JPH10130280A - Organic silicon compound and production of olefin polymer using the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound consisting of a specific organic silicon compound containing naphthyl group and useful as a catalyst component for the polymerization of an olefin such as propylene to give an olefin (co)polymer having a high stereoregularity and broad molecular weight distribution. SOLUTION: This new organic silicon compound is expressed by the formula I (R<1> and R<2> are each a 1-20C alkyl; R<3> to R<6> are each a 1-3C alkyl; R<7> is H or 1-3C alkyl; R<8> to R<14> are each H or a 1-10C alkyl or form a ring together with an adjacent group) or the formula II (R<15> is same as R<8> ). It is useful e.g. as a catalyst component for the polymerization of an olefin such as propylene to give an olefin (co)polymer having high stereoregularity and broad molecular weight distribution. The compound can be produced by reacting a Grignard reagent expressed by the formula III (X<2> is a halogen such as Cl or Br) or the formula IV with a monochlorinated organic silicon compound of the formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organosilicon compound and a method for producing an olefin polymer using the same. More specifically, an organosilicon compound having a bulky organic group and an olefin polymer or copolymer having good stereoregularity and a wide molecular weight distribution, particularly a propylene polymer or copolymer, using the same as a catalyst component. The present invention relates to a method for producing a polymer.

[0002]

2. Description of the Related Art Among polyolefins, polypropylene is a polymer having high crystallinity and excellent chemical resistance. In addition, it has good rigidity, tensile strength, optical properties and workability, and is used for various moldings. Further, polypropylene has a lower specific gravity than polystyrene or the like, and is widely used in the field of containers, packaging materials and the like.

However, polypropylene is inferior to polystyrene and ABS resin in rigidity and heat resistance.
Therefore, in order to impart the same physical properties as the rigidity and heat resistance of polystyrene and ABS to polypropylene, and to expand the use as a substitute for them, studies on improving the stereoregularity and, consequently, the crystallinity of polypropylene have been conducted. It has been done.

[0004] A typical example is a solid catalyst component containing magnesium, titanium, halogen and an electron donor as essential components and an organoaluminum compound, as well as Si-O such as phenyltriethoxysilane and ethyltrimethylsilane.
An organosilicon compound having a -C bond, or a general formula Si
By using an organosilicon compound represented by R′R ″ _n (OR) _3-n (R ′, R ″ and R represent a hydrocarbon group, and n = 0 to 2), the steric properties of the resulting polypropylene can be improved. It improves regularity.

[0005] However, polymers produced by these catalyst systems have a new problem of poor moldability in the field of large molded articles because of their narrow molecular weight distribution.
On the other hand, there is a method of expanding the molecular weight distribution by multi-stage polymerization, but this method has problems such as an increase in the size of the apparatus and a decrease in productivity.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides an organosilicon compound having a bulky organic group which is effective as an olefin polymerization catalyst component, and has a good stereoregularity and a high molecular weight distribution by using it as a catalyst component. It is an object of the present invention to provide a method capable of stably producing an olefin polymer or copolymer having a wide range, particularly a propylene polymer or copolymer.

[0007]

Means for Solving the Problems In order to achieve the above object, as a result of diligent research, a novel organosilicon compound having a bulky organic group effective as an olefin polymerization catalyst component as shown below has been found. The present inventors have found that by using the compound as a catalyst component, it is possible to stably produce an olefin polymer or copolymer having good stereoregularity and a wide molecular weight distribution, particularly a propylene polymer or copolymer. Was completed. (1) General formula (I)

[0008]

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(Where R¹And R^TwoIs 1 to 20 carbon atoms
Represents an alkyl group, which may be the same,
They may be different from each other. R^Three, R^Four, R^FiveAnd R⁶Is charcoal
Represents an alkyl group having 1 to 3 prime numbers,
May be different from each other. R⁷Is a hydrogen atom or
Represents an alkyl group having 1 to 3 carbon atoms. Also, R⁸, R
⁹, R^Ten, R¹¹, R¹², R¹³And R¹⁴Is a hydrogen atom or charcoal
Represents an alkyl group having a prime number of 1 to 10, which are the same and
May be different from each other or form a ring with an adjacent group.
You may. An organosilicon compound represented by the formula: (2) General formula (II)

[0010]

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(Where R¹And R^TwoIs 1 to 20 carbon atoms
Represents an alkyl group, which may be the same,
They may be different from each other. R^Three, R^Four, R^FiveAnd R⁶Is charcoal
Represents an alkyl group having 1 to 3 prime numbers,
May be different from each other. R⁷Is a hydrogen atom or
Represents an alkyl group having 1 to 3 carbon atoms. Also, R⁸, R
⁹, R^Ten, R¹¹, R¹², R¹³And R^FifteenIs a hydrogen atom or charcoal
Represents an alkyl group having a prime number of 1 to 10, which are the same and
May be different from each other or form a ring with an adjacent group.
You may. An organosilicon compound represented by the formula: (3) Titanium compound, magnesium compound and electron donation
Solid catalyst component obtained by contacting and reacting
Luminium compound and general formula (I)

[0012]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same as described above. The organosilicon compound represented by the general formula (II)

[0014]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁵ are the same as above. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin using a catalyst comprising a combination of the organosilicon compounds represented by the formula (1). (4) The method for producing an olefin polymer according to the above (3), wherein the olefin is propylene.

[0016]

Embodiments of the present invention will be described below. One of the organosilicon compounds of the present invention has the general formula
(I)

[0017]

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## EQU1 ## Of the above general formula (I)
 R¹And R^TwoRepresents a hydrocarbon group having 1 to 20 carbon atoms.
You. Specifically, methyl group, ethyl group, propyl group and the like
Linear hydrocarbon group, isopropyl group, isobutyl group, t
-Branched hydrocarbon groups such as butyl group and texyl group,
Saturated cyclic such as butyl and cyclopentyl cyclohexyl
Hydrocarbon group, phenyl group, pentamethylphenyl group, etc.
And unsaturated cyclic hydrocarbon groups. Also, R ¹And R
^TwoMay be the same or different. Among these
Is particularly preferably a methyl group or an ethyl group.
A substituted or unsubstituted texyl group (VII) of the formula (I)

[0019]

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R ³ , R ⁴ , R ⁵ and R ⁶ each represent an alkyl group having 1 to 3 carbon atoms, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Specific examples of the substituted or unsubstituted texyl group include 1,1,2-trimethylpropyl group (Texyl group), 1,1,2-trimethylbutyl group, 1,1-dimethyl-2-ethylbutyl group, , 1,2,3-tetramethylbutyl group, 1,1,
2-trimethylpentyl group, 1,1,3-trimethyl-
A 2-ethylbutyl group is exemplified.

The substituted or unsubstituted α-naphthyl group (VIII) of the above formula (I)

[0022]

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R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Or a ring may be formed with an adjacent group. Specific examples of the substituted or unsubstituted α-naphthyl group include an α-naphthyl group, a 2-methyl-α-naphthyl group, and a 3-methyl-α
-Naphthyl group, 4-methyl-α-naphthyl group, 6-methyl-α-naphthyl group, 7-methyl-α-naphthyl group, 8
-Methyl-α-naphthyl group, 9-methyl-α-naphthyl group, 2,3-dimethyl-α-naphthyl group, 2,4-dimethyl-α-naphthyl group, 2,6-dimethyl-α-naphthyl group, 2,7-dimethyl-α-naphthyl group, 2,8-dimethyl-α-naphthyl group, 2,9-dimethyl-α-naphthyl group, 2,3,4-trimethyl-α-naphthyl group,
6,7,8-trimethyl-α-naphthyl group, 6,7,
8,9-tetramethyl-α-naphthyl group, 2,3,4
A 6,7,8,9-heptamethyl-α-naphthyl group can be mentioned.

Specific examples of the compound represented by the general formula (I) include 1,1,2-trimethylpropyl-α-naphthyldimethoxysilane and 1,1,2-trimethylpropyl-2-methyl-α- Naphthyldimethoxysilane, 1,
1,2-trimethylpropyl-7-methyl-α-naphthyldimethoxysilane, 1,1,2-trimethylpropyl-8-methyl-α-naphthyldimethoxysilane, 1,
1,2-trimethylpropyl-2,7-dimethyl-α-
Naphthyldimethoxysilane, 1,1,2-trimethylpropyl-2,8-dimethyl-α-naphthyldimethoxysilane, 1,1,2-trimethylbutyl-α-naphthyldimethoxysilane, 1,1,2-trimethylbutyl-2 −
Methyl-α-naphthyldimethoxysilane, 1,1,2-
Trimethylbutyl-7-methyl-α-naphthyldimethoxysilane, 1,1,2-trimethylbutyl-8-methyl-α-naphthyldimethoxysilane, 1,1,2-trimethylbutyl-2,7-dimethyl-α-naphthyl Dimethoxysilane, 1,1,2-trimethylbutyl-2,8-dimethyl-α-naphthyldimethoxysilane, 1,1-dimethyl-2-ethylbutyl-α-naphthyldimethoxysilane, 1,1-dimethyl-2-ethylbutyl- 2-methyl-α-naphthyldimethoxysilane, 1,1-dimethyl-
2-ethylbutyl-7-methyl-α-naphthyldimethoxysilane, 1,1-dimethyl-2-ethylbutyl-8-
Methyl-α-naphthyldimethoxysilane, 1,1-dimethyl-2-ethylbutyl-2,7-dimethyl-α-naphthyldimethoxysilane, 1,1-dimethyl-2-ethylbutyl-2,8-dimethyl-α-naphthyldimethoxy Silane, 1,1,2,3-tetramethylbutyl-α-naphthyldimethoxysilane, 1,1,2,3-tetramethylbutyl-2-methyl-α-naphthyldimethoxysilane,
1,1,2,3-tetramethylbutyl-7-methyl-α
-Naphthyldimethoxysilane, 1,1,2,3-tetramethylbutyl-8-methyl-α-naphthyldimethoxysilane, 1,1,2,3-tetramethylbutyl-2,7-
Dimethyl-α-naphthyldimethoxysilane, 1,1,
2,3-tetramethylbutyl-2,8-dimethyl-α-
Naphthyldimethoxysilane, 1,1,2-trimethylpentyl-α-naphthyldimethoxysilane, 1,1,2-
Trimethylpentyl-2-methyl-α-naphthyldimethoxysilane, 1,1,2-trimethylpentyl-7-methyl-α-naphthyldimethoxysilane, 1,1,2-trimethylpentyl-8-methyl-α-naphthyldimethoxysilane , 1,1,2-trimethylpentyl-2,7-
Dimethyl-α-naphthyldimethoxysilane, 1,1,2
-Trimethylpentyl-2,8-dimethyl-α-naphthyldimethoxysilane, 1,1,2-trimethylisopropylbutyl-α-naphthyldimethoxysilane, 1,1,
2-trimethylisopropylbutyl-2-methyl-α-
Naphthyldimethoxysilane, 1,1,2-trimethylisopropylbutyl-7-methyl-α-naphthyldimethoxysilane, 1,1,2-trimethylisopropylbutyl-8-methyl-α-naphthyldimethoxysilane, 1,
1,2-trimethylisopropylbutyl-2,7-dimethyl-α-naphthyldimethoxysilane, 1,1,2-trimethylisopropylbutyl-2,8-dimethyl-α-
Naphthyldimethoxysilane, 1,1,3-trimethyl-
2-ethylbutyl-α-naphthyldimethoxysilane,
1,1,3-trimethyl-2-ethylbutyl-2-methyl-α-naphthyldimethoxysilane, 1,1,3-trimethyl-2-ethylbutyl-7-methyl-α-naphthyldimethoxysilane, 1,1,3- Trimethyl-2-ethylbutyl-8-methyl-α-naphthyldimethoxysilane, 1,1,3-trimethyl-2-ethylbutyl-2,
7-dimethyl-α-naphthyldimethoxysilane, 1,
Examples thereof include 1,3-trimethyl-2-ethylbutyl-2,8-dimethyl-α-naphthyldimethoxysilane, and the like, and in addition to these compounds, compounds having a diethoxy group instead of the dimethoxy group in the compound. Among the compounds represented by the general formula (I), the general formula (V)

[0025]

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The compounds represented by the following formulas are preferred. The above general formula
R ^{20 in} (V) represents a methyl group or an ethyl group. R ³ , R
⁴ , R ⁵ , R ⁶ and R ⁷ are the same as above. Specific examples of the compound represented by the general formula (V) include 1,1,2
-Trimethylpropyl-α-naphthyldimethoxysilane, 1,1,2-trimethylbutyl-α-naphthyldimethoxysilane, 1,1-dimethyl-2-ethylbutyl-
α-naphthyldimethoxysilane, 1,1,2,3-tetramethylbutyl-α-naphthyldimethoxysilane, 1,
1,2-trimethylpentyl-α-naphthyldimethoxysilane, 1,1,2-trimethylisopropylbutyl-
α-naphthyldimethoxysilane, 1,1,3-trimethyl-2-ethylbutyl-α-naphthyldimethoxysilane, and the like, and in addition to these compounds, compounds in which dimethoxy groups are substituted for dimethoxy groups in the compounds are exemplified. . Particularly preferred compounds include 1,1,2
-Trimethylpropyl-α-naphthyldimethoxysilane and 1,1,2-trimethylpropyl-α-naphthyldiethoxysilane. Another one of the organosilicon compounds of the present invention has the general formula (II)

[0027]

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## EQU1 ## In addition, the above general formula
In (II), R ¹ and R ² and a substituted or unsubstituted texyl group (V
II)

[0029]

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R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same as described above. Further, a substituted or unsubstituted β-naphthyl group (IX) of the above general formula (II)

[0031]

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R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁵ each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Or a ring may be formed with an adjacent group. Specific examples of the substituted or unsubstituted β-naphthyl group include a β-naphthyl group, a 2-methyl-β-naphthyl group, and a 3-methyl-β
-Naphthyl group, 4-methyl-β-naphthyl group, 6-methyl-β-naphthyl group, 7-methyl-β-naphthyl group, 8
-Methyl-β-naphthyl group, 9-methyl-β-naphthyl group, 2,3-dimethyl-β-naphthyl group, 2,4-dimethyl-β-naphthyl group, 2,6-dimethyl-β-naphthyl group, 2,7-dimethyl-β-naphthyl group, 2,8-dimethyl-β-naphthyl group, 2,9-dimethyl-β-naphthyl group, 2,3,4-trimethyl-β-naphthyl group,
6,7,8-trimethyl-β-naphthyl group, 6,7,
8,9-tetramethyl-β-naphthyl group, 2,3,4
6,7,8,9-heptamethyl-β-naphthyl group.

Specific examples of the compound represented by the general formula (II) include 1,1,2-trimethylpropyl-β-naphthyldimethoxysilane and 1,1,2-trimethylpropyl-2-methyl-β- Naphthyldimethoxysilane, 1,
1,2-trimethylpropyl-8-methyl-β-naphthyldimethoxysilane, 1,1,2-trimethylbutyl-
β-naphthyldimethoxysilane, 1,1,2-trimethylbutyl-2-methyl-β-naphthyldimethoxysilane, 1,1,2-trimethylbutyl-8-methyl-β-
Naphthyldimethoxysilane, 1,1-dimethyl-2-ethylbutyl-β-naphthyldimethoxysilane, 1,1-
Dimethyl-2-ethylbutyl-2-methyl-β-naphthyldimethoxysilane, 1,1-dimethyl-2-ethylbutyl-8-methyl-β-naphthyldimethoxysilane,
1,1,2,3-tetramethylbutyl-β-naphthyldimethoxysilane, 1,1,2,3-tetramethylbutyl-2-methyl-β-naphthyldimethoxysilane, 1,
1,2,3-tetramethylbutyl-8-methyl-β-naphthyldimethoxysilane, 1,1,2-trimethylpentyl-β-naphthyldimethoxysilane, 1,1,2-trimethylpentyl-2-methyl-β- Naphthyldimethoxysilane, 1,1,2-trimethylpentyl-8-methyl-β-naphthyldimethoxysilane, 1,1,2-trimethylisopropylbutyl-β-naphthyldimethoxysilane, 1,1,2-trimethylisopropylbutyl-2
-Methyl-β-naphthyldimethoxysilane, 1,1,2
-Trimethylisopropylbutyl-8-methyl-β-naphthyldimethoxysilane, 1,1,3-trimethyl-2
-Ethylbutyl-β-naphthyldimethoxysilane, 1,
1,3-trimethyl-2-ethylbutyl-2-methyl-
β-naphthyldimethoxysilane, 1,1,3-trimethyl-2-ethylbutyl-8-methyl-β-naphthyldimethoxysilane, and the like, and in addition to these compounds, a diethoxy group was used instead of the dimethoxy group in the compound. Compounds. Among the compounds represented by the general formula (II), the general formula (VI)

[0034]

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The compounds represented by the following formulas are preferred. The above general formula
R ^{20 in} (VI) represents a methyl group or an ethyl group. R ³ , R
⁴ , R ⁵ , R ⁶ and R ⁷ are the same as above. Specific examples of the compound represented by the general formula (VI) include 1,1,2
-Trimethylpropyl-β-naphthyldimethoxysilane, 1,1,2-trimethylbutyl-β-naphthyldimethoxysilane, 1,1-dimethyl-2-ethylbutyl-
β-naphthyldimethoxysilane, 1,1,2,3-tetramethylbutyl-β-naphthyldimethoxysilane, 1,
1,2-trimethylisopropylbutyl-β-naphthyldimethoxysilane, 1,1,3-trimethyl-2-ethylbutyl-β-naphthyldimethoxysilane, and the like, and in addition to these compounds, instead of the dimethoxy group in the compound, A compound having a diethoxy group is exemplified.
Particularly preferred compounds include 1,1,2-trimethylpropyl-β-naphthyldimethoxysilane, 1,1,2
-Trimethylpropyl-β-naphthyldiethoxysilane. The organosilicon compounds represented by the general formulas (I) and (II) of the present invention can be synthesized as described below.

First, a hydrosilylation reaction between a substituted olefin corresponding to the general formula (VII) and HSiCl ₃ yields a compound of the general formula (X)

[0037]

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Wherein R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷
Is the same as above. ), And then converted to the general formula (XI) with lithium aluminum hydride.

[0039]

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Wherein R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷
Is the same as above. ) And reacting it with anhydrous copper chloride and a catalytic amount of copper iodide to give the general formula (XII)

[0041]

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Wherein R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷
Is the same as above. ) Can be obtained. In the above hydrosilylation reaction,
Radical initiators such as azoisobutyronitrile are converted to HSiC
respect l ₃ 1 mole, it may added 0.01 mol. Also, substituted olefins, relative HSiCl ₃ 1 mole, it may be 0.1 to 1.0 moles. The reaction temperature is generally 0 to 200 ° C, preferably 60 to 150 ° C.
It is preferable to set it in the range.

When the general formula (X) is converted to the general formula (XI) by using lithium aluminum hydride, the reaction is preferably carried out in an ether solvent such as tetrahydrofuran (THF). (X) It is preferable to react 1 to 5 mol per 1 mol. At the time of the reaction, it is desirable to heat and reflux. In addition, when reacting anhydrous copper chloride with a catalytic amount of copper iodide in the general formula (XI), the reaction is preferably carried out in an ether solvent such as tetrahydrofuran (THF). It is preferable to react 1 to 3 mol of copper iodide with respect to 1 mol of XI) and 0.1 to 0.25 mol of copper iodide with respect to 1 mol of general formula (XI). The reaction temperature is usually 0 to 250.
C, preferably in the range of 10 to 50C. On the other hand, the general formula (XIII) or (XIV)

[0044]

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(Wherein R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ , R ¹⁴ and R ^{15 each} represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may be the same or different, or may form a ring with an adjacent group. X ² represents a halogen atom such as a chlorine atom or a bromine atom. The Grignard reagent represented by the general formulas (VIII) and (IX)
By reacting a halide (chloride or bromide) of naphthyl or substituted naphthyl corresponding to the above with magnesium in an ether solvent such as diethyl ether or THF. Next, the above general formula (XII)

[0046]

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Wherein R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷
Is the same as above. ) And a general formula (XIII) or (XIV)

[0048]

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(Wherein R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ , R ¹⁴ , R ¹⁵ and X ² are the same as above. By reacting with a Grignard reagent represented by the general formula
(XV) or (XVI)

[0050]

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(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R
¹⁵ is the same as above. To obtain an organosilicon compound (intermediate). The above general formula (XII) and general formula (XIII) or (X
The reaction with (IV) is usually performed by reacting 1 to 5 mol of the general formula (XIII) or (XIV) with respect to 1 mol of the general formula (XII) in an ether solvent such as diethyl ether or THF. can get. The reaction temperature is usually in the range of 0 to 100 ° C, preferably 10 to 50 ° C. Then
The above organosilicon compound (intermediate) and the general formula (XVII) or
(XVIII) R ¹ OH (XVII) or R ² OH (X
VIII) wherein R ¹ and R ² each represent an alkyl group having 1 to 20 carbon atoms, which may be the same or different from each other. And the desired general formula (I) or (II)

[0052]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R
¹⁴ and R ¹⁵ are the same as above. ) Can be synthesized. The reaction of the above general formula (XV) or (XVI) with the general formula (XVII) or (XVIII)
By reacting 2 to 100 moles of the general formula (XVII) or (XVIII) with respect to 1 mole of the general formula (XV) or (XVI) in the presence of a catalyst in an ether solvent such as diethyl ether or THF. can get. Preferably, the heating is performed under reflux.

Examples of the catalyst include metal alkoxides such as sodium methoxide and sodium ethoxide, transition metals such as platinum and palladium, and transition metal compounds such as palladium chloride, chloroplatinic acid and bistriphenylphosphine palladium dichloride. These may be used alone or in combination of two or more. Usually, these catalysts are preferably used in an amount of 0.05 to 0.20 mol based on the organosilicon compound represented by the general formula (XV) or (XVI).

Among the solid catalyst components used in the production of the olefin polymer of the present invention, as the magnesium compound, a magnesium compound represented by the general formula (III) MgR ¹⁶ R ¹⁷ ... (III) may be used. it can.
In the general formula (III), R ¹⁶ and R ¹⁷ represent a hydrocarbon group, an OR ¹⁸ group (R ¹⁸ is a hydrocarbon group), or a halogen atom. More specifically, the hydrocarbon group has 1 to 1 carbon atoms.
12 alkyl groups, cycloalkyl groups, aryl groups,
And aralkyl groups, as OR ¹⁸ group, an alkyl group R ¹⁸ is 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, such things as aralkyl groups, the halogen atom, chlorine, bromine, iodine , Fluorine and the like. Also,
R ¹⁶ and R ¹⁷ may be the same or different.

Magnesium represented by the above general formula (III)
Specific examples of the compound include Mg (CH_Three)_Two, Mg (C_Two
H_Five)_Two, Mg (i-C_ThreeH₇)_Two, Mg (C_FourH₉)_Two, M
g (C₆H₁₃)_Two, Mg (C₈H₁₇)_Two, Mg (C_TwoH_Five)
(C_FourH₉), Mg (C₆H_Five)_Two, Mg (C₆H₁₁)_Two, Mg
(OCH_Three)_Two, Mg (OC_TwoH_Five)_Two, Mg (OC_FourH ₉)
_Two, Mg (OC₆H₁₃)_Two, Mg (OC₈H₁₇)_Two, Mg
(OC₆H_Five)_Two, Mg (OC₆H₁₁)_Two, Mg (C_TwoH_Five)
Cl, Mg (C_FourH₉) Cl, Mg (C₆H₁₃) Cl, M
g (i-C_FourH₉) Cl, Mg (t-C_FourH₉) Cl, Mg
(C₆H_Five) Cl, Mg (CH_TwoC₆H_Five) Cl, Mg (C
_TwoH_Five) Br, Mg (C_FourH₉) Br, Mg (C₆H_Five) B
r, Mg (C_FourH₉) I, Mg (OC_FourH₉) Cl, Mg
(OC₆H₁₃) Cl, Mg (OC₆H_Five) Cl, Mg (O
C_TwoH_Five) Br, Mg (OC_FourH₉) Br, Mg (OC_TwoH
_Five) I, MgCl_Two, MgBr_Two, MgI_TwoEtc.
be able to. The magnesium compound is a metal magnet.
Prepared from compounds containing calcium or magnesium
be able to.

The magnesium compound may be brought into contact with a halide in advance. Examples of the halide include SiCl ₄ , SiBr ₄ , SnCl ₄ ,
SnBr ₄ , HCl and the like can be mentioned. Among these, SiCl ₄ is particularly preferred. Further, the magnesium compound may be supported on a support such as silica or alumina. The above magnesium compounds may be used alone or in combination of two or more.
In addition, halogens such as iodine, silicon, other elements such as aluminum may be contained, alcohol, ether,
It may contain an electron donor such as esters.

Titanium compounds among the solid catalyst components of the present invention
Is represented by the general formula (IV) TiX¹ _p(OR¹⁹)_4-p ... (IV) (where X¹Is preferably a halogen atom, especially a chlorine atom
K, R¹⁹Is a hydrocarbon group having 1 to 10 carbon atoms,
Or a branched alkyl group;¹⁹Where there are multiple
In that case they may be the same or different. p is 0
-4. Using a titanium compound represented by
be able to. Specifically, Ti (OCH_Three) _Four, Ti
(OC_TwoH_Five)_Four, Ti (On-C_ThreeH₇)_Four, Ti (O
-Ic_ThreeH₇) _Four, Ti (On-C_FourH₉)_Four, Ti
(OiC_FourH₉)_Four, Ti (OC₆H₁₁)_Four, Ti (O
C₆H_Five)_Four Such as tetraalkoxy titanium, TiC
l_Four, TiBr _Four, TiI_FourSuch as tetrahalogenated
Tan, Ti (OCH_Three) Cl_Three, Ti (OC_TwoH_Five) C
l_Three, Ti (OiC_ThreeH₇) Cl_Three, Ti (On-
C_ThreeH₇) Cl _Three, Ti (On-C_FourH₉) Cl_Three, Ti
(OC_TwoH_Five) Br_ThreeTrihalogenated alkoxythio
Tan, Ti (OCH_Three)_TwoCl_Two, Ti (OC_TwoH_Five)_TwoC
l_Two, Ti (OiC_ThreeH₇)_TwoCl_Two, Ti (On-
-C_ThreeH₇)_TwoCl_Two, Ti (OC_TwoH_Five)_TwoBr_TwoSuch as
Dialkoxytitanium dihalide, Ti (OCH_Three)_ThreeC
l, Ti (OC_TwoH_Five)_ThreeCl, Ti (OiC_ThreeH₇)
_ThreeCl, Ti (On-C_ThreeH₇)_ThreeCl, Ti (On
-C_FourH₉)_ThreeMonohalogenated trialkoxy such as Cl
Titanium and the like can be mentioned. Among these, high ha
Rogen-containing titanium compounds, especially TiCl_FourIs preferred.
These titanium compounds may be used alone.
And two or more of them may be used in combination.

Among the solid catalyst components of the present invention, examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, malonic acids, esters of organic or inorganic acids, monoethers, diethers and polyethers. And nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates. Of these, esters of carboxylic acids are preferred, and esters of aromatic carboxylic acids are more preferred. Particularly, esters of aromatic dicarboxylic acids are preferred. Further, an aliphatic hydrocarbon in which the organic group in the ester portion is linear, branched or cyclic is preferable.

Specifically, phthalic acid, naphthalene-1,
2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-1,2
Methyl, ethyl, n- of dicarboxylic acids such as -dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-2,3-dicarboxylic acid, indane-4,5-dicarboxylic acid, indane-5,6-dicarboxylic acid; Propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methyl Pentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl,
3-ethylbutyl, n-hexyl, cyclohexyl, n
-Heptyl, n-octyl, n-nonyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 2
-Ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methylpentyl, 3-methylpentyl,
And dialkyl esters such as -ethylpentyl and 3-ethylpentyl.

Of these, phthalic acid diesters are preferable, and linear or branched aliphatic hydrocarbons having 4 or more carbon atoms in the organic group in the ester portion are preferable. Specific examples thereof include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, and diethyl phthalate. These aromatic carboxylic acid diester compounds may be used alone or in combination of two or more.
In order to obtain the solid catalyst component of the present invention, the magnesium compound, the titanium compound and the electron donor described above may be contacted and reacted by a usual method. It is preferred that

The amount of the titanium compound to be used is generally 0.5 to 100 mol, preferably 1 to 50 mol, per 1 mol of magnesium atom of the magnesium compound. The amount of the electron donor used is:
Usually, 0.01 to 10 mol, preferably 0.0 to 10 mol, per 1 mol of magnesium atom of the magnesium compound.
The range is preferably 5 to 1.0 mol. Further, SiCl ₄ may be added as a halogenating agent. The contact / reaction temperature is usually -20 to 200 ° C, preferably 20 to 200 ° C.
The contact / reaction time is usually 1 minute to 24 hours, preferably 10 minutes to 6 hours.

This contact procedure is not particularly limited. For example, each component may be contacted and reacted in the presence of an inert solvent such as a hydrocarbon, or each component may be diluted and contacted and reacted with an inert solvent such as a hydrocarbon in advance. As the inert solvent, for example, aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, n-octane, isooctane, benzene, toluene,
An aromatic hydrocarbon such as xylene or a mixture thereof can be mentioned. Further, it is preferable that the contact and reaction of the titanium compound are performed twice or more, and the titanium compound is sufficiently supported on the magnesium compound serving as a catalyst carrier. The solid catalyst component obtained by the above contact and reaction is preferably washed with an inert solvent such as a hydrocarbon. This inert solvent may be the same as described above. The solid product can also be stored dry or in an inert solvent such as a hydrocarbon.

The organoaluminum compound used for producing the olefin polymer of the present invention includes an alkyl group,
Having a halogen atom, a hydrogen atom, an alkoxy group,
Aluminoxanes and mixtures thereof can be used. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, dialkylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dialkyl such as dioctylaluminum monochloride Examples thereof include alkylaluminum sesquihalides such as aluminum monochloride and ethylaluminum sesquichloride, and chain aluminoxanes such as methylaluminoxane. Among these organoaluminum compounds, trialkylaluminum having a lower alkyl group having 1 to 5 carbon atoms, particularly trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferable. These organoaluminum compounds may be used alone or in combination of two or more. The organosilicon compound used in the olefin-based polymerization catalyst of the present invention has the general formula (I)

[0065]

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Or the general formula (II)

[0067]

Embedded image

Is represented by In the general formula (I) or the general formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
^{R 7, R 8, R 9} , R 10, R 11, R 12, R 13, R 14 and R ¹⁵ are the same as above. The method for producing an olefin polymer of the present invention comprises contacting and reacting the above magnesium compound, titanium compound and electron donor with an organic aluminum compound and a general formula (I) or a general formula (II). ) In which an olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising a combination of the organosilicon compounds represented by the formula (1). Olefins that can be used for polymerization include ethylene,
Propylene, 1-butene, 1-octene, 1-decene,
Α-olefins such as 3-methyl-1-pentene and 4-methyl-1-pentene can be mentioned. Carbon number 3
It may be applied to the polymerization of more than one α-olefin, especially propylene. Further, the present invention can be applied to copolymerization of propylene with ethylene, 1-butene or 1-hexene.

This production method is not particularly limited as to the polymerization method and its conditions, and can be applied to any of solution polymerization, slurry polymerization, gas phase polymerization, bulk polymerization and the like.
Further, the present invention is applicable to both single-stage polymerization and continuous polymerization, and is also applicable to two-stage polymerization and multi-stage polymerization under different conditions. Further, a catalyst which has been preliminarily polymerized with an α-olefin such as ethylene, propylene, 1-butene, or 1-hexene may be used as a catalyst at the time of polymerization. Examples of the solvent that can be used for polymerization include, for example, aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, n-octane, and isooctane; benzene, toluene, and aromatic hydrocarbons such as xylene; Mixtures can be mentioned.

The amount of the solid catalyst component added under the polymerization conditions is usually 0.001 to 0.1 as titanium atom of the solid catalyst component in the case of slurry polymerization or solution polymerization.
Mmol / liter, preferably 0.005 to 0.0
5 mmol / l, the general formula
The amount of the organosilicon compound represented by (1) is Si / Ti
The atomic ratio is usually 1 to 5000, preferably 5 to 100.
0, and the amount of the organoaluminum compound to be added is usually at an Al / Ti atomic ratio of 5 to 1000.
0, preferably in the range of 50 to 5000.

These may be charged into a polymerization vessel by a usual method, and the contact procedure and the like are not particularly limited. The pressure of the polymerization system is usually from normal pressure to 200 kg / cm ² , preferably
In the range of ^{2 to} 150 kg / cm ² , the polymerization temperature is usually
The polymerization time is usually 10 minutes to 10 hours, preferably 10 minutes to 5 hours. An inert gas such as nitrogen may be present.

The molecular weight at the time of polymerization is controlled by the polymerization temperature,
It is possible to some extent depending on the polymerization conditions such as the catalyst concentration and the catalyst molar ratio, but it is more effective to carry out by adding hydrogen.

[0073]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 1,1,2-Trimethylpropyl-α-naphthyldimethoxysilane [(Thhexyl) (α-Naph
Synthesis of tyl) Si (OMe) ₂ ] in a 300 ml autoclave
Put butene (75ml, 0.60ml) and add HS
iCl ₃ (240 g, 1.8 mol) and azoisobutyronitrile (18 g, 0.11 ml) were added, and the mixture was heated at 120 ° C.
For 22 hours. Thereafter, the solution was taken out by decantation and distilled under reduced pressure (76 ° C., 6 mmHg),
ThexylSiCl ₃ was obtained.

A 1-liter three-necked flask was charged with THF (500 m).
l), and LiAlH ₄ (67.8 g, 1.8)
4 ml) was added (exothermic). Next, the above Thexyl
A THF solution of SiCl ₃ (131.9 g, 0.6 ml) was added dropwise. After the dropwise addition, the mixture was heated to 65 ° C. and refluxed overnight.
Thereafter, excess LiAlH ₄ was hydrolyzed, and the organic layer was separated. It is concentrated and distilled (95-98 ° C) to give T
It was obtained hexylSiH _3.

Subsequently, ether (600 ml), ThexylSiH ₃ (45.0 g,
0.39 mol) and cooled to 0 ° C.
₂ (104.9 g, 0.78 mol), CuI (1.5
6 g, 8.2 mmol) and stirred at room temperature for 48 hours. After the precipitate was filtered off, the solution was concentrated and distilled (distilled at 134 to 142 ° C.) to obtain TexylSiH ₂ Cl.
Was obtained (34.3 g, 0.23 mol).

The α prepared separately in a 50 ml three-necked flask
-NaphtylMgBr / THF (36.0 mmol
l) and then add ThexylSiH ₂ Cl / THF to it.
(3.6 g, 24.0 mmol) was added dropwise. After dripping,
The mixture was further stirred for 2.5 hours. Then, excess α-Nap
The htylMgBr was hydrolyzed, and the organic layer was separated. It was concentrated and distilled under reduced pressure (fraction at 125 ° C, 1.0 mmH
g), (Thexyl) (α-Naphthyl) SiH ₂
(3.81 g, 17.4 mmol).

In a 30 ml two-necked flask, MeOH (30
ml), Na (23 mg, 1.0 mg)
(Thexyl) (α-Naphthyl) SiH ₂ (2.
(5 g, 10.3 mmol). After refluxing for 17 hours,
The solvent was distilled off to obtain a white solid. This was recrystallized using a hexane solvent, and (Thexyl) (α-Nap
htyl) Si (OMe) ₂ was obtained as white crystals (1.4).
1 g, 4.6 mmol). The NMR spectrum of this product was measured, and the results are as follows.

Example 2 (1) Preparation of Solid Catalyst Component In a 500-ml three-necked flask equipped with a stirrer and purged with nitrogen, 16 g of diethoxymagnesium (0.14 mol) was added.
l) was added, and 60 ml of dehydrated heptane was added. Heated to 40 ° C. and 2.45 ml of silicon tetrachloride (22.
After stirring for 20 minutes, 12.7 mmol of di-n-butyl phthalate was added. The temperature of the solution was raised to 80 ° C., and 77 ml (0.70 mol) of titanium tetrachloride was subsequently added dropwise using a dropping funnel. The internal temperature was 110 ° C., and the mixture was stirred for 2 hours to perform a loading operation. Thereafter, washing was sufficiently performed using dehydrated heptane. Further, 122 ml (1.12 mol) of titanium tetrachloride was added, the internal temperature was set to 110 ° C., and the mixture was stirred for 2 hours to perform a second loading operation. Thereafter, the solid catalyst component was sufficiently washed with dehydrated heptane to obtain a solid catalyst component.

(2) Polymerization of Slurry of Propylene A stainless steel autoclave with an internal volume of 1 liter and equipped with a stirrer was sufficiently dried, and after replacement with nitrogen, 400 ml of dehydrated heptane was added to the inside. Further, 0.5 mmol of triethylaluminum, followed by 0.25 mm of 1,1,2-trimethylpropyl-α-naphthyldimethoxysilane
ol, the solid catalyst component was added in an amount of 0.005 mmol per titanium atom, and hydrogen gas was added at 1.0 kg / cm.
² G, followed by the introduction of propylene. The autoclave temperature was 80 ° C., the total pressure was 8 kg / cm ² G, and the temperature was 8
The polymerization was carried out at 0 ° C. for 2 hours.

Thereafter, the temperature was lowered and the pressure was released, the contents were taken out, and the contents were poured into 2 liters of methanol, followed by vacuum drying to obtain polypropylene. Its catalytic activity, intrinsic viscosity
[η], stereoregularity [mmmm] and Mw / Mn are 1st
It is shown in the table. The intrinsic viscosity [η] was measured at 135 ° C. after dissolving the polymer in decalin. Stereoregularity [m
[mmm] is obtained by dissolving a polymer in 1,2,4-trichlorobenzene and using ¹³ C-NMR (EX-400 manufactured by JEOL).
It measured using. Mw / Mn is GPC (Wat
ers 150C).

Comparative Example 1 (1) Preparation of Solid Catalyst Component The procedure was the same as in Example 1. (2) Slurry polymerization of propylene The same procedure as in Example 1 was carried out except that cyclohexylmethyldimethoxysilane was added instead of 1,1,2-trimethylpropyl-α-naphthyldimethoxysilane. The results are shown in Table 1.

Example 3 (1) Preparation of Solid Catalyst Component In a three-necked flask equipped with a stirrer having an inner volume of 500 ml and purged with nitrogen, 13.3 g (0.1%) of magnesium chloride (anhydride) was added.
4 mol), 70 ml of decane and 65.5 ml (0.42 ml) of 2-ethylhexyl alcohol, and 13
A heating reaction was performed at 0 ° C. for 2 hours to obtain a homogeneous solution. afterwards,
3.12 g (0.021 mmol) of phthalic anhydride was added to this solution.
l) was added, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the above homogeneous solution.

After the homogeneous solution thus obtained was cooled to room temperature, titanium tetrachloride 37 kept at -20 ° C.
The whole amount was dropped into 3 ml (3.36 mol) over 1 hour. After the dropwise addition, the temperature of the obtained homogeneous solution was raised to 110 ° C over 4 hours, and when the temperature reached 110 ° C, di-n-
5.39 ml (0.035 mol) of butyl phthalate was added, followed by stirring at 110 ° C. for 2 hours.

After completion of the reaction for 2 hours, a solid product was collected by hot filtration, resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. . After the completion of the reaction, the solid product was collected again by filtration while hot, and washed with decane and hexane at 110 ° C.
This washing was performed until no titanium compound was detected in the washing solution, to obtain a solid catalyst component. (2) Slurry polymerization of propylene It was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 (1) Preparation of Solid Catalyst Component The procedure was the same as in Example 2. (2) Slurry polymerization of propylene, granulation and evaluation The same procedure as in Example 2 was carried out except that cyclohexylmethyldimethoxysilane was added instead of 1,1,2-trimethylpropyl-α-naphthyldimethoxysilane. The results are shown in Table 1.

[0086]

[Table 1]

[0087]

Industrial Applicability The novel organosilicon compound of the present invention can be effectively used as a catalyst component for olefin polymerization. According to the method for producing an olefin polymer using the organosilicon compound of the present invention, it is possible to provide an olefin polymer having good stereoregularity and a wide molecular weight distribution, particularly a polypropylene having the above-mentioned features.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a process for preparing a catalyst component in the method for producing an olefin polymer of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Go Ota 1-1, Anesaki Beach, Ichihara City, Chiba Prefecture (72) Inventor Toshio Isozaki 1, 1 Anesaki Beach, Ichihara City, Chiba Prefecture (72) Inventor Seiwa Katayama Ichihara, Chiba Prefecture 1 Anesaki Beach 1

Claims (4)

[Claims] 1. A compound of the general formula (I)(Where R¹And R^TwoIs an alkyl group having 1 to 20 carbon atoms
Which may be the same or different
You may. R^Three, R^Four, R^FiveAnd R⁶Is 1 to 3 carbon atoms
Represents an alkyl group, which may be the same,
They may be different from each other. R⁷Is a hydrogen atom or carbon number 1
Shows three alkyl groups. Also, R⁸, R ⁹, R^Ten, R
¹¹, R¹², R¹³And R¹⁴Is a hydrogen atom or 1 to 10 carbon atoms
Alkyl groups, which are the same or different
Or a ring with an adjacent group may be formed. )so
Organosilicon compounds represented. 2. A compound of the general formula (II)(Where R¹And R^TwoIs an alkyl group having 1 to 20 carbon atoms
Which may be the same or different
You may. R^Three, R^Four, R^FiveAnd R⁶Is 1 to 3 carbon atoms
Represents an alkyl group, which may be the same,
They may be different from each other. R⁷Is a hydrogen atom or carbon number 1
Shows three alkyl groups. Also, R⁸, R ⁹, R^Ten, R
¹¹, R¹², R¹³And R^FifteenIs a hydrogen atom or 1 to 10 carbon atoms
Alkyl groups, which are the same or different
Or a ring with an adjacent group may be formed. )so
Organosilicon compounds represented. 3. A titanium compound, a magnesium compound and an electrode.
A solid catalyst component obtained by contacting and reacting a child donor,
Organoaluminum compound and general formula (I)(Where R¹And R^TwoIs an alkyl group having 1 to 20 carbon atoms
Which may be the same or different
You may. R^Three, R^Four, R^FiveAnd R⁶Is 1 to 3 carbon atoms
Represents an alkyl group, which may be the same,
They may be different from each other. R⁷Is a hydrogen atom or carbon number 1
Shows three alkyl groups. Also, R⁸, R ⁹, R^Ten, R
¹¹, R¹², R¹³And R¹⁴Is a hydrogen atom or 1 to 10 carbon atoms
Alkyl groups, which are the same or different
Or a ring with an adjacent group may be formed. )so
An organosilicon compound represented by the general formula (II):(Where R¹And R^TwoIs an alkyl group having 1 to 20 carbon atoms
Which may be the same or different
You may. R^Three, R^Four, R^FiveAnd R⁶Is 1 to 3 carbon atoms
Represents an alkyl group, which may be the same,
They may be different from each other. R⁷Is a hydrogen atom or carbon number 1
Shows three alkyl groups. Also, R⁸, R ⁹, R^Ten, R
¹¹, R¹², R¹³And R^FifteenIs a hydrogen atom or 1 to 10 carbon atoms
Alkyl groups, which are the same or different
Or a ring with an adjacent group may be formed. )so
A catalyst consisting of a combination of the organosilicon compounds represented
Olefin polymerization or copolymerization using
A method for producing a characteristic olefin polymer. 4. The method according to claim 3, wherein the olefin is propylene.
3. The method for producing an olefin polymer according to item 1.