JP2873064B2 - Method for producing poly-α-olefin - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing poly-α-olefin.

2. Description of the Related Art When a poly-α-olefin is produced using a catalyst component containing magnesium, titanium, chlorine and an electron-donating compound, it has a Si—O—C bond together with an organoaluminum compound, or has the general formula SiR ¹ R ² _n (OR ³ ) _3-n (n = 0 to
It is known that the use of the organosilicon compound represented by 2) improves the stereoregularity of the resulting polymer (for example, JP-A-54-94690, JP-A-56-36203, and JP-A-57-36203).
63310, 58-83016, 62-11705, etc.).

Polymers obtained using the organosilicon compounds described in the above publications generally have a narrow molecular weight distribution.

Problems to be Solved by the Invention When the molecular weight distribution of a polymer is expanded, the rigidity of the polymer,
Fluidity, processability, etc. can be improved.

As a method for expanding the molecular weight distribution of a polymer, a method using a plurality of polymerization vessels having different polymerization conditions, that is, a so-called multistage polymerization method is generally used.

However, when the multi-stage polymerization method is employed, the process becomes complicated, the cost of the polymer increases, and the polymerization activity of the polymerization catalyst decreases.

An object of the present invention is to provide a method capable of producing a poly-α-olefin having a wide molecular weight distribution in a single step in a high yield.

Means for Solving the Problems The present inventors have conducted intensive studies and as a result, by using a polymerization catalyst using two kinds of specific organic silicon compounds in combination,
The inventors have found that the object of the present invention can be achieved, and reached the present invention.

SUMMARY OF THE INVENTION That is, the present invention provides (A) a solid catalyst component comprising magnesium, titanium, halogen and an electron donating compound as essential components; (B) a general formula R _n AlX _3-n (where R is an alkyl group or An aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom, and n is an arbitrary number in the range of 1 ≦ n ≦ 3); and (C) a general formula [However, R ¹ is the number 1 to 10 hydrocarbon group having a carbon, OR _^3, SiR ^{4 3}
Or OSiR ⁵ _3, R ² represents a 1-10 hydrocarbon group or SiR ⁶ ₃ carbon atoms, showing a R ^3, R ^4, R ⁵ and R ⁶ having 1 to 10 carbon atoms each hydrocarbon radical . And a dimethoxysilane compound represented by the general formula (D): (However, R ⁷ is a hydrocarbon group having 2 to 10 carbon atoms or SiR
¹¹ ₃ , R ⁸ is a hydrocarbon group having 1 to 10 carbon atoms or Si
R ¹² ₃ , R ⁹ and R ¹⁰ represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, and R ¹¹ and R ¹² represent hydrocarbon groups having 1 to 10 carbon atoms. ] The method for producing a poly-α-olefin comprises polymerizing the α-olefin in the presence of a polymerization catalyst comprising the alkoxysilane compound.

Solid Catalyst Component The solid catalyst component (hereinafter, referred to as component A), which is one component of the polymerization catalyst used in the present invention, contains magnesium, titanium, halogen, and an electron donating compound as essential components. When a magnesium compound, a titanium compound, an electron donating compound, and each of the above compounds has no halogen, the compound is prepared by contacting with a halogen-containing compound.

(1) Magnesium compound The magnesium compound is represented by the general formula MgR ¹ R ² .
In the formula, R ¹ and R ² represent the same or different hydrocarbon groups, OR groups (R is a hydrocarbon group), and halogen atoms. More specifically, as the hydrocarbon group of R ¹ and R ² , an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group, Twelve alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups include chlorine, bromine, iodine, and fluorine as halogen atoms.

Specific examples of these compounds are shown below.In the chemical formula, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl,
He: Hexyl, Oct: Octyl, Ph: Phenyl, cyHe: Cyclohexyl.

MgMe ₂ , MgEt ₂ , Mgi-Pr ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgBtBu, M
_{gPh 2, MgcyHe 2, Mg (} OMe) 2, Mg (OEt) 2, Mg (OBu) 2, Mg
(OHe) ₂ , Mg (OOct) ₂ , Mg (OPh) ₂ , Mg (OcyHe) ₂ , EtMgC
l, BuMgCl, HeMgCl, i-BuMgCl, t-BuMgCl, PhMgCl, PhCH ₂ Mg
Cl, EtMgBr, BuMgBr, PhMgBr, BuMgI, EtOMgCl, BuOMgCl, HeOM
gCl, PhOMgCl, EtOMgBr, BuOMgBr, EtOMgI, MgCl 2, MgBr 2, MgI
₂ .

When preparing the component A, the magnesium compound
It is also possible to prepare from metallic magnesium or other magnesium compounds. Examples thereof include metallic magnesium, halogenated hydrocarbons and the general formula X _n M (OR) _mn
Wherein X is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
Is a boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is a valence of M, and m> n ≧
Indicates 0. ] Is contacted. Examples of the hydrocarbon group of X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl (Pr),
alkyl groups such as i-propyl (i-Pr), butyl (Bu), i-butyl (i-Bu), hexyl (He), and octyl (Oct); cycloalkyl groups such as cyclohexyl (cyHe) and methylcyclohexyl; Examples thereof include alkenyl groups such as allyl, propenyl and butenyl, phenyl (Ph), aryl groups such as tolyl and xylyl groups, and aralkyl such as phenethyl and 3-phenylpropyl. Among these,
Particularly, an alkyl group having 1 to 10 carbon atoms is desirable. Hereinafter, specific examples of the alkoxy group-containing compound will be described.

Compound where M is carbon C (OMe) ₄ , C (OEt) ₄ , C (OP) contained in formula C (OR) ₄
r) ₄ , C (OBu) ₄ , C (Oi-Bu) ₄ , C (OHe) ₄ , C (OOct) ₄ :
HC (OMe) ₃ , HC (OEt) ₃ , HC contained in formula XC (OR) ₃
(OPr) ₃ , HC (OBu) ₃ , HC (OHe) ₃ , HC (OPh) ₃ ; MeC (OM
e) ₃ , MeC (OEt) ₃ , EtC (OMe) ₃ , EtC (OEt) ₃ , cyHeC (OE
t) ₃ , PhC (OMe) ₃ , PhC (OEt) ₃ , CH ₂ ClC (OEt) ₃ , MeCHBr
C (OEt) ₃ , MeCHClC (OEt) ₃ ; ClC (OMe) ₃ , ClC (OEt) ₃ ,
_{ClC (Oi-Bu) 3,} BrC (OEt) 3; within Formula X ₂ C _{(OR) 2}
MeCH (OMe) ₂ , MeCH (OEt) ₂ , CH ₂ (OMe) ₂ , CH ₂ (OEt) ₂ ,
CH ₂ ClCH (OEt) ₂ , CHCl ₂ CH (OEt) ₂ , CCl ₃ CH (OEt) ₂ , CH ₂
BrCH (OEt) ₂ , PhCH (OEt) ₂ .

Compound when M is silicon Si (OMe) ₄ , Si (OEt) ₄ , Si contained in formula Si (OR) ₄
(OBu) ₄ , Si (Oi-Bu) ₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si
(OPh) ₄ : HSi (OEt) ₃ , HSi (O) contained in the formula XSi (OR) ₃
Bu) ₃ , HSi (OHe) ₃ , HSi (OPh) ₃ ; MeSi (OMe) ₃ , MeSi (O
Et) ₃ , MeSi (OBu) ₃ , EtSi (OEt) ₃ , PhSi (OEt) ₃ , EtSi
(OPh) ₃ ; ClSi (OMe) ₃ , ClSi (OEt) ₃ , ClSi (OBu) ₃ , Cl
Si (OPh) ₃ , BrSi (OEt) ₃ ; Me contained in the formula X ₂ Si (OR) _{2
2 Si (OMe) 2, Me} 2 Si (OEt) 2, Et 2 Si (OEt) 2; MeClSi (OE
t) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ SiH (OEt) ₂ ; MeBrSi (OE
t) ₂ : Me ₃ SiOMe, Me ₃ SiOEt, Me ₃ SiOBu, Me contained in X ₃ SiOR
₃ SiOPh, Et ₃ SiOEt, Ph ₃ SiOEt.

Compound where M is boron B (OEt) ₃ , B (OBu) ₃ , B (OH) contained in formula B (OR) ₃
e) ₃ , B (OPh) ₃ .

Compound when M is aluminum Al (OMe) ₃ , Al (OEt) ₃ , Al contained in formula Al (OR) ₃
(OPr) ₃ , Al (Oi-Pr) ₃ , Al (OBu) ₃ , Al (Ot-Bu) ₃ , Al
(OHe) ₃ , Al (OPh) ₃ .

Compound when M is phosphorus P (OMe) ₃ , P (OEt) ₃ , P (OB) contained in formula P (OR) ₃
u) ₃ , P (OHe) ₃ , P (OPh) ₃ .

Further, as the magnesium compound, a complex with an organic compound of a metal (M) of Group II or Group IIIa of the periodic table can also be used. The complex is represented by the general formula MgR ¹ R ² · n (MR ³ _m ). Examples of the metal include aluminum, zinc, and calcium, and R ³ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
M represents the valence of the metal M, and n represents a number of 0.1 to 10. M
Specific examples of the compound represented by R ³ _m include AlMe ₃ , AlE
_{t 3, Ali-Bu 3,} AlPh 3, ZnMe 2, ZnEt 2, ZnBu 2, ZnPh 2, CaEt 2, Ca
Ph _{2 and the} like.

(2) Titanium compound The titanium compound is a compound of trivalent and tetravalent titanium, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, dichlorodiethoxytitanium, and dichlorodichlorotitanium. Butoxytitanium, dichlorodiphenoxytitanium, chlorotriethoxytitanium, chlorotributoxytitanium, tetrabutoxytitanium, titanium trichloride and the like. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxytitanium, dichlorodibutoxytitanium and dichlorodiphenoxytitanium are desirable, and titanium tetrachloride is particularly desirable.

(3) Electron-donating compound Examples of the electron-donating compound include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, ethers, ketones, amines, amides, nitriles, Aldehydes, alcoholates, phosphorus bonded to an organic group via carbon or oxygen,
Examples include arsenic and antimony compounds, phosphoamides, thioethers, thioesters, carbonate esters and the like. Of these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols and ethers are preferably used.

Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid, malonic acid, and succinic acid. , Glutaric acid, adipic acid, sebacic acid, maleic acid, aliphatic dicarboxylic acids such as fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid,
Cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexane dicarboxylic acid,
Aromatic carboxylic acids such as cis-4-methylcyclohexene-1,2-dicarboxylic acid, aromatic monocarboxylic acids such as benzoic acid, toluic acid, anisic acid, p-tert-butyl benzoic acid, naphthoic acid, and cinnamic acid Carboxylic acid, phthalic acid, isophthalic acid,
Aromatic polycarboxylic acids such as terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid, and melitic acid are exemplified.

As the carboxylic acid anhydride, the acid anhydrides of the above carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutylate, propyl pivalate, isopropyl pivalate, and acrylic acid. Ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, diisobutyl adipate Dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, ditartrate Chill, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-tert-butyl benzoate, ethyl p-anisate, ethyl α-naphthoate, α-naphthoate Isobutyl, ethyl cinnamate,
Monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate,
Dioctal phthalate, di-2-ethylhexyl phthalate,
Diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate,
Examples include dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, tetrabutyl pyromellitate, and the like.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used, and specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride, butyric acid bromide, butyric acid iodide, and pivalin. Acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride,
Methacrylic acid bromide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid bromide, succinic acid chloride, succinic acid bromide, glutaric acid chloride, glutaric acid bromide, adipic acid chloride,
Adipic acid bromide, sebacic acid chloride, sebacic acid bromide, maleic acid chloride, maleic acid bromide,
Fumaric acid chloride, fumaric acid bromide, tartaric acid chloride, tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, 1-cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid bromide Benzoyl chloride, benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid chloride, p-anisic acid bromide,
α-naphthoic acid chloride, cinnamate chloride, cinnamate bromide, phthalic dichloride, phthalic dibromide,
Isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, naphthalic acid dichloride. Also, adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride,
Monoalkyl halides of dicarboxylic acids such as butyl phthalate chloride may also be used.

Alcohols are represented by the general formula ROH. In the formula, R is an alkyl, alkenyl, cycloalkyl, aryl, aralkyl having 1 to 12 carbon atoms. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol,
Allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p
-Tert-butylphenol, n-octylphenol and the like. Ethers represented by the general formula ROR ^1. In the formula, R and R ¹ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R and R ¹ may be the same or different. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, and ethylphenyl ether. .

As a method for preparing Component A, a magnesium compound (Component 1), a titanium compound (Component 2), and an electron donating compound (Component 3) are contacted in that order. Component 1 and component 3
And then contact component 2. Component 1, Component 2
And the method of contacting the component 3 simultaneously.
It is also possible to contact with a halogen-containing compound before contacting with component 2.

Halogen-containing compounds include halogenated hydrocarbons,
Examples thereof include a halogen-containing alcohol, a silicon halide compound having a hydrogen-silicon bond, and a halide (hereinafter, referred to as a metal halide) of a Group IIa, IVa, or Va element of the periodic table.

Examples of the halogenated hydrocarbon include mono- and polyhalogen-substituted saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. Specific examples of those compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride,
Carbon tetrabromide, carbon tetraiodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methyl chloroform, methyl bromoform, methyl iodoform, 1,1 1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-di Chlorpropane, hexachloropropylene, octachloropropane,
Decabromobutane, chlorinated paraffins, alicyclic compounds chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, hexachlorocyclohexane, aromatic compounds chlorobenzene, bromobenzene, o-dichlorobenzene, p -Dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloride and the like. These compounds may be used alone or in combination of two or more.

As the halogen-containing alcohol, a mono- or polyhydric alcohol having one or two or more hydroxyl groups in one molecule means a compound in which any one or two or more hydrogen atoms other than a hydroxyl group are substituted with a halogen atom. I do. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and a chlorine atom is preferable.

Illustrating those compounds are 2-chloroethanol,
1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1 -Hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-
Chlor- (m, o) -cresol, 6-chloro- (m, o)-
Cresol, 4-chloro-3,5-dimethylphenol,
Chlorohydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m, o, p) -chlorophenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-chlororesorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-
2-propanol, 1-bromo-2-butanol, 2-
Brom-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (m, o, p) -bromophenol, 4-bromoresorcin, (m, o, p) -fluorophenol, p -Iodophenol; 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-chloro-1- (α-chloromethyl) -1-propanol, 2 , 3-Dibromo-1
-Propanol, 1,3-dibromo-2-propanol,
2,4-dibromophenol, 2,4-dibromo-1-naphthol: 2,2,2-trichloroethanol, 1,1,1-trichloro-2-propanol, β, β, β-trichloro-tert
-Butanol, 2,3,4-trichlorophenol, 2,4,5-
Trichlorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,3,5-tribromo-2-hydroxytoluene, 2,3,5-tribromo-4-
Hydroxytoluene, 2,2,2-trifluoroethanol, α, α, α-trifluoro-m-cresol, 2,4,
6-triiodophenol: 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,
Examples include 3,3-tetrafluoro-1-propanol, 2,3,5,6-tetrafluorophenol, tetrafluororesorcin and the like.

HSiCl ₃ , H ₂ SiCl ₂ , H ₃ SiCl, HCH ₃ SiCl ₂ , HC ₂ H ₅ SiCl ₂ , HSiCl _{3
(T-C 4 H 9)} SiCl 2, HC 6 H 5 SiCl 2, H (CH 3) 2 SiCl, H (i-
_{C 3 H 7) 2 SiCl,} H 2 C 2 H 5 SiCl, H 2 (n-C 4 H 9) SiCl, H 2 (C 6 H 4
CH ₃ ) SiCl, HSiCl (C ₆ H ₅ ) _{2 and the} like.

As metal halides, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb,
As, Sb, Bi include chloride, fluoride, bromide, iodide, especially BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ , AlBr ₃ , GaCl ₃ , GaBr ₃ , InCl
₃ , TlCl ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF _{5 and the} like are preferred.

Component 1, Component 2 and Component 3, as well as contact with a halogen-containing compound that can be contacted if necessary, are mixed and stirred in the presence or absence of an inert medium, but are mechanically co-ground. This is done by: The contact can be performed under heating at 40 to 150 ° C.

As the inert medium, saturated aliphatic hydrocarbons such as hexane, heptane and octane, saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene can be used.

A desirable method for preparing Component A in the present invention is described in
-264607, 58-198503, 62-146904 and the like. More specifically, it is obtained by contacting (a) metallic magnesium, (b) a halogenated hydrocarbon, and (c) a compound of the general formula X _n M (OR) _mn (the same as the above-mentioned alkoxy group-containing compound). A method in which a magnesium-containing solid is contacted with (d) a halogen-containing alcohol and then with (e) an electron-donating compound and (f) a titanium compound (JP-A-63-2646).
No. 07), (a) magnesium dialkoxide and (b) hydrogen-
After contacting with a silicon halide compound having a silicon bond, (c) contact with a titanium halide compound, and then (d) contact with an electron donating compound (and further contact with a titanium halide compound as necessary) Method (Japanese
62-146904), (a) magnesium dialkoxide and (b) hydrogen-
After contacting a silicon halide compound having a silicon bond, (c) contact with an electron donating compound, and then (d)
This is a method of contacting with a titanium compound (JP-A-58-198503).

 Of these, the particular method is most desirable.

The component A is prepared as described above, and the component A may be washed with the above-mentioned inert medium, if necessary, and further dried.

Further, the component A may further contain an olefin polymer formed in the component A by being brought into contact with an olefin in the presence of an organoaluminum compound. The organic aluminum compound is selected from the following organic aluminum compounds which are one component of the catalyst of the present invention.

As the olefin, propylene other than ethylene, 1-
Alpha-olefins such as butene, 1-hexane, 4-methyl-1-pentene, and the like can be used. Contact with the olefin is
It is desirable to carry out in the presence of the above-mentioned inert medium. Contact is
Usually, it is carried out at a temperature of 100 ° C. or less, preferably -10 to + 50 ° C. The amount of the olefin polymer contained in the component A is usually 0.1 to 100 g per 1 g of the component A.

The contact between the component A and the olefin may cause the electron donating compound to be present together with the organoaluminum compound. The electron donating compound is selected from compounds used for preparing the component A, organic silicon compounds having a Si—O—C bond or a Si—N—C bond, and the like. Component A, which has come into contact with the olefin, can be optionally washed with the above-mentioned inert medium and further dried.

Organoaluminum Compound Organoaluminum compound (hereinafter referred to as component B)
It is represented by the general formula R _n AlX _3-n (where R represents an alkyl group or an aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom, and n is an arbitrary number in the range of 1n3). Yes, for example, having 1 carbon atom such as trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide and dialkylaluminum monohydride.
Particularly preferred are alkyl aluminum compounds having from 18 to 18, preferably 2 to 6 carbon atoms, or mixtures or complex compounds thereof. Specifically, trimethyl aluminum,
Triethyl aluminum, tripropyl aluminum,
Trialkylaluminums such as triisobutylaluminum and trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, dialkylaluminum monohalides such as diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum Monoalkylaluminum dihalide such as dibromide, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride, alkylaluminum sesquihalide such as ethylaluminum sesquichloride, dimethylaluminum methoxide, diethylaluminum ethoxide,
Examples thereof include dialkylaluminum monoalkoxides such as diethylaluminum phenoxide, dipropylaluminum ethoxide, diisobutylaluminum ethoxide, diisobutylaluminum phenoxide, dimethylaluminum hydride, diethylaluminum hydride, and dialkylaluminum hydrides such as dipropylaluminum hydride and diisobutylaluminum hydride. Among these, trialkyl aluminum, particularly triethyl aluminum and triisobutyl aluminum are desirable. Further, these trialkylaluminums are other organic aluminum compounds, for example, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride, or mixtures or complex compounds thereof, which are easily available industrially. Etc. can be used in combination.

Dimethoxysilane Compound A dimethoxysilane compound (hereinafter, referred to as component C), which is one component of the polymerization catalyst used in the present invention, is represented by the general formula. In the formula, as the hydrocarbon group of R ^{1 to} R ⁶ , an alkyl group, an alkenyl group, a cycloalkyl group,
Examples thereof include a cycloalkenyl group, a cycloalkadienyl group, an aryl group, and an aralkyl group.

Examples of the alkyl group include methyl, ethyl, propyl, i
-Propyl, butyl, i-butyl, s-butyl, t-butyl, amyl, i-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, decyl group and the like, and alkenyl groups such as vinyl, allyl and propenyl , 1-butenyl, 1-pentenyl, 1-hexenyl, 1-octenyl, 1-decenyl, 1-methyl-1-pentynyl, 1-
Methyl-1-heptenyl and the like, as a cycloalkyl group, cyclopentyl, cyclohexyl, methylcyclohexyl group and the like, as a cycloalkenyl group, cyclopentenyl, cyclohexenyl, methylcyclohexenyl group and the like, and as a cycloalkadienyl group. , Cyclopentadienyl, methylcyclopentadienyl, indenyl group, etc., the aryl group is phenyl, tolyl, xylyl group, etc., and the aralkyl group is benzyl, phenethyl, 3-phenylpropyl group, etc. .

Specific examples of the component C are described below by chemical formulas. In the formula, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, Pt: pentyl, Hex: hexyl, Oct: octyl, Dec:
Shows decyl (same for component D).

_{(Me) 2 Si (OMe)} 2, (Et) 2 Si (OMe) 2, (n-Pr) 2 S
_{i (OMe) 2, (i} -Pr) 2 Si (OMe) 2, (n-Bu) 2 Si (OM
e) ₂ , (i-Bu) ₂ Si (OMe) ₂ , (s-Bu) ₂ Si (OMe) ₂ ,
_{(T-Bu) 2 Si (} OMe) 2, (n-Pt) 2 Si (OMe) 2, (n-
Hex) ₂ Si (OMe) ₂ , (Me) (Et) Si (OMe) ₂ , (Me) (n
-Pr) Si (OMe) ₂ , (Me) (n-Bu) Si (OMe) ₂ , (Me)
(T-Bu) Si (OMe) ₂ , (Me) (n-Hex) Si (OMe) ₂ ,
(Et) (i-Pr) Si (OMe) ₂ , (Et) (n-Bu) Si (OM
e) ₂ , (Et) (t-Bu) Si (OMe) ₂ , (Et) (n-Hex) S
i (OMe) ₂ , (n-Pr) (i-Pr) Si (OMe) ₂ , (n-P
r) (t-Bu) Si (OMe) ₂ , (n-Pr) (n-Pt) Si (OM
e) ₂ , (n-Bu) (t-Bu) Si (OMe) ₂ , (i-Bu) (t
−Bu) Si (OMe) ₂ , (t−Bu) (t−Pt) Si (OMe) ₂ ,
(T-Bu) (s- Pt) Si (OMe) 2, (t-Pt) 2 Si (OM
e) _2, [(n-Pr) (Me) CH ] _{2 Si (OMe) 2, (} t-Pt)
(S-Pt) Si (OMe ) 2, [(Me) ₃ C · CH _{2] 2} Si (OMe) _2,
[(Et) (Me) CH · CH 2 ] _{2 Si (OMe) 2, (} t-Pt) [(M
r) ₃ C · CH ₂ ] Si (OMe) ₂ , [(n-Pr) (Me) ₂ C] (t
-Pt) Si (OMe) _{2, [(Et) (Me) 2 C} · CH 2 ] (t-Pt)
Si (OMe) _2, [(n-Pr) (Me) 2 C ] ₂ Si (OMe) _2, [(E
_{t) (Me) 2 C ·} CH 2 ] ₂ Si (OMe) _{2, [(Me) 3 C · C 2} H 4 ] ₂ S
_{i (OMe) 2, (t} -Hex) _{[(Et) (Me) 2 C} · CH 2 ] Si (OM
e) ₂ ; (Me ₃ Si) (Me) Si (OMe) ₂ , (Me ₃ Si) (Et) Si
(OMe) ₂ , (Me ₃ Si) (i-Pr) Si (OMe) ₂ , (Me ₃ Si)
(T-Bu) Si (OMe ) 2, (Me 3 Si) (n-Bu) Si (OM
_{e) 2, (Me 3 Si} ) (s-Bu) Si (OMe) 2, (Me 3 Si) ( _{cyclopentyl) Si (OMe) 2, (} Me 3 Si) ( cyclopentadienyl) Si (OMe) ₂ , (Me ₃ Si) ₂ Si (OMe) ₂ , (Et ₃ Si) (M
e) Si (OMe) ₂ , (Et ₃ Si) (Et) Si (OMe) ₂ , (Et ₃ Si)
(I-Pr) Si (OMe ) 2, (Et 3 Si) (t-Bu) Si (OM
_{e) 2, (Et 3 Si} ) (n-Bu) Si (OMe) 2, (Et 3 Si) (s-
Bu) Si (OMe) ₂ , (Et ₃ Si) (cyclopentyl) Si (OM
e) ₂ , (Et ₃ Si) (cyclopentadienyl) Si (OMe) ₂ ,
(Me ₃ Si) ₂ Si (OMe) ₂ ; (Me ₃ SiO) (Me) Si (OMe) ₂ ,
(Me ₃ SiO) (Et) Si (OMe) ₂ , (Me ₃ SiO) (i-Pr) Si
(OMe) ₂ , (Me ₃ SiO) (t-Bu) Si (OMe) ₂ , (Et ₃ SiO)
(Me) Si (OMe) ₂ , (Et ₃ SiO) (Et) Si (OMe) ₂ , (Et ₃ S
iO) (i-Pr) Si (OMe) ₂ , (Et ₃ SiO) (t-Bu) Si (O
Me) ₂ ; (EtO) (i-Pr) Si (OMe) ₂ , (i-PrO) (M
e) Si (OMe) ₂ , (i-PrO) (n-Pr) Si (OMe) ₂ , (n
-PrO) (t-Pt) Si (OMe) ₂ , (i-PrO) (n-Hex)
Si (OMe) ₂ , (n-BuO) (Me) Si (OMe) ₂ , (t-BuO)
(Me) Si (OMe) ₂ , (s-BuO) (Et) Si (OMe) ₂ , (i
-BuO) (i-Pr) Si (OMe) ₂ , (t-BuO) (t-Bu) S
i (OMe) ₂ , (n-BuO) (s-Bu) Si (OMe) ₂ , (t-Bu
O) (n-Pt) Si (OMe) ₂ , (n-PtO) (i-Pr) Si (O
Me) ₂ , (t-PtO) (t-Bu) Si (OMe) ₂ , (t-PtO)
(T-Pt) Si (OMe) ₂ , (t-PtO) (Me) Si (OMe) ₂ ,
(N-PtO) (Et) Si (OMe) ₂ , (n-Hex) (Me) Si (O
Me) ₂ , (n-Hex) (Et) Si (OMe) ₂ , (n-HexO) (i
-Pr) Si (OMe) ₂ , (n-HexO) (t-Bu) Si (OMe) ₂ ,
(N-HexO) (n-Hex) Si (OMe) ₂ , (n-HexO) (n
-Oct) Si (OMe) ₂ , (n-OctO) (Me) Si (OMe) ₂ ,
(N-OctO) (n-Oct) Si (OMe) ₂ , (i-PrO) (cyclohexyl) Si (OMe) ₂ , (i-PrO) (cyclopentyl) Si (OMe) ₂ , (i-PrO) ( Cyclopentadienyl)
Si (OMe) ₂ , (n-BuO) (cyclohexyl) Si (OM
e) ₂ , (n-BuO) (cyclopentyl) Si (OMe) ₂ , (n
—BuO) (cyclopentadienyl) Si (OMe) ₂ , (i-Bu
O) (cyclohexyl) Si (OMe) ₂ , (i-BuO) (cyclopentyl) Si (OMe) ₂ , (i-BuO) (cyclopentadienyl) Si (OMe) ₂ , (t-BuO) (cyclohexyl) Si
(OMe) ₂ , (t-BuO) (cyclopentyl) Si (OMe) ₂ ,
(T-BuO) (cyclopentadienyl) Si (OMe) ₂ , (t
-PtO) (cyclohexyl) Si (OMe) ₂ , (t-PtO)
(Cyclopentyl) Si (OMe) ₂ , (t-PtO) (cyclopentadienyl) Si (OMe).

Alkoxysilane compound A siloxy silane compound (hereinafter referred to as component D), which is one component of the polymerization catalyst used in the present invention, is represented by the above general formula. In the formula, examples of the hydrocarbon group represented by R ^{7 to} R ¹² include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group, and an aralkyl group.

Examples of the alkyl group, methyl (except in the case of R ^7), ethyl, propyl, i- propyl, butyl, i-
Butyl, s-butyl, t-butyl, amyl, i-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, decyl group and the like;
Allyl, propenyl, 1-butenyl, 1-pentenyl,
1-hexenyl, 1-octenyl, 1-decenyl, 1-
Methyl-1-pentynyl, 1-methyl-1-heptenyl and the like, cycloalkyl groups include cyclopentyl, cyclohexyl, methylcyclohexyl group and the like, and cycloalkenyl groups include cyclopentenyl, cyclohexenyl, methylcyclohexenyl group and the like. And cycloalkadienyl groups such as cyclopentadienyl, methylcyclopentadienyl and indenyl groups, aryl groups such as phenyl, tolyl and xylyl groups, and aralkyl groups such as benzyl, phenethyl and -Phenylpropyl group and the like. Among the hydrocarbon groups represented by R ⁹ and R ¹⁰ , an alkyl group is desirable, and a methyl and ethyl group are particularly desirable.

 Specific examples of the component D are shown below.

_{(EtO) 2 Si (OMe)} 2, (n-PrO) 2 Si (OMe) 2, (i-
_{Pr0) 2 Si (OMe) 2} , (t-Bu0) 2 Si (OMe) 2, (s-Bu
_{0) 2 Si (OMe) 2} , (n-Bu0) 2 Si (OMe) 2, (i-Bu0) 2
_{Si (OMe) 2, (t} -Pt0) 2 Si (OMe) 2, (n-Pt0) 2 Si
_{(OMe) 2, (n-} Hex0) 2 Si (OMe) 2, (n-Oct0) 2 Si
_{(OMe) 2, (n-} Dec0) 2 Si (OMe) 2, (n-Pr0) 2 Si (O
_{Et) 2, (i-Pr0} ) 2 Si (OEt) 2, (t-Bu0) 2 Si (OEt)
_{2, (s-Bu0) 2} Si (OEt) 2, (n-Bu0) 2 Si (OEt) 2,
_{(I-Bu0) 2 Si (} OEt) 2, (t-Pt0) 2 Si (OEt) 2, (n
_{-Pt0) 2 Si (OEt) 2} , (n-Hex0) 2 Si (OEt) 2, (n-O
_{ct0) 2 Si (OEt) 2} , (n-Dec0) 2 Si (OEt) 2; (EtO)
(I-Pr0) Si (OMe) ₂ , (EtO (n-Bu0) Si (OMe) ₂ ,
(EtO) (s-Bu0) Si (OMe) ₂ , (EtO) (n-Pt0) Si
(OMe) ₂ , (i-Pr0) (n-Bu0) Si (OMe) ₂ , (n-Pr
O) (t-Bu0) Si (OMe) ₂ , (t-Bu0) (n-Bu0) Si
_{(OMe) 2, (s-} Bu0) (i-Bu0) 2 Si (OMe) 2, (t-P
t0) (n-PrO) Si (OMe) ₂ , (n-Pt0) (i-Pr0) Si
(OMe) ₂ , (n-Bu0) (t-Pt0) Si (OMe) ₂ , (s-Bu0)
0) (s-Pt0) Si (OMe) ₂ , (i-Bu0) (n-Pt0) Si
(OMe) ₂ , (t-PtO) (n-PtO) Si (OMe) ₂ , (t-Pt
0) (n-Hex0) Si (OMe) ₂ , (MeO) (i-Pr0) Si (OE
t) ₂ , (Me0) (n-BuO) Si (OEt) ₂ , (i-Pr0) (n
-Bu0) Si (OEt) ₂ , (n-Pr0) (t-Bu0) Si (OE
t) ₂ , (t-Bu0) (n-Bu0) Si (OEt) ₂ , (s-Bu0)
(I-Bu0) Si (OEt) ₂ , (t-Pt0) (n-Pr0) Si (O
Et) ₂ , (n-Pt0) (i-Pr0) Si (OEt) ₂ , (n-Bu0)
(T-Pt0) Si (OEt) ₂ , (s-Bu0) (s-Pt0) Si (OE
t) ₂ , (i-Bu0) (n-Pt0) Si (OEt) ₂ , (t-Pt0)
(N-Pt0) Si (OEt) ₂ , (t-Pt0) (n-Hex0) Si (O
Et) ₂ ; (EtO) Si (OMe) ₃ , (i-Pr0) Si (OMe) ₃ , (n
−Bu0) Si (OMe) ₃ , (s−Bu0) Si (OMe) ₃ , (i−Bu0)
0) Si (OMe) ₃ , (t-Bu0) Si (OMe) ₃ , (t-Pt0) Si
(OMe) ₃ , (n-Pt0) Si (OMe) ₃ , (n-Hex0) (OMe)
₃ , (n-Oct0) Si (OMe) ₃ , (n-DecO) Si (OMe) ₃ ,
(MeO) Si (OEt) ₃ , (i-PrO) Si (OEt) ₃ , (n-Bu
0) Si (OEt) ₃ , (s-Bu0) Si (OEt) ₃ , (i-Bu0) Si
(OEt) ₃ , (t-Bu0) Si (OEt) ₃ , (t-Pt0) Si (OE
t) ₃ , (n-Pt0) Si (OEt) ₃ , (n-Hex0) Si (OEt) ₃ ,
(N-Oct0) Si (OEt ) 3, (n-DecO) (OEt) 3; Me 3 SiO
Si (OMe) ₃ , Et ₃ SiOSi (OMe) ₃ , Me ₃ SiOSi (OEt) ₃ , Et ₃ Si
OSi (OEt) ₃ , (Me ₃ SiO) ₂ Si (OMe) ₂ , (Et ₃ SiO) ₂ Si
(OMe) ₂ , (Et ₃ SiO) ₃ Si (OEt) ₂ , (Et ₃ SiO) ₂ Si (OE
t) ₂ ; Si (OEt) ₄ .

The polymerization catalyst used in the present invention is composed of Component A, Component B, Component C, and Component D.
Is from 1 to 2,000 gmol, preferably from 20 to 500 gmol, per mole of titanium in component A, and the total amount of component C and component D is 0.001 to 10 mol, preferably 0.01 to 1.0 mol, per mol of component B. It is used so that In addition, the component C and the component D
10 to 90 mol%, preferably 20 to 80 mol%, and the component D is 90 to 90 mol%.
Each is used in an amount of 10 mol%, preferably 80 to 20 mol%.

Polymerization of α-olefin The present invention is to produce a polyα-olefin by polymerizing an α-olefin in the presence of the above-mentioned polymerization catalyst.

The α-olefin is an α-olefin having 3 to 10 carbon atoms, such as propylene, 1-butene, 4-methyl-
Examples thereof include 1-pentene, 1-hexene, and 1-octene.

The present invention provides, besides the homopolymerization of α-olefins, those α-olefins having two or more carbon atoms such as ethylene.
Random copolymerization or block copolymerization with 10 other monoolefins or diolefins having 3 to 10 carbon atoms is also possible.

The polymerization reaction may be either a gas phase or a liquid phase, and when polymerizing in the liquid phase, an inert carbon such as normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. It can be carried out in hydrogen and in liquid monomers. The polymerization temperature is usually in the range of -80C to + 150C, preferably 40 to 120C. The polymerization pressure is, for example, 1 to 60
Atmospheric pressure is fine. Adjustment of the molecular weight of the resulting polymer is performed by the presence of hydrogen or other known molecular weight regulators. In the copolymerization, the amount of the other olefin to be copolymerized with the α-olefin is usually selected up to 30% by weight, especially in the range of 0.3 to 15% by weight, based on the α-olefin. The polymerization reaction in the present invention is carried out by a continuous or batch-type reaction, and the conditions may be those usually used.
Further, the copolymerization reaction may be performed in one stage, or may be performed in two or more stages.

Effect of the Invention According to the method of the present invention, a poly-α-olefin having a wide molecular weight distribution can be produced while maintaining catalytic polymerization activity, as compared with the case where component C or component D is used alone.

Examples The present invention will be specifically described with reference to examples and application examples.
The percentages (%) in the examples are by weight unless otherwise specified.

The molecular weight distribution of the polymer is expressed as w (weight average molecular weight) /
Indicated by n (number average molecular weight), it is a value measured by GPC.

Example 1 Preparation of Component A In a single reaction vessel equipped with a reflux condenser, 8.3 g of chip-shaped metallic magnesium (purity 99.5%, average particle size 1.6 mm) and 250 ml of n-hexane were placed under a nitrogen gas atmosphere. , 68 ℃
After stirring for 1 hour, magnesium metal was taken out and dried at 65 ° C. under reduced pressure to obtain preactivated metal magnesium.

Next, n-butyl ether was added to the metallic magnesium.
A suspension containing 140 ml and 0.5 ml of an n-butyl ether solution of n-butylmagnesium chloride (1.75 mol /) was maintained at 55 ° C., and a solution obtained by dissolving 38.5 ml of n-butyl chloride in 50 ml of n-butyl ether was further added for 50 minutes. Was dropped. After conducting the reaction at 70 ° C for 4 hours with stirring, the reaction solution was cooled to 25 ° C.
Held.

Next, 55.7 ml of HC (OC ₂ H ₅ ) _{3 was} added dropwise to the reaction solution over 1 hour. After completion of the dropwise addition, the reaction was carried out at 60 ° C. for 15 minutes, and the reaction product solid was washed six times with 300 ml each of n-hexane, dried at room temperature under reduced pressure for 1 hour, and dried with 19.0% magnesium.
31.6 g of a magnesium-containing solid containing 28.9% of chlorine was recovered.

300ml equipped with reflux condenser, stirrer and dropping funnel
In a reaction vessel, a solid containing magnesium under a nitrogen gas atmosphere
6.3 g and 50 ml of n-heptane were put into a suspension, and a mixed solution of 20 ml (0.02 mmol) of 2,2,2-trichloroethanol and 11 ml of n-heptane was dropped from the dropping funnel over 30 minutes while stirring at room temperature. The mixture was further stirred at 80 ° C. for 1 hour. The obtained solid was separated by filtration, washed four times with 100 ml each of n-hexane at room temperature, and twice with 100 ml each of toluene to obtain a solid component.

40 ml of toluene was added to the above solid component, and titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. Under stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, followed by stirring at 120 ° C. for 2 hours. The obtained solid substance is 90
It was filtered off at 90 ° C. and washed at 90 ° C. twice with 100 ml each of toluene. Furthermore, a new volume ratio of titanium tetrachloride / toluene
Titanium tetrachloride was added to 3/2, and the mixture was stirred at 120 ° C for 2 hours. The obtained solid substance was separated by filtration at 110 ° C. and washed seven times with 100 ml of n-hexane at room temperature to obtain 5.5 g of a component A.

Polymerization of propylene In a 1.5 stainless steel autoclave equipped with a stirrer, under a nitrogen gas atmosphere, the component A11.3m obtained above was obtained.
g, 4 ml of a solution containing 0.1 mol of triethylaluminum (hereinafter referred to as TEAL) in n-heptane 1 and 1.4 ml of a solution containing 0.02 mol of t-butoxymethyldimethoxysilane in n-heptane 1 and n-heptane 1 0.0 in
1.2 ml of a solution containing 1 mole of tetraethoxysilane was mixed and held for 5 minutes. Next, 600 ml of hydrogen gas as a molecular weight controlling agent and liquid propylene 1 were injected under pressure, and then the temperature of the reaction system was raised to 70 ° C. to polymerize propylene for 1 hour. After completion of the polymerization, unreacted propylene was purged to obtain a white polypropylene powder.

The polymerization activity of the catalyst was 21.1 kg / g · Component A. The w / n of the obtained polypropylene was 7.5.

Examples 2 to 5 Propylene was polymerized in the same manner as in Example 1 except that the components C and D shown in Table 1 were used in the proportions shown in Table 1, respectively. The results are shown in Table 1. Was.

Comparative Examples 1 to 7 Propylene was polymerized in the same manner as in Example 1 except that the components C and D were not used, and the results are shown in Table 1.

Example 7 Preparation of Component A 170 g of commercially available magnesium diethoxide was placed in 400 stainless steel (SUS316) balls having a diameter of 12 mm, and the internal volume was 1.2.
After placing in a stainless steel (SUS316) mill pot under a nitrogen gas atmosphere and attaching this mill pot to a shaker,
Contact was performed by shaking at an amplitude of 10 mm and a rotation speed of 1420 rpm for 2 hours to obtain a ground product (I).

200ml equipped with reflux condenser, dropping funnel and stirrer
Is sufficiently replaced with nitrogen gas. After putting 8.3 g of the pulverized product (I) and 42 ml of n-heptane into this reactor, 14.9 g of trichlorosilane and n-heptane were stirred at room temperature.
A mixed solution of 30 ml of heptane was dropped from the dropping funnel over 30 minutes, and the mixture was further stirred at 65 ° C. for 4 hours. 65
The mixture was separated by filtration at 100C and washed twice by contacting 100 ml of n-heptane at room temperature twice and 100 ml of toluene at room temperature three times with stirring for 10 minutes to obtain a toluene slurry of the reaction solid (I).

51 ml of TiCl ₂ was added to a toluene slurry composed of 8.5 g of the reaction solid (I) and 26 ml of toluene, and the internal temperature was raised to 80 ° C. over 20 minutes. After the temperature was raised, di-n-butyl phthalate was added.
A mixed solution consisting of 1.7 g and 8 ml of toluene was added dropwise over 15 minutes using a dropping funnel. Thereafter, the temperature was further raised to 115 ° C., and the mixture was stirred at the same temperature for 2 hours. After removing the supernatant by decantation, the mixture was washed twice by stirring at a temperature of 90 ° C. for 10 minutes using 100 ml of toluene. Next, 21 ml of fresh toluene and 51 ml of TiCl ₂ were added, and the mixture was stirred at 115 ° C. for 2 hours.

The obtained solid substance was separated by filtration at 115 ° C., and washed eight times with 100 ml of n-heptane at room temperature to obtain a heptane slurry of the component A.

Polymerization of propylene Component A obtained above, Component C and Component D shown in Table 2
And propylene was polymerized in the same manner as in Example 1 except that triisobutylaluminum was used instead of TEAL and the polymerization temperature was set to 80 ° C., and the results are shown in Table 2.

Example 8 Propylene was polymerized in the same manner as in Example 7 except that the compounds shown in Table 2 were used as the components C and D, and the results are shown in Table 2.

Comparative Examples 8 and 9 Propylene was polymerized in the same manner as in Example 7 except that Component C or Component D was not used. The results are shown in Table 2.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a process for preparing a polymerization catalyst used in the present invention.

Continued on the front page (72) Inventor Hiroyuki Furuhashi 1-3-1, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama Prefecture Inside Tonen Co., Ltd. (72) Inventor Satoshi Ueki 1-3-3, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama No. 1 Tonen Research Institute (72) Inventor Rinko Aoki 1-3-1 Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Tonen Research Institute (58) Field surveyed (Int. Cl. ⁶ , DB name) ) C08F 4/60-4/70

Claims (1)

(57) [Claims] 1. A solid catalyst component comprising (A) magnesium, titanium, a halogen and an electron donating compound as essential components, (B) a general formula R _n AlX _3-n (where R is an alkyl group or an aryl group, X Represents a halogen atom, an alkoxy group or a hydrogen atom, and n is an arbitrary number in the range of 1 ≦ n ≦ 3.) (C) a general formula (However, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, OR ³ , Si
R ⁴ _3, or OSiR ⁵ _3, R ² represents a 1-10 hydrocarbon group or SiR ⁶ ₃ carbon ^{atoms, R 3, R 4, R} 5 and R ⁶ having 1-10 carbon respectively carbide Shows a hydrogen group. And a dimethoxysilane compound represented by the general formula (D): (However, R ⁷ is a hydrocarbon group having 2 to 10 carbon atoms, or Si
R ¹¹ _3, R ⁸ is 1 to 10 carbon atoms hydrocarbon group or Si
R ¹² ₃ , R ⁹ and R ¹⁰ represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, and R ¹¹ and R ¹² represent hydrocarbon groups having 1 to 10 carbon atoms. ] A method for producing a poly-α-olefin, comprising polymerizing an α-olefin in the presence of a polymerization catalyst comprising the alkoxysilane compound.