JPS5949241B2 - Method for producing stereoregular polyolefin - 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.
The present invention relates to a process for producing stereoregular polyolefins using novel catalysts that are sufficiently active in small amounts so that removal of the catalyst is not necessary and that can produce highly stereoregular products.

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, their polymerization activity is not sufficiently high, and therefore a step is required to remove catalyst residues remaining in the resulting polymers.

As a solution to this problem, various methods have been developed in recent years that dramatically improve the polymer yield per transition metal and solid catalyst component by immobilizing transition metal compounds on carriers, making it possible to substantially omit the catalyst removal step. A method is proposed. However, in these methods, the content of the transition metal component in the generally used solid catalyst component is often as low as 1 to 3% by weight based on the solid catalyst component. For this reason, although the polymer yield per transition metal was high, the polymer yield per solid catalyst component was not sufficiently high. For example, in the method shown in Example 1 of Japanese Patent Publication No. 52-39431,
The content of solid catalyst component is 0.99% by weight. 65℃
, 6 hours in liquefied propylene and boiling n-
A polymer having a heptane extraction residue of 93.5% was obtained.

The polymer yield per 19 titanium atoms is 30 KP, but the polymer yield per 1f solid catalyst component is as low as 0.3 KP. The inventors of the present inventors have carried out intensive research and have found that the content of titanium atoms in the solid catalyst component is high, the polymer yield is high per titanium atom and per solid catalyst component, and the stereoregular polymer is produced at a high yield. The present inventors have discovered a method for preparing a new solid catalyst component that can be produced in the following manner, and have completed the present invention.

4-a-b That is, the present invention is based on [A] (1) Formula RBSiO? (However, R1 is an alkyl group, an aryl group, an aralkyl group,
selected from the group consisting of an alkoxy group and an alloxy group, a is an integer of 0, 1 or 2, b is an integer of 1, 2 or 3, and a
The reaction product of a linear or cyclic hydropolysiloxane having a structural unit represented by +b≦3) and a Grignard reagent is given the general formula A hydrocarbon group of numbers 1 to 12, M is an aluminum atom or a silicon atom, z represents its valence and is a number of 3 or 4, X is a halogen atom, n is 0 to (z-1) represents the number of

) A reaction product obtained by reacting one or more compounds represented by (b), (2) At least one selected from ether compounds, ketone compounds, phosphorus-containing compounds, nitrogen-containing compounds, and sulfur-containing compounds. A catalyst consisting of a solid catalyst component obtained by contacting one kind of electron-donating compound and (3) at least one titanium halogen compound, [B] an organic anol penium compound and [C] an organic acid ester. The present invention relates to a method for producing a stereoregular polyolefin, which is characterized in that when α-olefin is polymerized using the catalyst according to the method of the present invention, not only is the polymer yield per titanium atom extremely high; Since the titanium content in the solid catalyst component is increased, the polymer yield per solid catalyst component is also high.

Therefore, almost no adverse effects due to titanium halogen compounds etc. in the obtained polymer are observed even without performing expensive operations such as catalyst removal. In addition, the present catalyst system has a small change in activity during polymerization, can produce a highly stereoregular polymer over a long period of time, and is capable of stable continuous polymerization.

In addition, this catalyst system is sensitive to a small amount of molecular weight regulator such as hydrogen, so it is extremely easy to control the molecular weight of the resulting polymer. Not only does this method not cause a decrease in the production ratio of stereoregular polymers as observed in the catalyst systems used in this invention, but there is also almost no decrease in polymerization activity, making it possible to produce a wide variety of grades.

Furthermore, the polyolefin obtained by this catalyst system has a uniform, spherical powder shape and a high powder bulk density, so it has excellent flowability in polymer slurry and dried polymer powder, and is easy to handle. It has many advantages such as, and its industrial value 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 in the production of the reaction product (a) in the present invention has the following general formula (where R1 is selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, an alkoxy group, and an alloxy group). Monovalent organic group, a is 0.1 or 2
, b represent 1, 2 or 3, and a+b≦3.

) is a chain or cyclic hydropolysiloxane having a structural unit shown in the following formula, and is a compound of any degree of polymerization, or a mixture thereof, and has a viscosity of 100,000 cm at 25°C, ranging from a low viscosity liquid with a low degree of polymerization. Examples include those in the form of grease or wax with various degrees of polymerization up to Stokes, and those in the form of solids. 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,
Examples include tetramethylcyclotetrasiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, ethoxyhydropolysiloxane, cyclooctylhydropolysiloxane, and chlorophenylhydropolysiloxane. The Grignard reagent used in the production of the reaction product (a) in the present invention has the general formula (where R
3 represents a hydrocarbon group, X represents a halogen atom, p and q represent a number of O to 1, and have the relationship p+q=1.

), its ether complex compound, or a mixture thereof, for example, R3M where p is 0 and q is 1
The so-called Grignard reagent in the narrow sense, denoted by 9X, where p is 1 and q is O, R? Dihydrocarpyl magsacium represented by M9, other (M9R?) p・(R3M9X
) Various organic magnesium halides represented by q, their ether complexes, or mixtures thereof. These Grignard reagents can be prepared by adding an appropriate amount of a complexing agent such as ether or amine in an ether solvent such as diethyl ether, dibutyl ether, or tetrahydrofuran, or in a hydrocarbon solvent such as heptane, octane, benzene, or toluene. easily synthesized in the presence of 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 while stirring.
This can be done by heating for a predetermined period of time after everyone has been added.

This reaction proceeds at room temperature with a strong exotherm, but in order to complete the reaction, the reaction mixture must be heated to 50-100°C.
It is preferable to heat for 1 to 5 hours. However, this operation is not always necessary. The charging ratio of hydropolysiloxane and Grignard reagent is preferably such that M9R3:Si is in a molar ratio of 0.05 to 1:1.
The reaction product (a) thus obtained can be used as a reaction mixture in the production of the reaction product (b) in the present invention, but it is preferable if it contains a large amount of ethers derived from Grignard. Generally, some or all of the solvent is removed from the reaction mixture containing the reaction product (a), and the reaction product is dissolved or suspended in an inert hydrocarbon solvent. (
b).

However, this reaction product (a) has the property of being soluble in aromatic hydrocarbon solvents such as toluene. Therefore, in order to produce the reaction product (b) smoothly and with good reproducibility, and to obtain a homogeneous reaction product (b), the reaction product (a) must be dissolved in an aromatic hydrocarbon solvent to form a homogeneous solution. It is preferable to use the reaction product (b) as a reaction product. General formula R2nM (
Z) , n represents a number from O to (z-1).

The compound represented by ) is a halogen-containing compound of aluminum or silicon, and includes various compounds based on the type of R2 and the combination of values of N and z. That is, n
When is 0, it is represented by M (Otsu)
These include alkyl silicon halides. Specific examples of these compounds include benium trichloride, anolbenium tribromide, aluminum triiodide, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride,
Examples of silicon compounds include ethylaluminum dichloride and isobutylaluminum dichloride; examples of silicon compounds include silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylmonochlorosilane, ethyltrichlorosilane, butyltrichlorosilane, phenyltrichlorosilane, and silicon tetrabromide. Can be mentioned. These general formulas R2
Of course, the above compounds represented by nM(Z)Xz-o can also be used as a mixture. The reaction product (b) in the present invention is the reaction product (a) and the general formula R
It can be obtained by reacting with a compound represented by 2nM (3)Xz-n or a mixture thereof. Although the reaction can be carried out either in the presence or absence of an inert hydrocarbon solvent, it is generally preferred to carry out the reaction in the presence of an inert hydrocarbon solvent. In particular, using an aromatic hydrocarbon solvent such as benzene, toluene, etc. as an inert hydrocarbon solvent and using the reaction product (a) as a homogeneous solution of these solvents facilitates the reaction and provides a homogeneous solution. It is extremely preferred from the viewpoint of producing the reaction product (5) with good reproducibility and constant quality, always obtaining homogeneous solid catalyst component [A] with constant quality, and obtaining a polyolefin with excellent powder properties.

Both can be reacted in any ratio, but R2nM per 1 mol of magnesium in the reaction product (a)
It is preferable to use the compound represented by (Z)
Generally, the temperature is 10°C to 120°C for 5 minutes to 20 hours.

In particular, in order to obtain preferable powder characteristics such as bulk specific gravity and particle size distribution of polyolefin, it is appropriate to heat the mixture at 0°C to 80°C for 1 to 8 hours.

The reaction product (b) thus obtained may be used as it is in the preparation of the solid catalyst component [A], or the reaction mixture may be washed with an inert hydrocarbon solvent such as hexane, heptane, kerosene, etc. Only the reaction product (b) insoluble in the inert hydrocarbon solvent may be separated and recovered from the reaction mixture and used for the preparation of the solid catalyst component [A].

In particular, when an alkyl aluminum halide or the like is used when producing the reaction product (b), the transition metal content in the solid catalyst component increases significantly and the catalyst becomes expensive. The latter operation is preferable because it becomes difficult to obtain a polymerization catalyst that exhibits efficiency and the production rate of stereoregular polymers decreases.

In addition, when using the reaction product (b) separated and recovered after washing with an inert hydrocarbon solvent, it should be sufficiently dried by a method such as vacuum drying, or it should be washed in an inert hydrocarbon solvent. As a dispersed product, it may be used by any method; and the electron donating compound is at least one selected from ether compounds, ketone compounds, phosphorus-containing compounds, nitrogen-containing compounds, and sulfur-containing compounds. but,
To give specific examples, ether compounds and ketone compounds include diethyl ether, methyl ethyl ether,
Di-n-propyl ether, di-1-propyl ether, di-n-butyl ether, diphenyl ether, anisole, ethylene oxide, propylene oxide, epichlorohydrin, diethylene oxide dimethyl ether, dimethyl ketone, benzophenone, methyl ethyl ketone, cyclohexanone, anthraquinone acetophenone and phenylpropyl ketone.

Examples of sulfur-containing compounds include thioethers, metal salts of sulfonic acids, and specific examples include dimethyl thioether, diethyl thioether, dipropyl thioether, diphenyl thioether, sodium benzenesulfonate, sodium toluenesulfonate, and dimethyl sulfoxide. , diphenyl sulfone, dimethyl sulfone and the like. Examples of phosphorus-containing compounds include phosphines, phosphites, phosphates, and phosphoric acid amides, and specific examples thereof include trimethylphosphine, tributylphosphine, triphenylphosphine, trimethylphosphite, and triphenylphosphine. , trimethyl phosphate, triethyl phosphate, triphenyl phosphate and hexamethyl phosphoric triamide.

Examples of nitrogen-containing compounds include aliphatic amines, aromatic amines, heterocyclic amines, lactams, imines, urethane derivatives, urea and urea derivatives.Specific examples include methylamine, ethylamine, diethylamine, Triethylamine, tributylamine, aniline, N-methylaniline, N,N-dimethylaniline,
Examples include pyridinequinoline, α-picoline, ε-caprolactam, γ-butyrolactam, N-methylpyrrolidone, ethyleneimine, N-methylurethane, N,N-dimethylurethane, urea, and dimethylurea.

The amount of the electron-donating compound to be used is not particularly limited, but is 0.05 to 1 mole of Mfl atom in the reaction product (b).
The amount is in the range of 1 to 20 mol, preferably 0.5 to 5 mol, and one or more types can be used. moreover,
As a titanium halogen compound, the general formula TiXm(0
R4) 4-m (wherein, X represents a halogen atom, R4 represents a hydrocarbon group having 1 to 8 carbon atoms, and m represents an integer of 1 to 4), and its specific Examples include TiC24, TiBr4. Ti (0C2H5)
C23Ti(0C,H9)Cl,. Ti (0C4H9)
2Cj12 and the like. The amount of the titanium halogen compound to be used is not particularly limited, but it is preferably in the range of 0.1 to 150 mol per 1 mol of magnesium in the reaction product (b), and one or more types can be used.
Reaction product (b). The method of bringing the electron donating compound and the titanium halogen compound into contact with each other is not particularly limited, but for example, when preparing the reaction product (b) in 1), the reaction product (a) and the general formula R are also (Z)X
, -o together with an electron-donating compound, and the resulting mixture with the reaction product (b) is brought into contact with a titanium halogen compound.

2) A method of contacting the reaction product (b) with an electron donating compound and then contacting a titanium halogen compound 03) A method in which the reaction product (b), the electron donating compound, and the titanium halogen compound are brought into contact at the same time. How to make contact.

4) Any method 0 may be used in which the reaction product (b) is brought into contact with a titanium halogen compound and then an electron-donating compound is brought into contact with the reaction product (b).

Also, the reaction product (b). The electron-donating compound and the titanium halogen compound can be brought into contact with each other by co-pulverization in a rotating or vibrating mill, or in the presence or absence of an inert hydrocarbon solvent.

Furthermore, the temperature and time when these three are brought into contact are not limited, but may be 20 to 150°C for 10 minutes to 2
It is generally carried out within a range of 0 hours. Thus,
A solid catalyst component is produced, and the reaction mixture is washed with an inert hydrocarbon solvent such as hexane, heptane, or kerosene.
The solid catalyst component [A] is recovered by removing the soluble components, and if necessary, this solid catalyst component or the above reaction mixture is further treated with a titanium halogen compound, and then treated with an inert hydrocarbon solvent or the like. A solid component obtained by washing may be used as a solid catalyst component.

This method is effective in maintaining a high level of stereoregularity and further increasing activity.

This solid catalyst component is dried by vacuum drying or the like or dispersed in an inert solvent for the preparation of the polymerization catalyst. The organoaluminum compound used in the present invention is A hydrocarbon group having 1 to 8 carbon atoms, X represents a halogen atom, a hydrogen atom or an alkoxy group, and 2 represents an integer of 1 to 3.

) Specific examples of organic anol benium compounds include trimethylaluminum, triethylaluminum, tributylaluminum, diethylaluminium, tributylaluminum, diethylaluminium chloride, dibutylaluminum chloride, ethylaluminum sesquichloride, diethylaluminium hydride, dibutylaluminum hydride, diethylaluminum ethoxy One or more types of these can be used.

Furthermore, examples of organic acid esters include aliphatic carboxylic esters, aromatic carboxylic esters, and alicyclic carboxylic esters.

Among these, aromatic carboxylic acid esters are most preferred;
Specific examples include methyl benzoate, ethyl benzoate,
Examples include methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, etc. The olefin polymerization catalyst used in the present invention combines the solid catalyst component, organoaluminum compound, and organic acid ester described above with an inert hydrocarbon. It can be obtained by contacting in the presence or absence of a solvent.

There are no particular limitations on the method of bringing these three into contact, but for example, a catalyst system can be easily formed by simultaneously charging and stirring these three in the presence of a solvent in a catalyst preparation vessel or polymerization reaction vessel. You can force it. The preferred ratio of these three to form the olefin polymerization catalyst is 1 to 1000 gram atoms of aluminum of the organobenium compound per gram atom of titanium in the solid catalyst component, particularly preferably 10 to 200 gram atoms of the organic The molar ratio of the acid ester to the organic acid ano I benium compound is 0.05 to 0.6. The amount of the solid catalyst component used is essentially determined by the content of titanium atoms contained in the solid catalyst. It is preferable to use within the range of 0.1 to 5 Twi1, preferably 0.2 to 2.0 Twi1 per titanium atom. In addition, the amount of organoaluminum compound used is determined by the content of titanium atoms in the solid catalyst component and the amount used, and is used within the molar ratio range mentioned above. When carrying out in a hydrogen chloride solvent, it is preferable to use 0.1 nTn0j or more, preferably in the range of 0.3 to 5 mm01 per solvent 11.

Further, the amount of the organic acid ester to be used is determined by the amount of the organoaluminum compound used, and is used within the above-mentioned molar ratio range. When a polymerization catalyst is prepared in a polymerization reactor using these three catalyst components, after the formation of the catalyst, olefin is fed into the same vessel, or when the polymerization catalyst is prepared in a separate vessel. The catalyst suspension 15
The olefin can be easily polymerized by charging the suspension into a polymerization reactor and supplying the olefin into the same container.

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 20 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 a batch method, a continuous method, or other methods. Any method is acceptable〇The preferred polymerization temperature is 30-200℃
, especially 40 to 100°C, and the polymerization pressure is 1 to 50K.
f/Cw? is preferred.

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 is to add hydrogen to the polymerization system. It's a method.

The olefins to be polymerized are 1-olefins having 3 or more carbon atoms, such as propylene, 1+35 butene, styrene, and 4-methyl-1-benzene, and their copolymer components include vinyl groups such as ethylene, butadiene, isoprene, etc. are olefins and diolefins with

As mentioned above, the present catalyst system has extremely high polymerization activity, so the amount of residual catalyst in the polyolefin obtained even without any catalyst removal operation is extremely small.

As a result, the residual catalyst has almost no negative effect on the quality of conventional polyolefins, and it has many advantages such as molded products with excellent color tone and strength can be obtained by processing it as is. It is extremely large. Example 1 a) Preparation of reaction product (a) of 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 (n-butylmagnesium chloride 0.167 m02) was collected, and while stirring, 10.51 fL1 of methylhydropolysiloxane (viscosity at 25°C of about 30 centistokes) whose ends were capped with trimethylsilyl groups (0.17 m as Si) was collected.
5m00 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, the solution was kept at 70°C for 1 hour, and then cooled to room temperature to obtain a dark brown transparent solution. A portion of this solution was taken and the method of Gilman et al. (J. Am. C.
hem. SOc. 472OO2 (1925) for the presence or absence of unreacted n-butylmagnesium chloride, it was found that there was no unreacted n-butylmagnesium chloride. The solvent was distilled off under reduced pressure while maintaining the solution at 50° C., yielding 38.69% of the reaction product a) as a white solid. The amount of tetrahydrofuran contained in this white solid was 0.44 m01 per M9l atom. (The amount was determined using hydrolysis gas chromatography.)
)) Production of reaction product (b) The above white solid reaction product r) 12.5f! was collected and dissolved in 200ml of toluene, and SiC242O.
49 was added dropwise to the mixture at 44 to 60° C. over 1.5 hours while stirring.

Thereafter, the reaction was carried out at the same temperature for 1.5 hours.゛After the reaction,
Separate the solid phase and add 500 ml of n-hexane. Gradient filtration washing was performed four times with ILI. This was then dried under reduced pressure at 50°C to obtain 7.29 of a white reaction product (b).

This reaction product (b) 1f! M9 content in 17117
1V (703mm01) Chlorine content 402 (5.74
mm01), silicon content 111η (3.75mm01)
It was hot.

c) Production of solid catalyst component The above white reaction product (b) 4.29 was collected in a glass reactor whose inside was thoroughly dried and purged with nitrogen, and then 80 ml of toluene and 1 triphenyl phosphate were added thereto. 6.149 was added.

After that, TiC24 2599 was added and the reaction was carried out at 70° C. for 2 hours and under reflux for 2 hours. After the reaction was completed, the solid phase was separated and washed five times with 300a of n-hexane. 5. Next, drying under reduced pressure at 50°C. A solid catalyst component 10 of O9 was obtained. The titanium content in this solid catalyst component 19 was 47.3'l7.

d) In a stainless steel autoclave with an internal volume of 1.2J, equipped with a stirrer, a heating and cooling jacket, the interior of the polymerization reaction was thoroughly dried and purged with nitrogen. 600ml of n-hexane, well purified according to a conventional method, 1 triethyl benium O, 45 mmol.
, methyl p-tonoleinoleate O. 13 mmol and 12.720 mv of the above-mentioned solid catalyst component were sequentially added.

The polymerization system was then heated to a temperature of 70° C., propylene was introduced, and the total pressure was raised to 7.0 Kf/~ to initiate polymerization. After polymerization was carried out for 1 hour while keeping the temperature and total pressure constant, the introduction of propylene was stopped, the temperature was cooled to room temperature, and the temperature and total pressure were kept constant.
5 The reaction propylene was purged. The polymer was separated using a glass filter and dried under reduced pressure at 50° C. for 5 hours to obtain 66.89 g of white powdered polypropylene. On the other hand, the amount of the polymerization solvent-insoluble polymer recovered from the polymerization solvent was 3.1 g, and the production ratio of the polymerization solvent-insoluble polymer to the total produced polymer was 95.6%.

Further, the residual ratio of the polymerization solvent-insoluble polymer after extraction with boiling n-heptane (hereinafter abbreviated as ■I) was 96.4%.
35 The polymer production efficiency per 19 solid catalyst components and per 19 titanium atoms of this catalyst is 5.5 Kf/f, respectively! cat hr, 116.5Kf
It was 9 Tihr. Example 2
40c) Production Example 1 of solid catalyst component
The solid catalyst component was produced under the same method conditions as in Example 1-c), except that triphenylphosphate in the production of the solid catalyst component in -c) was changed to triphenylphosphite 17.59. .

5.39 of the solid catalyst component was obtained, and the titanium content in 19 of this was 75.5 m (l).

d) Polymerization Reaction Polymerization of propylene was carried out under the same method conditions as in Example 1-d) except that the amount of the solid catalyst component used was 7.9 kg.

39.39% of white powdered polypropylene and 3.39% of polymerization solvent soluble polymer were obtained.

The production ratio of the polymerization solvent-insoluble polymer was 92.3%, and I■ was 95.3%.

per 19 solid catalyst components of this catalyst and 1 fl titanium atom
Polymer production efficiency per unit is 5.39 Kf/9 ca.
thr, 71. It was OK'/9Tihr.

Example 3c) Preparation of solid catalyst component Same as Example 1-c) except that triphenyl phosphate was replaced with n-butyl ether 4.69 in Example 1-c). A solid catalyst component was produced using the method and conditions described below.

5.8f! A solid catalyst component of 19 was obtained, and the titanium content in 19 was 87.6η.

1) Polymerization reaction Propylene was polymerized in the same manner and under the same conditions as in Example 1-d, except that the amount of the solid catalyst component used was 6.8 m (l).

44.69 white powder polypropylene 3.9f! A polymerization solvent-soluble polymer was obtained.

The production ratio of polymerization solvent-insoluble polymer was 92.0%, and
I was 94.9%.

Solid catalyst component 1f of this catalyst! Polymer production efficiency per titanium atom and 19 titanium atoms are 7.13 kg and 9 ca, respectively.
thr, 80.8 Kf/9 Tihr.

Example 4)) Production of reaction product (b) Using a glass reactor, 10.39 g of reaction product (a) obtained in the same manner as in Example 1-a) was collected and dissolved in 80 ml of toluene. Then 4.59 g of benzophenone was added.

Toluene solution containing SiCl416.89
! fLl was added dropwise at 54 to 60° C. over 1 hour while stirring.

Thereafter, the reaction was continued for 2 hours at the same temperature. After the reaction was completed, the mixture was cooled and used in the next step of producing a solid catalyst component.

c) Production of solid catalyst component The reaction mixture containing the reaction product (b) obtained in the previous section was allowed to stand, and after the solid components were sufficiently precipitated, most of the supernatant was removed.

Next, TiCl43459 was added and the reaction was carried out under reflux with stirring for 2 hours. After the reaction was completed, the solid phase was separated and n-
After degrading and over-washing 5 times with 300 d of hexane and drying under reduced pressure, a solid catalyst component of 5.1 f1 was obtained.
The titanium content inside was 38.977?1.

d) Polymerization Reaction Polymerization of propylene was carried out in the same manner and under the same conditions as in Example 1-d), except that the amount of the solid catalyst component used was 15.4 TI1f.

70.3f10) Powdered polypropylene and 5.49 polymerization solvent soluble polymers were obtained.

The production ratio of polymerization solvent-insoluble polymer was 92.9%, and 1
1 was 95.0%.

Solid catalyst component 1f of this catalyst! per and titanium atom 1g
Polymer production efficiency per unit is 4.92KP/Flcathr
, l26.2Kp/GTihr〇Example 5c
) Production of a solid catalyst component In the production example of a solid catalyst component in Example 1-c), triphenyl phosphate was replaced with diphenyl ether 7.7f!
The reaction product (5) diphenyl ether and TiCl4 were reacted in the same manner as in Example 1-c) except that .

After the reaction, the solid phase was thoroughly washed with n-hexane,
Then, 73 g of TiCl4 was added again and the reaction was carried out under reflux for 2 hours. After the reaction, the solid phase was separated, decanted 5 times with 300 d of n-hexane, dried under reduced pressure, and then
．． 7 g of solid catalyst component was obtained. The titanium content in 19 of this product was close to 89.3 d) Polymerization reaction The same method and conditions as in Example 1-d) were used except that the amount of the solid catalyst component used was 6.7 mf. Polymerization of propylene was carried out at

58.0f! 0) Powdered polypropylene and 3.8f! The production ratio of the polymerization solvent-insoluble polymer was 93.9%, and the production ratio of the polymerization solvent-insoluble polymer was 93.9%.
It was 5.5%.

Solid catalyst component 1f of this catalyst! per, and titanium atom 1
The polymer production efficiency per 9 p/9c is 9.22, respectively.
athr, 103.0Kp/9Tihr Example 6-) Production of solid catalyst component Example 5-c) All the procedures were performed except that diphenyl ether was replaced with pyridine 2.4f1 in the production example of solid catalyst component 5-c). A solid catalyst component was produced using the same method and conditions as in Example 5.

A solid catalyst component of 5.59% was obtained, and the titanium content in 19 of this product was 76.6η.

1) Polymerization reaction Propylene was polymerized in the same manner and under the same conditions as in Example 1-d), except that the amount of the solid catalyst component used was 7.8 TRf.

52.290) Powdered polypropylene and 4.49 polymerization solvent-soluble polymers were obtained.

The production ratio of polymerization solvent-insoluble polymer is 92.2%, 11 is 9
It was 4.0%.

per 1f1 solid catalyst component of this catalyst, and 1 titanium atom
Polymer production efficiency per f1 is 7.26KP/9cath
r, 94.3Kf/FITihr 〇〈Example 7
c) Production of a solid catalyst component In the production example of a solid catalyst component in Example 5-c), all methods and conditions were the same as in Example 5-c), except that diphenyl ether was replaced with diethylthioether 2.79%. A solid catalyst component was produced.

A solid catalyst component of 4.89 was obtained, and the titanium content in 19 of this was 50.4 mf.

d) Polymerization Reaction Polymerization of propylene was carried out in the same manner and under the same conditions as in Example 1-d), except that the amount of the solid catalyst component used was 11.9%.

34.89% of powdered polypropylene and 3.09% of polymerization solvent soluble polymer were obtained.

The production ratio of polymerization solvent-insoluble polymer is 92.1%, 11 is 9
It was 5.8%.

per 19 solid catalyst components of this catalyst, and 1f titanium atoms
The production efficiency of each polymer is 3.18 KP/f!
Cathr, 63.0Kf/1 Tihr.

Example 8 d) In a stainless steel autoclave with a capacity of 1.21 and equipped with a stirrer and a heating/cooling jacket, the interior of the polymerization reaction was dried and purged with nitrogen, and 600 ml of hexane well purified according to a conventional method was added.
1, 0.60 mm of triethylaluminum, 015 mm of methyl p-toluate, and 8.5 m of the solid catalyst component obtained in Example 1-c) were sequentially added.

Next, after adding hydrogen to the polymerization system at 0.07 K9/calendar, the temperature of the polymerization system was increased to 60'C.
-Introducing butene-1, total pressure 2.5Kf/Cri? Polymerization was started at .

After polymerizing for 1 hour while keeping the temperature and total temperature constant, n-
The introduction of butene-1 was stopped, and the unreacted n-1 was cooled to room temperature.
Butene-1 was purged.

The contents were poured into a large amount of methanol to obtain a white polymer. Then, after tear separation, Masuda heating drying (50°C, 5 hours)
A white solid polymer 22.69 was obtained. The polymer production rate per gram of titanium atom of this catalyst is 56.5Kf/
It is GTihr. On the other hand, when this polymer was extracted in boiling diethyl ether for 18 hours, the insoluble matter was
It was confirmed that it was a highly stereoregular polymer.

In addition, the melt index (ASTMll) of this polymer
) - According to 1238, 190'C, load 2.16Kf
(measured at ) was 0.24y/10 rot 71.

Examples 9 to 12 d) Polymerization reaction using the solid catalyst components obtained in Examples 2, 3, 4 and 5,
The usage amount is 5.3~, 4.61n (i!, 1
All the same as Example 8- except that it was 0.3m9 and 4.5~
Polymerization of butene-1 was carried out using the same method and conditions as in d).

The polymerization results are summarized in Table 1.

Claims (1)

[Claims] 1 [A] (1) Formula R^1aHbSiO (4-a-b/
2) (However, 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, a is an integer of 0, 1, or 2, and b is an integer of 1, 2, or 3.
The reaction product (a) of a linear or cyclic hydropolysiloxane having a structural unit represented by (a+b≦3) and a Grignard reagent has the general formula R^2nM^(
^Z^)Xz-n (However, in the formula, R^2 is a carbon number of 1 to 12
a hydrocarbon group, M represents an aluminum atom or a silicon atom, z represents its valence, and represents the number of 3 or 4,
represents a halogen atom, and n represents a number from 0 to (z-1). ) A reaction product obtained by reacting one or more compounds represented by (b), (2) at least one selected from ether compounds, ketone compounds, phosphorus-containing compounds, nitrogen-containing compounds, and sulfur-containing compounds. Using a catalyst consisting of a solid catalyst component obtained by contacting one type of electron-donating compound and (3) at least one type of titanium halogen compound, [B] an organoaluminum compound, and [C] an organic acid ester. A method for producing a stereoregular polyolefin, characterized by: