JPS588684B2 - Method for producing novel highly 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, and more specifically, in obtaining polyα-olefins such as polypropylene,
The present invention relates to a novel method for producing polyolefins using a novel catalyst which is sufficiently active in small amounts so that removal of the catalyst is not necessary and can reproducibly and stably 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 catalysts such as dialkyl aluminum halides. This is a catalyst system consisting of an aluminum compound.

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 the transition metal compound on a carrier, which makes it possible to substantially omit the catalyst removal step. A method is proposed.

As one of the methods, the present inventors reacted a reaction product of a specific silicon compound and a Guerignard reagent with a halogen compound of aluminum and/or silicon and a halogen compound of titanium in the presence of an organic acid ester. We proposed the use of a catalyst consisting of a solid catalyst component obtained by this process and an organoaluminum compound.

(Japanese Patent Application No. 53-14059) Later, the inventors discovered that the above-mentioned catalysts had sufficiently high activity and were able to obtain polyolefins with high stereoregularity, but as a result of further research, they discovered the following. We found that there are some practical difficulties.

That is, when polymerizing olefins using the above catalyst system, the molar ratio of the organoaluminum compound added to the polymerization system and the titanium atoms in the solid catalyst component (hereinafter, the molar ratio of the organoaluminum compound and titanium atoms is referred to as the organic AI). /Ti.

) has a great effect on the catalytic activity and the stereoregularity of the resulting polymer, and in all the catalyst systems mentioned in the examples of the previous proposal (Japanese Patent Application No. 5.3-14059), the organic As the Al/Ti ratio increases, the catalyst activity increases, but the stereoregularity of the polymer decreases.

In particular, the amount of produced amorphous rubber-like polymers having an organic Al/Ii ratio of 30 or more and having substantially little utility value increases significantly.

Therefore, in order to make the production ratio of the stereoregular polymer in the produced polymer 85% or more, for example, in the catalyst of Reference Example 1, the organic Al/Ti ratio needs to be 15 or less, and in particular the stereoregularity To maintain the polymer production ratio at 94-95% or higher,
The organic Al/Ti ratio must be 6 or less.

Of course, even at the low organic Al/Ti ratio mentioned above, the catalytic activity is sufficiently high that there is no need to remove the catalyst residue, and there is essentially no loss in the usefulness of this catalyst system. It's not something you can do.

However, the fact that this catalyst system has the above-mentioned characteristics may cause considerable inconvenience for the purpose of achieving stable polymerization with good reproducibility.

In other words, this catalyst system maintains an extremely high polymerization activity for a long time, and the amount of polymer produced per titanium atom is extremely high. For example, in the case of propylene, the amount of polypropylene produced per 1 g of titanium atom is several hundred kg or more. P.

For this reason, it is necessary to avoid adding a large amount of catalyst into the polymerization system at once.

The reason for this is (i) Reaction heat cannot be removed smoothly throughout the polymerization reaction period, making it difficult to control the reaction.

(ii) When using a slurry polymerization method, etc., if the solid polymer concentration in the polymerization system becomes unnecessarily high and exceeds a certain concentration, it becomes impossible to maintain a slurry state with excellent fluidity, so it is difficult to control the reaction. Handling of the slurry after the reaction is extremely difficult, and the efficiency of polymer production per catalyst is reduced.

Therefore, in order to stably polymerize olefin using this catalyst, whether the polymerization method is a batch method or a continuous method, the above-mentioned (i), (i
The amount of catalyst must be adjusted within an appropriate range so that the phenomenon described in i) does not occur.

However, on the other hand, considering the above-mentioned (i) and (ii), and in order to maintain the stereoregularity of the obtained polymer at a high level, the following points are necessary to keep the organic A1/Ti ratio low. A new problem arises.

(iii) Due to various reasons such as productivity, quality, economic efficiency, etc., the production ratio of stereoregular polymer in all produced polymers is 94 to 95.
% or more, but as already mentioned, in this catalyst system proposed earlier, the organic Al/Ti ratio must be 6 or less.

However, considering the extremely high polymerization activity of this catalyst system and the above-mentioned (i) and (ii), the amount of catalyst used must be extremely small.

An example of polymerization conditions that can satisfy these conditions is as follows.

Polymerization conditions for Reference Examples 5 and 6 Under these polymerization conditions, the influence of extremely small amounts of impurities, particularly water, present in the polymer system cannot be ignored.

That is, under the polymerization conditions shown above, the n-
Assuming that 1 ppm of water is contained in hexane, the absolute water content is 0.022 mmol, which is comparable to the amount of titanium atoms added as a catalyst, and it also affects the organic AI/Ti ratio of the polymerization system. This results in fluctuations in the active and stereoregular polymer production ratios,
This makes it extremely difficult to carry out polymerization with good reproducibility.

The present inventors' future proposal (Japanese Patent Application No. 53-14059)
As a result of continuing intensive research to resolve the deficiencies of the catalyst, etc. in In order to keep the molar ratio between the organoaluminum compound and the total organic acid ester including the organic acid ester contained in the solid catalyst component within a specific range, an organic aluminum compound is newly added to the polymerization system. By adding an acid ester, we have found an excellent catalyst system that has an extremely high stereoregular polymer production ratio and polymerization activity, and also eliminates the deficiencies of the previously proposed catalyst system.

This organic acid ester has been widely known as having the effect of improving the production ratio of stereoregular polymers, and for example, in US Pat. It is described that ethylene glycol diacetate is used as a third component in the system catalyst, but other third components that provide similar effects include benzyl acetate, α-valerolactone, butyl oxalate, butyl benzoate, and isoprobil. There are examples of phthalates, etc., and in Japanese Patent Publication No. 42-27051, ethyl acetate, ethyl propionate, methyl benzoate are used as the third component in aluminum sesquihalide or aluminum monoalkyl dihalide to titanium trihalide catalysts. Furthermore, in Japanese Patent Publication No. 46-12140, benzoic acid derivatives such as ethyl benzoate, ethyl P-toluate, and ethyl P-anisate are added to dialkyl aluminum monohalide to titanium trihalide catalysts. There are examples in which they are used as three components, and it has been shown that all three components improve the production ratio of stereoregular polymers.

The present inventors used these organic acid esters, set the usage amount within a specific range, and set the molar ratio of the organoaluminum compound and the titanium atoms in the solid catalyst component within a specific range, thereby achieving steric We have discovered an excellent catalyst system that not only has a high production ratio of regular polymers but also has extremely high activity and can perform polymerization extremely stably and with good reproducibility, and has completed the present invention. It is.

That is, a is selected from the group consisting of a kyl group, an aryl group, an aralkyl group, an alkoxy group, and an alloxy group, and a is 0,
An integer of 1 or 2, b indicates 1, 2 or 3, a+b
≦3), a chain or cyclic hydropolysiloxane, a Grignard reagent, and the reaction product (a) has the general formula R2nM(z)
In the formula, R2 represents a hydrocarbon group having 1 to 12 carbon atoms, M represents an aluminum atom and/or a silicon atom, 2 represents its valence and represents the number of 3 or 4, X represents a halogen atom,
n represents a number from 0 to (z-1).

A reaction product (b) obtained by reacting one or more compounds represented by (b) with one or more titanium halogen compounds in the presence of an organic acid ester. When producing polyolefin using a catalyst system consisting of solid catalyst component 8, organoaluminum compound (B), and organic acid ester (C), (i) organoaluminum compound (B) and solid catalyst component A
The molar ratio of titanium atoms contained in the solid catalyst component (A) is within the range of 10 to 80, and (ii) the organoaluminum compound (6 ) (hereinafter this molar ratio will be referred to as total organic acid ester/organic AI ratio) is within the range of 0.1 to 0.4.

When α-olefin is polymerized using the catalyst according to the method of the present invention, the above-mentioned disadvantages can be solved and the stereoregular polymer can be produced stably and reproducibly over a long period of time while maintaining the production ratio at a high level. Polymerization can be carried out well.

Moreover, since the yield of polyolefin per titanium atom and the yield of polyolefin per solid catalyst component are extremely high, there is no adverse effect due to titanium halogen compounds in the obtained polymer without performing expensive operations such as catalyst removal. Almost unrecognized.

In addition, this catalyst system is sensitive to small amounts of molecular weight regulators such as hydrogen, making it extremely easy to control the molecular weight of the resulting polymer. Not only does the observed decrease in the production ratio of stereoregular polymers occur, but also there is 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 and spherical powder shape, has a high powder bulk specific gravity, and has a particle size of 105 μ or more and 350 μ or less, accounting for more than 95% of the total, and has a narrow particle size. It has many advantages such as excellent fluidity of polymer slurry and dry polymer powder and easy handling due to its small particle size distribution, especially the small fraction of 3% or less of 105μ or less. It has the following.

Furthermore, the method for producing the solid catalyst component A in the present invention involves reacting the reaction product (a) of a hydropolysiloxane and a Grignard reagent with an aluminum compound or a silicon compound, and then converting the obtained reaction product into an organic acid ester. The manufacturing method of the solid catalyst component is simple, as it only requires reacting titanium with a rogen compound in the presence of titanium, and it has the advantage of being able to easily produce a solid catalyst component of constant quality with good reproducibility. Its industrial value is extremely large.

In this way, by keeping the organic AI/Ti ratio and the total organic acid ester/organic Al ratio in the polymerization system within specific ranges, extremely high catalytic activity and a high production ratio of stereoregular polymer can be maintained. In addition, the fact that polymerization can be achieved extremely stably and with good reproducibility is a surprising fact that the present inventors could not have expected at first.

At present, it is not possible to provide a sufficient explanation for this phenomenon, but it is simply the solid catalyst component (A
), but also the interaction between the specific organosilicon compound and the Grignard reagent (a) and the halogen compound of aluminum and/or silicon (b). ) is thought to play a major role as a substrate for the solid catalyst component (A), causing some kind of structural change in the solid catalyst and producing a phenomenon that can be said to be specific.

Moreover, the structural change of the solid catalyst component 8 using this reaction product (b) as a substrate is caused by adding the organic acid ester (
It is thought that C) is suppressed and leads to excellent effects.

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). 1
It is a valent organic group, a represents 0, 1 or 2, b represents 1, 2 or 3, and a+b≦3.

) is a chain or cyclic hydrobolysiloxane having a structural unit represented by the formula (2), and is a compound of any degree of polymerization or a mixture thereof, and has a viscosity of 100,000 centistokes at 25°C from a low-viscosity liquid with a low degree of polymerization. Examples include grease-like or 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,
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 a general formula obtained by the reaction of a halogen-containing organic compound and magnesium metal (wherein, R3 is a hydrocarbon group, X is a halogen atom, or , p and q are 0 to 1
, and has the relationship p+q=1.

), its ether complex compound, or a mixture thereof, for example, R3M where p is 0 and q is 1
Dihydrocarbylmagnesium represented by R7Mg, a so-called Grignard reagent in the narrow sense, represented by gX, where p is 1 and q is O, and other various organic magnesium halides represented by (MgR:)p・(R3MgX)q, and the like. ether complex compounds or mixtures thereof.

These Grignard reagents are prepared in the presence of an appropriate amount of a complexing agent such as an ether or an amine in an ether solvent such as diethyl ether, dibutyl ether, or tetrahydrofuran, or in a hydrocarbon solvent such as hebutane octane, benzene, or toluene. It is easily synthesized below.

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, 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 the molar ratio of MgR3:Si is 0.05 to 1:1.

The reaction product (a) thus obtained can be used as a reaction mixture for producing the reaction product (b) in the present invention, but it is not preferable if it contains a large amount of ethers derived from the Grignard reagent. Generally, some or all of the solvent is removed from the reaction mixture containing reaction product (a), and the reaction product (a) 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 and reacted as a homogeneous solution. It is preferable to use it for the production of product (b).

The general formula R2nM(Z)Xz-n (wherein R3 is a hydrocarbon having 1 to 12 carbon atoms, M is an aluminum atom or a silicon atom, represents its valence and the number 3 or 4,
X represents a halogen atom, and n represents a number from 0 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, when n is 0, it is represented by M(z)Xz, which is aluminum halide, silicon halide, and R3
is an alkyl group, an alkyl aluminum halide,
Alkyl silicon halides and the like.

Specific examples of these compounds include aluminum trichloride, aluminum tribromide, aluminum triiodide, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride, etc. Examples of silicon compounds include silicon tetrachloride, methyltrichlorosilane, dimethylchlorosilane, trimethylmonochlorosilane, ethyltrichlorosilane, butyltrichlorosilane, phenyltrichlorosilane, and silicon tetrabromide.

These compounds represented by the general formula R2nM(Z)Xz-n can of course be used as a mixture.

The reaction product (b) in the present invention is the reaction product (
It is obtained by reacting a) with a compound represented by the above general formula R3nM(z)Xz-n or a mixture thereof.

Although the reaction can be carried out 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, an aromatic hydrocarbon solvent such as benzene, toluene, etc. is used as the inert hydrocarbon solvent, and the reaction product (a
) as a homogeneous solution of these solvents allows the reaction to proceed smoothly, produces a homogeneous reaction product (b) with good reproducibility and a constant quality, and makes it possible to always produce a homogeneous solid catalyst component with a constant quality. It is extremely preferable also from the viewpoint of obtaining a polyolefin having excellent powder characteristics.

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)Xz-n or a mixture thereof in a proportion of 0.1 to 10 moles.

Although the reaction temperature and reaction time for both can be arbitrarily selected, they are generally in the range of -10°C to 120°C and 5 minutes to 20 hours.

In particular, in order to obtain preferable powder characteristics such as bulk specific gravity and particle size distribution of the polyolefin, a temperature of 0° C. to 80° C. for 1 hour to 8 hours is suitable.

The reaction product (b) thus obtained may be used as a reaction mixture for preparing a solid catalyst component, or the reaction mixture may be washed with an inert hydrocarbon solvent such as hexane, heptane, kerosene, etc. Only the reaction product (b) that is insoluble in the inert hydrocarbon solution may be separated and recovered 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 when preparing the next step solid catalyst component (A). The latter operation is preferable because it becomes difficult to obtain a polymerization catalyst exhibiting high catalytic efficiency and the production rate of stereoregular polymers decreases.

When using the reaction product (b) separated and recovered by washing with an inert hydrocarbon solution, it should be thoroughly dried by a method such as vacuum drying, or it should be washed in an inert hydrocarbon solvent. Any method may be used as a dispersed product.

Then, the reaction product (b) in the presence of an organic acid ester
The halogen-containing compound of titanium used in the reaction between the halogen compound of titanium and the halogen compound of titanium has the general formula TiXm (OR4).
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 specific examples include TiC
14, TiBr4, Ti(OC2H5)C13, Ti(
OC4H9)Cl3, Ti(OC2H5)2Cl2, T
i(OC3H7)2C12, Ti(OC4H,)2Cl
2nd prize is mentioned.

The reaction between the reaction product (b) and the titanium-containing halogen compound can be carried out in the presence or absence of an inert hydrocarbon solvent.

Although both can be reacted in any ratio, it is preferable to use the halogen-containing titanium compound in a ratio of 0.1 to 150 mol per 1 mol of magnesium in the reaction product (b).

Further, in the reaction of the reaction product (b) with the titanium halogen compound, examples of organic acid esters that are allowed to coexist include aliphatic carboxylic acid esters, aromatic carboxylic acid esters, and aliphatic carboxylic acid 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, and ethyl anisate.

The amount of the organic acid ester used is in the range of 0.1 to 20 mol, preferably 0.5 to 5 mol, per 1 mol of Mg atoms in the reaction product (b).

The method for adding an organic acid ester is (1) When preparing the reaction product (b), the reaction product (a
) and a compound represented by the general formula R2nX(z)Xz-n.

(2) A method in which the reaction product (b) is mixed with the titanium halogen compound in advance before the reaction product (b) is reacted with the titanium halogen compound.

(3) A method in which a halogen compound of titanium is added to the reaction product (b) at the same time as the reaction is carried out.

(4) A method in which a titanium halogen compound is added after being added to the reaction product (b).

Either of these may be used.

The reaction temperature and reaction time between the reaction product (b) and the titanium halogen compound in the presence of an organic acid ester are not particularly limited, but may be 50°C to 150°C, 30 minutes to 2
It is generally carried out within a range of 0 hours.

Thus, a solid catalyst component is produced, and the solid catalyst component 8 is recovered by washing the reaction mixture with an inert hydrocarbon solvent such as hexane, heptane, kerosene, etc. to remove soluble components.

The solid catalyst component thus obtained is used as an olefin polymerization catalyst together with the organoaluminum compound (β) and the organic acid ester (C), and the organic AI/Ti ratio and the total organic acid ester/organic AI ratio are If both are kept within the specific ranges described in this invention, polymers with sufficiently high activity and high stereoregularity can be produced; A solid component obtained by further treating the mixture with a titanium halogen compound and 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 thus obtained (A9 usually contains 0.
Contains 5% to 10% of titanium atoms by weight, and the molar ratio of organic acid ester to titanium atoms in the solid catalyst component is 0.6 to 4.
．． It is within the range of 0.

This solid catalyst component is dried by vacuum drying or the like, or is dispersed in an inert solvent and used for preparing a polymerization catalyst.

The organoaluminum compound (B) used in the present invention has the general formula AIR51X3-1 (wherein, R5 is a hydrocarbon group having 1 to 8 carbon atoms, X is a halogen atom, a hydrogen atom, or an alkoxy group, and 1 is 1 to 3 represents an integer.

) Specific examples of the organoaluminum compound (8) include trimethylaluminum, triethylaluminum, tributylaluminum, diethylaluminium chloride,
Examples include dibutylaluminum chloride, ethylaluminum sesquichloride, diethylaluminum hydride, dibutylaluminum hydride, diethylaluminum ethoxide, and one or more of these may be used in combination.

Furthermore, examples of the organic acid ester (C) 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, and ethyl anisate.

These organic acid ester ports may be the same as or different from the organic acid ester used in the production of the solid catalyst component.

The olefin polymerization catalyst used in the present invention is prepared by bringing the solid catalyst component (A), organoaluminum compound (B), and organic acid ester (C) into contact with each other in the presence or absence of an inert hydrocarbon solvent. It can be obtained by

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 container or polymerization reactor. You can force it.

The preferred ratio of these three components to form the olefin polymerization catalyst is the most important part of the present invention.

The molar ratio of the organoaluminum compound β] and the titanium atoms in the solid catalyst component A is kept within the range of 10 to 80, and at the same time the sum of the organic acid ester and the organic acid ester (C) in the solid catalyst component (A) organoaluminum compound (B) for
By keeping the molar ratio in the range of 0.1 to 0.4, the object of the present invention can be achieved for the first time.

That is, when the organic Al/Ti ratio is less than 10, it becomes extremely difficult to perform stable polymerization with good reproducibility due to the reasons mentioned above, and at a high ratio of 80 or more, the production ratio of stereoregular polymers decreases. do.

Of course, the production rate of the polymerization solvent-soluble polymer can be lowered by increasing the amount of organic acid ester (C) added, but the residual rate after extraction with boiling n-heptane will still decrease and the production ratio of the stereoregular polymer will decrease. This results in a number of unfavorable results, such as a decrease in the amount of carbon dioxide, or a significant decrease in catalytic activity.

Furthermore, total organic acid ester/organoaluminum compound (5)
If the molar ratio of A large amount of coalescence is generated.

Further, when the ratio is 0.4 or more, although the production ratio of stereoregular polymers does increase, the catalytic activity decreases significantly, and the object of the present invention cannot be achieved.

The amount of solid catalyst component 8 to be used is essentially determined by the content of titanium atoms contained in the solid catalyst, and for example, in the case of polymerization in an inert hydrocarbon solvent, it is determined per liter of solvent. 0.1 to 5 ■, preferably 0 in terms of titanium atoms
．． It is preferable to use it within the range of 2 to 2.0 mg.

Further, the amount of the organoaluminum compound (B) to be used is determined by the content of titanium atoms in the solid catalyst component N and the amount used, and is used within the above molar ratio range, but does not cause polymerization. When carried out in an activated hydrocarbon solvent, the amount is 0.1 mmol or more, preferably 0.3 to 5 per liter of solvent.
It is preferable to use it in the mmol range.

In addition, the amount of organic acid ester (C) used is the solid catalyst component (
A) Content of organic acid ester and solid catalyst component N
It is determined by the usage amount of the organic aluminum compound (B) and the usage amount of the organoaluminum compound (B) determined as described above, and is used within the molar ratio range specified above.

In this way, the usage amounts of each of the solid catalyst component (A), organoaluminum compound, and organic acid ester (C) are determined, and when preparing a polymerization catalyst in a polymerization reactor using these catalyst components, After the formation of the catalyst, by feeding the olefin into the same container, or if the polymerization catalyst is prepared in a separate container, the catalyst suspension is charged into the polymerization reactor and the olefin is fed into the same container. By doing so, the olefin can be easily polymerized.

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.

For polymerization, a suspension polymerization method in a suitable insoluble solvent, a solventless polymerization method in a monomer solvent, or a gas phase polymerization method may be adopted, and the polymerization method may be a batch method, a continuous method, or any other method. But that's fine.

The preferred polymerization temperature is 30 to 200°C, especially 60 to 100°C.
℃, and the polymerization pressure is preferably 5 to 50 kg/cm2.

The molecular weight of the polymer obtained by the method of the present invention is determined by the polymerization temperature,
Although it can be adjusted as desired by changing the amount of catalyst used, the most effective adjustment method is to add hydrogen to the polymerization system.

The olefins to be polymerized are 1-olefins having 3 or more carbon atoms, such as propylene, 1-butene, styrene, 4-methyl-1-pentene, and copolymerized components thereof such as ethylene, butadiene, isoprene, etc. These are olefins and diolefins that have vinyl groups.

As mentioned above, the present catalyst system has extremely high polymerization activity, so even if no catalyst removal operation is performed, the amount of residual catalyst in the polyolefin obtained is extremely small.

As a result, the residual catalyst has almost no negative effect on the quality of conventional polyolefins, and molded products with excellent color tone and strength can be obtained even when processed as is. Sex is a very big thing.

Reference Example 1 (a) Preparation of reaction product (a) of hydrobolysiloxane and Grignard reagent Place 75 ml of a tetrahydrofuran solution of n-butylmagnesium chloride (n-butylmagnesium chloride) in a glass reactor whose interior has been thoroughly dried and purged with nitrogen. 0.167 mol) of methylhydropolysiloxane (viscosity at 25°C of about 30 centistokes) whose ends were capped with trimethylsilyl groups was collected while stirring.
．． 5 ml (0.175 mol as Si) was gradually dropped.

Because it generates heat, the reactor is cooled with a refrigerant to maintain an internal temperature of 70°C.
After adding the entire amount, the mixture was kept at 70°C for 1 hour, and then cooled to room temperature to obtain a dark brown transparent solution.

Take a portion of this solution and use the method of Gilman et al. (J. Am.
．． Chem. Soc. 47 2002 (1925), the presence or absence of unreacted n-butylmagnesium chloride was investigated, and as a result, no unreacted n-butylmagnesium chloride was present.

The solvent was distilled off under reduced pressure while maintaining this solution at 50° C. to obtain 38.6 g of a white solid reaction product (a).

The amount of tetrahydrofuran contained in this white solid is Mg
The amount was 0.44 mol per atom.

(Quantitated by gas chromatography after hydrolysis.

) (b) Production of reaction product (b) 12.5 g of the above white solid reaction product (a) was collected into a glass reactor whose interior had been thoroughly dried and purged with nitrogen, dissolved in 200 ml of toluene, and SiCl420 ．．
4 g was added dropwise 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, the solid phase was separated and diluted with 500 ml of n-hexane.
Rotary gradient filtration washing was performed.

This was then dried under reduced pressure at 50°C to obtain a white reaction product (b
) 7.2ft was obtained.

The Mg content in this reaction product (b) IP is 171m? (
7.03 mmol) Chlorine content 402■ (5.74 mm
ol), silicon content 111~(3.95 mmol)
there were.

(C) Production of solid catalyst component 8 5.5 g of the above white reaction product (b) was collected into a glass reactor whose interior had been thoroughly dried and purged with nitrogen, and then 750 ml of n-hexane was added thereto. The reaction product (b) was suspended.

Thereafter, 208 g of TiCl4 was added, and the reaction was carried out under reflux for 1 hour.

Next, 10 ml of an n-hexane solution containing 5.81 ml of ethyl benzoate was added thereto, and the reaction was again carried out under reflux for 2 hours.

After completion of the reaction, the solid phase portion was separated, filtered and washed four times with 500 ml of n-hexane, and then dried under reduced pressure at 50° C. to obtain 4.6 g of solid catalyst component 8.

The titanium content in 1 g of this solid catalyst component (A) is 24.
The content of ethyl benzoate was 167.1 mg (1.113 mmol).

(d) In a stainless steel autoclave with an internal capacity of 1.2 liters, equipped with a stirrer whose interior was dried and purged with nitrogen, and a jacket for heating and cooling, n-hexane 600 well purified according to a conventional method was added.
7 ml of triethylaluminum, 3 mmol of triethylaluminum, and 16.0 mg (0.00835 mmol in terms of titanium atoms) of the above-mentioned solid catalyst component (A) were sequentially added (the molar ratio of the organoaluminum compound and titanium atoms during polymerization was 36).

) Next, the polymerization system was heated to a temperature of 70° C., and then propylene was introduced to bring the total pressure to 7.0 kg/cm 2 to start polymerization.

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.

The polymer was separated using a glass filter and dried under reduced pressure at 50°C for 5 hours to obtain white powdered polypropylene 103.7
I got g.

The bulk specific gravity of this powder is 0.35 g/ml, and the particle size distribution is narrow, with particles with particle sizes in the range of 150 μ to 250 μ accounting for 95% of the total, and microparticles of 105 μ or less accounting for 1.9%. , the average particle size was 188μ.

On the other hand, the amount of the polymerization solvent-soluble polymer recovered from the polymerization solvent was 22.4 g, and the production ratio of the polymerization solvent-insoluble polymer to the total produced polymer was 82.2%, which was quite low. The residual rate after extraction with boiling n-hebutane was 80.6%, which was also quite low.

The polymer production rate per 11 titanium atoms of this catalyst is 315.
It was 2 kg/gTihr.

The results are collectively shown in Table 3 together with the results of Reference Examples, Examples, and Comparative Examples described below.

Reference Examples 2 to 6 (d) Polymerization reaction All procedures were as in Reference Example 1, except that the solid catalyst component 8 obtained in Reference Example 1 was used, and the amounts of triethylaluminum and solid catalyst component 8 were as shown in Table 1. Polymerization of propylene was carried out under the same conditions and method.

The polymerization results are summarized in Table 3.

As is clear from the results in Table 3, Reference Examples 1, 2, 4, and 5
, and 6, it is clear that as the molar ratio of the organoaluminum compound and Ti atoms during polymerization decreases, the catalyst efficiency decreases, and the yield of the stereoregular polymer conversely increases. .

Further, as is clear from the results of Reference Example 3, if a large amount of catalyst is added to the polymerization system at once, it becomes difficult to maintain a predetermined polymerization temperature and it becomes almost impossible to carry out the polymerization normally.

Furthermore, as is clear from the results of Reference Examples 5 and 6, when the amount of organoaluminum compound used becomes extremely small, the reproducibility of polymerization becomes extremely poor.

In particular, the fluctuations in catalyst efficiency are large.

Reference Example 7 (b) Production of reaction product (b) AICI was placed in a glass reactor whose interior was thoroughly dried and purged with nitrogen.
311.1 g was collected and suspended in 300 ml of toluene, and 12.5 g of ethyl benzoate was added thereto.

Next, 105 ml of a toluene solution containing 17.3 g of reaction product (a) obtained in the same manner as in Example 1-(a) was added dropwise at 37 to 41° C. over 4.5 hours with stirring.

After dropping, reaction was carried out at the same temperature for 2 hours, and then 83-85
The temperature was raised to 0.degree. C., and the reaction was further carried out for 1 hour, and the mixture was used for the next step of producing solid catalyst component (A).

(c) Production of solid catalyst component 8 After the above reaction mixture was allowed to stand and the produced white solid reaction product (b) was sufficiently precipitated, 250 ml of the supernatant solution was taken out, and then 14,433 g of TiC was added and the mixture was refluxed. The reaction was carried out for 2 hours.

After the reaction was completed, the solid phase portion was separated, filtered and washed five times with 500 ml of n-hexane, and dried under reduced pressure to obtain 9.7 g of solid catalyst component particles.

The titanium content in 1 g of this solid catalyst component (A) is 10.
7 mg (0.223 mmol), and the ethyl benzoate content was 119.6 mg (0.796 mmol).

(d) Polymerization reaction The amounts of triethylaluminum and solid catalyst component (A) used were 0.3 mmol and 37.4 m9 (Ti
Polymerization of propylene was carried out in the same manner and under the same conditions as in Reference Example 1, except that the amount was changed to 0.00835 mmol (in terms of atoms).

The polymerization results are summarized in Table 3.

Reference Examples 8 to 9 (d) Polymerization reaction Using the solid catalyst component (A) obtained in Reference Example 7, the amounts used were 111.97 mg and 134.3 ~, respectively, and the amount of triethylaluminum used was 0.3 mmol, respectively. Polymerization of propylene was carried out in the same manner and under the same conditions as in Reference Example 1, except that the amount was changed to 0.18 mmol.

However, only in Reference Example 8, the polymerization time was 30 minutes.

The polymerization results are summarized in Table 3.

As is clear from Reference Examples 7, 8, and 9, as in Reference Examples 1 to 6, the organoaluminum compound and Ti during polymerization
A phenomenon in which activity decreases and stereoregularity improves as the molar ratio of atoms decreases is clearly observed.

Example 1 (d) Polymerization reaction Using the solid catalyst component 8 obtained in Reference Example 1, 0.3 mmol of triethylaluminum, 0.04 ethyl benzoate
All procedures were the same as in Reference Example 1, except that 16.0 mg (0.00835 mmol as titanium atoms) of the solid catalyst component (A) were used sequentially. Polymerization of propylene was carried out under process conditions.

72.6 g of white powdery polypropylene insoluble in the polymerization solvent was obtained, and the bulk specific gravity of this powder was 0.37 g/ml.
The particle size distribution is extremely narrow, with particles with a particle size in the range of 150 to 205μ accounting for more than 95% of the total, and microparticles with a particle size of 105μ or less accounting for 1.7%, with an average particle size of 172μ. It had excellent physical characteristics.

On the other hand, the amount of the polymerization solvent-soluble polymer recovered from the polymerization solvent was 0.7 g, and the production ratio of the polymerization solvent-insoluble polymer to the total produced polymer was 99.1%. The extraction residual rate was 96.0%.

In addition, the polymer production rate per Ig of titanium atom of this catalyst is 1
83.2kg/g. It was hr.

The results are collectively shown in Table 3 together with other Examples and Comparative Examples.

Examples 2 to 3 Using the solid catalyst component 8 obtained in Reference Example 1, the amounts used were 57.6 mg and 19.2 mg (0.03 and 0.01 mmol as titanium atoms), respectively, and the use of organic aluminum was Polymerization of propylene was carried out in the same manner and under the same conditions as in Reference Example 1, except that the amounts used were 0.3 and 0.8 mmol, respectively, and the amounts of ethyl benzoate were 0.01 and 0.16 mmol, respectively.

The polymerization results are summarized in Table 3.

In addition, in these particle size distributions, since more than 95% of the total particles have a particle size in the range of 150 to 205μ, the particle size 1
The proportion of microparticles smaller than 0.05 μm was 1.6% and 1.7%, respectively, and the average particle diameter was 178 μm and 174 μm.

Comparative Examples 1 to 6 All the same as Reference Example 1 except that solid catalyst component 8 obtained in Reference Example 1 was used and the amounts of triethylaluminum, ethyl benzoate, and solid catalyst component 8 were changed to the amounts listed in Table 2. Polymerization of propylene was carried out under the following method and conditions.

The polymerization results are summarized in Table 3.

As is clear from Table 3, when the molar ratio of the organoaluminum compound and Ti atom during polymerization becomes 100 or more, the production ratio of the polymer insoluble in the polymerization solvent hardly changes, but the boiling n
- The extraction residue with hebutane decreases, and the overall stereoregular polymer production ratio decreases.

In particular, the molar ratio of organoaluminum compound and Ti atom is 18
When it becomes extremely high as 0, not only the production ratio of the stereoregular polymer decreases, but also the catalyst efficiency decreases.

It is also clear that when the amount of organic acid ester added is increased in order to increase the production ratio of the stereoregular polymer, the activity is significantly lowered.

Furthermore, as can be seen from the results of Comparative Examples 5 and 6, even if the molar ratio of the organoaluminum compound and the Ti atom is maintained appropriately, if the total amount of the organic acid ester and the molar ratio of the organoaluminum compound are outside the appropriate range, the activity will be impaired. is sufficiently high, but the production ratio of the stereoregular polymer is greatly reduced, or even though the production ratio of the stereoregular polymer is sufficiently high, the activity is extremely reduced.

Examples 4 to 6 (d) Polymerization reaction Using the solid catalyst component (A) obtained in Reference Example 7, the amount of triethylaluminum used was 0.3, 0.8, and 0.3 m, respectively.
mol and the amount of ethyl benzoate used were 0.04 and 0.04, respectively.
18, 0.007 mmol, and the amount of solid catalyst component used was 37.4, 44.8, and 111.9 mm, respectively (0.00835, 0.01, and 0.025 mm as titanium atoms, respectively).
Polymerization of propylene was carried out in the same manner and under the same conditions as in Reference Example 1, except that ol was used.

The polymerization results are summarized in Table 3.

In addition, the particle size distribution of this material is such that particles with a particle size in the range of 175 to 250μ account for more than 95% of the total, and particles with a particle size of 10
The proportion of microparticles of 5μ or less was 2% or less in all cases, and the average particle diameters were 210, 214, and 204μ, respectively.

Comparative Examples 7 to 9 The solid catalyst component (A) obtained in Reference Example 7 was used, and the amount used was 44.8 ■ (0.01 mmol. as titanium atom).
, the use of triethylaluminum was 0.8 and 0.8, respectively.
Polymerization of propylene was carried out in the same manner and under the same conditions as in Reference Example 1, except that the amounts of ethyl benzoate used were 0.33, 0.33, and 0.29 mmol.

The polymerization results are summarized in Table 3.

As is clear from the results in Table 3, when the molar ratio of the total amount of organic acid ester to the organoaluminum compound and the molar ratio of the organoaluminum compound to the Ti atom exceed the appropriate range, the results of Comparative Examples 1 to 6 above Similarly, the catalyst efficiency may be extremely reduced or the production ratio of stereoregular polymers may be reduced.

Example 7 (b) Production of reaction product (b) The reaction product (b) obtained in the same manner as in Reference Example 1-[a] was placed in a glass reactor whose interior had been thoroughly dried and purged with nitrogen.
a) 20.8 g was taken and dissolved in 200 ml of toluene, and then 30.0 g of ethyl benzoate was added.

Toluene solution containing 34.0 g of SiC 80
ml was added dropwise at 55-60° C. over 3 hours 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 solid catalyst component 8.

(e) Production of solid catalyst component (A) Ti is added to the white reaction mixture containing the reaction product (b).
ll4259j' was added and the reaction was carried out under reflux for 2 hours with stirring.

After completion of the reaction, the solid phase portion was separated, filtered and washed four times with 500 ml of n-hexane, and dried under reduced pressure to obtain 8.2 g of solid catalyst component (A).

The titanium content in 1 g of this solid catalyst component (A) is 19.
The content of ethyl benzoate was 105.0 mg (0.699 mmol).

(e) Polymerization reaction 0.3 mmol of triethylaluminum, 0.04 mmol of ethyl benzoate and the above solid catalyst component [A120
．． 2mg (0.00835mmol as titanium atom)
Polymerization of propylene was carried out in the same manner and under the same conditions as in Reference Example 1, except that the following was used.

The results are summarized in Table 3.

In addition, the particle size distribution of this product was such that particles with a particle size in the range of 150μ to 205μ accounted for more than 95% of the total, microparticles with a particle size of 105μ or less accounted for 1.5%, and the average particle size was 182μ. .

Example 8 (d) Polymerization reaction Using solid catalyst component 8 obtained in Example 7, 0.3 m of triisobutylaluminum was used instead of triethylaluminum.
Polymerization of propylene was carried out under the same conditions as in Example 7-(d) except that mol was used.

The results are shown in Table 3. Example 9 (e) TiCl4 treatment of solid catalyst component (A) 3.2 g of solid catalyst component [A] obtained in Example 7 was collected in a glass reactor that had been previously dried and purged with nitrogen, and then 30 ml of n-hexane was added. Add and suspend.

Thereafter, 104 g of TiCl4 was added and the mixture was treated under reflux for 2 hours with stirring.

After the treatment reaction, the solid phase portion was separated and washed by gradient filtration four times with 300 ml of n-hexane. After drying under reduced pressure, 3.1 g of solid catalyst component 8 treated with TiCl4 was obtained.

The titanium content in 1 g of the TiCl4 treated solid catalyst component A is 21.7 mg (0.453 mmol), and the content of ethyl benzoate is 68.7 to (0.457 mmol).
Met.

(d) Polymerization reaction 0.3 mmol of triethylaluminum, 0.05 mmol of ethyl benzoate and T of the solid catalyst component (A)
iCl4 treated product 18.4 mg (0.0 as titanium atom)
Pleropile was polymerized using the same method and conditions as in Reference Example 1, except that O835 mmol) was used.

The results are shown in Table 3. Example 10 (e) Production of solid catalyst component (A) Reaction product 9 obtained in the same manner as in Reference Example 1-(b).
3 g was taken into a glass reactor whose inside was thoroughly dried and purged with nitrogen, and then 75 ml of n-hexane and 151 ml of ethyl benzoate were added thereto and suspended for 30 minutes with stirring.

Next, 4259 g of TiCl was added and the reaction was carried out under reflux for 2 hours.

After the reaction is complete, the solid content is sufficiently settled and 150 ml of supernatant liquid is added.
After removing the TiCl4173? was added thereto, and the reaction was further carried out under reflux for 2 hours.

After the reaction, the solid phase was separated and diluted with 500 ml of n-hexane.
Rotary gradient filtration washing was performed.

Next, drying was performed under reduced pressure at 50° C. to obtain 8.71 solid catalyst component A.

The titanium content in 1 g of this solid catalyst component (A) is 25.
2~(0.526 mmol), and the content of ethyl benzoate was 90.9 mg (0.605 mmol).

(d) Polymerization reaction 0.3 mmol of triethylaluminum, 0.07 mmol of ethyl benzoate and 15 of the above solid catalyst component (A)
．． Polymerization of propylene was carried out in the same manner and under the same conditions as in Reference Example 1, except that 9-(0.00835 mmol as titanium atoms) was used.

The results are shown in Table 3.

In addition, the particle size distribution of this material is such that more than 95% of the total particles have a particle size in the range of 150 to 205μ, and the particle size is 10
The proportion of microparticles larger than 5μ is 1.6%, and the average particle size is 18%.
It was 0μ.

Example 11 (d) Polymerization reaction Using the solid catalyst component obtained in Example 10-[c), 0.07 mmo of methyl p-toluate was used instead of ethyl benzoate.
Polymerization of propylene was carried out under the same conditions as in Example 10-(d) except that 1 was used.

The results are summarized in Table 3.

In addition, the melt index (A
According to STM-D 1238, 230°C, load 2.16
Measured at k9, hereinafter abbreviated as MI2.

) was 0.07g/10min.

Example 12 (d) Polymerization reaction Using the solid catalyst component 8 obtained in Example 10-(c), the usage amounts of triethylaluminum, methyl p-toluate, and solid catalyst component 8 were the same as in Example 11-(d). be the same,
Polymerization of propylene was carried out under the same method conditions as in Reference Example 1, except that 0.1 kg/cm2 of hydrogen was added to the polymerization system.

The polymerization results are shown in Table 3.

In addition, M■2 of the polymerization solvent-insoluble polymer is It was 1.35g/lOmin.

As is clear from the comparison with the results of Example 11, the decrease in both the production ratio of the active stereoregular polymer is extremely small.

Example 13 (c) Production of solid catalyst component 8 The procedure was carried out in the same manner and under the same conditions as in Example 1-(c), except that ethyl benzoate was replaced with 5.3 g of methyl benzoate.
8 g of solid catalyst component was obtained.

Titanium content in 1 g of this solid catalyst component (A): 20.3
mg (0.434 mmol), methyl benzoate content 1
It was 17.4 mg (0.862 mmol).

(d) Polymerization reaction Triethylaluminum 0.3 mmol, ethyl benzoate 0.04 mmol and the above solid catalyst component 'A) 19
．． 7mg (0.00835mmol as titanium atom)
Polymerization of propylene was carried out in the same manner and under the same conditions as in Reference Example 1, except that each of the following was used.

The polymerization results are shown in Table 3. Example 14 (b) Production of reaction product (b) Reaction product (a) obtained in the same manner as in Example 1-(a)
) 12.5g in 200ml of toluene, then CH
317 g of 3SiCl was added dropwise at 60 to 70°C over 2 hours, and after the dropwise addition was completed, the reaction was continued at the same temperature for an additional 2 hours.

After the reaction was completed, it was washed with n-hexane in the same manner as in Reference Example 1-(b) to obtain 6.1 g of a white reaction product (b).

(C) Production of solid catalyst component 8 5.5 g of the above reaction product (b) was added to 50 ml of n-hexane.
Solid catalyst component 8 was produced in exactly the same manner as in Reference Example 1-(c).

44 g of solid catalyst component 8 was obtained, and the titanium content in 1 g of this was 16.8-(0.351 mmol) and the ethyl benzoate content was 122.0 mg (0.812 mmol).
l).

(d) Polymerization reaction Triethylaluminum 0.3 mmol, ethyl benzoate 0.04 mmol, and the above solid catalyst component [A] 2
3.8■ (0.00835 mmol as titanium atom)
Polymerization of propylene was carried out in the same manner and under the same conditions as in Reference Example 1 except for using each of the following.

The results are shown in Table 3. Example 15 (b) Production of reaction product (b) Reaction product 6 obtained in the same manner as in Reference Example 1-(a).
Toluene solution 5 containing 4.3 g of diethyl aluminum monochloride after dissolving 3 g in 100 ml of toluene
0ml was added dropwise at 20-30°C over 1 hour.

Thereafter, the reaction was carried out at the same temperature for 2 hours.

After the reaction is completed, it is carried out in the same manner as in Reference Example t-(b), and 3.
5 g of white reaction product (b) was obtained.

(e) Production of solid catalyst component 8 3.0 g of the above reaction product (b) was added to 50 ml of n-hexane.
Then, 3.02 g of ethyl benzoate was added, and after stirring at room temperature for 30 minutes, 173 g of TiCl4 was added and the reaction was carried out under reflux for 2 hours.

After completion of the reaction, the solid phase portion was separated, filtered and washed five times with 300 ml of n-hexane, and dried under reduced pressure to obtain a solid catalyst component 8 with a weight of 2.72.

The titanium content in 1 g of this solid catalyst component (A) is 18.
The content of ethyl benzoate was 108-077V (0.719 mmol).

(d) Polymerization reaction 0.3 mmol of triethylaluminum, 0.04 mmol of methyl p-toluate and the above solid catalyst component [A
l22.1■ (0.00835 mmo as a titanium atom
The same method as in Reference Example 1 except that l) was used respectively,
Polymerization of propylene was carried out under the following conditions.

The polymerization results are shown in Table 3. Example 16 (c) Production of solid catalyst component 8 The solid catalyst component obtained by the same method as Example 7-(c) was further treated with Ti by the same method as Example 9-(c).
A Cl4 treatment was performed to obtain solid catalyst component 8.

The titanium content in 1 g of this solid catalyst component (A) is 22
．． The content of ethyl benzoate was 69.7 mg (0.464 mmol).

(d) In a stainless steel autoclave with an internal capacity of 1.2 liters, equipped with a stirrer whose interior was dried and purged with nitrogen, and a jacket for heating and cooling, 600 ml of n-hexane was thoroughly purified according to a conventional method.
1, 0.60 mmol of triethylaluminum, 0.15 mmol of methyl P-toluate, and 17.8 mmol of the above solid catalyst component A (0.00835 m in terms of titanium atoms).
mol) were added sequentially.

(In this example, the molar ratio of the organoaluminum compound to the titanium atom during polymerization was 72, and the molar ratio of the total organic acid ester to the organoaluminum compound was 0.26.

) Next, after adding 0.07 kg/cm3 of hydrogen to the polymerization system, the temperature of the polymerization system was raised to 60°C, whereupon n-butene-1 was introduced and polymerization was started at a total pressure of 2.8 kg/cm3. .

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

The contents were poured into a large amount of methanol to obtain a white polymer.

Next, after filtering, drying under reduced pressure and heating (50° C., 5 hours) was performed to obtain 65.3 g of a white solid polymer.

The polymer production rate per gram of titanium atom of this catalyst is 163
．． 5 kg/g Tihr.

On the other hand, when this polymer was extracted in boiling diethyl ether for 18 hours, the insoluble content was 96.0%, confirming that it was a highly stereoregular polymer.

In addition, the tart index of this polymer (190°C, load 2.16 according to ASTM D-1238)
kg) was 0.21 g/10 min.

Example 17 (c) Production of solid catalyst component 8 A solid catalyst component was produced in the same manner as in Example 10-(c), and 24.0 mg (0.0 mg) of titanium atoms were contained in 1 gram of solid catalyst component. A solid catalyst component (A) containing 501 mmol) and 80.5 mg (0.546 mmol) of ethyl benzoate was obtained.

(d) Polymerization reaction The amounts of triethylaluminum, P-methyl toluate, and the solid catalyst component 8 above were each 0.3 mmo.
l, 0.085 mmol, 16.7 ~ (0.00835 mmol in terms of titanium atoms), and the amount of hydrogen added was 0.085 mmol.
Polymerization of n-butene-1 was carried out in the same manner and under the same conditions as in Example 16-(d), except that the weight was 20 kg/cm3.

(In this example, the molar ratio of the organoaluminum compound to the titanium atom during polymerization was 36, and the molar ratio of the total organic acid ester to the organoaluminum compound was 0.31.

) A white polymer 49.2f was obtained by the same treatment method as in Example 16-(d).

The polymer production rate per gram of titanium atom of this catalyst is 123.
0 kg/gTihr.

On the other hand, as a result of extraction of this polymer in boiling diethyl ether for 18 hours, the insoluble content was 96.6%.

Also, the melt index (measured by the same method as in Example 16) of this product is 104? /10mm.

Claims (1)

[Scope of Claims] 1 selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, an alkoxy group, and an alloxy group, a represents an integer of 0, 1 or 2, and b represents 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 R2nM(z)Xz-n (wherein R2 is a hydrocarbon group having 1 to 12 carbon atoms, M represents an aluminum atom or a silicon atom, and 2 represents its valence;
The number 3 or 4, X is a halogen atom, n is 0 to (z
-1) represents the number. ) is obtained by reacting the reaction product (b) obtained by reacting one or more compounds represented by (b) with one or more titanium halogen compounds in the presence of an organic acid ester. When producing a polyolefin using a catalyst consisting of a solid catalyst component (A), an organoaluminum compound (B), and an organic acid ester (C), (i
) Organoaluminum compound [B] and solid catalyst component (A)
(ii) the molar ratio of titanium atoms contained in the organic aluminum compound (B) to the sum of the organic acid ester and the organic acid ester (C) contained in the solid catalyst component (A); ) is within the range of 0.1 to 0.4.