JPS6323202B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for polymerizing olefins having 3 or more carbon atoms using a novel catalyst, and more specifically, to a method for polymerizing olefins having 3 or more carbon atoms, and more specifically, to
In obtaining olefins, a small amount is sufficient to produce a product of high activity and stereoregularity such that removal of the catalyst is not necessary. This invention relates to a method for producing polyolefin using a novel catalyst. Conventionally, many proposals have been made regarding catalysts for producing highly stereoregular polymers of α-olefins, but the most well-known are solid titanium halides and organic aluminum halides such as dialkyl aluminum halides. It is a catalyst system consisting of compounds. However, although these catalyst systems produce highly stereoregular polymers, they do not have sufficiently high polymerization activity, and therefore require a step to remove catalyst residues remaining in the resulting polymers. As a solution to this problem, in recent years various methods have been developed that dramatically improve the polymer yield per transition metal and solid catalyst component by fixing transition metal compounds on carriers, thereby making it possible to substantially omit the catalyst removal step. However, the process for producing the solid catalyst component is long and complicated;
It wasn't necessarily easy. For example, according to the method described in JP-A-50-126590, anhydrous magnesium halide and an organic acid ester are co-pulverized for a long time of 72 hours, and then treated with a titanium halide compound or anhydrous magnesium halide is A method has been proposed in which a complex of titanium and organic acid ester is co-pulverized with a titanium halogen compound for a long time of 100 hours. In addition, according to the method described in JP-A-51-28189, anhydrous magnesium halide is treated with a compound containing active hydrogen such as ethyl alcohol, and then treated with an organic acid ester, an organometallic compound, etc. A method of reacting with a compound has been proposed, but according to the experience of the present inventors, when anhydrous magnesium halide is brought into contact with a compound such as ethyl alcohol, the reactant swells significantly and becomes a viscous slurry that is difficult to handle. Moreover, this creates an unfavorable situation, making it extremely difficult to maintain uniform reaction and stirring. The drawbacks of this method, such as treating a solid support with a specific compound and then contacting it with a titanium halogen compound, are that the reaction time is long and the reaction process is complicated, making it difficult to obtain a solid catalyst component with good reproducibility. However, it is still not fully satisfactory from these points of view. As a method for solving the above-mentioned drawbacks, the present inventors have developed a method for converting the reaction product of a specific organosilicon compound and a Grignard reagent into a titanium halogen compound in the presence of an organic acid ester or an electron-donating compound other than the organic acid ester. A method for obtaining a solid catalyst component by reacting with
No. 14330 was proposed. Furthermore, as a result of intensive research, the present inventors have discovered a novel method that can produce a highly stereoregular polymer with a narrower particle size distribution in extremely high yield compared to the previous application, and that the preparation method is simple and reproducible. The present invention was completed by discovering a method for obtaining a homogeneous solid catalyst component with good properties. That is, the present invention has the formula R ¹ aHbSiO4-ab/2 (where R ¹ is selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, an alkoxy group, and an alloxy group, and a is an integer of 0, 1, or 2, b represents 1, 2, or 3, and a+b≦3) A reaction product (a) of a chain or cyclic hydropolysiloxane having a structural unit represented by (a+b≦3) and a Grignard reagent is added to the reaction product (a). A solid catalyst component [A] obtained by reacting with one or more TiX ₄ (X is a halogen) in the presence of 2 to 20 aromatic hydrocarbon solvents and an organic acid ester per 1 mole of Mg and an organic The present invention relates to a method for producing a polymer of _C3 or higher α-olefin, which is characterized by using a catalyst comprising an aluminum compound [B]. The reaction product (a) of the hydropolysiloxane and Grignard reagent used in the production of this catalyst is soluble in aromatic hydrocarbon solvents such as benzene, toluene, xylene, etc., so this reaction product (a) is prepared as a homogeneous solution. can be handled. This is of great significance in the catalyst preparation method, as the reaction between titanium and a titanium halide compound in the presence of an organic acid ester can be carried out extremely easily, and the organic acid ester is a reaction product (a ) It is an extremely simple preparation method, as it only needs to be mixed into a homogeneous solution. Therefore, reproducibility is very good, and a solid catalyst component of constant quality can always be supplied. Furthermore, when α-olefin is polymerized using the catalyst of the present invention, the yield of polyolefin per titanium halide and the yield of polyolefin per solid catalyst component [A] are extremely high, and expensive operations such as catalyst removal are not necessary. At the very least, a highly stereoregular polymer can be produced over a long period of time with almost no adverse effects caused by titanium halides or the like in the obtained polymer. In addition, this catalyst system has a small change in activity during polymerization,
Since the polymerization activity lasts for a long time, stable continuous polymerization is possible, and since it is sensitive to a small amount of molecular weight regulator such as hydrogen, it is easy to control the molecular weight of the resulting polymer. Manufacture is possible. In addition, the polyolefin obtained using this catalyst system has a narrow particle size distribution and a uniform, spherical powder shape, so it has many advantages such as good fluidity of polymer slurry and dried polymer powder. have. As described above, in the present invention, by using a reaction product of a specific organosilicon compound and a Grignard reagent, a novel solid catalyst component can be prepared extremely easily and conveniently, and the obtained solid catalyst component [A ] is surprisingly capable of producing a polymer with extremely high activity and high stereoregularity, and its industrial usefulness is extremely large. The method of the present invention will be explained in more detail below. The solid catalyst component used in the present invention is usually prepared as follows. First, the hydropolysiloxane used to produce the reaction product (a) has the following general formula R ¹ aHbSiO4-ab/2 (where R ¹ is an alkyl group, aryl group, aralkyl group, alkoxy group, or alloxy group). A monovalent organic group selected from the group consisting of, a represents 0, 1 or 2, b represents 1, 2 or 3, and a+b≦3
It is. ) A chain or cyclic hydropolysiloxane having a structural unit shown in the following formula, a compound of any degree of polymerization, or a mixture thereof, and having a low viscosity liquid with a low degree of polymerization and a viscosity of 100,000 centistokes at 25°C. Examples include grease-like to wax-like products with various degrees of polymerization, as well as solid-state products. Since the structure of the terminal group of this hydropolysiloxane does not significantly affect the activity, it may be capped with any inert group such as a trialkylsilyl group. Specific examples include tetramethyldisiloxane, diphenyldisiloxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, ethoxyhydropolysiloxane, cyclooctylhydropolysiloxane, and chlorophenyl. Examples include hydropolysiloxane. The Grignard reagent used in the production of the reaction product (a) in the present invention has the general formula (MgR ² ₂ )p・(R ² MgX)q (wherein R ² represents a hydrocarbon group, X represents a halogen atom, and p and q represent numbers from 0 to 1,
It has the relationship p+q=1. ),
The ether complex compound or a mixture thereof, for example, _a so-called Grignard reagent represented by R ² MgX ^where p is 0 and q is 1. Hydrocarbyl magnesium, other (MgR ² ₂ ) p.
These include various organic magnesium halides represented by (R ² MgX)q, their ether complexes, and mixtures thereof. These Grignard reagents can be prepared, for example, in an ether solvent such as diethyl ether, dibutyl ether, or tetrahydrofuran, or in heptane, octane, or
It is easily synthesized in a hydrocarbon solvent such as benzene or toluene in the presence of an appropriate amount of a complexing agent such as an ether or an amine. The reaction product (a) used in the present invention can be easily obtained by reacting the hydropolysiloxane represented by the above formula with a Grignard reagent by any method. For example, the reaction between a hydropolysiloxane and a Grignard reagent can be carried out by adding the hydropolysiloxane little by little to a Grignard reagent synthesized in an appropriate solvent with stirring, and then heating the mixture for a predetermined period of time after adding the entire amount. This reaction proceeds at room temperature with a strong exotherm, but in order to complete the reaction it is preferred to heat the reaction mixture at 50-100°C for 1-5 hours. However, this operation is not always necessary. The charging ratio of hydropolysiloxane and Grignard reagent is preferably such that the molar ratio of MgR ² :Si is 0.05 to 1:1. The reaction product (a) thus obtained is subjected to the production of solid catalyst component [A] after removing part or all of the solvent from the reaction mixture and dissolving it in an aromatic hydrocarbon solvent. . Next, when the reaction product (a) is reacted with the titanium halogen compound, the organic acid esters that are allowed to coexist include aliphatic carboxylic acid esters, aromatic carboxylic acid esters, and alicyclic carboxylic acid esters. Among these, aromatic carboxylic acid esters are most preferred, and specific examples thereof include methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, and ethyl anisate. If the amount of organic acid ester added is too large, the catalytic efficiency will be extremely reduced, and if it is too small, the catalytic efficiency will increase, but the proportion of stereoregular polyolefin produced will be small, and the resulting polyolefin will have a wide particle size distribution. , Mg1 in reaction product (a)
It is preferable to set it as 0.1-1.5 mol with respect to mol. The organic acid ester can be added by simply mixing it together with the reaction product (a) in an aromatic hydrocarbon solvent to form a homogeneous solution before adding the titanium halogen compound. This method is extremely simple compared to a method in which a solid carrier and an organic acid ester are brought into contact with each other through co-pulverization, or a method in which a solid carrier is suspended in an inert solvent and brought into contact with an organic acid ester. This method is a major factor in the synthesis of solid catalyst components with good reproducibility and constant catalytic performance. The titanium halogen compound used in the production of this catalyst has the general formula TiXn(OR ⁴ ) _4-o (where X is a halogen atom, R ⁴ is a hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer from 1 to 4), examples include TiCl ₄ ,
_{TiBr4 ,} Ti _{( OC2H5} ) _Cl3 , Ti( _OC4H9 ) _Cl3 , Ti
(OC ₂ H ₅ ) ₂ Cl ₂ , Ti(OC ₃ H ₇ ) ₂ Cl ₂ , Ti(OC ₄ H ₉ ) ₂ Cl ₂
etc. can be mentioned. In particular, in the present invention, when n=4, ie, titanium halide gives good results. If the amount of this titanium halogen compound added is too large, the catalytic efficiency will increase, but the proportion of stereoregular polyolefin formed will be small, and if it is too small, the catalytic efficiency will be extremely reduced. The amount is preferably 5 to 20 mol. In the presence of an organic acid ester, the reaction product (a)
When reacting the halogen compound of titanium with the halogen compound of titanium, use an aromatic hydrocarbon solvent such as benzene, toluene, or xylene that dissolves the reaction product (a), the organic acid ester, and the halogen compound of titanium. It is necessary to adjust the amount to 2 to 20 per mol of Mg in the reaction product (a). If the amount of aromatic hydrocarbon solvent used is above this range, the produced polyolefin powder will have many fine particles, and if it is below this range, the activity will be greatly reduced, and the produced polyolefin powder will be This is not preferable because it increases the amount of coarse particles. Further, the reaction temperature is preferably carried out in the range of -10 to 130°C, and the reaction time is not particularly limited, but it is generally carried out in the range of 5 minutes to 20 hours. In this way, solid catalyst component [A] is produced,
The solid catalyst component [A] is recovered from the reaction mixture by washing with an inert hydrocarbon solvent such as hexane, heptane, kerosene, etc. to remove soluble components. Solid catalyst component [A] obtained in this way
When used as an olefin polymerization catalyst together with an organoaluminum compound, it can produce a polymer with sufficiently high activity and high stereoregularity, but if necessary, this solid catalyst component [A] can be further added. A solid component obtained by treating titanium with a halogen compound and then washing with an inert hydrocarbon solvent or the like may be used as the solid catalyst component. This method is effective in maintaining a high level of stereoregularity and further increasing activity. The solid catalyst component [A] thus obtained is dried by vacuum drying or the like, or dispersed in an inert solvent and used for preparing a polymerization catalyst. As a method for producing a solid catalyst component other than those described above, for example, after making an organic acid ester and the reaction product (a) into a homogeneous mixed solution using an aromatic hydrocarbon solvent, the reaction product such as n-hexane, etc. After a precipitate is generated by adding a large amount of a solvent that does not dissolve (a) or removing an aromatic hydrocarbon solvent by distillation, a halogen compound of titanium is reacted with the precipitate. There is a method for obtaining a solid catalyst component, and a method in which the reaction product (a) is suspended in a solvent that does not dissolve the reaction product (a), brought into contact with an organic acid ester, and then reacted with a titanium halogen compound. Therefore, methods for obtaining a solid catalyst component can be considered, but all of these methods involve complicated reaction steps, making it difficult to consistently obtain a solid catalyst component of a constant quality with good reproducibility, and the catalyst has little industrial utility. Comparative Examples 3 and 4 described later demonstrate that only those with high performance can be obtained. The organoaluminum compound used in the present invention has the general formula AlR ³ nX _3-o (wherein R ³ is a hydrocarbon group having 1 to 8 carbon atoms,
X represents a halogen atom, a hydrogen atom or an alkoxy group, and n represents an integer of 1 to 3. ) Specific examples of organoaluminum compounds include trimethylaluminum, triethylaluminum,
Tributylaluminum, diethylaluminum chloride, dibutylaluminum chloride,
Examples include ethylaluminum sesquichloride, diethylaluminum hydride, dibutylaluminum hydride, and diethylaluminum ethoxide. The olefin polymerization catalyst used in the present invention can be produced by contacting the solid catalyst component [A] with the organoaluminum compound in the presence or absence of an inert solvent, for example, in a catalyst preparation container or in a polymerization reaction. It is easily prepared by charging both in the presence of a solvent in a container and stirring. The preferred ratio of the two to form the olefin polymerization catalyst is from 1 to 1000 gram atoms of aluminum per gram atom of titanium in the catalyst. If the polymerization catalyst is prepared in a polymerization reactor, after the formation of the catalyst, the olefin can be fed into the same vessel, or if the polymerization catalyst is prepared in a separate vessel, the catalyst suspension can be polymerized. The olefin can be easily polymerized by charging it into a reactor and supplying the olefin into the same container. Furthermore, in order to control the stereoregularity of the α-olefin having 3 or more carbon atoms, an electron donor may be present, and among the organic acid esters, aromatic carboxylic acid esters are particularly preferred. These may be used in the form of addition reaction products with the organoaluminum compounds. The polymerization reaction of α-olefin according to the method of the present invention is carried out in the same manner as the polymerization reaction of olefin using a conventional Ziegler-Natsuta type catalyst. That is, the reaction is conducted in the substantial absence of oxygen and moisture.
The polymerization may be carried out by a suspension polymerization method in a suitable insoluble solvent, a solventless polymerization method in a monomer solvent, or a gas phase polymerization method, and the polymerization method may be batchwise, continuous or any other method. good. The preferred polymerization temperature is 30 to 200°C, especially 60 to 100°C.
The polymerization pressure is preferably normal pressure to 100 kg/cm ² . In this case, the amount of catalyst used is 0.1 to 50 mmol of organometallic compound per solvent, especially 0.3 to 50 mmol.
Preferably, the amount is 10 mmol. The molecular weight of the polymer obtained by the method of the present invention can be adjusted arbitrarily by changing the polymerization temperature, the amount of catalyst used, etc., but the most effective adjustment method is to add hydrogen to the polymerization system. be. The olefins to be polymerized are 1-
Olefins, such as propylene, 1-
Butene, styrene, 4-methyl-1-pentenone, and their copolymerized components are olefins and diolefins having vinyl groups, such as ethylene, butadiene, isoprene, and the like. As mentioned above, since the present catalyst system has extremely high polymerization activity, the amount of residual catalyst in the polyolefin obtained even without any catalyst removal operation is extremely small. As a result, there is almost no negative effect of the residual catalyst on the quality of conventional polyolefins, and there is the advantage that molded products with excellent color tone and strength can be obtained even if processed as is. Furthermore, since it is sensitive to molecular weight regulators such as hydrogen, it is easy to control the molecular weight, and a wide variety of grades can be produced. Example 1 a Preparation of reaction product (a) between hydropolysiloxane and Grignard reagent Into a glass reactor whose interior had been thoroughly dried and purged with nitrogen, 75 ml of a tetrahydrofuran solution of n-butylmagnesium chloride (0.167 mL as n-butylmagnesium chloride) mo) was collected, and while stirring, the terminals of methylhydropolysiloxane (25
Viscosity at °C approximately 30 centistokes) 10.5 ml (Si
0.175 mo) was gradually added dropwise. Because it generates heat, the reactor is cooled with a refrigerant until the internal temperature reaches 70℃.
After adding the entire amount, adjust the temperature so that it does not exceed 70℃.
The mixture was kept for 1 hour at room temperature and cooled to room temperature to obtain a dark brown clear solution. A portion of this solution was examined for the presence or absence of unreacted n-butylmagnesium chloride using the method of Gilman et al. (J.Am Chem.Soc. 47 2002 (1925)). No chloride was present.The solvent was distilled off under reduced pressure while keeping this solution at 50°C, yielding 38.6g of white solid reaction product (a).The amount of tetrahydrofuran contained in this white solid was It was 0.44 mo per Mg atom.
(Quantitated by gas chromatography after hydrolysis.) b. Production of solid catalyst component [A] The above white solid reaction product (a) was placed in a glass reactor whose interior had been thoroughly dried and replaced with nitrogen.
9.2gr (40mmo in terms of Mg atoms) was collected,
Then 220ml of toluene, 20mmo of ethyl benzoate
After adding and stirring well to make a homogeneous solution,
A mixed solution consisting of 176 mmo of TiCl ₄ and 100 ml of toluene was added dropwise at room temperature over 2 hours. After the dropwise addition was completed, the reaction was carried out under reflux for 2 hours. After the reaction, the solid portion was separated and thoroughly washed with n-hexane to obtain solid catalyst component [A]. The titanium content in 1 g of the component was 16.0 mg, and the ethyl benzoate content was 46.0 mg. c Polymerization reaction 600 ml of well-purified n-hexane was placed in a stainless steel autoclave with a capacity of 1.5 and equipped with a stirrer whose inside was dried and replaced with nitrogen, and a jacket for heating and cooling according to a conventional method, and the autoclave was heated at 40°C in a propylene atmosphere. Triethyl aluminum under
0.3mmo and ethyl benzoate 0.0145mmo
Solid catalyst component [A]
40 mg (0.0134 mmo in terms of titanium atoms) was charged. The polymer element was heated to raise its temperature, and when it reached 60℃, propylene was introduced and the total pressure was 7.0.
Kg/cm ² and polymerization was started. After polymerization was carried out for 1 hour while keeping the temperature and total pressure constant, the introduction of propylene was stopped, the reactor was cooled to room temperature, and unreacted propylene was purged. Separate the polymer with a glass filter and heat at 50℃5
Drying under reduced pressure was carried out for hours to obtain 107.5 gr of white powdery polypropylene. This powder was a powder with good fluidity, and its particle size distribution was 7.0% of particles of 100μ or less and 2.1% of particles of 400μ or more. In addition, the extraction residual rate with boiling n-heptane is
It was 94.0%. On the other hand, the amount of the polymerization solvent soluble polymer recovered from the polymerization solvent was 1.9 gr. The polymerization activity per gram of titanium atom of this catalyst is
It is 170.4Kg/gTi・hr. The results are shown in Table 1 together with the results of Examples and Comparative Examples described below. Example 2 b Production of solid catalyst component [A] Solid catalyst component [A] was obtained under the same conditions as in Example 1 except that the amount of ethyl benzoate added was 28 mmo. The titanium content in 1g of this ingredient is 14.2mg, and the ethyl benzoate content is
It was 52.5 mg. c. Polymerization reaction Propylene was polymerized under the same conditions as in Example 1, except that the amount of solid catalyst component [A] used was 45.2 mg. The polymerization results are collectively shown in Table 1. Example 3 b Production of solid catalyst component [A] The amount of ethyl benzoate added was 40 mmo,
Solid catalyst component [A] was obtained under the same conditions as in Example 1 except that the amount of Ticl ₄ added was 360 mmo. The titanium content in 1 g of this component was 22.0 mg, and the ethyl benzoate content was 83.5 mg. c Polymerization reaction Propylene polymerization was carried out under the same conditions as in Example 1 except that the amount of solid catalyst component [A] used was 29.2 mg. The polymerization results are collectively shown in Table 1. Example 4 b Production of solid catalyst component [A] Solid catalyst component [A] was prepared under the same conditions as Example 1 except that the amount of toluene in which the reaction product (a) and ethyl benzoate were mixed and dissolved was changed to 440 ml. ] was obtained. The titanium content in 1 g of the component was 11.5 mg, and the ethyl benzoate content was 32.4 mg. c. Polymerization reaction Propylene was polymerized under the same conditions as in Example 1 except that the amount of solid catalyst component [A] used was 55.8 mg. The polymerization results are collectively shown in Table 1. Example 5 b Production of solid catalyst component [A] All procedures were carried out except that the amount of toluene used to mix and dissolve the reaction product (a) and ethyl benzoate was 120 ml, and the amount of toluene used to dilute TiCl ₄ was set to 40 ml. A solid component was obtained under the same conditions as in Example 1. Next, 3.5 gr of this fixed component was suspended in 25 ml of n-hexane, 228 mmo of TiCl ₄ was added, and the mixture was treated under reflux for 2 hours. After the treatment, the solid portion was separated and thoroughly washed with n-hexane to obtain solid catalyst component [A]. The component 1
The titanium content in g was 19.9 mg, and the ethyl benzoate content was 56.2 mg. c. Polymerization reaction Propylene was polymerized under the same conditions as in Example 1 except that the amount of solid catalyst component [A] used was 32.3 mg and the amount of ethyl benzoate added was 0.0281 mmo. The polymerization results are collectively shown in Table 1. Example 6 b Production of solid catalyst component [A] The amount of ethyl benzoate added was 40 mmo,
The amount of TiCl ₄ used in the reaction of reaction product (a) with TiCl ₄ in the presence of ethyl benzoate in toluene is
Solid catalyst component [A] was obtained under all the same conditions as in Example 5 except that the amount was 360 mmo. The component 1
The titanium content in g was 15.0 mg, and the ethyl benzoate content was 34.5 mg. c. Polymerization reaction Propylene was polymerized under the same conditions as in Example 1, except that the amount of solid catalyst component [A] used was 42.5 mg, and the amount of ethyl benzoate added was 0.0304 mmo. The polymerization results are collectively shown in Table 1. Example 7 c Polymerization reaction The solid catalyst component [A] obtained in Example 5 was
Polymerization of propylene was carried out under the same conditions as in Example 1 except that 32.3 mg of methyl benzoate was used and 0.0141 mmo of methyl P-toluate was used instead of ethyl benzoate. The polymerization results are collectively shown in Table 1. Example 8 b Production of solid catalyst component [A] When reacting the reaction product (a) with TiCl ₄ in toluene in the presence of ethyl benzoate, TiCl ₄
Example 5 except that the dropping conditions were 0°C for 2 hours, and the reaction conditions after dropping were 0°C and 2 hours.
Solid catalyst component [A] was obtained under the same conditions as above. The titanium content in 1 g of this component was 10.2 mg, and the ethyl benzoate content was 116 mg. c Polymerization reaction The amount of solid catalyst component [A] used was 62.9 mg,
Polymerization of propylene was carried out under the same conditions as in Example 1 except that the amount of ethyl benzoate added was 0.00749 mmo. The polymerization results are collectively shown in Table 1. Example 9b Production of solid catalyst component [A] Solid catalyst component [A] was obtained under the same conditions as in Example 8 except that the amount of ethyl benzoate added was 10 mmo. The titanium content in 1g of the ingredient is 25.7mg, and the content of ethyl benzoate is
It was 120 mg. c Polymerization reaction The amount of solid catalyst component [A] used was 25.0 mg,
Polymerization of propylene was carried out under the same conditions as in Example 1 except that the amount of ethyl benzoate added was 0.0203 mmo. The polymerization results are collectively shown in Table 1. Example 10c Polymerization reaction The solid catalyst component [A] obtained in Example 9 was
25.0mg was used, and instead of ethyl benzoate, P-
Polymerization of propylene was carried out under the same conditions as in Example 1 except that 0.0102 mmo of methyl toluate was used. The polymerization results are collectively shown in Table 1. Comparative Example 1b Production of solid catalyst component Same as Example 5 except that the amount of toluene used to mix and dissolve the reaction product (a) and ethyl benzoate was 900 ml, and the amount of toluene used to dilute TiCl ₄ was 100 ml. A solid catalyst component was obtained under these conditions. The titanium content in 1 g of the component was 25.4 mg, and the ethyl benzoate content was 28.7 mg. c. Polymerization reaction Propylene was polymerized under the same conditions as in Example 1, except that the amount of solid catalyst component used was 25.3 mg and the amount of ethyl benzoate added was 0.0281 mmo. The polymerization results are collectively shown in Table 1. The polymerization results show that when the amount of aromatic hydrocarbon solvent used in producing the solid catalyst component is too large, the produced polypropylene powder contains many fine particles. Comparative Example 2 b Production of solid catalyst component The amount of toluene in which the reaction product (a) and ethyl benzoate are mixed and dissolved is 38 ml, and the reaction product (a) and TiCl ₄ are mixed in toluene in the presence of ethyl benzoate.
A solid catalyst component was obtained under the same conditions as in Example 5, except that the amount of toluene used to dilute TiCl ₄ was changed to 10 ml when reacting. The titanium content in 1 g of the component was 33.8 mg, and the ethyl benzoate content was 39.4 mg. c. Polymerization reaction Propylene was polymerized under the same conditions as in Example 1, except that the amount of solid catalyst component used was 19.1 mg and the amount of ethyl benzoate added was 0.0281 mmo. The polymerization results are collectively shown in Table 1. The polymerization results show that if the amount of aromatic hydrocarbon solvent used during the production of the solid catalyst component is too small, the catalyst efficiency will be greatly reduced, and moreover, the produced polypropylene powder will contain many coarse particles. Comparative Example 3 b Production of solid catalyst component The reaction product (a) obtained in Example 1 was placed in a glass reactor whose interior was thoroughly dried and purged with nitrogen.
9.2 g (40 mmo in terms of Mg) was collected, then 20 ml of toluene and 40 mmo of ethyl benzoate were added, stirred thoroughly to form a homogeneous solution, and 200 ml of n-hexane was added dropwise at room temperature to form a white solid powder. Thereafter, the solid portion was separated, thoroughly washed with n-hexane, and dried. This solid component is n-
After suspending in 50 ml of hexane,
Add 910 mmo of TiCl ₄ at room temperature and reflux for 2 hours.
After the reaction, the solid part is separated,
A solid catalyst component was obtained by thorough washing with n-hexane. The titanium content in 1 g of the component was 22.0 mg, and the ethyl benzoate content was 102 mg. c. Polymerization reaction Propylene was polymerized under the same conditions as in Example 1 except that the amount of solid catalyst component used was 29.2 mg. The polymerization results are collectively shown in Table 1. When producing the solid catalyst component, if the reaction product (a) and the titanium halogen compound are not reacted in an aromatic hydrocarbon solvent, the produced polypropylene powder will contain many fine particles, resulting in stereoregular polymers. It was found that the production rate of was decreased and the catalyst efficiency was not sufficiently high. Comparative Example 4 b Production of solid catalyst component The reaction product (a) obtained in Example 1 was placed in a glass reactor whose interior was thoroughly dried and purged with nitrogen in advance.
9.2 (40 mmo in terms of Mg) was collected and suspended in 100 ml of n-heptane. Next, 12 mmol of ethyl benzoate was added at room temperature, and the reaction was carried out at 80°C for 2 hours. After the reaction, the solid part was separated, thoroughly washed with n-hexane, and dried. The above solid component was suspended in 910 mmo of TiCl ₄ and reacted at 80° C. for 2 hours. After the reaction, the solid portion was separated and thoroughly washed with n-hexane to obtain a solid catalyst component. The titanium content in 1g of this ingredient is 40.7mg, and the ethyl benzoate content is
It was 34.2mg. c. Polymerization reaction Propylene was polymerized under the same conditions as in Example 1 except that the amount of solid catalyst component used was 15.8 mg. The polymerization results are summarized in Table 1.

【table】

[Table] *1 Represents the polypropylene production rate per unit time per titanium atom.
When producing the solid catalyst component, if an aromatic hydrocarbon solvent is not used extensively, the polypropylene powder produced from the polymerization result will contain a large number of fine particles, and the catalyst efficiency will also be considerably lower than in the examples. I know what will happen.

[Brief explanation of the drawing]

The flowchart in the drawings shows the procedure for preparing a catalyst applying the present invention. However, the amount of aromatic hydrocarbon added in the drawings is 2 to 20 per mole of Mg in the reaction product (a).

Claims (1)

[Claims] 1 Formula R ¹ aHbSiO(4-a-b)/2 (wherein R ¹ is selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, an alkoxy group, and an alloxy group, and a
is an integer of 0, 1 or 2, b is 1, 2 or 3, and a+b≦3) A reaction product of a linear or cyclic hydropolysiloxane with a Grignard reagent ( a) in the reaction product (a)
One or more titanium halides, TiX ₄ (however, X
is characterized by using _a catalyst consisting of a solid catalyst component [A] obtained by reacting with a halogen) and an organoaluminum compound [B].
- A method for producing an olefin polymer.