JPH06116325A - Polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To efficiently obtain a polymer excellent in particle characteristics and stereoregularity by polymerizing an alpha-olefin in the presence of a specific catalyst without the need for a large quantity of any titanium compound. CONSTITUTION:This polymer can be obtained by polymerizing an alpha-olefin such as propylene using a catalyst composed of (A) a solid catalytic component obtained by contact between (1) a solid component obtained by reaction of a hydrocarbon solvent-soluble organomagnesium component of formula I (M is group I or III metal; R<1>-R<3> are each 2-20C hydrocarbon) with a chlorosilane compound of formula II (R<4> is 1-20C hydrocarbon) in the presence of an aromatic hydrocarbon solvent, (2) a titanium compound of formula III (R<5> is 2-10C hydrocarbon; D is halogen) and (3) an aromatic carboxylic ester, (B) an organoaluminum compound of formula IV (R<6> is 1-20C hydrocarbon) and (C) an alkoxysilane compound of formula V (R<7> and R<8> are each the same as R<6>).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved method for polymerizing .alpha.-olefins. More specifically, the present invention, even at high temperature and long time polymerization,
The present invention relates to an α-olefin polymerization method suitable for efficiently and economically producing an α-olefin polymer having excellent particle characteristics and high stereoregularity.

[0002]

2. Description of the Related Art Heretofore, as a catalyst for stereoregular polymerization of olefins, the present inventors have previously proposed Japanese Patent Publication Nos. 57-9567 and 60-9.
-11924 and 62-5925, a halogen-containing magnesium solid obtained by reacting an organomagnesium component with a chlorosilane compound containing a Si-H bond is contacted with a halogen compound of titanium and an aromatic carboxylic acid ester. We have proposed a catalyst system consisting of the solid component obtained, aromatic carboxylic acid ester or alkoxysilane, and an organoaluminum compound, and found that a polymer having high activity and high stereoregularity can be obtained. After that, as a result of further intensive study, as an organomagnesium component, an organomagnesium component soluble in a hydrocarbon solvent and containing an alkoxy group in a specific range is used, and a halogen-containing magnesium solid is reacted with a chlorosilane compound having a Si-H bond. Using a solid catalyst component obtained by contacting the solid with a halide of titanium and an aromatic carboxylic acid ester in the presence of an aromatic hydrocarbon solvent, an organoaluminum compound and an alkoxysilane. According to the above, it was found that a polymer having excellent particle characteristics even at a higher polymerization temperature, and even for a longer time of polymerization, and a polymer having high stereoregularity can be efficiently produced, and applied for a patent. (JP-A-2-138312, JP-A-4-216804)

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
No. 12 and JP-A-4-216804. Although the catalyst using the prior art previously proposed by the present inventors has already been able to produce a polymer having sufficiently high activity and stereoregularity, it is possible to use an organic solvent soluble in a hydrocarbon solvent which is available. The magnesium component was limited to those containing a relatively large amount of alkoxy groups, and it was still insufficient in terms of polymerization activity per Ti in the solid catalyst component.

[0004]

Means for Solving the Problems As a result of intensive studies on these points, the present inventors have found that even when an organomagnesium component containing a relatively small amount of an alkoxy group is used, the magnesium component and the Si--H bond are When the halogen-containing magnesium solid obtained by the reaction with the chlorosilane compound, the titanium halide, and the aromatic carboxylic acid ester are brought into contact with each other in the presence of an aromatic hydrocarbon solvent, the total amount of the titanium compound (b) used is The molar ratio to the aromatic carboxylic acid ester (C) is 1 or more 150
The amount is in the range of less than 40 ° C., and after contacting at a temperature of less than 40 ° C., the titanium compound (b) is further added for heat treatment, and after separation, contact is made with the heated aromatic hydrocarbon solvent to give a solid. The inventors have found that a polymer having a dramatically high polymerization activity per Ti in the catalyst component and having a high stereoregularity can be economically produced, and thus reached the present invention.

That is, the present invention uses a catalyst comprising the following (A), (B) and (C): α-
Olefin Polymerization Method (A) (I) (i) General Formula (M) _i (Mg) _j (R ¹ ) _p
(R ² ) _q (OR ³ ) _r [In the formula, M is a metal atom belonging to Group I to Group III of the Periodic Table, and R ¹ , R ² and R ³ are hydrocarbon groups having 2 to 20 carbon atoms. Yes, i, j, p, q, and r are numbers that satisfy the following relationship.

0 ≤ i, 0 <j, 0 ≤ p, 0 ≤ q,
0.5 <r / (i + j) <1.0, ki + 2 j = p + q +
r (where k is the valence of M)], and an organomagnesium component soluble in a hydrocarbon solvent, and (ii) the general formula H _a Si Cl _b R ⁴ _{4- (a + b)} (wherein R is ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, a
And b are numbers that satisfy the following relationship.

A solid component obtained by reacting with a chlorosilane compound having a Si-H bond represented by 0 <a, 0 <b, a + b≤4), (b) a general formula Ti (OR ⁵ ) _m D _{4- m} [wherein R ⁵ is a hydrocarbon group having 2 to 10 carbon atoms, D is a halogen atom, and m is a number satisfying the relationship of 0 ≤ m <4], and (c) an aromatic compound In the method of contacting a carboxylic acid ester in the presence of an aromatic hydrocarbon solvent, the total amount of titanium compound (b) used is in the range of 1 or more and less than 150 as a molar ratio to the aromatic carboxylic acid ester (c). After contacting at a temperature of less than 40 ° C., a titanium compound (b) is further added for heat treatment, and after separation, a solid catalyst component brought into contact with a heated aromatic hydrocarbon solvent, (B) general formula Al R ⁶ ₃ (wherein R ⁶ is a hydrocarbon having 1 to 20 carbon atoms) Group), and (C) a general formula R ⁷ _s Si (OR ⁸ ) _4-s (wherein R ⁷ and R ⁸ are hydrocarbon groups having 1 to 20 carbon atoms, and s is 0 ≦ s. <The number satisfying the relationship of <4>). The present invention will be described in detail below.

The general formula (A) (a) (i) used in the present invention (
M) _i (Mg) _j (R ¹ ) _p (R ² ) _q (OR ³ ) _r (wherein
The organomagnesium component (i) of i, j, p, q, r, M, R ¹ , R ² , and R ³ has the above-mentioned meanings). Relational expression of symbols i, j, p, q, r p + q + r =
mi + 2j represents the stoichiometry of the valence of the metal atom and the substituent. This compound is an organomagnesium complex compound containing an alkoxy group soluble in a hydrocarbon solvent, and comprises an organomagnesium complex compound soluble in a hydrocarbon solvent and an alcohol having a hydrocarbon group represented by R ³ above. Or a method of mixing an organomagnesium complex compound soluble in a hydrocarbon solvent with a hydrocarbyloxymagnesium compound having a hydrocarbon group represented by R ³ and soluble in a hydrocarbon solvent.

The organic magnesium complex compound soluble in the hydrocarbon solvent used here will be described. General formula (
M) _i (Mg) _j (R ¹ ) _p (R ² ) _q , the hydrocarbon group represented by R ¹ or R ² in the organic magnesium complex compound soluble in the hydrocarbon solvent is an alkyl group, An alkyl group or an allyl group, for example, methyl,
Examples thereof include ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl and phenyl groups, preferably R ₁ is an alkyl group.

When i> 0, a metal element belonging to Group I to Group III of the Periodic Table can be used as the metal atom M, and examples thereof include lithium, sodium, potassium, beryllium, zinc, boron and aluminum. Among them, aluminum and zinc are particularly preferable. The ratio j / i of magnesium to the metal atom M can be set arbitrarily, but is preferably in the range of 0.1 to 30, particularly preferably 1 to 20.

The relationship between the symbols i, j, p and q is expressed by the equation p + q = k.
i + 2j, which shows the stoichiometry of the valence of the metal atom and the substituent. These organomagnesium compounds or organomagnesium complexes have the general formula R ¹ ₂ Mg
An organic magnesium compound represented by the formula (R ¹ has the above-mentioned meaning) and a compound represented by the general formula, MR ² _k or MR ² _k-1 H
(M, R ² , and k have the above-mentioned meanings), and react with an organometallic compound in an inert hydrocarbon medium such as hexane, heptane, cyclohexane, benzene, and toluene at room temperature to 150 ° C. Can be obtained.

When a certain organomagnesium compound with i = 0 is used, for example, when R ¹ is sec-butyl and R ³ is an alkyl group having a side chain at the 2 position, a hydrocarbon solvent is used. Are soluble in water and such compounds also provide favorable results for use in the present invention. Used in the present invention,
General formula (M) _i (Mg) _j (R ¹ ) _p (R ² ) _q (OR ³ ) _r
In the above, the relation between R ¹ and R ² and the alkoxy group OR ^{3 in} the case of i = 0 are shown below.

First, regarding the relationship between R ¹ and R ² when α = 0, it is recommended to be one of the following three groups (1), (2) and (3). (1) At least one of R ¹ and R ² has 4 to 6 carbon atoms.
Is a secondary or tertiary alkyl group, preferably R ¹ and R ² both have 4 to 6 carbon atoms, and at least one is a secondary or tertiary alkyl group.

(2) R ¹ and R ² are alkyl groups having different carbon atoms from each other, preferably R ¹ is an alkyl group having 2 or 3 carbon atoms and R ² is 4 carbon atoms. The above alkyl group. (3) At least one of R ¹ and R ² is a hydrocarbon group having 6 or more carbon atoms, and preferably both R ¹ and R ² are alkyl groups having 6 or more carbon atoms.

Hereinafter, these groups will be specifically shown. (1)
The secondary or tertiary alkyl group having 4 to 6 carbon atoms is sec-butyl, tert-butyl, 2-methylbutyl, 2-ethylpropyl, 2,2-dimethylpropyl, 2-methylpentyl, 2- Ethylbutyl, 2,2-dimethylbutyl,
2-Methyl-2-ethylpropyl and the like are used, and sec-butyl is particularly preferable.

Next, in (2), the number of carbon atoms is 2 or 3.
Examples of the alkyl group include an ethyl group and a propyl group, and the ethyl group is particularly preferable. Examples of the alkyl group having 4 or more carbon atoms include a butyl group, an amyl group, a hexyl group and an octyl group, and a butyl group and a hexyl group are particularly preferable. Examples of the alkyl group having 6 or more carbon atoms in (3) include a hexyl group, an octyl group, a decyl group,
Examples thereof include a phenyl group, an alkyl group is preferable, and a hexyl group is particularly preferable.

Generally, if the number of carbon atoms of the alkyl group is increased, it becomes easier to dissolve in a hydrocarbon solvent, but the viscosity of the solution tends to be high, and it is not preferable in terms of handling to use a long-chain alkyl group. Next, the alkoxy group (OR ³ ) contained in the organomagnesium component used in the present invention will be described.

The hydrocarbon group represented by R ³ is preferably an alkyl group having 3 to 10 carbon atoms or an allyl group. Specifically, for example, n-propyl, n-butyl, se
c-propyl, sec-butyl, tert-butyl, amyl, 2-methylpentyl, 2-ethylhexyl, octyl, decyl,
Examples thereof include a phenyl group. For the reaction of a hydrocarbon-soluble organomagnesium component with an alcohol, the reaction is carried out by an inert reaction medium, for example, hexane, an aliphatic hydrocarbon such as heptane, an aromatic hydrocarbon such as benzene, toluene, xylene, cyclohexane, It can be carried out in an alicyclic hydrocarbon such as methylcyclohexane or a mixed solvent thereof. Regarding the reaction sequence, either a method of adding an alcohol to the organomagnesium component, a method of adding the organomagnesium component to the alcohol, or a method of adding both of them at the same time can be used. Regarding the reaction ratio between the hydrocarbon-soluble organomagnesium component and the alcohol, 0.5 <r / (i + j) <1.
It is preferably in the range of 0. When this ratio is 0.5 or less, the activity of the obtained catalyst is not sufficient, and the stereoregularity of the obtained polymer is not sufficient. Further, if this ratio is 1.0 or more, the activity per Ti in the solid catalyst component cannot be made sufficiently high.

Next, (ii) the general formula H _a Si Cl _b R ⁴
_{4- (a + b)} (in the formula, a, b and R ⁴ have the above-mentioned meanings)
The H-Si bond-containing chlorosilane compound represented by will be described. The hydrocarbon group represented by R ⁴ in the above formula is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and examples thereof include methyl, ethyl, propyl and
Butyl, amyl, hexyl, decyl, cyclohexyl,
Examples thereof include a phenyl group, preferably an alkyl group having 1 to 10 carbon atoms, and a lower alkyl group such as methyl, ethyl or propyl is particularly preferable. Also, a and b are a + b ≦ 4
It is a number larger than 0 satisfying the relationship of, and b is preferably 2 or 3.

These compounds include HSiCl ₃ ,
HSiCl ₂ CH ₃ , HSiCl ₂ C ₂ H ₅ , HSiC
_{l 2 n- C 3 H 7,} HSiCl 2 iso-C 3 H 7, HSiCl 2 n-C 4 H 9, HSiCl 2 C 6 H 5, H
SiCl ₂ (4-Cl-C ₆ H ₄ ), HSiCl ₂ CH = CH
₂ , HSiCl ₂ CH ₂ C ₆ H ₅ , HSiCl ₂ (1-C ₁₀
H ₇ ), HSiCl ₂ CH ₂ CH = CH ₂ , H ₂ SiCl
_{CH 3, H 2 SiClC 2 H} 5, HSiCl (CH 3)
₂ , HSiCl (C ₂ H ₅ ) ₂ , HSiClCH ₃ (iso-C
₃ H ₇ ), HSiClCH ₃ (C ₆ H ₅ ), HSiCl (C ₆
H ₅ ) _{2 and the} like, and chlorosilane compounds composed of a mixture of these compounds and compounds selected from these compounds are used, and trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, etc. Preferred are trichlorosilane and monomethyldichlorosilane.

Next, an alkoxy group-containing organomagnesium component (i) soluble in a hydrocarbon solvent and a chlorosilane compound (ii)
The reaction with is explained. In the reaction, a chlorosilane compound is previously added to an inert reaction medium, for example, n-hexane,
Aliphatic hydrocarbons such as n-heptane, benzene, toluene,
Aromatic hydrocarbons such as xylene, alicyclic hydrocarbons such as cyclohexane and methyl cyclohexane, or 1,2-
It is preferable to use after diluting with a chlorinated hydrocarbon such as dichloroethane, o-dichlorobenzene, dichloromethane, or a mixed medium thereof. The reaction temperature is not particularly limited, but is preferably in the range of 40 ° C. or higher and lower than the boiling point of the reaction medium in order to accelerate the reaction.

The ratio of both components in the reaction is 1 mol of the organomagnesium compound (based on magnesium)
On the other hand, the chlorosilane compound is preferably in the range of 0.01 to 100 mol, particularly preferably 0.1 to 10 mol. The solid component obtained by the above reaction is separated by filtration or a decantation method, and then thoroughly washed with an inert solvent such as n-hexane or n-heptane to remove unreacted substances or by-products. It is preferable.

Next, the general formula Ti (OR ⁵ ) _m D _4-m (wherein
R ⁵ and m have the above-mentioned meanings. The titanium compound represented by) will be described. The hydrocarbon group represented by R ⁵ in the above formula is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and examples thereof include ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl and phenyl. Examples thereof include a group, and an alkyl group is particularly preferable. Specific examples include, for example, titanium tetrachloride, titanium tetrabromide,
Examples thereof include titanium tetraiodide, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, dibutoxytitanium dichloride, tributoxytitanium chloride, and the like, with titanium tetrachloride being particularly preferred.

The aromatic carboxylic acid ester used in the present invention is preferably an aromatic carboxylic acid monoester or diester. Preferred specific examples include, for example, esters of monocarboxylic acids such as benzoic acid, P-toluic acid and P-anisic acid such as methyl, ethyl, propyl and butyl, and dimethyl phthalate, diethyl, di-n-propyl and diiso. -Propyl, di-n-butyl, di-iso-butyl, di-n-heptyl, di2-
Examples thereof include dicarboxylic acid diesters such as ethylhexyl and dioctyl. Further, these aromatic carboxylic acid esters may be used alone or in combination.

Any method may be used as a method for contacting the solid component (a) with the titanium compound (b) and the aromatic carboxylic acid ester (c) used for preparing the solid catalyst component (A) in the present invention. However, in any method, it is essential to contact each component in the presence of an aromatic hydrocarbon solvent. . As a preferred method, first, (a) and (c) are brought into contact in the presence of an aromatic hydrocarbon solvent, and further contacted with (b), (a), (b),
And (c) are brought into contact with each other at the same time, and further (b) is brought into contact therewith, and the particularly preferable method is.

As the contacting means, any means such as a method of contacting in a liquid phase or a gas phase, a combination of contacting in a liquid phase or a gas phase and crushing can be used. Next, a specific example of the method of contacting (a), (b) and (c) will be described. It is one of the characteristics of the present invention to use an aromatic hydrocarbon as a reaction medium to coexist, and examples of the aromatic hydrocarbon include benzene, toluene, xylene, ethylbenzene, styrene, n-propylbenzene and the like. Alternatively, a mixed medium thereof can be used, but among them, it is preferable to use toluene and ethylbenzene.

The total amount of the titanium compound (b) used in the contact is such that the molar ratio of the titanium compound to the aromatic carboxylic acid ester component is in the range of 1 or more and less than 150, preferably 5 or more and less than 130. If the total amount of the titanium compound (b) used is within this range, the titanium compound (b) may be contacted in two or more divided portions. If the molar ratio of the titanium compound to the aromatic carboxylic acid ester component at the time of contact is less than 1, the performance of the resulting catalyst is insufficient, while if it is 150 or more, the amount of the titanium compound used is not reduced, which is the object of the present invention. Not preferable.

As a specific method of contacting (a), (b), and (c), first, (a) and (c) are used at a temperature lower than 40 ° C., particularly preferably in a temperature range of 20 ° C. to 40 ° C. Alternatively, contacting (a), (b), and (c) is important in the present invention. At that time, the contact time was 0.
It is in the range of 5 to 5 hours, preferably 1 to 3 hours. Regarding the temperature at the time of contact, if the catalyst is not sufficiently contacted at a temperature of less than 40 ° C. but immediately contacted at a temperature of 40 ° C. or more, the performance of the obtained catalyst is not sufficient, which is not preferable. At that time, the amount of the titanium compound used is 0 when the molar ratio of the titanium compound to the aromatic carboxylic acid ester component is expressed.
It is in the range of 50 to 50, particularly preferably in the range of 5 to 30.

After contacting at a temperature lower than 40 ° C., a titanium compound (b) is further added, preferably higher than 80 ° C. 13
Heat treatment is performed at a temperature lower than 0 ° C. At that time, the contact time is 0.5 to 5 hours, preferably 1 to 3 hours.
If the temperature and time during the heat treatment are out of this range, the performance of the obtained solid catalyst component is not sufficient. Regarding the ratio of the titanium compound and the aromatic carboxylic acid ester to the solid component (a) at the time of contact, the total amount of the titanium compound is preferably 0.5 mol to 20 mol per 1 mol of magnesium contained in the solid component (a). Mol, particularly preferably 1 mol to 1
In the range of 5 mol, for aromatic carboxylic acid esters, 0.01 mol to 1.0 mol, particularly preferably 0.0 mol.
A range of 5 moles to 0.3 moles is recommended.

After the above treatment, the solid catalyst component is separated,
Further, it is brought into contact with a heated aromatic hydrocarbon solvent. The temperature at the time of contact is preferably higher than 80 ° C. and lower than 120 ° C. and contacted with the aromatic hydrocarbon solvent. When the temperature is out of the above range, not only the performance of the obtained solid catalyst component is insufficient, but also the polymerization activity per Ti amount in the solid catalyst component is not sufficient. The amount of the aromatic hydrocarbon solvent to be contacted is 10 to 100 with respect to 1 g of the solid catalyst component.
It is preferable to use cc, preferably 20 to 60 cc.

The contact time is preferably in the range of 0.5 to 8 hours, preferably 1 to 6 hours, and it is also preferable to repeat the contact with the aromatic hydrocarbon solvent within the above range. There is one. Solid catalyst component (A) in the present invention obtained by these contact or treatment
The composition and the structure of the compound vary depending on the type of starting material and the contact conditions, but from the composition analysis value, the specific surface area of the solid catalyst containing titanium of about 0.5 to 3% by weight, 50 to 300 m ² / It was found to be a solid catalyst.

The general formula AlR ⁶ ₃ used as the component (B)
(In the formula, R ⁶ has the above-mentioned meaning.) Will be described. Trialkylaluminum compounds include trimethylaluminum, triethylaluminum, tri-n-
Propyl aluminum, tri-iso-propyl aluminum, tri-n-butyl aluminum, tri-iso-butyl aluminum, tri-n-hexyl aluminum, tri-n-
Octyl aluminum, tri-n-decyl aluminum,
Tri-n-dodecyl aluminum, tri-n-hexadecyl aluminum, etc. and mixtures thereof.

Next, the alkoxysilane compound as the component (C) used in the present invention will be explained. This compound has the general formula
R ⁷ _s Si (OR ⁸ ) _4-s (in the formula, R ⁷ , R ⁸ and s have the above-mentioned meanings). First, Si (
OR ⁸ ) ₄ includes Si (OCH ₃ ) ₄ and Si (OC ₂ H
₅ ) ₄ , Si (On-C ₃ H ₇ ) ₄ , Si (Oiso-C ₃ H ₇ )
_{4, Si (On-C 4} H 9) 4, Si (Osec-C 4 H 9) 4 and the like.

Next, RSi (OR ')₃As CH₃S
i (OCH₃)₃ , C₂H_FiveSi (OC₂H_Five)₃ , Iso-C
₃H₇Si (OCH₃)₃ n-C_FourH₉Si (OCH₃)₃ ,
iso-C_FourH₉Si (OCH₃)₃ , C₆H _FiveSi (OCH
₃)₃ , C₆H_FiveCH₂Si (OCH₃)₃ , CH₂= CH
Si (OCH₃)₃ , CH [Si (OCH₃)₃ ]₃, (C
H₃O)₃SiCH₂Si (OCH ₃)₃, (CH₃O)₃
SiCH₂CH₂Si (OCH₃)₃, CF₃CH₂C
H ₂Si (OCH₃)₃ , CCl₃Si (OCH₃)₃ , C
H₃CHClSi (OCH ₃)₃ , CH₂ClCH₂Si
(OCH₃)₃ , CH₃Si (OC₂H_Five)₃ , C₂H _FiveS
i (OC₂H_Five)₃ , N-C₃H₇Si (OC₂H_Five)₃ , N-
C_FourH₉Si (OC ₂H_Five)₃ , N-C_FiveH₁₁Si (OC₂
H_Five)₃ , Cyclo-C₆H₁₁Si (OC₂H_Five)₃, C₆H_Five
Si (OC₂H_Five)₃ , CH₂= CHSi (OC₂H_Five)
₃ , CH3 CH = CHSi (OC₂H_Five)₃ , CH2 = C
HCH2 Si (OC₂H_Five)₃ , (C₂H _FiveO)₃SiCH
₂Si (OC₂H_Five)₃ , CH [Si (OC₂H_Five)
₃ ]₃, CF₃C₆H_FourSi (OC₂H_Five)₃ , CH₂C
lSi (OC₂H_Five)₃ , CCl₃Si (OC₂H_Five)₃ ,
CH₂ClCH₂Si (OC₂H_Five)₃ , CH₂ClCH
ClSi (OC₂H_Five)₃ , And the like.

R₂Si (OR ')₂As (CH₃)₂ 
Si (OCH₃)₂ , (C₂H_Five)₂ Si (OCH₃)₂ , (N
-C₃H₇)₂ Si (OCH₃)₂ , (Iso- C₃H₇)₂ Si
(OCH₃)₂(n-C_FourH₉)₂ Si (OCH₃)₂ , (Tert-
C_FourH₉)₂ Si (OCH₃)₂ , (C₆H_Five)₂ Si (OC
H₃)₂ , (C₆H_Five)₂ Si (OC₂H_Five)₂ , (C₆H_Five)
(CH₃) Si (OCH₃)₂ , Cyclo-C₆H₁₁(CH₃) S
i (OCH₃) ₂ , (CH₃)₂ Si (OC₂H_Five)₂ , (C
H₃) (C₂H_Five) Si (OC₂H_Five)₂ , (CH₃) (C₆H
_Five) Si (OC₂H_Five)₂ , (Iso- C₃H₇) (iso- C_FourH₉)
Si (OCH₃)₂ , C₂H_FiveSiH (OC₂H_Five)₂ , (
C₂H_Five)₂ Si (OC₂H_Five)₂Etc.

R₃As SiOR ', (CH₃)₃ Si
OCH₃, (C₂H_Five)₃ SiOCH₃, (CH₃)₃ Si
OC₂H _Five, (CH₃)₂(n-C₃H₇) SiOC₂H_Five, (
CH₃)₂(C₆H_Five) SiOC₂H_Five, Etc.
CH is preferred₃Si (OCH₃)₃ , C₂
H _FiveSi (OCH₃)₃ , Iso-C₃H₇Si (OCH₃)₃ 
C₆H_FiveSi (OCH₃)₃, C₆H_FiveSi (OC₂H_Five)₃
 , (Iso- C₃H₇)₂ Si (OCH₃)₂ , Cyclo-C ₆H
₁₁(CH₃) Si (OCH₃)₂ , C₆H_FiveSi (OC₂H
_Five)₃ (iso- C₃H₇) (iso- C_FourH₉) Si (OCH₃)₂ 
 , (C₆H_Five)₂ Si (OCH₃)₂ , Si (OC₂H_Five)_Four
 Is.

These alkoxysilanes may be used alone or as a mixture, and may be in the form of a reaction product or an adduct with an organoaluminum compound, or may be used in combination with a complex compound such as an ether, an ester or an amine. Absent. The catalyst components (A), (B) and
The proportion of (C) used is 1 g of the solid component (A), while (B) is
(B) converted to aluminum atoms in 1 to 3000 mmol, preferably 0 in the range of 5 to 1000 mmol, and
(C) is 0.01-100 in terms of silicon atoms in (C).
It is preferably used in an amount of 0 mmol, preferably 0.05 to 100 mmol.

These catalyst components (A), (B) and (C) may be used by bringing them into contact with each other during the polymerization, or may be used by bringing them into contact with each other before the polymerization. Only two arbitrary parties may be freely selected and brought into contact with each other. The contact may be in an inert gas atmosphere or an olefin atmosphere. The present invention utilizes α-olefins such as propylene, butene-1, pentene-1, 4-methyl-pentene-1, 3-methyl-butene-1 and other olefins, especially propylene, for stereoregular polymerization at higher temperatures. Suitable for cases. Further, the activity is hardly decreased with the lapse of polymerization time, and it is suitable for so-called block polymerization, in which the α-olefin is copolymerized with ethylene or another olefin and has a relatively long residence time in the polymerization machine.

In order to control the molecular weight of the polymer, hydrogen,
It is also possible to add a halogenated hydrocarbon or an organometallic compound which easily causes chain transfer. As the polymerization method, usual suspension polymerization, polymerization in a liquid monomer, and gas phase polymerization are possible. Particularly, in the polymerization of the present invention, it can be preferably used for polymerization in a liquid monomer and gas phase polymerization which are carried out at a relatively high polymerization temperature.

In suspension polymerization, a catalyst is introduced into a reactor together with a polymerization solvent such as hexane or an aliphatic hydrocarbon such as heptane, and an olefin such as propylene is introduced under pressure of 1 to ²⁰ Kg / cm ² under an inert gas atmosphere. The polymerization can be carried out at a temperature of room temperature to 150 ° C. In the polymerization in a liquid monomer, the olefin can be polymerized using a liquid olefin as a polymerization solvent under the condition that the catalyst is a liquid olefin such as propylene. For example, in the case of propylene, at a temperature of room temperature to 90 ° C, 10 to 45 Kg /
The polymerization can be carried out in liquid propylene under a pressure of cm ² .

On the other hand, the gas phase polymerization is carried out in the absence of a solvent under the condition that an olefin such as propylene is a gas in an amount of 1 to 50 kg.
Polymerization by taking measures such as mixing in a fluidized bed, a moving bed, or a stirrer so that the contact between the olefin such as propylene and the catalyst is good under the temperature condition of room temperature to 120 ° C. at a pressure of / cm ^2. It can be performed.

[0042]

EXAMPLES The present invention will be described below with reference to examples. The boiling heptane extraction residue used in the examples means the extraction residue after extraction of the obtained polymer with boiling n-heptane for 6 hours. It means the percentage based on the weight of the polymer.

[0043]

Reference Example 1 (I) Synthesis of Organomagnesium Component Containing Alkoxy Group Composition formula AlMg ₆ (C ₂ H ₅ ) ₃ (n-C ₄ H ₉ ) synthesized in advance from triethylaluminum and dibutylmagnesium
_An n-heptane solution containing 250 millimoles (based on magnesium) of the organomagnesium complex component shown in ₁₂ was placed in a 1-liter flask sufficiently replaced with nitrogen, cooled in an ice bath and stirred while n-using a dropping funnel. Butyl alcohol 22.8 cc (250 mmol) was slowly added dropwise over 1 hour to react, and further reacted at room temperature for 1 hour with stirring. A relatively viscous colorless and transparent solution was obtained and analyzed to find that the solution contained 0.96 mol of n-butoxy group per 1 mol of Mg and had a magnesium concentration of 1.0 mol / liter.

(II) Synthesis of Magnesium-Containing Solid by Reaction with Chlorosilane Compound Trichlorosilane was added as a 1 mol / liter n-heptane solution to a 1-liter flask sufficiently replaced with nitrogen.
The amount of 00 mmol was charged, the temperature was maintained at 65 ° C. with stirring, the total amount of the n-heptane solution of the above-mentioned organomagnesium component containing an alkoxy group was added over 1 hour, and the mixture was further reacted at 65 ° C. for 1 hour with stirring. The white solid formed is filtered off, washed thoroughly with n-hexane and dried to give a white solid (A).
29.5 g were obtained. As a result of analyzing this solid substance, 1 g of the solid contained 7.45 mmol of Mg, 4.2 mmol of CL, and 2.32 mmol of butoxy group.
The specific surface area measured by the method was 193 m ² / g.

(III) Synthesis of Solid Catalyst Component 10 g of the solid obtained in (II) above and titanium tetrachloride 200
cc and 50 cc of toluene were added, and 2.0 cc (7.5 mmol) of di-n-butyl phthalate was further added, and the mixture was stirred with stirring.
The reaction was carried out at 0 ° C for 2 hours. After completion of the reaction, a solid was collected by filtration, and this solid was further suspended in 200 cc of titanium tetrachloride, and reacted at 120 ° C. for 2 hours while stirring. After completion of the reaction, the solid was separated by hot filtration, thoroughly washed with hot n-heptane, further washed with n-hexane, and then used as a solid catalyst component (B) as an n-hexane slurry. When a part of this was taken and analyzed, the Ti content in the solid catalyst component was 3.8% by weight. The molar ratio of the titanium compound to the aromatic carboxylic acid ester component used in the catalyst synthesis was 484.

(IV) Polymerization in liquid propylene.
Hydrogen gas was introduced into the toclave so that the MFI of the produced polymer was 5 and 350 g of liquefied propylene was introduced, and then 2.0 mmol of triethylaluminum and 0.2 mmol of phenyltriethoxysilane and n-containing solid catalyst component were added. Hexane slurry (B) was added to the autoclave in the order of 7 mg in terms of solid catalyst component, and immediately stirred to 80
The temperature was raised to ℃ and the polymerization was carried out for 2 hours to obtain 206 g of a polymer.

The activity per gram of the solid catalyst component is 29,400.
It was g-PP / g-Solid, and the activity per 1 mmol of Ti in the solid catalyst component was 774 Kg-PP / gTi. The boiling n-heptane extraction residue of this polymer was 97.0%, and the bulk density of the polymer powder was 0.47 g / cc.

[0048]

Example 1 (III) Synthesis of solid catalyst component Titanium tetrachloride (20 cc) and toluene (200 cc) were placed in a 500 cc flask containing 10 g of the solid component obtained in (II) of Reference Example 1 and sufficiently replaced with nitrogen. In addition, di-n-butyl phthalate 2.0 cc (7.5 mmol)
Was added, and the mixture was contacted at room temperature for 1 hour with stirring. After the contact, the supernatant was removed, 60 cc of titanium tetrachloride was further added, the temperature was raised, and contact was continued at a temperature of 120 ° C. for 3 hours. After completion of the reaction, the solid was separated by hot filtration, brought into contact with 200 cc of toluene heated to 100 ° C. three times, and further washed with n-hexane to obtain a solid component (B-1) as an n-hexane slurry.

When a part of this was taken and analyzed, the Ti content in the solid component was. It was 1.5% by weight. The amount of titanium tetrachloride used was 1/5 as compared with the reference example. The molar ratio of the titanium compound to the aromatic carboxylic acid ester component used in the catalyst synthesis was 110.

(IV) Polymerization in liquid propylene.
Hydrogen gas was introduced into the toclave so that the MFI of the produced polymer was 5 and further 350 g of liquefied propylene was introduced, and then 1.2 mmol of triethylaluminum, diphenyldimethoxysilane. The n-hexane slurry (B-2) containing 012 mmol and the solid catalyst component was added to the autoclave in the order of 7 mg in terms of the solid catalyst component, and immediately heated to 80 ° C. under temperature stirring to carry out polymerization for 2 hours to obtain a polymer. 326g
Got

The activity per gram of solid catalyst component is 46,600
It was g-PP / g-Solid, and the activity per 1 mmol of Ti in the solid catalyst component was 3110 Kg-PP / gTi. The boiling n-heptane extraction residue of this polymer was 98.5%, and the bulk density of the polymer powder was 0.48 g / cc.

[0052]

Comparative Example 1 Solid component 1 obtained in (II) of Reference Example 1
20 cc of titanium tetrachloride and 200 cc of toluene were added to a 500 cc flask in which 0 g was sufficiently replaced with nitrogen, and 2.0 cc (7.5 mmol) of di-n-butyl phthalate was further added, followed by immediate heating. And contacted at a temperature of 120 ° C. for 2 hours. After completion of the reaction, the solid was separated by hot filtration, contacted with 200 cc of toluene heated to 100 ° C. three times, and further washed with n-hexane to obtain a solid component (C-1) as an n-hexane slurry. When a part of this was collected and analyzed, the Ti content in the solid component was 1.1% by weight.

Polymerization was carried out in the same manner as in Example 1 using this solid catalyst component (C-1) to obtain 112 g of a polymer.
The activity per gram of solid catalyst component is 16000 g-PP / g-Soli
d, and the activity per 1 mmol of Ti in the solid catalyst component was 1454 kg-PP / gTi. The boiling n-heptane extraction residue of this polymer was 94.5%.

[0054]

[Comparative Example 2] The same procedure as in Example 1 was carried out except that hot toluene was not used, and a solid component (C-2) was obtained as an n-hexane slurry. When a part of this was sampled and analyzed, the Ti content in the solid component was 2.5.
% By weight. Polymerization was carried out in the same manner as in Example 1 using this solid catalyst component (C-2) to obtain 182 g of a polymer.

The activity per gram of solid catalyst component is 26000
It was g-PP / g-Solid, and the activity per 1 mmol of Ti in the solid catalyst component was 1040 Kg-PP / gTi. The boiling n-heptane extraction residue of this polymer was 95.5%.

[0056]

Example 2 A solid catalyst component (B-2) was obtained in the same manner as in Example 1 except that the aromatic hydrocarbon solvent used in the synthesis of the solid catalyst component of Example 1 was changed to ethylbenzene. When a part of this was taken and analyzed, the Ti content in the solid component was 1.3% by weight.

Polymerization was carried out in the same manner as in Example 1 using this solid catalyst component (B-2) to obtain 305 g of a polymer. The activity per 1 g of solid catalyst component is 43600 g-PP / g-Solid
The activity per 1 mmol of Ti in the solid catalyst component was 3354 Kg-PP / gTi. Boiling of this polymer n-
The heptane extraction residue was 98.2%.

[0058]

Example 3 Reference was made except that in the synthesis of the (I) alkoxy group-containing organomagnesium component in Reference Example 1, the alcohol used was changed to 2-ethylhexyl alcohol and the amount used was changed to 9.5 cc (188 mmol). Synthesis was carried out under the same conditions as in Example 1 to obtain an alkoxy group-containing organomagnesium component. Hereinafter, a solid catalyst component containing 1.7% by weight of Ti component as a result of synthesis in the same manner as in Example 1.
I got (B-3). Polymerization was carried out using this solid component in the same manner as in Example 1 to obtain 266 g of a polymer. The activity per 1 g of the solid catalyst component is 38000 g-PP / g-Solid,
The activity per 1 mmol of Ti in the solid catalyst component was 2235.
It was Kg-PP / gTi. The boiling n-heptane extraction residue of this polymer was 98.0%.

[0059]

Examples 4 to 6 Solid catalyst components (B-4 to B-6) were prepared in the same manner as in Example 1, except that the substances shown in Table 1 were used as the alkoxy-containing organomagnesium component used in Reference Example 1. ) Was synthesized, and polymerization was evaluated in the same manner as in Example 1 to obtain the results shown in Table 1.

[0060]

[Table 1]

[0061]

Examples 7 to 10 In the synthesis of the solid catalyst component of Example 1, the solid catalyst component (B-7 to B-7) was used in the same manner as in Example 1 except that the substances shown in Table 1 were used as the aromatic carboxylic acid ester. B-1) was synthesized and polymerized in the same manner as in Example 1 to obtain the results shown in Table 2.

[0062]

[Table 2]

[0063]

INDUSTRIAL APPLICABILITY When synthesizing a solid catalyst component using a halogen-containing magnesium solid obtained from an organomagnesium component containing a relatively small amount of an alkoxy group as in the present invention, in the presence of an aromatic hydrocarbon solvent. By using the solid catalyst component which is brought into contact with an aromatic carboxylic acid ester and a titanium compound under a specific condition and then brought into contact with a heated aromatic hydrocarbon solvent, the amount of Ti per solid catalyst component is increased. It is possible to economically produce a polymer having extremely high polymerization activity and high stereoregularity.

[Brief description of drawings]

FIG. 1 is a flow chart illustrating aspects of the present invention.

Claims (1)

[Claims] 1. A method for polymerizing an α-olefin, which comprises using a catalyst comprising the following (A), (B) and (C): (A) (a) (i) General formula (M) _i (Mg) _j (R ¹ ) _p
(R ² ) _q (OR ³ ) _r [In the formula, M is a metal atom belonging to Group I to Group III of the Periodic Table, and R ¹ , R ² and R ³ are hydrocarbon groups having 2 to 20 carbon atoms. Yes, i, j, p, q, and r are numbers that satisfy the following relationship. 0 ≤ i, 0 <j, 0 ≤ p, 0 ≤ q, 0.5 <r /
(I + j) <1.0, ki + 2 j = p + q + r (where k is the valence of M)], and an organomagnesium component soluble in a hydrocarbon solvent, and (ii) the general formula H _a Si Cl _b R ⁴ _{4- ( a + b)} (In the formula, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, and
And b are numbers that satisfy the following relationship. 0 <a, 0 <b, a + b ≤ 4) a solid component obtained by reacting with a chlorosilane compound having a Si-H bond, (b) general formula Ti (OR ⁵ ) _m D _4-m [formula Wherein R ⁵ is a hydrocarbon group having 2 to 10 carbon atoms, D is a halogen atom, m is a number satisfying the relationship of 0 ≤ m <4, and (c) an aromatic carboxylic acid ester In the method of contacting and in the presence of an aromatic hydrocarbon solvent, the total amount of titanium compound (b) used is in the range of 1 or more and less than 150 as a molar ratio to the aromatic carboxylic acid ester (c), and less than 40 ° C. After contacting at the temperature of, the titanium compound (b) is further added and heat-treated, and after separation, the solid catalyst component brought into contact with the heated aromatic hydrocarbon solvent, (B) the general formula Al R ⁶ ₃ ( In the formula, R ⁶ is represented by a hydrocarbon group having 1 to 20 carbon atoms) An organoaluminum compound, and (C) a general formula R ⁷ _s Si (OR ⁸ ) _4-s (wherein R ⁷ and R ⁸ are hydrocarbon groups having 1 to 20 carbon atoms, and s is 0 ≦ s <4). Alkoxysilane compound represented by the following formula).