JPS6124402B2 - - Google Patents

Description

[Detailed description of the invention]

[] Background of the Invention The present invention relates to a so-called Ziegler type catalyst. In another aspect, the present invention relates to a method for producing the transition metal component. According to the present invention, a highly active catalyst for olefin polymerization can be obtained. Olefin polymerization catalysts, generally known as Ziegler-type catalysts, are a combination of a transition metal component and a reducing organic component. However, for example, a combination of titanium trichloride and diethylaluminium chloride does not necessarily have a sufficiently high catalytic activity, resulting in a large amount of catalyst residue in the produced olefin polymer. Any attempt to improve it would require complicated purification processes such as catalytic decomposition with alcohol and neutralization with alkali. For this reason, highly active catalysts are desired, but improvement in catalytic activity seems to be primarily aimed at improving the transition metal component, and one such improvement is the use of magnesium compounds as a carrier. There is something to do. However, although catalysts containing titanium trichloride as a transition metal component and using a magnesium compound as a carrier are significant in terms of high activity per transition metal, many catalysts still have insufficient activity per carrier. It is desirable that the catalyst activity not only be high per transition metal but also high per support. As one such supported catalyst, one has been proposed that consists of a component made by blending magnesium dihalide pretreated with an electron donor, a silicon or tin halide, and a transition metal compound, and an organometallic compound. (Refer to Japanese Patent Application Laid-open Nos. 49-72383 and 88983). This known catalyst has high activity including the activity per carrier and is therefore preferred. The present inventors have also proposed a supported transition metal catalyst component prepared in a specific manner (Japanese Patent Application Laid-Open No.
No. 4295). [] Summary of the Invention The purpose of the present invention is to solve the above-mentioned problems and obtain a highly active catalyst, and attempts to achieve this purpose by using a supported transition metal catalyst component prepared in a specific manner. It is something. Therefore, the olefin polymerization catalyst according to the present invention is
It is characterized in that it is a combination of a catalyst component () which is a contact product of component A and component B described below and an organoaluminum compound (). Ingredient A Contains magnesium and titanium, and the following ingredients
A solid composition precipitated from a solution consisting of (1), (2) and (3). (1) A magnesium compound that can be represented by the general formula Mg(OR ¹ ) _2-o X _o (where R ¹ is alkyl, aryl or cycloalkyl having 1 to 10 carbon atoms, 0<n≦2), (2) a titanium compound represented by the general formula Ti( ^OR2 ) ₄ (where ^R2 is the same or different number of carbon atoms as ^R1) ,
~10 alkyl, aryl or cycloalkyl); (3) an electron-donating compound selected from alcohols and silanols; Component B (4) Liquid titanium halogen compound. Effect Using the Ziegler type catalyst according to the present invention, α-
When olefin is polymerized, the amount of polymer produced per transition metal and the amount of polymer produced per carrier are both higher than the above-mentioned known catalysts. The reason why a Ziegler catalyst with such high activity per transition metal and per carrier can be obtained using the catalyst of the present invention is not necessarily clear, but unlike the case of the above-mentioned known catalyst, components (1) and (3) are It is presumed that part of the reason for this is that it dissolves well in 2) to form a homogeneous solution, and the homogeneous solid precipitated from this solution is used as a component of the supported transition metal catalyst component. The feature of the present invention in that the carrier containing the magnesium compound is obtained by precipitating the magnesium compound from its solution makes it easier to control the particle size of the carrier than in the case of using conventional inherently solid carriers, and to reduce the amount of titanium in liquid form. The advantage is that it is easy to support the halogen compound on the carrier, but this advantage is not only advantageous in catalyst production, but also in terms of controlling the granularity of the produced polymer. . In other words, the particle size and distribution of the produced polymer are extremely important factors in industrial production; if the particle size is too small or too large, major problems such as clogging of pipes will occur, If the distribution is wide, the fluidity of the polymer will be poor. This problem can be effectively solved by controlling the properties of the catalyst used, but in the present invention, since the magnesium compound in the carrier is sufficiently dissolved before precipitation, this point can be easily and effectively controlled. It can be done. [] Detailed description of the invention The catalyst component () according to the invention consists of a contact product of component A and component B. 1 Component A Component A is a homogeneous mixture of components (1) to (3), that is, one precipitated from a solution. (1) Component (1) A magnesium compound that can be represented by the general formula Mg(OR ¹ ) _2-o X _o . Here, R ¹ is alkyl, preferably 1 to 4 carbon atoms, or cycloalkyl, preferably 4 to 10 carbon atoms, especially 5 to 8 carbon atoms, or aryl. , preferably phenyl, tolyl or xylyl. X is halogen, preferably chlorine. n is 0<
It is a number (not necessarily an integer) that satisfies n≦2. Specific examples of such magnesium compounds include magnesium dihalides, such as MgF ₂ , MgCl ₂ , MgBr ₂ , MgI ₂ , halohydrocarbyloxymagnesium, such as Mg
(OC ₂ H ₅ )Cl, Mg(OC ₆ H ₅ )Cl, and others. Mixtures of these are also suitable. Such a magnesium compound may be any compound that can be represented by the above formula. Therefore, for example, a mixture of MgCl ₂ and Mg(OC ₂ H ₅ ) ₂ is also considered a magnesium compound (component (1)) in the present invention.
included in Particularly preferred in the present invention is MgCl ₂ (the amount of component (1) to be used will be described later). (2) Component (2) A titanium compound represented by the general formula Ti(OR ² ) ₄ . Here, R ² is an alkyl, aryl or cycloalkyl having 1 to 10 carbon atoms, which is the same as or different from R ¹ (the preferred ones among these are the same as those described above for R ¹ ). Specific examples of such compounds include:
Ti(O-iC ₃ H ₇ ) ₄ , Ti(O-nC ₈ H ₇ ) ₄ , Ti
(O-nC ₄ H ₉ ) ₄ , Ti (O-iC ₄ H ₉ ) ₄ , Ti
(OC ₆ H ₅ ) ₄ etc. Preferred is Ti(O
−nC ₄ H ₉ ) ₄ (the amount of component (2) used will be described later). (3) Component (3) An electron-donating compound (hereinafter referred to as electron donor) selected from alcohols and silanols. Specifically, for example, there are the following. (b) Alcohols: about 1 to 20 carbon atoms, preferably 3 to 4
, monohydric or polyhydric alcohols (up to tetrahydric degree), ether alcohols, ester alcohols such as methanol,
Ethanol, isopropanol, n-butanol, hexanol, octanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoacetate, and others. (b) Silanols Silanols having about 1 to 20 carbon atoms in total, such as trimethylsilanol, dimethylsilanediol, phenylsilanetriol, and others. (The amount of component (3) used is described later). (4) Preparation of solutions of components (1) to (3) Components (1) and (3) are dissolved in component (2) to obtain a homogeneous solution. By mixing components (1) to (3) in amounts that will give such a homogeneous solution (see details later) and stirring at an appropriate temperature, for example, 0 to 200°C, preferably 50 to 150°C, the desired solution can be obtained. is obtained. The solution usually consists of only these three components, but if desired, the solution (which is generally viscous) containing only these three components may contain a diluent such as certain hydrocarbons, halogenated hydrocarbons, etc. (e.g. n-heptane, n-
Hexane, benzene, toluene, n-butyl chloride, 1,2-dichloroethane, 1,4
-dichlorobutane, carbon tetrachloride, chlorobenzene, etc.) may also coexist. A solution consisting of components (1) to (3) is generally colorless to pale yellow. (5) Precipitation from solution Component A of the catalyst component () for olefin polymerization according to the present invention is a magnesium and titanium-containing solid precipitated from a solution of the above components (1) to (3). The precipitation can be carried out in various ways (although the resulting catalytic activity is not necessarily the same). One method consists of lowering the temperature of the solution. Another method is to use a non-solvent for the magnesium- and titanium-containing solids to be precipitated, such as certain hydrocarbons (e.g.
-heptane, n-hexane, benzene, toluene, etc.). Another method of precipitation consists of adding certain halogen compounds. As the halogen compound, silicon or tin halogen compounds are particularly preferred. Specifically, for example, _SiCl4 , _CH3SiCl3 , _{SiHCl3 , SnCl4} ,
CH ₃ SnCl ₃ etc. Precipitating agents made of halogen compounds may react with the titanium compound of component (2) and precipitate together with the target magnesium- and titanium-containing solids, and may also act as the above-mentioned non-solvent for the precipitated solids. There is also. Precipitation using a precipitating agent consisting of such a halogen compound is carried out when the solution of components (1) to (3) has a temperature of −50 to
The precipitating agent may be added dropwise at a temperature of about 150°C, preferably about 0 to 100°C, and stirred as appropriate. The dropping of the precipitating agent and/or stirring after dropping is preferably carried out for about 0.5 to 5 hours. Precipitation should be carried out at the temperature and pressure conditions in which the solution is present. Among these precipitation methods, the method of adding a halogen compound is particularly preferred. The precipitated solids are sufficiently finely divided, but may be ground if desired. In addition, suitable additives such as electron donor compounds may be added during pulverization, and modification or ripening by heating may also be carried out. 2. Component B Component B, which is brought into contact with component A as described above to produce the catalyst component () according to the invention, is a liquid titanium halogen compound. Here, "liquid" includes not only those that are liquid themselves (including those that are complexed to become liquid) but also those that are liquid as a solution. Typical compounds include the general formula Ti
⁽ OR ^{3 )} ₄ ^- _o or different halogens, n is 0<n≦4
(indicating the number of ). Specific examples include TiCl ₄ , TiBr ₄ , Ti(O
_-nC4H9 ) _{Cl3 ,} Ti(O- _nC4H9 ) _{2Cl2 , Ti} (O
−nC ₄ H ₉ ) ₃ Cl, Ti(O−iC ₃ H ₇ ) ₃ Cl, Ti(O−
iC ₃ H ₇ ) ₂ Cl ₂ , Ti(O-iC ₃ H ₇ )Cl, Ti(O-
Examples include C ₆ H ₅ ) ₃ Cl, Ti(OC ₆ H ₅ ) ₂ Cl ₂ , and the like. 3. Contact between component A and component B The catalyst component () according to the present invention is obtained by contacting component A and component B as described above. The contact between the two can be carried out by any method that can be used to bring the magnesium-containing solid carrier and the liquid titanium compound into contact. Generally, both components may be brought into contact at a temperature range of -50°C to 200°C. The contact time is usually about 10 minutes to 5 hours. The contact between the two components is preferably carried out under stirring, and the contact between the two components can also be further completed by mechanically grinding with a ball mill, vibration mill, or the like. Contact of both components can also be carried out in the presence of a dispersion medium. Examples of the dispersion medium in this case include hydrocarbons, halogenated hydrocarbons, and the like. Specific examples of hydrocarbons include hexane, heptane, benzene, toluene, and cyclohexane, and specific examples of halogenated hydrocarbons include n-butyl chloride, n-butyl bromide, n-butyl iodide, chlorobenzene, and chloride. Examples include n-octyl, n-decyl chloride, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, benzyl chloride, benzylidene chloride, iodobenzene, and the like. In order to sufficiently support component B on component A, an organometallic compound, especially an organoaluminum compound, in a molar ratio of 0.5 to 5, preferably approximately equimolar amount to component (4), before or after the contact of both components, is added. can be added. 4 Amount Ratio The amount of each component to be used may be arbitrary as long as the effect of the present invention is observed, but it is generally preferred to be within the following range. (a) The amount of Ti (OR) ₄ (component (2)) used is Mg
(OR) 0.1 molar ratio to _2-o X _o (component (1))
It may be within the range of ~200, more preferably 1
~100. (b) The amount of electron donor (component (3)) used is Mg
(OR) 0.1 molar ratio to _2-o X _o (component (1))
It is preferably within the range of ~40, more preferably
It is between 0.5 and 20. (c) The amount of silicon or tin halogen compound to be used is the molar ratio to the total of Ti(OR) ₄ (component (2)) and electron donor (component (3)) used.
It is preferably within the range of 0.1 to 100, more preferably within the range of 0.3 to 10. (d) The amount of liquid titanium halogen compound (component (4)) to be used is preferably within the range of 0.1 to 100 in molar ratio to Mg(OR) _2-o X _o (component (1)), and Preferably it is within the range of 0.5-20. 5 Polymerization of α-olefins (1) Formation of catalyst The catalyst component ( ) according to the present invention can be used in the polymerization of α-olefins in combination with an organoaluminum compound ( ) as a cocatalyst. Specific examples of organoaluminum compounds used as cocatalysts include the general formula
R ⁴ _3-o AlX″ _o or R ⁵ _3-n Al(OR ⁶ ) _n (where
R ⁴ , R ⁵ , and R ⁶ are hydrocarbon residues having 1 to 20 carbon atoms, which may be the same or different, X″ is a halogen atom, and n and m are each 0n
The number is 2.0m1. ). Specifically, (a) trimethylaluminum,
Trialkylaluminum such as triethylaluminum, triisobutylaluminum, trioctylaluminum, tridecylaluminum, (b) Alkylaluminium halide such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, (c) Examples include alkyl aluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum butoxide, and diethylaluminium phenoxide. These organoaluminum compounds (a) to (c) can be used in combination within each group, within each group, and between each group, and organometallic compounds other than these organoaluminum compounds, such as R ⁵ _3-n Al An alkyl alkoxide represented by (OR ⁶ ) _n (1<m<3) can also be used in combination. For example, a combination of triethylaluminum and diethylaluminum monochloride, a combination of diethylaluminum monochloride and diethylaluminium ethoxide, a combination of diethylaluminum monochloride and ethylaluminum diethoxide, a combination of triethylaluminum, diethylaluminum monochloride, and diethylaluminum ethoxide. For example, it can be used in combination with The amount of these organometallic compounds to be used is not particularly limited, but it is preferably within the range of 0.5 to 1000 in weight ratio to the solid catalyst component of the present invention. (2) α-Olefin The α-olefin polymerized using the catalyst system of the present invention has the general formula R-CH=CH ₂ (where R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and a substituent ). Specifically, for example, ethylene, propylene, butene-1, pentene-1
1, hexene-1,4-methyl-pentene-
There are olefins such as 1. Particularly preferred are ethylene and propylene. Mixtures of these α-olefins can be used, for example in the case of ethylene polymerization, copolymerization with up to 20 weight percent, preferably 10 weight percent, of the α-olefins, based on ethylene, can be carried out. In addition, copolymerizable monomers other than the above α-olefin (e.g. vinyl acetate, diolefin)
It is also possible to perform copolymerization with. (3) Polymerization The catalyst system of the present invention is of course applicable to ordinary slurry polymerization, but it can also be applied to liquid-phase solvent-free polymerization or gas-phase polymerization, which uses substantially no solvent, and continuous polymerization. It is applicable to both batch polymerization and prepolymerization.
As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, pentane, cyclohexane, benzene, and toluene may be used alone or in mixtures.
Polymerization temperature is about room temperature to 200℃, preferably 50℃
~150°C, and hydrogen can be used as an auxiliary molecular weight regulator. 6 Experimental Examples Example 1 Manufacture of catalyst component Into a 500 ml flask that had been replaced with _N2 , put 100 ml of thoroughly degassed n-heptane, and then add MgCl ₂
0.05 mol of Ti(O-nC ₄ H ₉ ) 4 and 0.1 mol of Ti(O-nC 4 H 9 ) ₄ were introduced, and 0.3 mol of EtOH (ethanol) was introduced, and when the temperature was raised to 90°C and stirred for 2 hours, it was completely dissolved. The solution became homogeneous. temperature
The temperature was lowered to 70°C, 0.3 mol of SiCl ₄ was introduced, and the mixture was stirred for 1 hour. A fine solid (component A) precipitated. Next, 0.9 mol of TiCl ₄ (component B) was introduced and stirred for 2 hours. The obtained solid was thoroughly washed with n-heptane and used as a catalyst component. The Ti content in the catalyst component was measured by colorimetric method and was found to be 8.2% by weight. Polymerization of ethylene After repeating vacuum-ethylene displacement several times in a stainless steel autoclave with an internal volume of 1.5 liters equipped with a stirring and temperature control device, 800 ml of thoroughly dehydrated and deoxygenated n-heptane was fed, followed by 100 mg of triethylaluminum, 4.0 mg of the catalyst component synthesized above was introduced. The temperature was raised to 85° C., and hydrogen was introduced at a partial pressure of 4.5 Kg/cm ² and ethylene was introduced at a partial pressure of 4.5 Kg/cm ² to make the total pressure 9 Kg/cmG. Polymerization was carried out for 1 hour. These were kept under the same conditions during the polymerization. However, as the polymerization progressed, the pressure decreased and was kept constant by introducing only ethylene. After the polymerization was completed, ethylene and hydrogen were purged and the contents were taken out from the autoclave, and the polymer slurry was filtered and dried in a vacuum dryer overnight. 195 g of white polymer was obtained. This means that 48,300 g of polymer (PE) was obtained per 1 g of catalyst component [catalyst yield (g PE/
g/solid catalyst) = 48300]. This polymer is manufactured using ASTM
−D1238−65T method, load 2.16Kg at 190℃
The melt index (MI ₂ ) was measured. _MI2 =
It was 7.2. The bulk specific gravity of the polymer was 0.35 (g/cc). The particle size distribution of this polymer was as follows. (For comparison, the particle size distribution of the polymer of Comparative Example 1 described later is also shown.)

[Table] Comparative Example 1 In the production of the catalyst component of Example 1, Ti(O
The solid component was produced in exactly the same manner, except that -nC ₄ H ₉ ) ₄ was not added, and the polymerization of ethylene was carried out in exactly the same way. 73 g of polymer was obtained. Yield to catalyst (g・PE/g・solid) = 18300, MI ₂ = 6.5, and polymer bulk specific gravity is 0.28
(g/cc). Further, the polymer particle size distribution was as shown in Table 1 above. Examples 2 to 4 In the preparation of the catalyst component of Example 1, n-C ₄ H ₉ OH was used instead of EtOH, and Ti(O-
Catalyst components were produced by changing the amount of nC ₄ H ₉ ) ₄ as shown below, and ethylene polymerization was carried out under exactly the same conditions as in Example 1. Table 2 shows the results.
Shown below.

[Table] Example 5 In the production of the catalyst component of Example 3, Ti
Ethylene polymerization was carried out in exactly the same manner except that Ti(O-isoC ₃ H ₇ ) ₄ was used instead of (OC ₄ H ₉ ) ₄ . 210 g of polymer was obtained. The yield based on the catalyst was 52500, and the MI ₂ was 7.1. Example 6 In the production of the catalyst component of Example 3, Mg(OC 2 H 5 )Cl was used instead of MgCl ₂ and Mg(OC ₂ H ₅ )Cl was used instead of SiCl ₄ .
The procedure was carried out in exactly the same manner except that CH ₃ SiCl ₃ was used.
Polymerization of ethylene was carried out in exactly the same manner. 180g of polymer was obtained, yield relative to catalyst = 45000,
MI ₂ = 5.9. Example 7 and Comparative Examples 2 to 7 Ethylene polymerization was carried out in exactly the same manner as in Example 4 except that 0.1 mol of the electron donor was used as shown in Table 3 instead of C ₄ H ₉ OH. did exactly the same thing. The results are shown in Table-3.

[Table] Example 8 In the production of the catalyst component of Example 3, TiCl ₄ was dissolved in 100 ml of n-butyl chloride.

The production was carried out in exactly the same manner except that 15 g of [Formula] was used, and the polymerization of ethylene was carried out in the same manner. 136 g of polymer was obtained. The yield based on the catalyst was 34,000, and the MI ₂ was 4.8. Example 9 The catalyst component was produced in exactly the same manner as in Example 3, except that n-butyl chloride was used instead of n-heptane, and the polymerization of ethylene was carried out in the same manner. 257 g of polymer was obtained. The yield based on the catalyst was 64,200, and the MI ₂ was 7.8. Example 10 In the production of the catalyst component of Example 3, S _o Cl ₄ was used instead of SiCl ₄ and Ti(OC ₄ H ₉ ) was used instead of TiCl ₄ .
The procedure was exactly the same except that Cl ₃ was used, and the polymerization of ethylene was also carried out in exactly the same manner. 182 g of polymer was obtained. Yield to catalyst = 45600, MI ₂
= 6.8. Examples 11-12 Ethylene polymerization was carried out in exactly the same manner, except that the catalyst components produced in Example 3 were used, and the organoaluminum components shown in Table 4 below were used in place of triethylaluminum under the ethylene polymerization conditions. I did this. The results are shown in Table 4.

[Table] Example 13 Polymerization was carried out in exactly the same manner except that the catalyst component prepared in Example 3 was used and a mixed gas containing 2% by weight of propylene was used instead of ethylene.
240 g of polymer was obtained. Yield to catalyst = 60000
and MI ₂ =8.2. Example 14 Polymerization was carried out in exactly the same manner, except that the catalyst component produced in Example 3 was used, a mixed gas containing 10% by weight of butene was used instead of ethylene, and the polymerization temperature was lowered to 65°C. . 153 g of polymer was obtained. The yield based on the catalyst was 38,200, and the MI ₂ was 5.2. Example 15 100 mg of the catalyst component prepared in Example 8, 114 mg of triethylaluminum, and 30 mg of ethyl benzoate were introduced, and propylene was polymerized at 60° C. and 7 Kg/cm ² G for 1 hour. 152 g of polymer was obtained. Total II/Product II = 70/83 weight percent. Example 16 Production of catalyst component The production of the catalyst component in Example 2 was carried out in the same manner up to the introduction of SiCl ₄ , and then 0.05 mol of TiCl ₄ was introduced and stirred for 1 hour. Then, the temperature was lowered to room temperature, 0.05 mol of triethylaluminum was introduced, and the mixture was stirred for 1 hour. The obtained solid was washed once with n-heptane and used as a catalyst component. Polymerization of ethylene Ethylene polymerization was carried out under exactly the same conditions as in Example 2. 186 g of white polymer was obtained. The yield based on the catalyst was 46500, and the MI ₂ was 6.7. Example 17 Production of catalyst component 100 ml of thoroughly degassed and purified n-butyl chloride was placed in a 500 ml flask that was sufficiently purged with N ₂ , and then 0.05 mol of MgCl ₂ and Ti(O-nC ₄ H ₉ ) ₄ were added.
Add 0.1 mol and 0.03 mol of ethyl benzoate at 70°C.
The temperature was raised to , and the mixture was stirred for 1 hour. Then, the temperature was lowered to 50°C, 0.1 mol of SiCl ₄ was added, and the mixture was stirred for 1 hour. Next, 0.8 mol of TiCl ₄ was introduced, and the mixture was stirred at 70° C. for 1 hour. The obtained solid component was thoroughly washed with n-heptane to obtain a catalyst component. The Ti content in the catalyst component was measured by a colorimetric method and was found to be 2.6% by weight. Polymerization of propylene A stainless steel sootclave with an internal volume of 1.5 liters, equipped with stirring and temperature control equipment, was
After repeating propylene substitution several times, 800 ml of sufficiently dehydrated and deoxygenated n-heptane was introduced, followed by 114 mg of triethylaluminum and ethyl benzoate.
30 mg and 50 mg of the catalyst component synthesized above were introduced. The temperature was raised to 60°C, propylene was introduced up to 7 kg/cm ² G, and polymerization was carried out for 1 hour. The obtained solid component was filtered and dried overnight. 168 g of white polymer (PP) was obtained. Yield to catalyst = 3360 g.PP/g solid catalyst. The residual rate of polymer extraction with boiling n-heptane is 93
%, and 8.6 g of polymer was obtained by concentrating the filtrate. Example 18 In the preparation of the catalyst component of Example 17, instead of ethyl benzoate,

The catalyst components were produced in exactly the same manner, except that the following formula was used and SnCl ₄ was used instead of SiCl ₄ . Polymerization of propylene was also carried out in the same manner. 123g of polymer was obtained, yield based on catalyst = 2460
(g・PP/g・solid catalyst). Total II/Product II = 83/89%. Example 19 In the production of the catalyst component of Example 17, Ti(O-
The catalyst component was produced in exactly the same manner, except that 0.15 mol of Ti(O-iC ₃ H ₈ ) ₄ was used in place of nC ₄ H ₉ ) ₄ , and propylene polymerization was carried out in exactly the same manner. 148g of polymer was obtained, yield based on catalyst = 2960
(g・PP/g solid catalyst). All II/Product I.
I.=87/91%. Example 20 Using chlorobenzene instead of n-butyl chloride in the preparation of the catalyst component of Example 17,
The catalyst component was produced in exactly the same manner except that the amount of ethyl benzoate used was 0.03 mol, and the polymerization of propylene was also carried out in the same manner. 154g of polymer was obtained, yield based on catalyst = 3080
(g・PP/g solid catalyst). All II/Product I.
I.=90/95%. Example 21 In the preparation of the catalyst component of Example 17, instead of TiCl ₄

The catalyst component was produced in exactly the same manner, except that 0.3 mol of [Formula] was used, and the polymerization of propylene was also carried out in the same manner. 114g of polymer was obtained, yield based on catalyst = 2280
(g・PP/g solid catalyst). All II/Product I.
I.=89/93%. Example 22 Ethylene-propylene block polymerization was carried out using 20 mg of the catalyst component prepared in Example 17, 80 mg of triethylaluminum, and 20 mg of ethyl benzoate. Ethylene was first polymerized at 4 Kg/cm ² G for 0.5 hours, residual ethylene was purged, and propylene was polymerized at 7 Kg/cm ² G for 1.5 hours. 225 g of polymer (PP) was obtained, with a catalyst yield of 11250 (g·PP/g solid). All II/
Product II was 82/90%. Comparative Example 8 A commercially available anhydrous compound was prepared according to the synthesis of the coordination complex of Example 3 described in JP-A-49-90697.
A complex of MgCl ₂ and tetrahydrofuran was synthesized. The production of a solid catalyst component and the polymerization of ethylene were carried out in the same manner as in Example 3, except that this complex was used in place of MgCl ₂ . As a result, the yield relative to the catalyst was 6400.

Claims (1)

[Claims] 1. A catalyst component () which is a contact product of component A and component B below and an organoaluminum compound ()
A catalyst for olefin polymerization, characterized in that it is a combination of the following. Ingredient A Contains magnesium and titanium, and the following ingredients
A solid composition precipitated from a solution consisting of (1), (2) and (3). (1) A magnesium compound that can be represented by the general formula Mg(OR ¹ ) _2-o X _o (where R ¹ is alkyl, aryl or cycloalkyl having 1 to 10 carbon atoms, 0<n≦2). (2) A titanium compound represented by the general formula Ti(OR ² ) ₄ (where R ² is the same or different from R ¹ with 1 carbon number)
~10 alkyl, aryl or cycloalkyl). (3) Electron-donating compounds selected from alcohols and silanols. Component B (4) Liquid titanium halogen compound.