyl magnesium (27.60 g), 3.80 g of triethylaluminum, and 200 ml of hexane were introduced into a 500-ml flask having been purged with nitrogen. The mixture was reacted at 80"C for 2 hours to obtain a solution of an organomagnesium complex. Analysis of this complex showed that it had a composition of AlMg.o)C2H5((n-C4H9)i.i.

(ii) Synthesis of a solid material by the reaction with a chlorosilane compound.

To a 500-ml flask fitted with a dropping funnel and a water-cooled reflux condenser and having been freed of oxygen and moisture by drying and purging with dry nitrogen, there was fed under nitrogen atmosphere 200 mmol of monomethyl-dichlorosilane (HSiC12CH3) in hexane (2 mol/f). The temperature was then elevated to 650C. A hundred mmol of the above organomagnesium complex solution was taken in the dropping funnel by weighing, and added dropwise to monomethyl-dichlorosilane at 65"C with stirring for one hour.

Reaction was allowed to proceed for an additional hour at this temperature. A separated hydrocarbon-insoluble white precipitate was isolated, washed with hexane and dried to obtain 8.6 g of the white solid material. Analysis of this solid showed that it contained 9.27 mmol Mg, 17.7 mmol Cl, 1.65 mmol Si, and 0.51 mmol alkyl groups per gram of the solid.

The specific surface area measured by the B.E.T. method was 285 m2/g.

(iii) Reactions of the Mg-containing solid with a carboxylic acid derivative and titanium tetrachloride.

The above solid (5.0 g), and 4.0 mmol of ethyl benzoate in hexane (0.1 mol/e) were charged into an autoclave having been purged with nitrogen. The mixture was reacted with stirring at 800C for one hour. Thereafter, the solid portion was isolated by filtration, washed fully with hexane and dried to obtain a white solid. Analysis of this solid showed that is contained 0.54 mmol of ethyl benzoate per gram of the solid.

The above solid (4.5 g) and 60 ml of titanium tetrachloride were charged to an autoclave having been purged with nitrogen, and the mixture was reacted with stirring at 1000C for 2 hours. The solid portion obtained was separated by filtration, washed fully with hexane and dried to obtain a light yellow solid.

(iv) Synthesis of a solid catalyst component The solid portion (3.93 g) synthesized in (iii), above, and 0.16 g of titanium trichloride (Grade AA, TiC13. 1/ 3AlCl3, prepared by Toyo Stauffer Company) were charged into a vibration type ball mill with a capacity of 100 cm and containing 25 steel balls having 9 mm in diamter, and ground under nitrogen atmosphere at a rate.of 1,000 vib/min or higher for 5 hours. The solid catalyst component obtained (S-71) had a Ti content of 3.34 wt.%.

(v) Slurry polymerization of propylene Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 40 mg of the solid catalyst component (S-71) synthesized in (iv), above, and 2.4 mmol of triethylaluminum. Results obtained are given in Table 5.

Example 72 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 40 mg of the solid catalyst component (S-71) synthesized in Example 71, 2.4 mmol of triethylaluminum and 0.8 mmol of ethyl benzoate. Results obtained are given in Table 5.

Example 73 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using a preferred mixture of 1.6 mmol of triethylaluminum in hexane (lmol/f) and 0.8 mmol of ethyl benzoate in hexane (1 mol/C), and 30 mg of the solid catalyst component (S-71) synthesized in Example 71, and 0.8 mmol of triethylaluminum. Results obtained are given in Table 5.

Comparative Example 8 A solid catalyst component was synthesized in the same manner as in Example 71, except that magnesium chloride was used in place of the solid material prepared in Example 71 by the reaction of an organomagnesium complex compound with monomethyldichlorosilane.

The solid catalyst component had a Ti content of 1.63 wt.%.

Polymerization was carried out in a hexane solvent in the same manner as in Example 36, using 400 mg of the solid catalyst component, 3.2 mmol of triethylaluminum, and 1.2 mmol of ethyl benzoate. Results obtained are given in Table 5.

Table 5 Example Yield of Hexane- n-Heptane Catalyst yield hexane- soluble extraction g-PP/g-Ti compo insoluble portion residue of ment-hour-propylene polymer (g) polymer pressure (g) 71 158 17.4 86.2 11,800 72 142 4.5 96.1 10,600 73 145 6.2 94.9 14,500 Compara tiveEx.

8 92 8.0 77.8 1,410 Example 74 Liquid propylene (350 g) was charged into a 1.5-liter autoclave, the inside of which had been purged with nitrogen and deaerated to vacuum. The temperature was elevated up to 60"C. The solid catalyst component (S-71) (10 mg) synthesized in Example 71, 2.4 mmol of triethylaluminum, and 0.8 mmol of ethyl benzoate were added. Polymerization was carried out while keeping the inside temperature at 600C for 2 hours to obtain 130 g of a polymer.

The catalyst yield was 6,500 g of PP/ g of solid catalyst component-hour or 195,000 g of PP/g of Ti component-hour. After the polymer was extracted with boiling n-heptane, the remaining portion was 93.3%.

Example 75 A Mg-containing solid (3.85 g) synthesized as in part (ii), Example 71, 0.40 g of ethyl benzoate, 0.50 g of titanium tetrachloride, and 0.15 g of titanium trichloride (Grade AA of Toyo Stauffer Company, TiC13.1/3AlCl3) were ground under nitrogen atmosphere in a vibrating ball mill for 5 hours. The solid catalyst component obtained had a Ti content of 3.31 wt.%.

Polymerization was carried out in a hexane solvent in the same manner as in Example 36, using 40 mg of the solid catalyst component, 2.4 mmol of triethylaluminum and 0.8 mmol of ethyl benzoate. Results obtained are given in Table 6.

Example 76 A magnesium-containing solid (5.0 g) synthesized as in part (ii), Example 71, was first reacted with titanium tetrachloride, then with ethyl benzoate, in the same manner as in Example 71, (iii), to obtain a light purple solid. The solid (3.9 g) and 0.16 g of titanium trichloride (Grade AA, prepared by Toyo Stauffer Company) were ground in nitrogen atmosphere in a vibrating ball mill for 5 hours to give a solid catalyst component. The solid catalyst component obtained had a Ti content of 3.45 wt.%.

Polymerization was carried out in a hexane solvent in the same manner as in Example 36, using 40 mg of the solid catalyst component, 2.4 mmol of triethylaluminum and 0.8 mmol of ethyl benzoate. Results obtained are given in Table 6.

Example 77 A magnesium-containing solid (3.85 g) synthesized as in part (ii), Example 71, 0.35 g of ethyl benzoate and 0.16 g of titanium trichloride (Grade AA, TiCl3.1/3AlCl3, prepared by Toyo Stauffer Company) were ground in nitrogen atmosphere in a vibrating ball mill for 5 hours. The solid obtained (3.8 g) and 60 ml of titanium tetrachloride were charged into a flask, and the mixture was reacted with stirring at 1300C for 2 hours. The solid portion was isolated by filtration, washed fully with hexane and dried to obtain a solid catalyst component. Analysis of this solid showed a Ti content of 3.44 wt.%.

Polymerization was carried out in a hexane solvent in the same manner as in Example 36, using 40 mg of this solid catalyst component, 2.4 mmol of triethylaluminum, and 0.8 mmol of ethyl benzoate. Result obtained are given in Table 6.

Example 78 A magnesium-containing solid (5.0 g) synthesized as in part (ii), Example 71, was reacted with 40 mmol of-ethyl benzoate in the same manner as in part (iii), Example 71. A solid obtained (4.5 g) and 0.25 g of titanium trichloride (Grade AA, prepared by Toyo Stauffer Company) were ground in nitrogen atmosphere in a vibrating ball mill for 5 hours. The resultant solid (4.3 g) and 60 ml of titanium tetrachloride were reacted with stirring at 1300C for 2 hours. The solid portion obtained was isolated by filtration, washed fully with hexane and dried to obtain a solid catalyst component. Analysis of this catalyst component showed a Ti content of 3.47 wt.%.

Polymerization was carried out in the hexane solvent in the same manner as in Example 36, using 40 mg of the solid catalyst component, 2.4 mmol of triethylaluminum and 0.8 mmol of ethyl benzoate. Results obtamed are given in Table 6.

Example 79 A magnesium-containing solid (5.0 g) synthesized as in part (ii), Example 71, and 0.25 g of titanium trichloride (Grade AA, prepared by Toyo Stauffer Company) were ground under nitrogen atmosphere in a vibrating ball mill for 5 hours.

The ground solid (4.8 g) was reacted with ethyl benzoate, then with titanium tetrachloride, in the same manner as in part (iii), Example 71, to obtain a solid catalyst component. Analysis of this catalyst component showed a Ti content of 3.35 wt. %. Polymerization was carried out in a hexane solvent in the same manner as in Example 36, using 40 mg of the solid catalyst component. 2.4 mmol of triethylaluminum and 0.8 mmol of ethyl benzoate. Results obtained are given in Table 6.

Example 80 A magnesium-containing solid synthesized as in part (ii), Example 71 was reacted first with titanium tetrachloride. then with ethyl benzoate, following same procedure as Example 76.

The solid obtained was then ground together with titanium trichloride. The resulting solid (3.5 g) was reacted with 60 ml of titanium tetrachloride with stirring at 130"C for 2 hours. The solid portion was isolated by filtration. washed fully with hexane, and dried to obtain a solid catalyst component. Analysis of this catalyst component showed a Ti content of 4.25 wt. %.

Polymerization was carried out in a hexane solvent in the same manner as in Example 36, using 30 mg of the solid catalyst component, 2.4 mmol of triethylaluminum and 0.8 nimol of ethyl benzoate. Results obtained are given in Table 6.

Example 81 A magnesium-containing solid was reacted first with ethyl benzoate, then with titanium tetrachloride in the same manner as in Example 71, to obtain a solid which was ground together with titanium trichloride. The solid thus obtained (3.5 g) and 60 ml of titanium tetrachloride were reacted with stirring at 1300C for 2 hours. The resultant solid portion was isolated by filtration, washed fully with hexane and dried to obtain a solid catalyst component. Analysis of this catalyst component showed a Ti content of 4.14 wt.%.

Polymerization was carried out in a hexane solvent in the same manner as in Example 36, using 30 mg of the solid catalyst component, 2.4 mmol of triethylaluminum, and 0.8 mmol of ethyl benzoate. Results obtained are given in Table 6.

Table 6 Example Yield of Hexane- n-Heptane Catalyst yield hexane- soluble extraction g-PP/g-Ti compo insoluble portion residue of nent-hour-propylene polymer (g) polymer pressure (g) ( 75 97 4.3 94.4 7330 76 121 4.6 95.2 8770 77 74 3.1 94.7 5380 78 98 3.4 95.6 7060 79 88 3.5 - 95.2 6570 80 136 4.8 95.6 10700 81 161 4.7 96.3 13000 Example 82 (i) Synthesis of a hydrocarbon-soluble organomagnesium complex.

Di-n-butyl-magnesium (138 g), 19.0 g of triethylaluminum and 1 liter of n-heptane were introduced into a 2-liter flask having been purged with nitrogen. The mixture was reacted with stirring at 80"C for 2 hours to obtain a solution of an organomagnesium complex.

Analysis of this complex showed that it had composition of AlMg6.0(C2H5)2.s-(n-C4H9) 12.1 and an organometal concentration of 1.15 mol/e.

(ii) Synthesis of a solid material by the reaction with a chlorosilane compound A nitrogen, and 30 ml of titanium tetrachloride was added. The mixture was reacted with stirring at 1300C for 2 hours. The solid portion was filtered off, washed fully with n-hexane and dried to obtain a solid catalyst component (S-82). Analysis of this catalyst component showed a Ti content of 2.5 wt.%.

(iv) Slurry polymerization of propylene.

The solid catalyst component (30 mg) synthesized in (iii), above, 2.4 mmol of triethylaluminum, and 0.8 liter of fully deaerated and dehydrated hexane were introduced into a 1.5-liter autoclave, the inside of which had been purged with nitrogen and dried in vacuo. While the temperature inside was being maintained at 600 C, polymerization was allowed to proceed for 2 hours by supplying propylene at a pressure of 5.0 kg/cm2 so as to give a total age pressure of 4.8 kg/cm . There were obtained 154 g of a hexane-insoluble polymer and 8.9 g of a hexane-soluble portion. The catalyst yield was 2,570 g of PP/g of solid catalyst component-hour or 20,500 g of PP/g of Ti component-hour-propylene pressure.

After the hexane-insoluble polymer was, extracted with n-heptane the remaining portion was 86.8%.

Example 83 Slurry polymerization of propylene was carried out in the same manner as in Example 36, except that 30 mg of the solid catalyst component (S-82) synthesized in Example 82, 2.4 mmol of triethylaluminum and 0.8 mmol of ethyl benzoate were used. There were obtained 125 g of a n-hexane-insoluble polymer and 4.3 g of a n-hexane-soluble portion. The catalyst yield was 16,700 g of PP/g of Ti component-hour-propylene pressure. After the nhexane-insoluble polymer was extracted with n-heptane, the remaining portion was 95.6%.

The polymer had an inherent viscosity of 5.7 dl/g. As for its particle characteristics, the polymer had a bulk density of 0.35 g/cm3, and the particles of 35 - 150 mesh occupy as much as 91%.

Example 84 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using a solution in which 1.6 mmol of triethylaluminum in hexane (1 mol/ C) and 0.8 mmol of ethyl benzoate in hexane (1 mol/ were mixed in advance, with 30 mg of the solid catalyst component (S-82) synthesized in Example 82, and 0.8 mmol of triethylaluminum. There were obtained 172 g of a hexane-insoluble polymer and 5.6 g of a hexane-soluble portion.

After the hexane-insoluble polymer was extracted with n-heptane, the remining portion was 94.5%. The catalyst yield was 23,000 g of PP/g of Ti component-hour-propylene pressure.

Example 85 Liquefied propylene (350 g) was introduced into a 1.5-liter autoclave, the inside of which had been purged with nitrogen and dried in vacuo. While the temperature inside was maintained at 600 C, 10 mg of the solid catalyst component (S-82) synthesized in part (iii), Example 82, 1.6 mmol of triethylaluminum, and 0.6 mmol of ethyl benzoate were added.

Polymerization was carried out at 600C for 2 hours to obtain 141 g of polypropylene (PP).

The catalyst yield was 7,050 g of PP/g of solid catalyst component-hour or 282,000 g of PP/g of Ti component-hour. The formed polypropylene was extracted with n-heptane, and the remaining portion was 93.7%.

Comparative Example 9 A solid catalyst component was synthesized by using magnesium chloride in place of a solid material prepared in Example 82 by the reaction of an organomagnesium complex compound with a chlorosilane compound. Anhydrous magnesium chloride (5.0 g) was reacted 'with 30 ml of titanium tetrachloride at 1300C for 2 hours in the same manner as in part (iii), Example 82, and then further reacted with 4 mmol of ethyl benzoate in n-heptane at 800C for one hour. The solid obtained was ground and then treated with titanium tetrachloride to obtain a solid catalyst component. Analysis of this solid catalyst component showed a Ti content of 0.42 wt. %. Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 400 mg of the above solid catalyst component, 3.2 mmol of triethylaluminum and 1.2 mmol of ethyl benzoate. There were obtained 41.0 g of a hexaneinsoluble polymer and 12.4 g of a hexane-soluble portion. After the hexane-insoluble polymer was extracted with boiling n-heptane, the remaining portion was 75.5 %. The catalyst yield was 51.3 g of PP/g of solid catalyst component-hour or 2,440 g of PP/g of Ti component-hour-propylene pressure.

Comparative Example 10 In the reaction of an organomagnesium complex with a chlorosilane described in part (ii), Example 82, there was used methyltrichlorosilane (CH3SiC13) in place of,HSiCl3, the same reaction was carried out. A hundred mmol of CH3SiC13 solution in n-heptane (1 mol/ e) was charged into a 500-ml flask having been purged with nitrogen. The temperature was elevated up to 650C, and 100 mmol of an organomagnesium complex solution, synthesized as in (i), Example 82 was added dropwise with stirring at 65oC. Thereafter, the reaction was allowed to proceed for an additional one hour. The solid portion in the reaction mixture was then filtered off, washed with n-hexane, and dried to obtain a solid. This solid was reacted first with titanium tetrachloride, then with an ethyl benzoate solution, in the same manner as in Example 82. The solid obtained was ground and finally treated with titanium tetrachloride to obtain a solid catalyst component. Analysis of this catalyst component showed a Ti content of 5.8 wt.%.

Slurry polymerization of propylene was carried out in the same manner as in Example 36, using the above solid catalyst component (200 mg), 3.2 mmol of triethylaluminum, and 1.2 mmol of ethyl benzoate. There were obtained 52 g of a hexane-insoluble polymer and 7.3 g of a hexane-soluble portion. After the hexane-insoluble polymer was extracted with boiling n-heptane, the remaining portion was 72.2it. The catalyst yield was 130 g of PP/g of solid catalyst component-hour or 448 g of PP/g of Ti component-hour-propylene pressure. The hexane-insoluble polymer had a bulk density of 0.23 g/cm3.

Examples 86- 100 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 30 mg of the solid catalyst component (S-82) synthesized in Example 82, (iii), 2.4 mmol of triethylaluminum and 0.8 mmol of compounds listed in Table 7. Results obtained are giyen in Table 7.

Table 7 Polymerization results Example Compounds Polymer Hexane- n-Heptane Catalyst yield yield soluble extraction (g-PP/g-Ti com (g) portion residue of ponent-hour-propylene (g) polymer pressure) (%) 86 Benzoic acid 124 3.5 95.7 16500 87 p-Toluic acid 118 3.7 96.2 15700 88 Beozoic anhydride 101 5.0 94.8 13500 89 Methyl benzoate 132 4.0 95.2 17600 90 Isopropyl benzoate 126 5.1 93.8 16800 91 n-Butyl benzoate 121 4.4 94.6 16100 92 Methyl p-toluate 127 4.0 95.7 16900 93 Ethyl toluate 130 3.6 95.5 17300 94 Ethyl anisate 115 4.3 94.6 i5300 95 Methyl methacrylate 102 6.2 93.3 13600 96 Methyl maleate 99 4.5 92.9 13200 97 Ethyl n-heptanoate 122 4.1 95.0 16300 98 Methyl terephthalate 108 5.1 95.1 14400 99 Benzoyl chloride 99 4.6 93.2 13200 100 Toluyl chloride 103 5.1 93.4 13700 Example 101 A 2-liter flask fitted with a dropping funnel and a reflux condenser was fully purged with nitrogen. To this flask was charged under a nitrogen stream 1 mol of monomethyldichlorosilane (HSiCl2CH3) in one liter of n-heptane. The temperature was elevated up to 65"C.

A solution of 500 mmol of an organomagnesium complex, synthesized in the same manner as in part (i), Example 82, was added dropwise through the dropping funnel at 65"C over one hour, and then the mixture was reacted at this temperature for one hour. A white precipitate thus formed was filtered off, washed with n-hexane and dried to obtain 41.8 g of a white solid material (A-101). Analysis of this solid showed that it contained 9.23 mmol Mg, 19.0 mmol Cl, 1.80 mmol Si, and 0.61 mmol alkyl groups per gram of the solid. The specific surface area measured by the B.E.T. method was 260m2/g.

Thereafter, 8.0 g of the above white solid (A-101) was taken up in a flask having been purged with nitrogen, and. 240 ml of n-hexane, and 8,0 mmol of ethyl benzoate solution in n-hexane (0.5 mol/e) were added. The mixture was heated to a reflux temperature, and reaction was allowed to proceed with stirring for 1 hour. The solid obtained was filtered off, washed fully with n-hexane and dried to obtain a white solid (B-101).

The above solid (3.0 g) and 30 ml of titanium tetrachloride were charged into an autoclave, and reacted at 1 300C for 2 hours with magnetic stirring. Solid portion was filtered, washed fully with n-hexane to obtain a light yellowish white solid (C-101). The solid obtained was then transferred under a nitrogen stream into a steel mill 95 mm in diameter and 100 mm long, together with 25 steel balls 10 mm in diameter, and was ground on a vibrator for 5 hours. The solid (2.0 g) was taken out of the mill and charged into an autoclave, together with 30 ml of titanium tetrachloride. The mixture was treated at 130 OC with magnetic stirring for 2 hours. The solid portion was filtered, washed fully with n-hexane and dried to obtain solid catalyst component (S-101). Analysis of the solid catalyst showed a Ti content of 2.8 wt.%.

Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 30 mg of the above solid catalyst (S-101) and 2.4 mmol of triethylaluminum. Results obtained are given in Table 8.

Example 102 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 30 mg of the solid catalyst component (S-101) synthesized in Example 101,2.4 mmol of triethylaluminum and 0.8 mmol of ethyl benzoate. Results obtained are given in Table 8.

Example 103 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using a solution of a mixture of 1.6 mmol of triethylaluminum in hexane (1 mol/e) and 0.8 mmol of ethyl benzoate in hexane (1 mol/e), with 30 mg of the solid catalyst component (S-101) synthesized in Example 101, and 0.8 mmol of triethylaluminum. Results obtained are given in Table 8.

Table 8 Example Yield of Hexane- n-Heptane Catalyst yield

hexane- soluble extraction g-PP/g-Ti compo insoluble portion residue of nent-hour-propylene polymer (g) polymer pressure (g) (one) 101 158 8.2 86.8 18.800 102 132 3.6 95.7 16.000 103 182 5.1 94.6 22,100 Examples 104-113 Organomagnesium complexes were reacted with trichlorosilane (HSiCl3), titanium tetrachloride and ethyl benzoate, in the same manner as in parts (ii) and (iii), Example 82, using those organomagnesium complexes listed in Table 9 in place of AlMg6.0(C2H5)2.s(n-C4Hg) 12.1 described in (i), Example 82. Solids thus obtained were ground and further treated with titanium tetrachloride to obtain solid catalyst components. Polymerization was carried out in a hexane solvent in the same manner as in Example 36, using 30 mug of each solid catalyst component, 2.4 mmol of triethylaluminum and 0.8 mmol of ethyl benzoate. Conditions of catalyst synthesis and results of polymerization were as given in Table 9.

Table 9 Solid catalyst component Reaction condition with HSiCI3 Ti content in solid Example Organomagnesium compounds Mol ratio Temperature catalyst mg/Si ( C) x (wt.%) Time (hour) 104 AlMg6.0Et2.0-Bu9.5 O-Bu3.5 5/1 65 x 2 2.7

H AeMg6.oEt2.0 n-Bus.s(O $i-Et)3.s 105 Me 2/1 65 x 5 2.5 106 AeMg4.oEt2.9(n-C6H 13)5.0 1/3 60 x 2 2.9 107 ZnMg2.oEt2.on-Bu3.9 1/1 80 x 2 2.3 108 BeMg4.oEt o.7n-Pr6.3[N(n-Bu)2]3.9 1/1 80 x 5 2.8 109 B M g1.0Et2.8 n-Pr1.5(SEt)0.7 1/1 50 x 5 4.9 110 n-BuMgCe (ether solution) 1/1 65 x 2 2.5 111 sec-Bu2Mg 1/2 65 x 2 2.8 112 n-C,H9Mg C2H5 1/2 65 x 2 2.2 113 (n-C6Hl3)2Mg 1/2 65 x 2 2.1 Table 9 (continued) Polymerization result Example Polymer Hexane n-Heptane Catalyst yield

yield soluble extraction @ g-PP/g-Ti compo- (g) portion residue of nonent-hour-propylene (g) polymer pressure (%) 104 134 9.0 93.1 16500 105 114 3.5 95.8 @ 15200 106 103 6.1 93.4 11800 107 134 10.2 91.2 19400 108 94 3.0 95.7 11200 109 90 4.1 94.7 6100 110 91 3.3 93.5 12100 111 87 4.0 94.8 10400 112 130 11.0 94.5 19700 113 125 9.2 95.7 18100 Examples 114 - 123 An organomagnesium complex synthesized as in Example 82 was reacted with trich lorosilane (HSiCl3) to give a solid material, which was then reacted with titanium tetrach bride to obtain 1.9 g of a solid. This solid was reacted with 1.5 mmol of those compounds listed in Table 10 in place of 1.5 mmol of ethyl benzoate. Each solid thus obtained was ground as in Example 82, then treated with titanium tetrachloride. The solid portion was filtered, washed fully and dried to obtain a solid catalyst component. Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 30 mg of each solid catalyst component, 2.4 mmol of triethylaluminum and 0.8 mmol of a compound used as a liquid catalyst component listed in Table 10. Results obtained were as given in Table 10.

Table 10 Solid catalyst components Polymerization results Compounds Polymer Hexane- n-Heptane Catalyst yield used as yield soluble extraction (g-PP/g-Ti compo Ti liquid (g) portion residue of nent-hour-propylene content catalyst (g) polymer pressure) Example Compounds (%) component (%) 114 Benzoic acid 2.4 - 155 10.4 85.1 21500 115 " " Benzoic acid 126 4.6 94.6 17500 116 Benzoyl chloride 2.6 - 132 12.4 83.3 16900 117 " " Benzoyl chloride 109 4.2 95.1 14000 118 Benzoic anhydride 2.7 - 131 10.6 85.7 16200 119 " " Benzoic anhydride 111 4.7 94.3 13700 120 Ethyl p-toluate 2.5 - 165 7.2 88.0 22000 121 " " Ethyl p-toluate 134 3.3 95.7 17900 122 Methyl methacrylate 2.8 - 139 9.5 85.5 16500 123 " " Methyl methacrylate 116 4.4 95.2 13800 Example 124 A solid substance (B-101, 3.0 g) synthesized in Example 101 and 2.4 mmol of titanium tetrachloride were mixed and ground for 5 hours in a steel mill employed in Example 101.

Thereafter, the solid taken out (2.0 g) and 30 ml of titanium tetrachloride were introduced into an autoclave, and stirred magnetically at 1300C for 2 hours. The solid portion was then filtered, washed fully with n-hexane and dried to'obtain a solid catalyst component (S-124).

Analysis of this solid catalyst component showed a Ti content of 3.0 wt.%.

Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 30 mg of the above solid catalyst component (S-124) and 2.4 mmol of triethylaluminum. Results obtained are given in Table 11.

Example 125 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 30 mg of the solid catalyst component (S-124) synthesized in Example 124,2.4 mmol of triethylaluminum and 0.8 mmol of ethyl benzoate, Results obtained were are in Table 11.

Example 126 Slurry polymerization of polypropylene was carried out in the same manner as in Example 36, using a solution obtained by pre-mixing 1.6 mmol of triethylaluminum in hexane (1 mol/e) and 0.8 mmol of ethyl benzoate in.hexane ( mol/e) with 30 mg of the solid catalyst (S-124) synthesized in Example 124, and 0.8 mmol of triethylaluminum. Results obtained are given in Table 11.

Example 127 (i) Synthesis of a hydrocarbon-soluble organomagnesium complex Di-n-butyl magnesium (138 g), 19.0 g of triethyl aluminum and 1 liter of n-heptane were introduced into a 2-liter flask having been purged with nitrogen. The mixture was reacted at 80"C for 2 hours to synthesize a solution of an organomagnesium complex. Analysis of this complex showed that it had the composition of A1Mgs.o(CzH5)2.9(n-C4Hg) 12.1 and an organometal concentration of 1.16 mol/e.

(ii) Synthesis of a solid material by the reaction with a chlorosilane compound To a 2-liter flask having been fully dried and purged with nitrogen was charged 500 mmol of trichlorosilane (HSiCl3) in n-heptane (1 mol/e), and the temperature was elevated up to 65"C. Five hundred mmol of the organomagnesium complex synthesized in (i) was added dropwise through a dropping funnel with stirring at 650C over 1 hour. Reaction was further allowed to proceed at 650C for an additional hour. A white precipitate thus formed was isolated, washed with n-hexane and dried to obtain 42.3 g of a white solid (A-127). Analysis of this solid showed that it contained 9.20 mmol Mg, 19.21 mmol Cl, 1.70 mmol Si, and 0.57 mmol alkyl groups eer gram of the solid. The specific surface area measured by the B.E.T. method was 274 m /g.

(iii) Synthesis of a solid catalyst component The white solid synthesized in (ii) (20.1 g) and 200 ml of titanium tetrachloride were taken up in an autoclave under a nitrogen stream. The mixture was reacted with stirring for 2 hours.

The solid portion was then filtered, washed fully with n-hexane and dried to obtain a light purple solid (B-127). Analysis of this solid showed a Ti content of 2.1 wt.%.

The above solid (B-127, 10.0 g) was introduced in a vessel having been purged with nitrogen, and thereto were added 600 ml of n-hexane and 15 mmol of ethyl benzoate in n-hexane (0.25 mol/f). The mixture was reacted at 800C with stirring for 1 hour. The solid in the reaction mixture was filtered, washed fully with n-hexane and dried to obtain a light purple solid (C-127). The solid (C-127) was then ground in the same manner as in Example 101, giving 2.0 g of a solid, which was fed together with 20 ml of titanium tetrachloride in an autoclave under a nitrogen stream, and treated with stirring at 1300C for 2 hours. The solid portion was filtered, washed fully with n-hexane and dried to obtain a solid catalyst component (S-127). Analysis of this solid catalyst component showed a Ti content of 3.1 wt.%.

Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 30 mg of the above solid catalyst component (S-127) and 3.2 mmol of triethylaluminum. Results obtained are given in Table 11.

Example 128 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using 30 mg of the solid catalyst component (S-127) synthesized in Example 127,2.4 mmol of triethylaluminum and 0.8 mmol of ethyl benzoate. Results obtained are given in Table 11.

Example 129 Slurry polymerization of propylene was carried out in the same manner as in Example 36, using a solution obtained by mixing in advance 1.6 mmol of ethyl benzoate (1 mol/f), with 30 mg of the solid catalyst component (S-127) synthesized in Example 127, and 0.8 mmol of triethylaluminum. Results obtained are given in Table 11.

Table 11 Example Hexane- Hexane- n-Heptane- Catalyst yield insoluble soluble extraction (g-PP/g-Ti compo polymer portion residue of nent-hour-propylene (g) (g) polymer pressure) (%) 124 150 9.1 85.5 16700 125 128 4.0 95.0 14200 126 172 6.8 94.1 19100 127 136 10.8 83.9 14600 128 116 4.8 94.3 12500 129 159 6.1 93.1 17100 Example 130 The same material as the solid material (B-101) synthesized in Example 101 was synthesized. An amount of 3.0 g was taken up by weighing and introduced in a steel mill used in Example 56, together with 2.4 mmol of titanium tetrachloride. The mixture was ground for 5 hours. The ground solid (2.1 g) and 30 ml of titanium tetrachloride were introduced into an autoclave and the mixture was reacted at 1000C with magnetic stirring for 2 hours. The solid portion was then filtered, washed fully with n-hexane and dried to obtain a solid catalyst component (S-130). Analysis of this catalyst component showed a Ti content of 2.7 wt.%.

Using 10 mg of the above solid catalyst component (S-130), 1.8 mmol of triethylaluminum and 0.6 mmol of ethyl benzoate. the slurry polymerization of propylene was carried out in the same manner as in part (iv), Example 36, except that propylene was charged at a pressure of 10 kg/cm2. There were obtained 120 g of a hexane-insoluble polymer and 4.4 g of hexanesoluble portion. After the hexane-insoluble polymer was extracted with n-heptane, the remaining portion was 95.8%. The catalyst yield was 22,200 g of PP/g of Ti componenthour-propylene pressure. The hexane-insoluble polymer had an inherent viscosity of 5.0 dl/g and a bulk density of 0.328 g/cm3. The polymer contained 2 and 60 ppm of Ti and Cl, respectively.

Examples 131- 133 Slurry polymerization of propylene was carried out in the same manner as in part (iv), Example 36, using 30 mg of a solid catalyst component synthesized as in Example 82, 0.8 mmol of ethyl benzoate, and 2.4 mmol of those organometal compounds listed in Table 12.

Results obtained are given in Table 12.

Table 12 Polymerization results Example Organometal compounds Polymer Hexane n-Heptane Catalyst yield yield soluble extraction (g-PP/-Ti compo portion residue of nent-hour-propylene polymer pressure) (g) (g) ( ) Diethylaluminum 131 hydride 122 5.5 94.6 16300 132 Tri-isobutylaluminum 160 7.1 91.0 21300 AtMg6(C2H5)2.9- 133 (n-C4H9)12.1 114 6.0 92.2 15200 Example 134 Polymerization was carried out, using 30 mg of the solid catalyst component (S-124) synthesized in Example 124 and 2.4 mmol of triethylaluminum, and following the same procedure as Example 36. except that a propylene-ethylene gas mixture containing 2 mol % of ethylene was used in place of propylene. There was obtained 14g of a white polymer.

Example 135 Slurry polymerization of a propylene-ethylene mixture was carried out in the same manner as in Example 36, using 30 mg of the solid catalyst component (S-124) synthesized in Example 124, 2.4 mmol of triethylaluminum, 0.8 mmol of ethyl benzoate and a propyleneethylene gas mixture containing 2 mol % of ethylene. There was obtained 133 g of a white polymer.

Example 136 Polymerization was carried out, using 30 mg of the solid catalyst component (S-124) prepared in Example 124 and 2.4 mmol of triethylaluminum, and following the same procedure as in Example 36, except that a propylene-butene-1 gas mixture containing 2 mol % of butene- 1 was used in place of propylene. There was obtained 120 g of a white polymer.

Example 137 Polymerization was carried out, using 30 mg of the solid catalyst component (S-124) synthesized in Example 124 and 2.4 mmol of triethylaluminum, and following the same procedure as in Example 36, except that a propylene-4-methylpentene-1 gas mixture containing 2 mol % of a 4-methylpentene-1 was used in place of propylene. There was obtained 111 g of a white polymer.

Example 138 Polymerization of butene-1 was carried out in hexane in the same manner as in Example 36, using 400 mg of the solid catalyst component synthesized in (iii) of Example 36 and 6.0 mmol of triethylaluminum. There was obtained 36.7 g of a white polymer.

Example 139 Polymerization of butene-1 was carried out in hexane in the same manner as in Example 36, using 400 mg of the solid catalyst component synthesized in Example 56 and 6.0 mmol of triethylaluminum. There was obtained 86 g of a white polymer.

Example 140 Polymerization of butene-1 was carried out in hexane in the same manner as in Example 36, using 200 mg of the solid catalyst component (S-62) synthesized in Example 62 and 5.0 mmol of triethylaluminum. There was obtained 101 g of a white polymer.

Example 141 Polymerization of butene- 1 was carried out in hexane in the same manner as in Example 36, using 200 mg of the solid catalyst component synthesized as in Example 71 and 6.0 mmol of triethylaluminum. There was obtained 131 g of a white polymer.

Example 142 Polymerization of butene- 1 was carried out in hexane in the same manner as in Example 36, using 200 mg of the solid catalyst component (S-124) synthesized in Example 124 and 5.0 mmol of triethylaluminum. There was obtained 146 g of a white polymer.

Example 143 Polymerization of butene-1 was carried out in hexane in the same manner as in Example 36, using 200 mg of the solid catalyst component (S-124) synthesized in Example 124, 5.0 mmol of triethylaluminum and 1.2 mmol of ethyl benzoate. There was obtained 130 g of a white polymer.

Example 144 Polymerization of 4-methylpentene-1 was carried out in hexane in the same manner as in Example 36. using 400 mg of the solid catalyst component synthesized in Example 36 and 6.0 mmol of triethylaluminum. There was obtained 30.2 g of a white polymer.

Example 145 Polymerization of 4-methylpentene-1 was carried out in hexane in the same manner as in Example 36. using 400 mg of the solid catalyst component prepared in Example 56 and 6.0 mmol of triethyl aluminum. There was obtained 64 g of a white polymer.

Example 146 Polymerization of 4-methylpentene- 1 was carried out in hexane in the same manner as in Example 36. using 200 mg of the solid catalyst component (S-62) synthesized in Example 62 and 5.0 mmol of triethylaluminum. There was obtained 88 g of a white polymer.

Example 147 Polymerization of 4-methylpentene-1 was carried out in hexane in the same manner as in Example 36. using 200 mg of the solid catalyst component synthesized as in Example 71 and 6.0 mmol of triethylaluminum. There was obtained 93 g of a white polymer.

Example 148 Polymerization of 4-methylpentene-1 was carried out in hexane in the same manner as in Example 36, using 200 mg of the solid catalyst component (S-124) synthesized in Example 124 and 5.0 mmol of triethylaluminum. There was obtained 108 g of a white polymer.

Example 149 Polymerization of 4-methylpentene-1 was carried out in hexane in the same manner as in Example 36. using 200 mg of the solid catalyst component (S-124) synthesized in Example 124, 5.0 mmol of triethylaluminum and 1.2 mmol of ethyl benzoate. There was obtained'94 g of a white polymer.

Claims (26)

WHAT WE CLAIM IS:

1. A catalyst for polymerizing olefins comprising (A) A solid catalyst component comprising (1) a magnesium solid component, (2) a titanium and/or a vanadium compound having at least one halogen atom, and optionally (3) carboxylic acid or derivative thereof, wherein the magnesium solid component (1) is obtained by reacting i) an organomagnesium compound having the general formula MnMgssR tpR2qXrYs wherein a isO or a number greater than 0; p and p are each numbers greater than 0; q, rand s are each 0 or a number greater than 0, having the relationship p +q +r +s =ma +2p; Mis a metal of Groups I, II or III of the periodic Table, m is a valency of M; R l and R2 are the same or different hydrocarbon groups having 1 to 20 carbon atoms; X and Y are the same or different groups selected from halogen, OR3, OSiR4R5R6, NR7R8 or SR9, and R3, R4, R5, R6, R7 and R are each hydrogen or a hydrocarbon radical, and R9 is a hydrocarbon group, with ii) a chlorosilane containing at least one Si-H bond and having the general formula HaSiClbR4.(a+b) wherein a and b are numbers greater than 0 having the relationship a + b < 4 and a < 2 and R is hydrocarbon or chlorophenyl group, (B) an organometallic compound containing a metal of groups I, II, or III of the Periodic Table, and optionally (C) a carboxylic acid or derivative thereof.

2. A catalyst useful for polymerizing olefins according to claim 1 wherein said organomagnesium component (i) is a hydrocarbon soluble organomagnesium complex compound wherein a is a number greater than 0, M is a metal selected from aluminum, boron, zinc, and beryllium atoms; X and Y each does not contain halogen.

3. A catalyst useful for polymerizing olefins according to claim 1 or 2 wherein the ratio of ss/a is in the range of 0.5 - 10.

~

4. A catalyst useful for polymerizing olefins according to claim 1 wherein said organomagnesium compound is a hydrocarbon soluble organomagnesium compound wherein a is 0; X and Y each do not contain halogen.

5. A catalyst useful for polymerizing olefins according to any of claims 1 to 4 wherein the ratio of (r+s)/(a+p)'is inthe range of 0 - 0.8.

6. A catalyst useful for polymerizing olefins according to any one of claims 1 to 5 wherein R in-said chlorosilane compound containing Si-H bond (ii) is an alkyl group containing 1 - 10 carbon atoms.

7. A catalyst useful for polymerizing olefins according to any one of claims 1 to 6 wherein said titanium and/or vanadium compound (2) is a compound containing at least 3 halogen atoms.

8. A catalyst for polymerizing olefins according to any one of claims 1 to 6 wherein said titanium and/or vanadium compound (2) is titanium tetrachloride or titanium trichloride.

9. A catalyst for polymerizing olefins according to any one of claims 1 to 8 wherein said organometallic compound [B] is a hydrocarbon-soluble organomagnesium complex compound having the general formula M,MgsR'pRZqXrYs wherein a and p are numbers greate than 0, having the ratio of P/ a in the range of 0.1 - 10; p is a number greater than 0; q, rand s are 0 or numbers greater than 0 having the relationship of p+q+r+s=ma+2p, 0 < (r +s)/(a +p) < 1.0; Misa metal selected from aluminum, boron, zinc, and beryllium; m is a valency of M; R' and R2 are the same or different hydrocarbon groups having 1 - 10 carbon atoms; X and Y are same or different groups indicating OR3, OSiR4R5R6, NR7R8 or SR9 wherein R3, R4, R5, R6, R7 and R3 are hydrogen atom or a hydrocarbon group having 1 10 carbon atoms and R9 is a hydrocarbon group having 1 - 10 carbon atoms.

10. A catalyst useful for polymerizing olefins according to claim 9 wherein M in said organomagnesium complex compound [B] is aluminum.

11. A catalyst useful for polymerizing olefins according to any one of claims 1 to 8 wherein said organometallic compound [B] is an organoaluminum compound having the general formula AeR'tOZ3-t wherein Rl is a hydrocarbon group having 1 - 20 carbon atoms (inclusive); Z is a member selected from hydrogen, halogen, alkoxy, aryloxy and siloxy and t is a number of 2 - 3 (inclusive).

12. A catalyst useful for polymerizing olefins according to claim 11 wherein said organoaluminum compound is a trialkylaluminum or dialkylaluminum hydride.

13. A catalyst useful for polymerizing olefins according to any one of claims 1 to 12 wherein said carboxylic acid or its derivative (3) or (C) is a carboxylic acid, carboxylic halide, carboxylic anhydride or carboxylic acid ester.

14. A catalyst useful for polymerizing olefins according to any one of claims 1 to 12 wherein the amount of carboxylic acid or its derivative (3) used is in an amount of 0.001 mol 50 mol relative to one mol of alkyl group contained in said magnesium solid component (1).

15. A catalyst useful for polymerizing olefins according to any one of claims 1 to 12 wherein a said solid catalyst component [A] is formed by reacting and/or grinding a said magnesium solid component (1) with a titanium and/or vanadium compound having at least one halogen atom (2).

16. A catalyst useful for polymerizing olefins according to claim 15 wherein the reaction of said magnesium solid component (1) and a titanium and/or vanadium compound (2) is carried out at a temperature of 100"C or higher in the presence of liquid phase and at a concentration of titanium compound and/or vanadium compound of 4 niol/t or more.

17. A catalyst useful for polymerizing olefins according to any one of claims 15 to 16 wherein the method for subjecting said magnesium solid component (1) and said titanium and/or vanadium compound (2) to grinding to effect contact therebetween is the method in which reaction and grinding are performed simultaneously or sequentially.

18. A catalyst useful for polymerizing olefins according to any one of claims 15 - 17 wherein said solid catalyst component (A) is further treated with a treating agent selected from inorganic or organo-aluminum, tin or silicon halides.

19. A catalyst useful for polymerizing olefins according to any one of claims 1 to 14 wherein a said solid catalyst component [A] is obtained by reacting and/or grinding a said magnesium solid component (1) together with a titanium compound containing at least one halogen atom (2) and a carboxylic acid or its derivative (3).

20. A catalyst useful for polymerizing olefins according to any one of claims 1 to 14 wherein said solid catalyst component (A) is synthesized by subjecting said solid material (1), said titanium compound containing at least one halogen atom (2) and said carboxylic acid or its derivative (3) to reaction and/or grinding and then further treated with a tetravalent titanium compound containing at least one halogen atom (4).

21. A catalyst useful for polymerizing olefins according to claim 20 wherein said tetravalent titanium compound containing at least one halogen atom (4) is a titanium tetrachloride.

22. A catalyst useful for polymerizing olefins according to any one of claims 19 to 21 wherein the organometallic compound component (B) is used in combination with the carboxylic acid or its derivative (C).

23. A catalyst useful for polymerizing olefins substantially as described in any one of the Examples excluding Comparative examples.

24. A method for polymerizing olefins in the presence of a catalyst, in which a catalyst according to any one of Claims 1 to 22 is used.

25. A method according to Claim 4 substantially as described in any one of the Examples excluding Comparative examples.

26. A poly-olefin obtained by a process according to Claim 24 or 25.