JP2772575B2 - Catalyst component for α-olefin polymerization - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an α-olefin polymerization catalyst component.

2. Description of the Related Art Catalyst components for the polymerization of α-olefins containing metal oxides, magnesium, titanium, halogens and electron donating compounds are known. This metal oxide-supported catalyst has good polymerization performance such as high activity and high stereoregularity, and also has excellent particle characteristics such that the obtained polymer has a narrow particle size distribution and uniform particle shape such as spherical shape. .

If the particle strength of the catalyst component is low, the polymer formed by the polymerization is broken and pulverized. As a typical method for preventing this, there is a so-called prepolymerization in which a catalyst component is brought into contact with an olefin in advance, and a polymer formed there is incorporated into the catalyst component to increase the strength of the catalyst component particles. At the time of this pre-polymerization, by adding an electron-donating compound such as a silicon compound, the final poly-α-
Attempts have also been made to increase the stereoregularity of olefins.

However, the addition of an electron-donating compound during the prepolymerization usually has an effect such as a decrease in catalyst activity or a deterioration in performance during storage of the catalyst. In addition, as the silicon compound used in the prepolymerization, a compound having an aromatic group is often used from the viewpoint of its performance, but the silicon compound having an aromatic group is harmful depending on the purpose of use of the polymer. There is.

DISCLOSURE OF THE INVENTION An object of the present invention is to increase the strength of catalyst particles, improve the stereoregularity of a polymer obtained, maintain high activity of a catalyst, prevent performance deterioration during storage of a catalyst, and the like.

Means for Solving the Problems The present inventors have conducted intensive studies and as a result, when a specific compound is used as a silicon compound to be added at the time of prepolymerization, the same or higher performance as an organic silicon compound having an aromatic group is obtained. The present invention has been completed by finding that a poly-α-olefin can be obtained and that the object of the present invention can be achieved.

SUMMARY OF THE INVENTION That is, the gist of the present invention is to provide (A) a solid component containing metal oxide, magnesium, titanium, halogen and an electron donating compound as essential components, and (B) a general formula R _n AlX _3-n [ , 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 1 ≦ n ≦ 3. An organoaluminum compound represented by the general formula (C): [However, R ¹ , R ⁴ and R ⁵ are the same or different hydrocarbon groups having 1 to 10 carbon atoms, R ² is a hydrocarbon group having 1 to 10 carbon atoms or R ⁶ O, R ³ is a carbon group having 1 carbon atom. 1010 hydrocarbon groups or R ⁷ O, x is 2 or 3, and R ⁶ and R ⁷ are the same or different C 1-10 hydrocarbon groups. [D] olefin in the presence of an organosilicon compound represented by the following formula:

Solid component The solid component used in the present invention (hereinafter, referred to as component A)
Has metal oxide, magnesium, titanium, halogen and an electron donating compound as essential components, and such components are usually metal oxide, magnesium compound, titanium compound and electron donating compound, and each of the above compounds is halogen. In the case of a compound having no, the compound is prepared by contacting a halogen-containing compound with each other.

(1) Metal oxide The metal oxide used in the present invention is represented by the periodic table II of the element.
An oxide of an element selected from the group of group-Group IV element, To illustrate _{them, B 2 O 3, MgO,} Al 2 O 3, SiO 2, Ca
O, TiO ₂ , ZnO, ZrO ₂ , SnO ₂ , BaO, ThO _{2 and the} like. Among them, B ₂ O ₃ , MgO, Al ₂ O ₃ , SiO ₂ , TiO ₂ , Zr
O ₂ is desirable, and SiO ₂ is particularly desirable. Further, composite oxides containing these metal oxides, for example, SiO ₂ -MgO, SiO ₂ -Al _{2
O 3, SiO 2 -TiO 2,} SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO
_2- MgO or the like can also be used.

These metal oxides are usually in the form of powder. The shape such as the size and shape of the powder often affects the shape of the obtained olefin polymer, and thus it is desirable to appropriately adjust the shape. It is desirable that the metal oxide be fired at as high a temperature as possible and handled so as not to come into direct contact with the atmosphere for the purpose of removing poisonous substances during use.

(2) 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, and as an OR group, R has 1 to 1 carbon atoms. Twelve alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups, and examples of the halogen atom include chlorine, bromine, iodine and fluorine.

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 , MgEtBu, 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 (P
r), an alkyl group such as i-propyl (i-Pr), butyl (Bu), i-butyl (i-Bu), hexyl (He), octyl (Oct), and a cyclo group such as cyclohexyl (cyHe) and methylcyclohexyl. Alkyl group, allyl, propenyl,
Alkenyl groups such as butenyl, phenyl (Ph), tolyl,
And aryl groups such as xylyl, and aralkyl groups such as phenethyl and 3-phenylpropyl. Among these, an alkyl group having 1 to 10 carbon atoms is particularly 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 (OR) contained in formula XC (OR) ₃
r) ₃ , HC (OBu) ₃ , HC (OHe) ₃ , HC (OPh) ₃ ; MeC (OMe) ₃ ,
MeC (OEt) ₃ , EtC (OMe) ₃ , EtC (OEt) ₃ , cyHeC (OEt) ₃ ,
PhC (OMe) ₃ , PhC (OEt) ₃ , CH ₂ ClC (OEt) ₃ , MeCHBrC (OE
t) ₃ , MeCHClC (OEt) ₃ : ClC (OMe) ₃ , ClC (OEt) ₃ , ClC
_{(Oi-Bu) 3, BrC} (OEt) 3; MeC included in the formula X ₂ C _{(OR) 2}
H (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 BrC
H (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 gold include aluminum, zinc, calcium, and the like, 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.

(3) Titanium compound A titanium compound is a compound of trivalent and tetravalent titanium, and examples thereof include tetravalent titanium, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, dichlorodiethoxytitanium, and dichlorodiethoxytitanium. Examples thereof include rudibutoxytitanium, dichlorodiphenoxytitanium, chlorotriethoxytitanium, chlorotributoxytitanium, tetrabutoxytitanium, and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxytitanium, dichlorodibutoxytitanium, and dichlorodiphenoxytitanium are desirable, and titanium tetrachloride is particularly desirable.

(4) Electron-donating compound Examples of the electron-donating compound include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, ethers, ketones, amines,
Examples include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic, and antimony compounds bonded to an organic group via carbon or oxygen, phosphoamides, thioethers, thioesters, and carbonate esters. 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. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutylate, propyl pivalate, isobutyl pivalate, and acrylic. 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,
Dioctyl phthalate, di-2-ethylhexyl phthalate,
Diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate,
Examples include dibutyl naphthalate, trimethyl 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,
Examples include isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, naphthalic acid dichloride and the like. Further, monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride and phthalic acid butyl chloride can 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. It is.

The method for preparing component A includes metal oxide (component 1),
The magnesium compound (node 2), the titanium compound (component 3) and the electron donating compound (component 4) are contacted in that order. After contacting components 1 and 2, components 4 and 3 are contacted in that order. After the components 1 and 2 are brought into contact with each other, the components 3 and 4 are simultaneously used,
After contacting component 2 with component 3, contacting component 4 with component 1 in that order, after contacting component 2 with component 4,
Methods such as contacting component 3 with component 1 in that order, contacting component 2, component 3 and component 4 simultaneously, and then contacting component 1 can be employed. It is also possible to contact with a halogen-containing compound before contacting with Component 3.

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 of an element of Groups IIIa, IVa, and Va of the periodic table (hereinafter, referred to as metal halide).

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, ethylene 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 and the like, alicyclic compounds chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, hexachlorocyclohexane and the like aromatic compounds chlorobenzene,
Bromobenzene, o-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloride and the like can be mentioned. 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-bromoresorcinol, (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.

Examples of the halogenated silicon compound having a hydrogen-silicon bond include HSiCl ₃ , H ₂ SiCl ₂ , H ₃ SiCl, HCH ₃ SiCl ₂ , HC ₂ H ₅ SiCl ₂ , H
_{(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 , TiCl ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF _{5 and the} like are preferable.

Contact with component 1, component 2, component 3 and component 4, and optionally with a halogen-containing compound that can be contacted,
Mixing or stirring in the presence or absence of an inert medium,
This is done by mechanically co-milling. Contact is 40-15
It can be performed under heating at 0 ° 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.

Specific examples of the method for preparing component A in the present invention include JP-A-58-162607, JP-A-55-94909, JP-A-55-115405,
No. 57-108107, No. 61-21109, No. 61-174204, No. 6
For example, the methods disclosed in JP-A Nos. 1-174205, 61-174206, 62-7706 and the like can be mentioned. More specifically, a method in which a reaction product of a metal oxide and a magnesium dialkoxide is brought into contact with an electron-donating compound and a tetravalent titanium halide (JP-A-58-162607); A method in which a reaction product of a hydrocarbyl halide compound is contacted with a Lewis base compound and titanium tetrachloride (JP-A-55-94909). The reaction product of a porous carrier such as silica and an alkyl magnesium compound is treated with titanium. A method of contacting with an electron-donating compound and a silicon halide compound before contacting with a compound (JP-A-55-115405 and JP-A-57-108107), metal oxide, magnesium compound containing an alkoxy group, carboxyl at the ortho position Contacting an aromatic polycarboxylic acid having a group or a derivative thereof and a titanium compound (Japanese Patent Application Laid-Open No. 61-174204); Product, alkoxy-containing magnesium compound,
A method in which a silicon compound having a hydrogen-silicon bond, an electron donating compound and a titanium compound are brought into contact with each other (JP-A-61-174205).
Publication), metal oxides, alkoxy-containing magnesium compounds,
A method of contacting a halogen element or a halogen-containing compound, an electron donating compound and a titanium compound (Japanese Patent Application Laid-Open No.
174206), a method of contacting a reaction product obtained by contacting a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron-donating compound and a titanium compound (JP-A-61-21109), A method in which a solid obtained by contacting a metal oxide, a hydrocarbylmagnesium and a compound containing a hydrocarbyloxy group (corresponding to the above-mentioned alkoxy group-containing compound) is contacted with a halogen-containing alcohol, and further contacted with an electron donating compound and a titanium compound. (JP 62
-7706). Among these, the method (1) is preferable, and the method (2) is particularly preferable.

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.

Organoaluminum compound Organoaluminum compound (hereinafter, referred to as component B)
Is represented by the general formula R _n AlX _3-n (where R represents an alkyl group and 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). And C1-C18, preferably C2-C6, such as trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide and dialkylaluminum monohydride. Particularly preferred are alkyl aluminum compounds or mixtures or complex compounds thereof. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum ion Monoalkylaluminum dihalides such as dialkylaluminum dihalide such as diide, diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride, ethylaluminum Alkyl aluminum sesquihalides such as sesquilolide, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, dialkyl aluminum monoalkoxide such as diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum hydride And dialkylaluminum hydrides such as dipropylaluminum hydride and diisobutylaluminum hydride. Among these, trialkyl aluminum, particularly triethyl aluminum and triisobutyl aluminum are desirable.

Organosilicon Compound An organosilicon compound (hereinafter, referred to as component C), which is one component of the catalyst component of the present invention, is represented by the general formula. In the formula, a hydrocarbon group for R ^{1 to} R ⁵ and R ⁶ for OR ⁶ and OR ^7
6, as the hydrocarbon group for R ^7, alkyl group, alkenyl group, cycloalkyl group, aryl group, aralkyl group and the like.

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 group and the like, cycloalkyl group as cyclopentyl, cyclohexyl, methylcyclohexyl group and the like, aryl group as phenyl, tolyl, xylyl group and the like, aralkyl group as benzyl, phenethyl, And a 3-phenylpropyl group. Among these, an aliphatic hydrocarbon group such as an alkyl group and an alkenyl group is desirable, and an alkyl group is particularly desirable. Further, among the hydrocarbon groups for R ⁴ , methyl and ethyl groups are most desirable.

Component C is synthesized by reacting an ordinary general formula R ¹ R ² R ³ compounds of the general formula represented by SiOH (R ⁴ O) is represented by _{x + 1} SiR ⁵ _3-x compounds in the presence of an amine compound can do.

Hereinafter, specific examples of the component C are listed. In the following, Me = mel, Et = ethyl, Pr = propyl, Bu = butyl, Amy = amyl, and Hex = hexyl are shown, respectively.

○ R ¹ R ² R ³ SiOSi (OR ⁴ ) ₃ , where R ² and R ³ are hydrocarbon groups (shown as R ¹ / R ² / R ³ OR ⁴ , where R ¹ , R ² Or R ³
There when the same displays a _{^{R 1 3, R 1 2 /}} R 3 or the like. ) Me ₃ OMe, Me ₃ OEt, Et ₃ OMe, Et ₃ OEt, Me ₂ / n−PrO
Me, Me ₂ / n−PrOEt, Me ₂ / t−BuOMe, Me ₂ / t−BuOEt, Et
₂ / MeOMe, Et ₂ / MeOEt.

R R ¹ R ² R ³ SiOSi (OR ⁴ ) ₂ R ⁵ , where R ² and R ³ are hydrocarbon groups (shown as R ¹ / R ² / R ³ OR ⁴ / R ⁵ ; R ^1, when R ² or R ³ are the same, R ¹ _3, indicated as R ¹ ₂ / R ^3, _{etc..) Me 3 OMe / Me,} Me 3 OEt / Me, Me 3 OMe / Et, Me 3 OEt / Et,
Me ₃ OMe / i−Pr, Me ₃ OEt / i−Pr, Me ₃ OMe / t−Bu, Me ₃
OEt / t−Bu, Me ₃ OMe / n−Bu, Me ₃ OEt / n−Bu, Me ₃ OMe / s
−Bu, Me ₃ OEt / s−Bu, Et ₃ OMe / Me, Et ₃ OEt / Me, Et ₃ O
Me / i−Pr, Et ₃ OEt / i−Pr, Me ₂ / n−PrOMe / Me, Me ₂ / n−P
rOEt / Me, Me ₂ / t−BuOMe / Et, Me ₂ / t−BuOEt / Et, Me ₂ /
n−BuOMe / Me, Me ₂ / n−BuOEt / Me, Me ₂ / n−HexOMe / M
e, Me ₂ / n−HexOEt / Me, Me ₂ / s−AmyOMe / Me, Me ₂ / s−Amy
OEt / Me.

R ¹ R ² R ³ SiOSi (OR ⁴ ) ₃ , where R ² is a hydrocarbon group and R ³ is R ⁶ O (shown as R ¹ / R ² / R ⁶ OOR ⁴ , where R ¹ ,
When R ² are the same displays and R ¹ _{2. ) Me 2 / MeOOMe, Me 2} / MeOOEt, Me 2 / EtOOMe, Me 2 / EtO
OEt, Me ₂ / i−PrOOMe, Me ₂ / i−PrOOEt, Me ₂ / t−BuOOM
_{e, Me 2 / t-BuOOEt} , Me 2 / n-HexOOMe, Me 2 / n-HexOOE
t, Et ₂ / MeOOMe, Et ₂ / MeOOEt, Me / t−Bu / MeOOMe, Me / t
−Bu / MeOOEt, (i-Pr) ₂ ) / MeOOMe, (i-Pr) ₂ /
MeOOEt, Me / s-Amy / MeOOMe, Me / s-Amy / MeOOEt.

○ R ¹ R ² R ³ SiOSi (OR ⁴ ) ₂ R ^{5 When} R ² is a hydrocarbon group and R ³ is R ⁶ O (R ¹ / R ² / R ⁶ OOR ⁴ / R ⁵ Where,
When R ¹ and R ² are the same displays and R ¹ _{2. ) Me 2 / MeOOMe / Me,} Me 2 / MeOOEt / Me, Me 2 / EtOOMe / Me,
Me ₂ / EtOOEt / Me, Me ₂ / i−PrOOMe / Me, Me ₂ / i−PrOOEt
_{/ Me, Me 2 / s-} BuOOMe / Me, Me 2 / s-BuOOEt / Me, Me 2 / t-A
_{myOOMe / Me, Me 2 / t} -AmyOOEt / Me, Me 2 / n-HexOOMe / M
_{e, Me 2 / n-HexOOEt} / Me, Et 2 / MeOOMe / Me, Et 2 / MeOOEt
/ Me, Me / n-Pr / MeOOMe / Et, Me / n-Pr / MeOOEt / Et, Me / t
-Bu / MeOOMe / Me, Me / t-Bu / MeOOEt / Me, Me 2 / MeOOMe
_{/ Et, Me 2 / MeOOEt /} Et, Me 2 / MeOOMe / i-Pr, Me 2 / MeOOE
_{t / i-Pr, Me 2} / MeOOMe / t-Bu, Me 2 / MeOOEt / t-Bu.

○ R ¹ R ² R ³ SiOSi (OR ⁴ ) ₃ , where R ² is R ⁶ O and R ³ is R ⁷
In the case of O (shown as R ¹ / R ⁶ O / R ⁷ OOR ^4. However, when R ⁶ and R ⁷ are the same, they are displayed as (R ⁶ O) _2. ) Me / (MeO) ₂ OMe, Me / (MeO) ₂ OEt, Et / (MeO) ₂
OMe, Et / (MeO) ₂ OEt, Me / (EtO) ₂ OMe, Me / (Et
O) ₂ OEt, Me / (n-PrO) ₂ OMe, Me / (n-PrO) ₂
OEt, Me / (Me) / (t-BuO) OMe, Me / (MeO) / (t
-BuO) OEt.

○ R ¹ R ² R ³ SiOSi (OR ⁴ ) ₂ R ⁵ , where R ² is R ⁶ O and R ³ is R
^In the case of ⁷ O (shown as R ¹ / R ⁶ O / R ⁷ OOR ⁴ / R ^5. However, when R ⁶ and R ⁷ are the same, it is displayed as (R ⁶ O) _2. ) Me / (MeO ) ₂ OMe / Me, Me / (MeO) ₂ OEt / Me, Et / (M
_{eO) 2 OMe / Me, Et} / (EtO) 2 OEt / Me, i-Pr / (MeO)
₂ OMe / Me, i-Pr / (MeO) ₂ OEt / Me, n-Bu / (MeO) ₂
OMe / Me, n-Bu / (MeO) ₂ OEt / Me, Me / (n-PrO) ₂
OMe / Me, Me / (n -PrO) 2 OEt / Me, Me / (s-BuO) 2
OMe / Me, Me / (s -BuO) 2 OEt / Me, Me / MeO / n-HexO
OMe / Me, Me / MeO / n-HexOOEt / Me, Et / (MeO) ₂ OMe / E
t, Et / (MeO) ₂ OEt / Et, vinyl / (MeO) ₂ OMe / vinyl, vinyl / (EtO) ₂ OEt / vinyl.

Prepolymerization The prepolymerization of the solid component (component A) is performed by contacting with an olefin in the presence of an organoaluminum compound (component B) and an organosilicon compound (component C).

As olefins, in addition to ethylene, propylene, 1-
Α- such as butene, 1-hexene and 4-methyl-1-pentene
Olefins may be used.

The prepolymerization is preferably performed in the presence of the above-mentioned inert medium. The prepolymerization is usually performed at a temperature of 100 ° C or lower, preferably -30 ° C to + 30 ° C, more preferably -20 ° C to + 15 ° C. The polymerization system may be either a batch system or a continuous system, or may be performed in two or more stages. When the reaction is carried out in multiple stages, the polymerization conditions can of course be changed.

Component B has a concentration of 50 to 500 mmol /
, Preferably 80 to 200 mmol /, and 4 to 50,0 per gram atom of titanium in component A.
It is used in an amount of 008 mol, preferably 6 to 1,000 mol.

Component C has a concentration in the prepolymerized system of 1 to 100 mmol /
, Preferably 5 to 50 mmol /.

Olefin polymer is incorporated into component A by prepolymerization, and the amount of the polymer is 0.1 to 200 g per 1 g of component A,
In particular, it is desirable to be 0.5 to 50 g.

The catalyst component of the present invention prepared as described above can be diluted or washed with the above-mentioned inert medium.
From the viewpoint of preventing storage components from being deteriorated during storage, it is particularly desirable to wash them. After washing, it may be dried if necessary. When storing the catalyst component, it is desirable to store it at a temperature as low as possible.
A temperature range of 5 ° C is recommended.

Polymerization of α-Olefin The catalyst component of the present invention obtained as described above is used for homopolymerization of an α-olefin having 3 to 10 carbon atoms in combination with an organometallic compound and, if necessary, an electron-donating compound. Or other monoolefins or catalysts for copolymerization with diolefins having 3 to 10 carbon atoms, particularly α-olefins having 3 to 6 carbon atoms, such as propylene,
It shows extremely excellent performance as a catalyst for homopolymerization of 1-butene, 4-methyl-1-pentene, 1-hexene or the like, or random and block copolymerization with the above-mentioned α-olefins and / or ethylene.

Organometallic compounds which can be used include those of Groups I to II of the Periodic Table.
It is an organic compound of a Group I metal. As the compound, an organic compound of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, an organoaluminum compound is particularly preferable. The organoaluminum compound that can be used is appropriately selected from the compounds used in the prepolymerization of the solid component (component A), and is preferably a trialkylaluminum, particularly triethylaluminum or triisobutylaluminum. or,
These trialkylaluminum, other organic aluminum compounds, for example, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or complex compound thereof, which is easily available industrially Can be used together.

An organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can also be used. Such compounds include, for example, (C ₂ H ₅ ) ₂ AlOAl
(C ₂ H ₅ ) ₂ , Etc. can be exemplified.

As organic compounds of metals other than aluminum metal,
Diethyl magnesium, ethyl magnesium chloride,
Other examples include compounds such as diethyl zinc and the like such as LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Examples of the electron-donating compound that can be combined with the catalyst component and the organometallic compound of the present invention as needed include a compound used for preparing the component A and an organic silicon compound used for the prepolymerization ( In addition to being appropriately selected from component C), an electron-donating compound composed of an organic silicon compound other than the silicon compound, nitrogen, sulfur, oxygen,
An electron donating compound containing an ether atom such as phosphorus can also be used.

Specific examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane,
Tetraisobutoxysilane, tetraphenoxysilane,
Tetra (p-ethylphenoxy) silane, tetrabenzyloxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, Butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltriphenoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexyloxy Silane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane,
Dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane,
Diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane,
Methylphenyldimethoxysilane, chlorophenyldiethoxysilane and the like can be mentioned.

Specific examples of the electron-donating compound containing a hetero atom, as a compound containing a nitrogen atom, 2,2,6,6-tetramethylpiperidine, 2,6-dimethylpiperidine, 2,6-diethylpiperidine, 2,6 -Diisopropylpiperidine, 2,6
-Diisobutyl-4-methylpiperidine, 1,2,2,6,6-
Pentamethylpiperidine, 2,2,5,5-tetramethylpyrrolidine, 2,5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, 2,5-diisopropylpyrrolidine, 1,2,2,5,5-
Pentamethylpyrrolidine, 2,2,5-trimethylpyrrolidine, 2-ethylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-diisopropylpyridine, 2,6
-Diisobutylpyridine, 1,2,4-trimethylpiperidine, 2,5-dimethylpiperidine, methyl nicotinate, ethyl nicotinate, nicotinamide, benzoamide,
2-methylpyrrole, 2,5-dimethylpyrrole, imidazole, toluic acid amide, benzonitrile, acetonitrile, aniline, paratoluidine, orthotoluidine, metatoluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine, etc. Examples of the compound containing a sulfur atom include thiophenol, thiophene, ethyl 2-thiophenecarboxylate, ethyl 3-thiophenecarboxylate, 2-methylthiophene, methyl mercaptan, ethyl mercaptan,
Isopropyl mercaptan, butyl mercaptan, diethyl thioether, diphenyl thioether, methyl benzenesulfonate, methylsulfite, ethylsulfite, and the like, as compounds containing an oxygen atom, include tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, and 2-methyltetrahydrofuran. , 2,2,5,5-tetraethyltetrahydrofuran, 2,2,
5,5-tetramethyltetrahydrofuran, 2,2,6,6-tetraethyltetrahydrofuran, 2,2,6,6-tetramethyltetrahydropyran, dioxane, dimethyl ether,
Diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, anisole, acetophenone, acetone, methyl ethyl ketone, acetylacetone, o-tolyl-t-butyl ketone, methyl-2,6-
Di-t-butylphenylketone, 2-ethyl furarate, 2
-Isoamyl phthalate, 2-methyl methyl furarate, 2-propyl propyl furarate and the like, as a compound containing a phosphorus atom, triphenyl phosphine, tributyl phosphine, triphenyl phosphite, tribenzyl phosphite, diethyl phosphate, diphenyl phosphate and the like. No.

Two or more of these electron donating compounds may be used.
These electron donating compounds may be used when the organometallic compound is used in combination with the catalyst component, or may be used after being brought into contact with the organometallic compound in advance.

The amount of the organometallic compound to be used for the catalyst component of the present invention is generally 1 to 1 gram atom of titanium in the catalyst component.
2,000 gmol, especially 20-500 gmol, is desirable.

The ratio of the organometallic compound to the electron-donating compound is selected in the range of 0.1 to 40, preferably 1 to 25 g atoms, of the organometallic compound as aluminum per mole of the electron-donating compound.

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

Effect of the Invention The present invention can improve the strength of the catalyst component by adopting the above configuration, and the catalyst component has an α-
In the (co) polymerization of olefins, the catalyst component exhibits high stereoregularity while maintaining high activity, and in particular, the washed catalyst component exhibits an excellent effect of suppressing deterioration in performance during storage of the catalyst.

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 heptane-insoluble matter (hereinafter abbreviated as HI), which indicates the proportion of the crystalline polymer in the polymer, is the remaining amount when extracted with boiling n-heptane for 6 hours using an improved Soxhlet extractor.

Example 1 Preparation of Component A A 200 ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. Add silicon oxide (DA
VISON, trade name G-952) in nitrogen stream for 200
5 g of calcined at 700C for 2 hours and further at 700C for 5 hours and 40 ml of n-heptane were added. Further, 20 ml of a 20% n-heptane solution of n-butylethylmagnesium (hereinafter referred to as BEM) (manufactured by Texas Alkyls, trade name: MAGALA BEM)
And stirred at 90 ° C. for 1 hour.

After the suspension was cooled to 0 ° C, a solution of 11.2 g of tetraethoxysilane dissolved in 20 ml of n-heptane was dropped from the dropping funnel over 30 minutes. After completion of the dropwise addition, the temperature was raised to 50 ° C. over 2 hours, and stirring was continued at 50 ° C. for 1 hour. After completion of the reaction, the supernatant was removed by decantation, and the resulting solid was washed with 60 ml of n-heptane at room temperature.
Further, the supernatant was removed by decantation. This n
-Washing treatment with heptane was further performed four times.

To the above solid, 50 ml of n-heptane was added to form a suspension, and a solution of 8.0 g of 2,2,2-trichloroethanol dissolved in 10 ml of n-heptane was added thereto at 25 ° C from a dropping funnel at 25 ° C. It was dropped over a period of minutes. After completion of the dropwise addition, stirring was continued at 25 ° C. for 30 minutes. After completion of the reaction, 60 ml of n-
Washing was performed twice with heptane and three times with 60 ml of toluene. When the obtained solid (solid component I) was analyzed, it contained 36.6% of SiO ₂ , 5.1% of magnesium, and 38.5% of chlorine.

To the solid component I obtained above, 10 ml of n-heptane and 40 ml of titanium tetrachloride were added, and the temperature was raised to 90 ° C. to give n-heptane.
0.6 g of di-n-butyl phthalate dissolved in 5 ml was added over 5 minutes. Thereafter, the temperature was raised to 115 ° C., and the reaction was performed for 2 hours. After the temperature was lowered to 90 ° C., the supernatant was removed by decantation, and the mixture was washed twice with 70 ml of n-heptane. Furthermore,
15 ml of n-heptane and 40 ml of titanium tetrachloride were added and reacted at 115 ° C. for 2 hours. After the reaction is completed, the obtained solid substance is
Washing was performed eight times at room temperature with ml of n-hexane. Next, drying was performed at room temperature under reduced pressure for 1 hour to obtain 8.3 g of a catalyst component (component A). Component A contains 3.1% titanium, silicon oxide, magnesium, chlorine and di-n-phthalate.
Butyl was included.

Prepolymerization Under a nitrogen gas atmosphere, 2.0 g of the component A obtained above and 280 ml of n-heptane were put into a 500 ml reactor equipped with a stirrer, and cooled to 0 ° C with stirring. Next, a solution of triethylaluminum (hereinafter abbreviated as TEAL) in n-heptane (2.0 mol /) and 1,1,1-triethoxy-3,3,3-
An n-heptane solution (2.0 mol /) of trimethyldisiloxane (SOTES) was added so that the concentrations of TEAL and silane in the reaction system became 200 mmol / and 20 mmol /, respectively, and the mixture was stirred for 5 minutes. Next, after depressurizing the system, propylene gas was supplied, and
Polymerized for minutes. After completion of the polymerization, the vapor-phase propylene was purged with nitrogen gas, and n-heptane at 5 ° C. was added to dilute it five-fold. Thus, a slurry of the catalyst component was prepared. A part of the slurry was taken out, dried, and the amount of magnesium contained in the catalyst component was measured. As a result, the amount of prepolymerization was 2.4 g per 1 g of the component.

Here, SOTES was prepared as follows. That is, 0.452 mol of trimethylsilanol, 0.450 mol of tetraethoxysilane and 20.6 mmol of n-butylamine were placed in a 300 ml three-necked flask, and heated and stirred at 80 ° C. for 1 hour under a nitrogen atmosphere. After completion of the reaction, SOTES was obtained by distillation. The boiling point was 172 ° C.

Examples 2 and 3 In the prepolymerization of Example 1, the first
Except that the organosilicon compounds shown in the table and the organoaluminum compounds shown in Table 1 were used in place of TEAL at the concentrations shown in Table 1 and the prepolymerization conditions were as shown in Table 1, respectively. Preliminary polymerization of component A was performed in the same manner as in 1,
A catalyst component was prepared.

Comparative Example 1 A catalyst component (component A) was prepared in the same manner as in Example 1 except that prepolymerization was not performed.

Comparative Example 2 In the prepolymerization of Example 1, component A was prepolymerized in the same manner as in Example 1 except that SOTES was not used and the prepolymerization conditions were as shown in Table 1. Prepared.

Comparative Example 3 In the prepolymerization of Example 1, dimethyldimethoxysilane was used instead of SOTES, and the prepolymerization conditions were changed to the first.
Except as shown in the table, the component A was prepolymerized in the same manner as in Example 1 to prepare a catalyst component.

Reference Example 1 Component A was prepared in the same manner as in Example 1 except that phenyltriethoxysilane was used in place of SOTES in the prepolymerization of Example 1 and the prepolymerization conditions were as shown in Table 1. Polymerization was carried out to prepare a catalyst component.

Example 4 Preparation of Component A After contacting silicon oxide and BEM in the same manner as in Example 1 except that the stirring time at 90 ° C. was changed to 2 hours, the supernatant was removed by decantation, and the resulting solid was formed. 50
After washing at room temperature with ml of n-heptane, the supernatant was removed by decantation. This washing treatment with n-heptane was further performed four times.

20 ml of n-heptane was added to the above solid to form a suspension, and a solution obtained by dissolving 9.6 g of 2,2,2-trichloroethanol in 10 ml of n-heptane was added at 0 ° C from a dropping funnel.
For 30 minutes. After stirring at 0 ° C. for 1 hour, the temperature was raised to 80 ° C. over 1 hour, and stirring was continued at 80 ° C. for 1 hour. After completion of the reaction, the solid was washed twice with 50 ml of n-heptane and three times with 50 ml of toluene at room temperature to obtain a solid (solid component I).

To the solid component I obtained above, 20 ml of toluene and 0.6 g of di-n-butyl phthalate were added and reacted at 50 ° C. for 2 hours. Then, after adding 30 ml of titanium tetrachloride and reacting at 90 ° C. for 2 hours, the obtained solid substance was washed eight times at room temperature with 50 ml of n-hexane. Drying was performed at room temperature under reduced pressure for 1 hour to obtain 7.7 g of component A. In component A,
In addition to 3.0% titanium, silicon oxide, magnesium, chlorine and di-n-butyl phthalate were contained.

Prepolymerization The component A was prepolymerized in the same manner as in Example 1 except that the component A obtained above was used and the prepolymerization conditions were as shown in Table 1 to prepare a catalyst component.

Comparative Example 4 In the prepolymerization of Example 4, except that the electron-donating compound was not used and the prepolymerization conditions were as shown in Table 1.
A catalyst component was prepared in the same manner as in Example 4.

Reference Example 2 In the prepolymerization of Example 4, 1,1-dimethoxy-1
-Instead of methyl-3,3,3-trimethyldisiloxane,
The prepolymerization of Component A was carried out in the same manner as in Example 4 except that diphenyldimethoxysilane was used and the prepolymerization conditions were as shown in Table 1, to prepare a catalyst component.

Application Example 1 Polymerization of Propylene In a 1.5 stainless steel autoclave equipped with a stirrer, an n-heptane solution (0.1
Mol /) 4 ml and 1,1-dimethoxy-1-methyl-3,3,
A solution of 3-trimethylcidyloxane in n-heptane (0.01
Mol /) were mixed and kept for 5 minutes. Next, after injecting hydrogen gas 1 and liquid propylene 1 as a molecular weight controlling agent, the reaction system was heated to 70 ° C. After charging 40 mg of the catalyst component obtained in Example 1 to the reaction system, propylene was polymerized for 1 hour. After the completion of the polymerization, unreacted propylene was purged to obtain a white polypropylene powder having a HI of 97.8%. The amount of produced polypropylene (CE) per 1 g of Component A per hour was 21.5 kg.

Application Examples 2 to 5 Instead of the catalyst component obtained in Example 1, Examples 2 to 4
Using the catalyst component obtained in 1, and 1,1-dimethoxy-1
Propylene was polymerized in the same manner as in Application Example 1 except that the electron donating compounds shown in Table 2 were used or not in place of -methyl-3,3,3-trimethyldisiloxane, and the results were obtained. The results are shown in Table 2.

Application Examples 6 to 11 Comparative Examples 1 to 4 in place of the catalyst component obtained in Example 1.
Using the catalyst component obtained in 1, and 1,1-dimethoxy-1
Polymerization of propylene was carried out in the same manner as in Application Example 1 except that the electron donating compound shown in Table 2 was used instead of -methyl-3,3,3-trimethyldisiloxane, or no electron donating compound was used. The results are shown in Table 2.

Application Examples 12 and 13 Instead of the catalyst component obtained in Example 1, the catalyst component obtained in Reference Examples 1 and 2 was used, and 1,1-dimethoxy-1-
Methyl-3,3,3-trimethyl thidioxane
Propylene was polymerized in the same manner as in Application Example 1 except that the electron donating compound shown in the table was used or the electron donating compound was not used, and the results are shown in Table 2.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a process for preparing a catalyst component of the present invention.

Continued on the front page (72) Inventor Ryuji Sato 1-3-1, Nishi-Tsurugaoka, Oimachi, Irima-gun, Saitama Prefecture Inside Tonen Research Institute (72) Inventor Hiroyuki Furuhashi 1-3-3, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama No. 1 Inside the Tonen Research Laboratory (72) Inventor Satoshi Ueki 1-3-1 Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Inside the Tonen Research Laboratory (56) References JP-A-57-63312 (JP, A JP-A-58-111805 (JP, A) JP-A-56-155205 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 4/60-4/70

Claims (1)

(57) [Claims] 1. A solid catalyst component comprising (A) a metal oxide, magnesium, titanium, a halogen and an electron donating compound as essential components; (B) a general formula R _n AlX _{3-n wherein} 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. An organoaluminum compound represented by the general formula (C): [However, R ¹ , R ⁴ and R ⁵ are the same or different hydrocarbon groups having 1 to 10 carbon atoms, R ² is a hydrocarbon group having 1 to 10 carbon atoms or R ⁶ O, R ³ is a carbon group having 1 carbon atom. 1010 hydrocarbon groups or R ⁷ O, x is 2 or 3, and R ⁶ and R ⁷ are the same or different C 1-10 hydrocarbon groups. And (D) an olefin in the presence of an organosilicon compound represented by the following formula: