JP2873053B2 - Catalyst component for α-olefin polymerization - Google Patents

Description

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

2. Description of the Related Art Catalyst components for 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. By adding an electron-donating compound such as a silicon compound at the time of the preliminary polymerization, the particle strength is improved and the final poly-α is added.
-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 that (A) a solid component containing metal oxide, magnesium, titanium, halogen and an electron donating compound as essential components, (B) an organoaluminum compound, and (C) a general formula [However, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms or ▲
R ⁷ ₃ ▼ Si, R ² is a hydrocarbon group having 1 to 10 carbon atoms or R
⁸ O, R ³ is a hydrocarbon group having 1 to 10 carbon atoms or R ⁹ O, R ⁴
And R ⁵ are the same or different and have 1 to 10 carbon atoms, R ⁶
Is a hydrocarbon group having 1 to 10 carbon atoms, OR ¹⁰ or ▲ SiR ¹¹ ₃
And R ^{7 to} R ¹¹ are the same or different hydrocarbon groups having 1 to 10 carbon atoms. And (D) an olefin polymerization catalyst component 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 -A
_{l 2 O 3, SiO 2 -TiO} 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -T
iO 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, 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 , Mg-Pr ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgEt
_{Bu, MgPh 2, MgcyHe 2,} Mg (OMe) 2, Mg (OEt) 2, Mg (OBu) 2, M
g (OHe) ₂ , Mg (OOct) ₂ , Mg (OPh) ₂ , Mg (OcyHe) ₂ , EtMgCl, Bu
MgCl, HeMgCl, i-BuMgCl, t-BuMgCl, PhMgCl, PhCH ₂ MgCl, E
tMgBr, BuMgBr, PhMgBr, BuMgI, EtOMgCl, BuOMgCl, HeOMgCl,
PhOMgCl, EtOMgBr, BuOMgBr, EtOMgI, MgCl 2, MgBr 2, Mg
I _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 metal magnesium, halogenated hydrocarbons and an alkoxy group-containing compound of 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, M is boron, carbon, aluminum, silicon or a phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is a valence of M, m> n ≧ 0]. As the hydrocarbon group of X and R in the general formula of the alkoxy group-containing compound,
Methyl (Me), ethyl (Et), propyl (Pr), i-propyl (i-Pr), butyl (Bu), i-butyl (i-B
u), alkyl groups such as hexyl (He) and octyl (Oct), cycloalkyl groups such as cyclohexyl (cyHe) and methylcyclohexyl groups, alkenyl groups such as allyl, propenyl and butenyl, and phenyl (Ph), tolyl and xylyl groups. Aryl groups, phenethyl, aralkyls such as 3-phenylpropyl and the like. Among these, an alkyl group having 1 to 10 carbon atoms is particularly desirable. Specific examples of the alkoxy group-containing compound will be given below.

Compound when M is carbon C (OMe) ₄ , C (OEt) ₄ , C (OPr) ₄ , C (O) contained in the formula C (OR) _{4
Bu) 4, C (Oi-} Bu) 4, C (OHe) 4, C (OOct) 4: Formula XC (OR) HC contained in the _{3 (OMe) 3, HC (} OEt) 3, HC (OPr) 3 , HC (OBu) ₃ , HC (OBu
He) ₃ , HC (OPh) ₃ , MeC (OMe) ₃ , MeC (OEt) ₃ , EtC (OMe) ₃ , E
tC (OEt) ₃ , cyHeC (OEt) ₃ , PhC (OMe) ₃ , PhC (OEt) ₃ , CH ₂ Cl
C (OEt) ₃ , MeCHBrC (OEt) ₃ , MeCHClC (OEt) ₃ ; ClC (OMe) ₃ ,
_{ClC (OEt) 3, ClC (} Oi-Bu) 3, BrC (OEt) 3; wherein X ₂ C MeCH contained in _{(OR) 2 (OMe) 2} , MeCH (OEt) 2, CH 2 (OMe) 2, CH ₂ (OE
t) ₂ , CH ₂ ClCH (OEt) ₂ , CHCl ₂ CH (OEt) ₂ , CCl ₃ CH (OEt) ₂ , C
_{H 2 BrCH (OEt) 2,} PhCH (OEt) 2.

Compound where M is silicon Si (OMe) ₄ , Si (OEt) ₄ , Si (OB) contained in formula Si (OR) ₄
u) ₄ , Si (Oi-Bu) ₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (OPh) ₄ : Formula
HSi (OEt) ₃ , HSi (OBu) ₃ , HSi (OH) contained in XSi (OR) ₃
e) ₃ , HSi (OPh) ₃ , MeSi (OMe) ₃ , MeSi (OEt) ₃ , MeSi (OB
u) ₃ , EtSi (OEt) ₃ , PhSi (OEt) ₃ , EtSi (OPh) ₃ ; ClSi (OMe)
₃ , ClSi (OEt) ₃ , ClSi (OBu) ₃ , ClSi (OPh) ₃ , BrSi (OE
t) ₃ ; Me ₂ Si (OMe) ₂ , Me ₂ Si (OE) contained in the formula X ₂ Si (OR) ₂
t) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (OEt) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CC
l ₃ SiH (OEt) ₂ ; MeBrSi (OEt) ₂ : Me ₃ SiO contained in X ₃ SiOR ₂
Me, Me ₃ SiOEt, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ SiOEt, Ph ₃ SiO
Et.

B where M is contained in the compound formula B (OR) ₃ in the case of boron _{(OEt) 3, B (OBu} ) 3, B (OHe) 3, B (O
Ph) ₃ .

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

Compound when M is phosphorus P (OMe) ₃ , P (OEt) ₃ , P (OBu) ₃ , P (O) contained in the formula P (OR) ₃
He) 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. or,
m represents the valence of the metal M, and n represents a number of 0.1 to 10. MR ³ _m
Specific examples of the compound represented by are AlMe ₃ , AlEt ₃ ,
_{Ali-Bu 3, AlPh 3,} ZnMe 2, ZnEt 2, ZnBu 2, ZnPh 2, CaE
t ₂ , CaPh _{2 and the} like.

(3) 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.

(4) 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,
Dioctyl 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 almost 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, ethylphenyl ether and the like.

The method for preparing component A includes metal oxide (component 1),
A magnesium compound (component 2), a titanium compound (component 3) and an 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 and Component 3, contact Component 4 and Component 1 in that order. After contacting Component 2 and 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 IIa, 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, 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.

Examples of silicon halide compounds having a hydrogen-silicon bond include HSiCl ₃ , H ₂ SiCl ₂ , H ₃ SiCl, HCH ₃ SiCl ₂ , HC ₂ H ₅ SiC
l ₂ , H (tC ₄ H ₉ ) SiCl ₂ , HC ₆ H ₅ SiCl ₂ , H (CH ₃ ) ₂ SiCl, H (iC
_{3 H 7) 2 SiCl, H} 2 C 2 H 5 SiCl, H 2 (nC 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 and Bi chlorides, fluorides, bromides and iodides are mentioned, especially BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ , AlBr ₃ , GaCl ₃ and GaBr
₃ , InCl ₃ , TlCl ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF _{5 and the} like are suitable.

Contact with component 1, component 2, component 3 and component 4, and optionally with a halogen-containing compound that can be contacted,
In the presence or absence of an inert medium, mixing and stirring,
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 bringing into contact with an electron-donating compound and a silicon halide compound before contacting with a compound (JP-A-55-115405, JP-A-57-108107), metal oxides, alkoxy-containing magnesium compounds,
A method in which an aromatic polycarboxylic acid having a carboxyl group at the ortho position or a derivative thereof and a titanium compound are contacted (JP-A-61-174204), a metal oxide, an alkoxy-containing magnesium compound, and silicon having a hydrogen-silicon bond. A method of contacting a compound, an electron donating compound and a titanium compound (JP-A-61-174205), contacting a metal oxide, an alkoxy-containing magnesium compound, a halogen element or a halogen-containing compound, an electron-donating compound and a titanium compound Method (JP-A-61-17)
No. 4206), 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)
A compound 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). And has 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 triisopropylaluminum, tributylaluminum, triisobutylaluminum and trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, dialkylaluminum monohalide such as diisobutylaluminum chloride, and methylaluminum dichloride Monoalkylaluminum dihalides such as ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide and isobutylaluminum dichloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; dimethylaluminum methoxy Dialkylaluminum monoalkoxides such as diethylaluminum ethoxide, diethylaluminum phenoxide, dipropylaluminum ethoxide, diisobutylaluminum ethoxide, diisobutylaluminum phenoxide, dimethylaluminum hydride, dialkyl such as diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride Aluminum hydride is exemplified. Among these,
Trialkylaluminums, particularly triethylaluminum and triisobutylaluminum, are desirable.

Organic silicon compound An organic silicon compound (hereinafter, referred to as one component of the catalyst of the present invention)
Component C. ) Is represented by the above general formula. In the formula, the hydrocarbon group for R ^{1 to} R ¹¹ includes an alkyl group,
Examples include an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group, an 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 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. . As R ⁴ and R ⁵ , a methyl or ethyl group is particularly desirable.

Hereinafter, specific examples of the component C are listed. Incidentally, the general formula indicated as ^{R 1 / R 2 / R 3} OR 4 / OR 5 / R 6.

In the following, Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Amy = amyl, and Hex = hexyl, respectively.

R ¹ , R ² and R ³ are hydrocarbon groups and R ⁶ is OR ¹⁰ [R ¹ ,
R ¹ when R ² and R ³ are the same, ▲ R ¹ when R ¹ and R ² are the same
₂ ▼ / R ³ and OR ⁴ , OR ⁵ and OR ¹⁰ are the same when OR ⁴ and OR ⁴
When and ⁵ are the same, they are displayed as (OR ⁴ ) ₂ / OR ¹⁰ respectively. ] MeOMe, MeOEt, EtOMe, EtOEt, Me 2 / n-PrOMe, M
e ₂ / n−PrOEt, Me ₂ / t−BuOMe, Me ₂ / t−BuOEt, Et ₂ / Me
OMe, Et ₂ / MeOEt, Me (OMe) ₂ / OEt, Me (OMe) ₂ / Oi−P
r, Me (OMe) ₂ / Ot-Bu, Me (OEt) ₂ / On-Hex, Et (OMe) ₂ /
Oi−Pr, Me ₂ / t−Bu (OMe) ₂ / Ot−Bu, Et ₂ / Me (OMe) ₂ / On
-Hex.

When R ¹ is ▲ R ⁷ ₃ ▼ Si, R ² and R ³ are hydrocarbon groups and R ⁶ is OR ¹⁰ (When R ² and R ³ are the same, ▲ R ⁷ ₃ ▼ Si / ▲ R ² ₂ ▼ And OR ⁴ ,
OR ⁴ when OR ⁵ and OR ¹⁰ are the same, and OR ⁴ and OR ⁵ when the same
(OR ⁴ ) ₂ / OR ¹⁰ are displayed. Me ₃ Si / Me ₂ OMe, Me ₃ Si / Me ₂ OEt, Et ₃ Si / Me ₂ OMe,
Et ₃ Si / Me ₂ OEt, Me ₃ Si / Et ₂ OMe, Me ₃ Si / Et ₂ OEt, Et
₃ Si / Et ₂ OMe, Et ₃ Si / Et ₂ OEt, Me ₃ Si / Me / EtOMe, Et ₃
Si / Me / EtOEt, Me ₃ Si / Et / i−PrOEt, Et ₃ Si / Me / t−Bu
_{OMe, Me 3 Si / Me 2} (OMe) 2 / Ot-Bu, Me 3 Si / Me 2 (OEt) 2 / O
n−Hex, Et ₃ Si / Me ₂ (OMe) ₂ / Os−Amy, Me ₃ Si / Me / Et (OM
e) ₂ / Ot−Bu, Et ₃ Si / Me / Et (OEt) ₂ / On−Hex, Et ₃ Si / Me / i
−Pr (OEt) ₂ / t−Bu, Et ₃ Si / Me / t−Bu (OMe) ₂ / Os−Am
y.

When R ¹ , R ² and R ³ are hydrocarbon groups and R ⁶ is a hydrocarbon group [When R ¹ , R ² and R ³ are the same, R ¹ and when R ¹ and R ² are the same, ▲ and R ¹ ₂ ▼ / R ^3, when OR ⁴ and OR ⁵ are the same (OR ⁴⁾ ₂ / OR ⁶
Respectively. Me (OMe) ₂ / Me, Me (OEt) ₂ / Me, Me (OMe) ₂ / Et, Me (O
Et) ₂ / Et, Me (OMe) ₂ / i−Pr, Me (OEt) ₂ / i−Pr, Me (OM
e) ₂ / t−Bu, Me (OEt) ₂ / t−Bu, Me (OMe) ₂ / n−Bu, Me (O
Et) ₂ / n−Bu, Me (OMe) ₂ / s−Bu, Me (OEt) ₂ / s−Bu, Et
(OMe) ₂ / Me, Et (OEt) ₂ / Me, Et (OMe) ₂ / i−Pr, Et (OEt)
₂ / i−Pr, Me ₂ / n−Pr (OMe) ₂ / Me, Me ₂ / n−Pr (OEt) ₂ / Me,
_{Me 2 / t-Bu (OMe} ) 2 / Et, Me 2 / t-Bu (OEt) 2 / Et, Me 2 / n-B
_{u (OEt) 2 / Me,} Me 2 / n-Bu (OEt) 2 / Me, Me 2 / n-Hex (OM
e) ₂ / Me, Me ₂ / n−Hex (OEt) ₂ / Me, Me ₂ / s−Amy (OMe) ₂ / M
_{e, Me 2 / s-Amy} (OEt) 2 / Me, Me (OMe) 2 / cyclopentyl, Me (OMe) ₂ / cyclopentadienyl.

R ¹ is ▲ R ⁷ ₃ ▼ Si, R ² and R ³ are hydrocarbon groups, and R ⁶ is a hydrocarbon group (If R ² and R ³ are the same, ▲ R ⁷ ₃ ▼ Si / ▲ R ¹ ₂ ▼ and OR ⁴
When and ⁵ are the same, they are displayed as (OR ⁴ ) ₂ / R ⁶ respectively. Me ₃ Si / Me ₂ (OMe) ₂ / Me, Me ₃ Si / Me ₂ (OEt) ₂ / Me, Et ₃ S
_{i / Me 2 (OMe) 2} / i-Pr, Et 3 Si / Me 2 (OMe) 2 / n-Hex.

When R ¹ , R ² and R ³ are hydrocarbon groups and R ⁶ is ▲ SiR ¹¹ ₃ ▼ [When R ¹ , R ² and R ³ are the same, R ¹ and R ² and R ³ are the same when the _{^{▲ R 2 2 ▼ / R 3}} , when oR ⁴ and oR ⁵ are the same (oR ⁴⁾ ₂ /
Displayed as ▲ SiR ¹¹ ₃ ▼ respectively. ] _{Me (OMe) 2 / SiMe 3} , Me (OEt) 2 / SiMe 3, Me (OMe) 2 /
SiEt ₃ , Et (OMe) ₂ / SiMe ₃ , Et (OEt) ₂ / SiMe ₃ , Et (OM
_{e) 2 / SiEt 3, Et} (OEt) 2 / SiEt 3, Me 2 / n-Pr (OMe) 2 / S
iMe ₃ , Me ₂ / t−Bu (OMe) ₂ / SiMe ₃ , Et ₂ / i−Pr (OEt) ₂
/ SiEt _3.

R ¹ is ▲ R ⁷ ₃ ▼ Si, R ² and R ³ are hydrocarbon groups, and R ⁶ is ▲ SiR
¹¹ ₃ ▼ (When R ² and R ³ are the same, ▲ R ⁷ ₃ ▼ Si / ▲ R ² ₂ ▼ and OR ⁴
When OR ⁵ is the same, they are displayed as (OR ⁴ ) ₂ / ▲ SiR ¹¹ ₃ ▼, respectively. Me ₃ Si / Me ₂ (OMe) ₂ / SiMe ₃ , Me ₃ Si / Et ₂ (OMe) ₂ / S
iMe ₃ , Me ₃ Si / Me ₂ (OEt) ₂ / SiMe ₃ , Me ₃ Si / Me ₂ (OMe)
₂ / SiEt ₃ , Me ₃ Si / Me / Et (OEt) ₂ / SiMe ₃ , Et ₃ Si / Et _{2
(OEt) 2 / SiMe 3,} Et 3 Si / Et 2 (OEt) 2 / SiEt 3, Me 3 Si / Me
_{/ n-Bu (OEt) 2} / SiMe 3.

R ¹ and R ² are hydrocarbon groups, with R ³ is R ⁹ O, when when R ⁶ is OR ¹⁰ [wherein R ¹ and R ² are the same _{^{▲ R 1 2 ▼ / R 9}} O and, OR ^4, When OR ⁵ and OR ¹⁰ are the same, OR ⁴ and when OR ⁴ and OR ⁵ are the same, (OR
⁴ ) ₂ / OR ¹⁰ is displayed. ] _{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, Me ₂ / MeO (OMe)
₂ / OEt, Me ₂ / MeO (OEt) ₂ / Ot−Bu, Me ₂ / EtO (OMe) ₂ / On−H
ex, Me ₂ / EtO (OEt) ₂ / Oi−Pr, Et ₂ / MeO (OMe) ₂ / OEt, Et ₂ /
MeO (OEt) ₂ / Ot−Bu, Et ₂ / EtO (OMe) ₂ / On−Hex, Et ₂ / EtO
(OEt) ₂ / Oi−Pr, Me / t−Bu / MeOOMe / OEt / Oi−Pr, Et / i
-Pr-EtOOMe / OEt / On-Amy.

R ¹ is ▲ R ⁷ ₃ ▼ Si, R ² is a hydrocarbon group, R ³ is R ⁹ O, and R ⁶ is OR
For ¹⁰ [OR ^4, OR ⁵ and OR ¹⁰ is an OR ⁴ when the same, OR ⁴ and OR ⁵
When they are the same, they are displayed as (OR ⁴ ) ₂ / OR ⁹ respectively. Me ₃ Si / Me / MeOOMe, Me ₃ Si / Me / MeOOEt, Me ₃ Si / Me / EtO
OMe, Et ₃ Si / Et / MeOOMe, Et ₃ Si / Me / EtOOMe, Et ₃ Si / Me
/ MeOOEt, Et ₃ Si / Et / EtOOEt, Me ₃ Si / t−Bu / MeOOMe, E
t ₃ Si / i−Pr / EtOOEt, Me ₃ Si / Me / MeO (OMe) ₂ / Ot−Bu, Me
₃ Si / Et / MeO (OEt) ₂ / On−Pr, Me ₃ Si / Et / EtO (OEt) ₂ / Oi
−Pr, Et ₃ Si / Me / MeO (OEt) ₂ / Oi−Pr, Et ₃ Si / Et / EtO (OE
_{t) 2 / Oi-Pr,} Et 3 Si / Me / EtO (OMe) 2 / Os-Amy.

R ¹ and R ² are hydrocarbon groups, R ³ is in the R ⁹ O, when if R ⁶ is a hydrocarbon group [R ¹ and R ² are the same as _{^{▲ R 1 2 ▼ / R 9}} O, OR 4 And OR ⁵
When they are the same, they are displayed as (OR ⁴ ) ₂ / R ⁶ respectively. ] _{Me 2 / MeO (OMe) 2} / Me, Me 2 / MeO (OEt) 2 / Me, Me 2 / EtO
(OMe) ₂ / Me, Me ₂ / EtO (OEt) ₂ / Me, Me ₂ / i−PrO (OMe) ₂ / M
e, Me ₂ / i−PrO (OEt) ₂ / Me, Me ₂ / s−BuO (OMe) ₂ / Me, Me ₂ /
_{s-BuO (OEt) 2 /} Me, Me 2 / t-AmyO (OMe) 2 / Me, Me 2 / t-Am
_{yO (OEt) 2 / Me,} Me 2 / n-HexO (OMe) 2 / Me, Me 2 / n-HexO
_{(OEt) 2 / Me, Et} 2 / MeO (OMe) 2 / Me, Et 2 / MeO (OEt) 2 / Me, Me
/ n-Pr / MeO (OMe) ₂ / Et, Me / n-Pr / MeO (OEt) ₂ / Et, Me / t
−Bu / MeO (OMe) ₂ / Me, Me / t−Bu / MeO (OEt) ₂ / Me, Me ₂ / Me
_{O (OMe) 2 / Et,} Me 2 / MeO (OEt) 2 / Et, Me 2 / MeO (OMe) 2 / i
−Pr, Me ₂ / MeO (OEt) ₂ / i−Pr, Me ₂ / MeO (OMe) ₂ / t−Bu, M
_{e 2 / MeO (OEt) 2} / t-Bu, Me 2 / MeO (OMe) 2 / _{cyclohexyl, Me 2 / MeOOMe / OEt /} Et, Me 2 / EtOOMe / OEt / t-Bu, Et 2
/ MeOOMe / OEt / i-Pr, Me / t-Bu / MeOOMe / OEt / Me, Et / i
-Pr / EtOOMe / OEt / n-Hex.

R ¹ is ▲ R ⁷ ₃ ▼ Si, R ² is a hydrocarbon group, R ³ is R ⁹ O, and R ⁶ is a hydrocarbon group [When OR ⁴ and OR ⁵ are the same, (OR ⁴ ) ₂ / to display the R ^6. Me ₃ Si / Me / MeO (OMe) ₂ / Me, Me ₃ Si / Et / MeO (OMe) ₂ / Me,
Me ₃ Si / Et / EtO (OMe) ₂ / Me, Me ₃ Si / Et / EtO (OEt) ₂ / Et, Et
₃ Si / Me / MeO (OMe) ₂ / Me, Et ₃ Si / Et / MeO (OMe) ₂ / Me, Et ₃ S
i / Et / EtO (OMe) ₂ / Me, Et ₃ Si / Et / EtO (OEt) ₂ / Et, Me ₃ Si /
Et / MeO (OEt) ₂ / t−Bu, Et ₃ Si / Me / EtO (OMe) ₂ / s−Bu, Me
₃ Si / Me / MeOOMe / OEt / Me, Et ₃ Si / Et / MeOOMe / OEt / i−P
r.

R ¹ and R ² are hydrocarbon groups, R ³ is R ⁹ O, and R ⁶ is ▲ SiR ¹¹ ₃ ▼
When When [R ¹ and R ² are identical and _{^{▲ R 1 2 ▼ / R 9}} O, OR 4 and OR ⁵
When they are the same, they are displayed as (OR ⁴ ) ₂ / ▲ SiR ¹¹ ₃ ▼, respectively. Me ₂ / MeO (OMe) ₂ / SiMe ₃ , Me ₂ / EtO (OMe) ₂ / SiMe ₃ ,
_{Me 2 / MeO (OEt) 2} / SiMe 3, Me 2 / MeO (OMe) 2 / SiEt 3, Et
₂ / MeO (OMe) ₂ / SiMe ₃ , Et ₂ / EtO (OMe) ₂ / SiMe ₃ , Et ₂ /
_{MeO (OMe) 2 / SiEt 3} , Et 2 / EtO (OEt) 2 / SiEt 3, Me / Et / M
_{eO (OEt) 2 / SiMe 3} , Me / Et / EtO (OMe) 2 / SiEt 3, Me / t-B
_{r / EtO (OMe) 2 /} SiMe 3, Et / s-Amy / MeO (OEt) 2 / SiMe 3,
i-Pr / n-Bu / MeO (OMe) 2 / SiEt 3, Me / Et / MeOOMe / OEt /
_{SiMe 3, Et / t-Bu} / MeOOMe / OEt / SiEt 3.

R ¹ is ▲ R ⁷ ₃ ▼ Si, R ² is a hydrocarbon group, R ³ is R ⁹ O, and R ⁶ is ▲
In the case of SiR ¹¹ ₃ ▼ [When OR ⁴ and OR ⁵ are the same, (OR ⁴ ) ₂ / ▲ SiR ¹¹ ₃ ▼ is displayed. Me ₃ Si / Me / MeO (OMe) ₂ / SiMe ₃ , Me ₃ Si / Et / MeO (OMe)
₂ / SiMe ₃ , Me ₃ Si / Me / EtO (OMe) ₂ / SiMe ₃ , Et ₃ Si / Me / Me
O (OMe) ₂ / SiMe ₃ , Et ₃ Si / Et / MeO (OMe) ₂ / SiMe ₃ , Et ₃
Si / Et / EtO (OMe) 2 / SiMe 3, Et 3 Si / Me / MeO (OMe) 2 / Si
_{Et 3, Et 3 Si / Et} / EtO (OEt) 2 / SiEt 3, Me 3 Si / Me / MeOOM
e / OEt / SiMe ₃ , Et ₃ Si / Et / EtOOMe / OEt / SiEt ₃ .

When R ¹ is a hydrocarbon group, R ² is R ⁸ O, R ³ is R ⁹ O, and R ⁶ is OR ¹⁰ [When R ⁸ O and R ⁹ O are the same, R ¹ / (R ⁸ O) and _2, oR ^4, oR ⁵ and oR ¹⁰ is an oR ⁴ when the same, when oR ⁴ and oR ⁵ are the same (oR
⁴ ) ₂ / OR ¹⁰ is displayed. Me / (MeO) ₂ OMe, Me / (MeO) ₂ OEt, Et / (MeO) ₂ OMe, Et /
(MeO) ₂ OEt, Me / (EtO) ₂ OMe, Me / (EtO) ₂ OEt, Me / (n-Pr
O) ₂ OMe, Me / (n-PrO) OEt, Me / (MeO) / (t-Bu
O) OMe, Me / (MeO) / (t-BuO) OEt, Me / (MeO) ₂
(OMe) ₂ / Ot−Bu, Me / (MeO) ₂ (OEt) ₂ / Oi−Pr, Me / MeO / t−B
uO (OMe) ₂ / On-Hex, Et / EtO / i-PrO (OEt) ₂ / Oi-Bu, Me
/ EtO / n-BuOOMe / EtO / On-Hex.

When R ¹ is ▲ R ⁷ ₃ ▼ Si, R ² is R ⁸ O, R ³ is R ⁹ O and R ⁶ is OR ¹⁰ (When R ⁸ O and R ⁹ O are the same, ▲ R ⁷ ₃ ▼ Si / (R ⁸ O) ₂ and O
When R ^4, OR ⁵ and OR ¹⁰ are identical to the OR ^4, OR ⁴ and OR ⁵ is when the same displays respectively _{^{(OR 4) 2 / OR 10}} . Me ₃ Si / (MeO) ₂ OMe, Me ₃ Si / (EtO) ₂ OMe, Me ₃ Si / (Me
O) ₂ OEt, Et ₃ Si / (EtO) ₂ OMe, Et ₃ Si / (MeO) ₂ OEt, Et ₃
Si / (EtO) ₂ OEt, Me ₃ Si / (n-PrO) ₂ OMe, Et ₃ Si / EtOi
−PrOOEt, Me ₃ Si / MeO / n−BuOOMe, Me ₃ Si / (MeO) ₂ (O
Me) ₂ / Ot−Bu, Me ₃ Si / (EtO) ₂ (OMe) ₂ / On−Hex, Et ₃ Si /
(MeO) ₂ (OEt) ₂ / Oi−Pr, Me ₃ Si / MeO / t−BuO (OMe) ₂ / Os
_{-Amy, Et 3 Si / EtO /} i-PrOOMe / OEt / On-Hex.

When R ¹ is a hydrocarbon group, R ² is R ⁸ O, R ³ is R ⁹ O, and R ⁶ is a hydrocarbon group [When R ⁸ O and R ⁹ O are the same, R ¹ / (R ⁸ O) ₂ and OR ⁴ and OR ⁵
When they are the same, they are displayed as (OR ⁴ ) ₂ / R ⁶ respectively. Me / (MeO) ₂ (OMe) ₂ / Me, Me / (MeO) ₂ (OEt) ₂ / Me, Et / (Me
O) ₂ (OMe) ₂ / Me, Et / (EtO) ₂ (OEt) ₂ / Me, i−Pr / (MeO) ₂
O (OMe) ₂ / Me, i−Pr / (MeO) ₂ (OEt) ₂ / Me, n−Bu / (MeO) ₂
(OMe) ₂ / Me, n-Bu / (MeO) ₂ (OEt) ₂ / Me, Me / (n-PrO) ₂
(OMe) ₂ / Me, Me / (n-PrO) ₂ (OEt) ₂ / Me, Me / (s-BuO) ₂ (OM
e) ₂ / Me, Me / (s-BuO) ₂ (OEt) ₂ / Me, Me / MeO / n-HexO (OM
e) ₂ / Me, Me / MeO / n−HexO (OEt) ₂ / Me, Et / (MeO) ₂ (OMe) ₂
/ Et, Et / (MeO) ₂ (OEt) ₂ / Et, vinyl / (MeO) ₂ (OMe) ₂ /
Vinyl, vinyl / (EtO) ₂ (OEt) ₂ / vinyl, Me / (MeO) ₂
OMe / OEt / Me, Me / (EtO) ₂ OMe / OEt / Et, Et / (EtO) ₂ OMe / OE
t / Me, Et / (EtO) ₂ OMe / OEt / Et, Me / MeO / EtOOMe / OEt / Et,
Et / MeO / EtOOMe / OET / Et.

R ¹ is a hydrocarbon group, R ² is R ⁸ O, R ³ is R ⁹ O, and R ⁶ is ▲ SiR ¹¹ ₃
▼ [When R ⁸ O and R ⁹ O are the same, R ¹ / (R ⁸ O) ₂ and OR ⁴ and OR ⁵
When they are the same, they are displayed as (OR ⁴ ) ₂ / ▲ SiR ¹¹ ₃ ▼, respectively. Me / (MeO) ₂ (OMe) ₂ / SiMe ₃ , Me / (MeO) ₂ (OEt) ₂ / SiMe
₃ , Me / (MeO) ₂ (OMe) ₂ / SiEt ₃ , Et / (MeO) ₂ (OMe) ₂ / SiMe
₃ , Et / (EtO) ₂ (OMe) ₂ / SiMe ₃ , Et / (MeO) ₂ (OEt) ₂ / SiMe
₃ , Et / (MeO) ₂ (OMe) ₂ / SiEt ₃ , Et / (EtO) ₂ (OEt) ₂ / SiEt
₃ , Me / MeO / EtOOMe / OEt / SiMe ₃ , Et / MeO / EtOOMe / OEt / Si
Et ₃ , i-Pr / (MeO) ₂ (OMe) ₂ / SiMe ₃ , n-Bu / (MeO) ₂ (OM
e) ₂ / SiEt ₃ , Me / (s-BuO) ₂ (OEt) ₂ / SiMe ₃ , vinyl / (Me
O) ₂ OMe / OEt / SiMe ₃ .

R ¹ is ▲ R ⁷ ₃ ▼ Si, R ² is R ⁸ O, R ³ is R ⁹ O, and R ⁶ is ▲ SiR ¹¹ ₃
▼ (When R ⁸ O and R ⁹ O are the same, ▲ R ⁷ ₃ ▼ Si / (R ⁸ O) ₂ and OR ⁴
And when OR ⁵ are the same display _{^{(OR 4) 2 / ▲ SiR}} 11 3 ▼ respectively. Me ₃ Si / (MeO) ₂ (OMe) ₂ / SiMe ₃ , Me ₃ Si / (EtO) ₂ (OM
e) ₂ / SiMe ₃ , Me ₃ Si / (MeO) ₂ / (OEt) ₂ / SiMe ₃ , Me ₃ Si /
(MeO) ₂ (OMe) ₂ / SiEt ₃ , Me ₃ Si / (EtO) ₂ (OEt) ₂ / SiEt
_{3, Et 3 Si / (MeO} ) 2 (OMe) 2 / SiEt 3, Et 3 Si / (EtO) 2 (O
_{Et) 2 / SiEt 3, Me} 3 Si / MeO / EtO (OMe) 2 / SiMe 3, Me 3 Si /
(EtO) ₂ OMe / OEt / SiMe ₃ , Et ₃ Si / MeO / EtO (OMe) ₂ / SiMe
_{3, Et 3 Si / MeO /} EtOOMe / OEt / SiEt 3.

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 desirably carried out in the presence of the above-mentioned inert catalyst. The prepolymerization is usually carried out 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 /
l, preferably from 80 to 200 mmol / l, and from 4 to 50,000 per gram atom of titanium in component A.
Mol, preferably 6 to 1,000 mol.

Component C has a concentration of 1 to 100 mmol /
1, preferably 5 to 50 mmol / l.

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, commercially available diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl aluminum hydride or a mixture or complex compound thereof and the like 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 a hetero atom such as phosphorus can also be used.

Specific examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane,
Tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyl Triisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltriphenoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxy Silane, dimethyldibutoxysilane, dimethyldihexyloxysilane, dimethyldiphenoxysilane, diethyldiethoxysilane,
Diethyl diisobutoxy silane, diethyl diphenoxy silane, dibutyl diisopropoxy silane, dibutyl dibutoxy silane, dibutyl diphenoxy silane, diisobutyl diethoxy silane, diisobutyl diisobutoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, diphenyl dibutoxy silane, Examples include dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane, and chlorophenyldiethoxysilane.

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-methylpyridine, 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 compounds containing an ion atom include thiophenol, thiophene, ethyl 2-thiophenecarboxylate, ethyl 3-thiophenecarboxylate, 2-methylthiophene, methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, butyl mercaptan,
Diethylthioether, diphenylthioether, methyl benzenesulfonate, methylsulfite, ethylsulfite and the like include tetrahydrofuran, 2-methyltetrahydrofuran, and 3-methyltetrahydrofuran as compounds containing an oxygen atom.
Methyltetrahydrofuran, 2-methyltetrahydrofuran, 2,2,5,5-tetraethyltetrahydrofuran, 2,
2,5,5-tetramethyltetrahydrofuran, 2,2,6,6-tetraethyltetrahydropyran, 2,2,6,6-tetrahydroplan, dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, anisole , Acetophenone, acetone, methyl ethyl ketone, acetyl acetone, o-tolyl-t-butyl ketone, methyl-2,6-di-t-butyl phenyl ketone, ethyl 2-furate, isoamyl 2-furate, methyl 2-furate, 2-methyl Examples of compounds in which propyl phthalate or the like contains a phosphorus atom include triphenyl phosphine, tributyl phosphine, triphenyl phosphite, tribenzyl phosphite, diethyl phosphate, diphenyl phosphate and the like.

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 is as follows:
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 row 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-butylethyl magnesium (hereinafter referred to as BEM) (trade name: MAGALA BEN, manufactured by Texas Alkyls)
Was added 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.
Stirring was continued for 30 minutes. After the completion of the reaction, at room temperature, 60 ml
Was washed twice with n-heptane and three times with 60 ml of toluene. When the obtained solid (solid component 1) was analyzed, SiO ₂ 36.6%, magnesium 5.1%, and chlorine 38.
Contained 5%.

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, 1.9 g of the component A obtained above and 280 ml of n-heptane were placed in a 500 ml reactor equipped with a stirrer, and cooled to 0 ° C. with stirring. Next, n-heptane solution (2.0 mol / l) of triethylaluminum (hereinafter abbreviated as TEAL) and n of 1,1-dimethoxy-1,2,2,2-tetramethyldisilane (hereinafter referred to as XMMS). -A heptane solution (2.0 mol / n) was added so that the concentrations of TEAL and silane in the reaction system became 200 mmol / l and 20 mmol / l, respectively, and the mixture was stirred for 5 minutes. Next, after reducing the pressure inside the system, propylene gas was supplied, and prorylene was polymerized for 30 minutes. After completion of the weight, propylene in the gas phase 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 2.9 g per Alg of the component.

Examples 2 and 3 In the prepolymerization of Example 1, the organosilicon compounds shown in Table 1 were used instead of XMMS, and the organoaluminum compounds shown in Table 1 were used instead of TEAL at the concentrations shown in Table 1, respectively. Preliminary polymerization of Component A was carried out in the same manner as in Example 1 except that the used and the prepolymerization conditions were as shown in Table 1, to prepare a catalyst component.

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

Comparative Example 2 Example 1 was repeated except that XMMS was not used in the prepolymerization of Example 1 and the prepolymerization conditions were as shown in Table 1.
The prepolymerization of the component A was carried out in the same manner as in the above to prepare a catalyst component.

Comparative Example 3 Component A was prepared in the same manner as in Example 1 except that dimethyldimethoxysilane was used instead of XMMS in the prepolymerization of Example 1 and the prepolymerization conditions were as shown in Table 1.
Was prepolymerized to prepare a catalyst component.

Reference Example 1 In the prepolymerization of Example 1, phenyltriethoxysilane was used instead of XMMS, and
Except as shown in the table, the component A was prepolymerized in the same manner as in Example 1 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.

To the above solid, 20 ml of n-heptane was added to form a suspension, and a solution of 9.6 g of 2,2,2-trichloroethanol dissolved in 10 ml of n-heptane was added thereto at 0 ° C. for 30 minutes from a dropping funnel. Hanged and dropped. 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. This component A contains 3.0% titanium, silicon oxide, magnesium,
It contained chlorine and di-n-butyl phthalate.

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
-Preliminary polymerization of component A was carried out in the same manner as in Example 4 except that diphenyldimethoxysilane was used instead of cyclopentyl-2,2,2-trimethyldisilane, and the prepolymerization conditions were as shown in Table 1. Then, a catalyst component was prepared.

Application Example 1 Polymerization of propylene In a 1.5-liter stainless steel autoclave equipped with a stirrer, a TEAl n-heptane solution (0.1
Mol / l) 4 ml and a solution of XMMS in n-heptane (0.01 mol / l)
l) 2 ml was mixed and kept for 5 minutes. Then
After injecting hydrogen gas 1 and liquid propylene 1 as a molecular weight controlling agent, the reaction system was heated to 70 ° C. Example 1
After charging 40 mg of the catalyst component obtained in the above to the reaction system, propylene was polymerized for 1 hour. After completion of the polymerization, unreacted propylene was purged to obtain a white polypropylene powder having a HI of 97.6%. Component Alg. The amount of produced polypropylene (CE) per hour was 23.7 kg.

Application Examples 2 to 6 Instead of the catalyst component obtained in Example 1, Examples 2 to 4
Propylene was polymerized in the same manner as in Application Example 1 except that the catalyst component obtained in the above was used, and that the electron donating compounds shown in Table 2 were used in place of XMMS, or not. It is shown in the table.

Application Examples 7 to 12 Instead of the catalyst components obtained in Example 1, Comparative Examples 1 to 4
The polymerization of propylene was carried out in the same manner as in Application Example 1 except that the catalyst component was used and the electron-donating compound shown in Table 2 was used instead of XMMS, or the electron-donating compound was not used. Are shown in Table 2.

Application Examples 13 and 14 Instead of the catalyst component obtained in Example 1, the catalyst components obtained in Reference Examples 1 and 2 were used, and instead of XMMS, an electron-donating compound shown in Table 2 was used. Propylene was polymerized in the same manner as in Application Example 1 except that 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.

Continuation of the front page (72) Inventor Masako Ishikawa 1-3-1, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama Prefecture Inside the Tonen Research Institute (72) Inventor Sachi Usui 1-3-3, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama No. 1 Tonen Research Institute (72) Inventor Satoshi Ueki 1-3-1 Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture 1 Tonen Research Institute (58) Field surveyed (Int.Cl. ⁶ , DB name ) C08F 4/60-4/70

Claims (1)

(57) [Claims] 1. A solid component comprising (A) a metal oxide, magnesium, titanium, a halogen and an electron donating compound as essential components, (B) an organoaluminum compound and (C) a general formula [However, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms or ▲ R ⁷
₃ ▼ Si, R ² is a hydrocarbon group having 1 to 10 carbon atoms or R ⁸ O,
R ³ is a hydrocarbon group having 1 to 10 carbon atoms or R ⁹ O, R ⁴ and R
⁵ is the same or different hydrocarbon group having 1 to 10 carbon atoms, R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms, OR ¹⁰ or ▲ SiR ¹¹ ₃ ▼, and R ^{7 to} R ¹¹ are the same or different It is a hydrocarbon group having 1 to 10 carbon atoms. And (D) an olefin in the presence of an organosilicon compound represented by the following formula: