JPH06239919A - Catalyst component for polymerizing alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain the subject component excellent in rigidity in high yield by bringing a solid component composed of magnesium, titanium, a halogen and an electron donative compound into contact with an organosilicon compound in the presence of an organoaluminum compound. CONSTITUTION:(B) A solid component composed of (i) a magnesium compound [e.g. a compound, expressed by the formula MgR<1>R<2> (R<1> and R<2> are hydrocarbon group, etc.) and preparable from metallic magnesium or other magnesium compounds], (ii) a titanium compound (preferably titanium tetrachloride, 6-1000 mol/g-atom titanium in the solid component) and (iii) an electron donative compound (preferably formic acid, etc., 5-50mmol/l) and a halogen-containing compound such as a halogen-containing alcohol is brought into contact (prepolymerized) with (C) an organosilicon compound expressed by the formula [R1 is 1-10C alkylene, aryl, etc.; R2 and R3 are 1-10C (R3 is 3-10C) aliphatic, alicyclic, aromatic hydrocarbon, etc.; (x) is 1 or 2; (y) is 0 or 1; (z) is (4-x-y)] (e.g. an alkenyl group-containing alkoxysilane) in the presence of (A) an organoaluminum compound (preferably triethylaluminum, etc., 80-200mmol/l) to afford the objective component.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst component for .alpha.-olefin polymerization. More specifically, it relates to a catalyst component for α-olefin polymerization capable of producing a polymer having excellent rigidity with a high yield.

[0002]

2. Description of the Related Art Demand for highly crystalline polypropylene produced by using various types of highly stereoregular catalysts has been rapidly increasing in recent years because of its excellent rigidity and heat resistance. However, these properties are still insufficient depending on the purpose of use, and various methods for improving the rigidity have been proposed, but most of them are the methods of performing post-treatment such as adding a nucleating agent to polypropylene. is there. Therefore, the process cost is high, and the appearance of the molded product may be impaired depending on the additive. A method of improving rigidity by a polymerization method without treatment with an additive has been proposed, but the rigidity is insufficient in both cases.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an α-olefin polymerization catalyst component capable of producing an α-olefin polymer such as polypropylene having excellent rigidity in a high yield.

[0004]

As a result of intensive studies by the present inventors, a catalyst component obtained by contacting a magnesium-containing solid catalyst component with a specific organosilicon compound achieves the object of the present invention. The present invention has been completed by finding that it can be obtained. That is, in the present invention, (A) a solid component containing magnesium, titanium, a halogen, and an electron donating compound as essential components is added to (C) a general formula

[Chemical 2] [However, R ¹ is an alkylene group or arylene group having 1 to 10 carbon atoms, R ² is an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 10 carbon atoms or R ⁴ O and R ³ are carbon atoms. An aliphatic, alicyclic or aromatic hydrocarbon group having 3 to 10 carbon atoms, R ⁴ is an aliphatic, alicyclic or aromatic hydrocarbon group having 3 to 10 carbon atoms which is the same as or different from R ³ . x is 1 or 2, y is 0 or 1, and z is 4-xy. ] Α formed by contacting with an organosilicon compound represented by
-Summary is a catalyst component for olefin polymerization.

Solid Component Solid component used in the present invention (hereinafter referred to as component A)
Contains magnesium, titanium, a halogen and an electron donating compound as essential components. Such components are usually a magnesium compound, a titanium compound and an electron donating compound, and in the case where each of the above compounds is a compound having no halogen,
It is prepared by contacting each of the halogen-containing compounds.

(1) Magnesium Compound The magnesium compound is represented by the general formula MgR ¹ R ² . In the formula, R ¹ and R ² are the same or different hydrocarbon groups, OR groups (R is a hydrocarbon group), and halogen atoms.
More specifically, the hydrocarbon group of R ¹ and R ² is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the OR group is R having 1 to 10 carbon atoms Twelve alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups have chlorine as a halogen atom,
Examples include bromine, iodine and fluorine.

Specific examples of these compounds are shown below. In the chemical formulas, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, He: hexyl, Oct: octyl, Ph: phenyl, cyHe: cyclohexyl, respectively. Show. MgMe ₂ , MgEt ₂ , Mgi-P
r ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgE
tBu, MgPh ₂ , MgcyHe ₂ , Mg (OMe)
₂ , Mg (OEt) ₂ , Mg (OBu) ₂ , Mg (OH
e) ₂ , Mg (OOct) ₂ , Mg (OPh) ₂ , Mg
(OcyHe) ₂ , EtMgCl, BuMgCl, He
MgCl, i-BuMgCl, t-BuMgCl, Ph
MgCl, PhCH ₂ MgCl, EtMgBr, BuM
gBr, PhMgBr, BuMgI, EtOMgCl,
BuOMgCl, HeOMgCl, PhOMgCl, E
tOMgBr, BuOMgBr, EtOMgI, MgC
l _2, MgBr _2, MgI ₂ .

The above magnesium compound can be prepared from metallic magnesium or other magnesium compounds when the component A is prepared. As an example thereof, a compound containing metal magnesium, a halogenated hydrocarbon and an alkoxy group represented by the general formula X _n M (OR) _mn [wherein X is a hydrogen atom, a halogen atom or a carbon number of 1 to 20]
Hydrocarbon groups, M 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 ≧ 0. ] The method of making it contact is mentioned. The hydrocarbon groups represented by X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl (Pr), i-propyl (iP
r), butyl (Bu), i-butyl (i-Bu), hexyl (He), octyl (Oct) and other alkyl groups, cyclohexyl (cyHr), methylcyclohexyl and other cycloalkyl groups, allyl, propenyl, butenyl, etc. Alkenyl group, phenyl (Ph), tolyl, aryl group of xylyl group, phenethyl, aralkyl 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 where M is carbon C (OMe) ₄ , C (OE contained in the formula C (OR) ₄
t) ₄ , C (OPr) ₄ , C (OBu) ₄ , C (Oi-
Bu) ₄ , C (OHe) ₄ , C (OOct) ₄ : Formula XC
HC (OMe) ₃ , HC (OE contained in (OR) ₃
t) ₃ , HC (OPr) ₃ , HC (OBu) ₃ , HC
(OHe) ₃ , HC (OPh) ₃ ; MeC (OM
e) ₃ , MeC (OEt) ₃ , EtC (OMe) ₃ , E
tC (OEt) ₃ , cyHeC (OEt) ₃ , PhC
(OMe) ₃ , PhC (OEt) ₃ , CH ₂ ClC (O
Et) ₃ , MeCHBrC (OEt) ₃ , MeCHCl
C (OEt) ₃ ; ClC (OMe) ₃ , ClC (OE
t) ₃ , ClC (Oi-Bu) ₃ , BrC (OE
t) ₃ ; MeCH (OM included in the formula X ₂ C (OR) ₂
e) ₂ , MeCH (OEt) ₂ , CH ₂ (OMe) ₂ ,
CH ₂ (OEt) ₂ , CH ₂ ClCH (OEt) ₂ , C
HCl ₂ CH (OEt) ₂ , CCl ₃ CH (OE
t) ₂ , CH ₂ BrCH (OEt) ₂ , PhCH (OE
t) ₂ .

Compound when M is Silicon Si (OMe) ₄ , Si contained in the formula Si (OR) ₄
(OEt) ₄ , Si (OBu) ₄ , Si (Oi-Bu)
₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (O
Ph) ₄ : HSi (OE contained in the formula XSi (OR) ₃
t) ₃ , HSi (OBu) ₃ , HSi (OHe) ₃ , H
Si (OPh) ₃ ; MeSi (OMe) ₃ , MeSi
(OEt) ₃ , MeSi (OBu) ₃ , EtSi (OE
t) ₃ , PhSi (OEt) ₃ , EtSi (OP
h) ₃ ; ClSi (OMe) ₃ , ClSi (OE
t) ₃ , ClSi (OBu) ₃ , ClSi (OP
h) ₃ , BrSi (OEt) ₃ ; Formula X ₂ Si (OR) ₂
Included in Me ₂ Si (OMe) ₂ and Me ₂ Si (OE
t) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (OE
t) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ Si
H (OEt) ₂ ; MeBrSi (OEt) ₂ : X ₃ Si
Me ₃ SiOMe, Me ₃ SiOEt contained in OR,
Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ SiOE
t, Ph ₃ SiOEt.

Compound in which M is boron B (OEt) ₃ , B (OB contained in the formula B (OR) ₃
u) ₃ , B (OHe) ₃ , B (OPh) ₃ .

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

Compound in which M is phosphorus P (OMe) ₃ , P (OE) included in the formula P (OR) ₃
t) ₃ , P (OBu) ₃ , P (OHe) ₃ , P (OP
h) ₃ .

Further, the magnesium compound is a periodic table.
Complexes of Group II or Group IIIa metal (M) with organic compounds
Can also be used. The complex has the general formula MgR¹R²
・ N (MR³ _m). As the metal,
Minium, zinc, calcium, etc., R³Has 1 carbon
~ 12 alkyl groups, cycloalkyl groups, aryl
And an aralkyl group. In addition, m is the valence of the metal M
And n represents a number of 0.1 to 10. MR³ _mRepresented by
Specific examples of the compound include AlMe₃, AlEt ₃,
Ali-Bu₃, AlPh₃, ZnMe₂,, ZnEt
₂, ZnBu₂, ZnPh₂, CaEt₂, CaPh₂
Etc.

(2) Titanium Compound The titanium compound is a divalent, trivalent or tetravalent titanium compound, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium and dichlorotitanium. Examples thereof include rudiethoxy titanium, dichlorodibutoxy titanium, dichlorodiphenoxy titanium, chlorotriethoxy titanium, chlortributoxy titanium, tetrabutoxy titanium and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxy titanium, dichlorodibutoxy titanium, and dichlorodiphenoxy titanium are preferable, and titanium tetrachloride is particularly preferable.

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

Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid and other aliphatic monocarboxylic acids, and malonic acid. , Succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, tartaric acid and other aliphatic oxycarboxylic acids, cyclohexanemonocarboxylic acid, cyclohexenemonocarboxylic acid, cis-1,2- Cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,
Alicyclic carboxylic acids such as 2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, aromatic monocarboxylic acids such as p-tertiary butyl benzoic acid, naphthoic acid and cinnamic acid, phthalic acid, isophthalic acid, Terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid,
Examples thereof include aromatic polycarboxylic acids such as mellitic acid. As the carboxylic acid anhydride, acid anhydrides of the above carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above-mentioned carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, pivalic acid. Isobutyl, 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, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, p
-Ethyl tertiary butyl benzoate, ethyl p-anisate,
Ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di2-ethylhexyl phthalate, phthalic acid Diallyl, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromelliticate, tetraethyl pyromelliticate, tetrabutyl pyromelliticate. Etc.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used,
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, pivalic 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, cinnamic acid chloride,
Examples thereof include cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. Also, a monoalkyl halide of a dicarboxylic acid such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride, phthalic acid butyl chloride may be used.

Alcohols are represented by the general formula ROH. In the formula, R is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl. 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.

The ethers are 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,
Examples include diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole and ethyl phenyl ether.

The component A is prepared by contacting a magnesium compound (component 1), a titanium compound (component 2) and an electron donating compound (component 3) in that order. After contacting component 1 and component 3, component 2 is contacted. A method such as contacting the components 1, 2 and 3 at the same time can be adopted. It is also possible to contact with the halogen-containing compound before contacting with component 2.

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

The halogenated hydrocarbon has 1 to 1 carbon atoms.
Twelve saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbon mono- and polyhalogen substitutes. Specific examples of those compounds include, in aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, and tetrachloride. Carbon iodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-
Dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methylchloroform, methylbromoform, methyliodoform, 1,1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,
2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane,
Chlorinated paraffins are chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene and hexachlorocyclohexane for alicyclic compounds, and chlorobenzene, bromobenzene, o- for aromatic compounds.
Examples thereof include dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride and p-chlorobenzotrichloride. These compounds may be used alone or in combination of two or more.

As the halogen-containing alcohol, any one or two or more hydrogen atoms other than the hydroxyl group in a mono- or polyhydric alcohol having one or two or more hydroxyl groups in one molecule are substituted with a halogen atom. Means a compound. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and chlorine atom is preferable. Examples of these compounds include 2-chloroethanol and 1-chloro-
2-propanol, 3-chloro-1-propanol, 1
-Chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6
-Chlor-1-hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-
Chlorbenzhydrol, (m, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro-
(M, o) -cresol, 6-chloro- (m, o) -cresol, 4-chloro-3,5-dimethylphenol,
Chlorhydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m, o, p)
-Chlorophenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6
-Chlorthymol, 4-chlorresorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol, 1-bromo-2-butanol,
2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (m, o, p)-
Bromphenol, 4-bromoresorcin, (m, o,
p) -fluorophenol, p-iodophenol: 2,
2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-
Chlor-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, 2,2,3,3-tetrafluoro-1-propanol, 2,3,5,6-tetra Examples thereof include fluorophenol and tetrafluororesorcin.

As the silicon halide compound having a hydrogen-silicon bond, HSiCl ₃ , H ₂ SiCl ₂ , H ₃ S may be used.
iCl, HCH ₃ SiCl ₂ , HC ₂ H ₅ SiCl ₂ ,
_{H (t-C 4 H 9} ) SiCl 2, HC 6 H 5 SiC
l ₂ , H (CH ₃ ) ₂ SiCl, H (i-C ₃ H ₇ ) S
_{iCl, H 2 C 2 H 5} SiCl, H 2 (n-C 4 H 9)
SiCl, H ₂ (C ₆ H ₄ CH ₃ ) SiCl, HSiC
1 (C ₆ H ₅ ) _{2 and the} like.

As the metal halide, B, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, As, Sb, B
Examples thereof include chlorides, fluorides, bromides and iodides of i, particularly BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ and AlBr.
₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , TlCl ₃ ,
SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF _{5 and the} like are preferable.

The contact with Component 1, Component 2 and Component 3, and further with a halogen-containing compound which can be optionally contacted is carried out by mixing and stirring in the presence or absence of an inert medium, but mechanically. It is made by co-milling. The contact can be performed under heating at 40 to 150 ° C.

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

A preferable method for preparing the component A in the present invention is described in JP-A-63-264607 and JP-A-58-19850.
No. 3, No. 62-146904 and the like. More specifically,

(A) Metallic magnesium, (b) halogenated hydrocarbon, and (c) a magnesium-containing compound obtained by contacting with a compound of the general formula X _n M (OR) _mn (the same as the above-mentioned alkoxy group-containing compound) Solid (D)
A method of contacting with a halogen-containing alcohol and then contacting with (e) an electron donating compound and (f) a titanium compound (JP-A-63-264607),

After contacting (a) magnesium dialkoxide with (b) a silicon halide compound having a hydrogen-silicon bond, (a) a titanium halide compound, and then (d) an electron donating compound. (A further contact with a titanium halide compound if necessary) (JP-A-62-146904),

(A) A method in which a magnesium dialkoxide and (b) a silicon halide compound having a hydrogen-silicon bond are brought into contact with each other, then (c) an electron donating compound is brought into contact, and then (d) a titanium compound is brought into contact therewith. (JP-A-58
-198503). Of these, the method (1) is most preferable. Although the component A is prepared as described above, the component A may be washed with the above-mentioned inert medium, if necessary, and further dried.

Organoaluminum compound An organoaluminum compound (hereinafter referred to as component B) is represented by the general formula R _n AlX _3-n (wherein R represents an alkyl group or an aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom, n is any number within the range of 1 ≦ n ≦ 3), and examples thereof include trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide, and Particularly preferred are alkylaluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as dialkylaluminum monohydride, or mixtures or complex compounds thereof. Specifically, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, and trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum io Dialkyl aluminum monohalides such as diid, diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, isobutyl aluminum dichloride, etc. monoalkyl aluminum dihalides, ethyl aluminum aluminum Alkyl aluminum sesquihalides such as sesquichloride, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, dialkyl aluminum monoalkoxides such as diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum Hydride, dipropyl aluminum hydride,
Dialkyl aluminum hydrides such as diisobutyl aluminum hydride can be mentioned. Among these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum are preferable.

Organosilicon Compound An organosilicon compound (hereinafter referred to as component C) which is brought into contact with a solid component (component A) in the presence of an organoaluminum compound (component B).
Say. ) Is represented by the above general formula.

In the formula, the alkylene group of R ¹ is --C _n
H _2n − (n = 1 to 10), preferably −
It is represented by (poly) methylene group, and an iso-propylene group - (CH _{2) n.} The arylene group represents a divalent aromatic hydrocarbon, preferably a phenylene group, a biphenylene group or a naphthylene group, more preferably a phenylene group.

Examples of the aliphatic hydrocarbon group R ⁴ in R ^2, R ³ and OR ^4, alkyl group, such as an alkenyl group, as the肪環hydrocarbon group, cycloalkyl group, cycloalkenyl group, Shikuroaruka Examples of the aromatic hydrocarbon group such as a dienyl group and the like include an aryl group and an aralkyl group.

As the alkyl group, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl, t-butyl, amyl, i-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, As the alkenyl group such as a decyl group, vinyl, allyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl,
1-octenyl, 1-decenyl, 1-methyl-1-pentynyl, 1-methyl-1-heptenyl, 1-methylethenyl, 1-ethylethenyl, 1-n-propylethenyl, 1-n-butylethenyl and the like are cycloalkyl. Examples of the group include cyclopentyl, cyclohexyl, and methylcyclohexyl groups, examples of the cycloalkenyl group include cyclopentenyl, cyclohexenyl, and methylcyclohexenyl groups, and examples of the cycloalkadienyl group include cyclopentadienyl and methylcyclopentadienyl. Examples of aryl groups include phenyl and indenyl groups, and phenyl, tolyl,
A xylyl group and the like are benzyl as an aralkyl group,
Examples include phenethyl and 3-phenylpropyl groups.

Specific examples of the component C will be listed below. In addition,
In the following, V is CH₂= CH, and Me is CH
₃(Methyl group), Et is C₂H_Five(Ethyl group), Pr is
(C ₃H₇(Propyl group), Bu is C_FourH₉(Butyl
Group), Pe is C_FiveH₁₁(Pentyl group), Hex is C₆H
₁₃(Hexyl group), Ph is C₆H_Five(Phenyl group), c
y represents cyclo, respectively. In the chemical formula below
[OC (= CH₂) Me] C (= CH₂) Me is 1-
Methylethenyl was replaced with [OC (= CH₂) Et] C (=
CH₂) Et represents 1-ethylethenyl, respectively.

(1) When x = 1, y = 0, z = 3 VC₂H_Four-Si (Oi-Pr)₃, V-C₂H_Four−
Si (On-Bu)₃, V-C₂H_Four-Si (Os-B
u)₃, V-C₂H_Four-Si (Ot-Bu)₃, V-C
₂H_Four-Si (On-Pe)₃, V-C₂H_Four-Si
(On-Hex) ₃, V-C₂H_Four-Si [OC (= C
H₂) Me]₃, V-C₂H_Four-Si [OC (= C
H₂) Et]₃, V-C₃H₆-Si (Oi-P
r)₃, V-C₃H₆-Si (On-Bu)₃, V-C
₃H₆-Si (Os-Bu)₃, V-C₃H₆-Si
(Ot-Bu)₃, V-C₃H₆-Si (On-Pe)
₃, V-C₃H₆-Si (On-Hex) ₃, V-C₃
H₆-Si [OC (= CH₂) Me]₃, V-C₃H₆
-Si [OC (= CH₂) Et]₃, V-C_FourH₈-S
i (Oi-Pr)₃, V-C_FourH₈-Si (On-B
u)₃, V-C_FourH₈-Si (Os-Bu)₃, V-C
_FourH₈-Si (Ot-Bu)₃, V-C_FourH₈-Si
(On-Pe)₃, V-C_FourH₈-Si (On-He
x) ₃, V-C_FourH₈-Si [OC (= CH₂) Me]
₃, V-C_FourH₈-Si [OC (= CH₂) Et]₃，
V-C_FiveH_Ten-Si (Oi-Pr)₃, V-C_FiveH_Ten−
Si (On-Bu)₃, V-C_FiveH_Ten-Si (Os-B
u)₃, V-C_FiveH_Ten-Si (Ot-Bu)₃, V-C
_FiveH_Ten-Si (On-Pe)₃, V-C_FiveH_Ten-Si
(On-Hex) ₃, V-C_FiveH_Ten-Si [OC (= C
H₂) Me]₃, V-C_FiveH_Ten-Si [OC (= C
H₂) Et]₃, V-C₆H₁₂-Si (Oi-P
r)₃, V-C₆H₁₂-Si (On-Bu)₃, V-C
₆H₁₂-Si (Os-Bu)₃, V-C₆H₁₂-Si
(Ot-Bu)₃, V-C₆H₁₂-Si (On-Pe)
₃, V-C₆H₁₂-Si (On-Hex) ₃, V-C₆
H₁₂-Si [OC (= CH₂) Me]₃, V-C₆H₁₂
-Si [OC (= CH₂) Et]₃, V-C₂H_Four-S
i (OPh)₃, V-C₂H_Four-Si (OcyHex)
₃, V-C_FourH₈-Si (OPh)₃, V-C_FourH₈−
Si (OcyHex)₃, V-C₆H₁₂-Si (OP
h)₃, V-C₆H₁₂-Si (OcyHex)₃, V-
C₆H_Four-Si (Oi-Pr)₃, V-C₆H_Four-Si
(Ot-Bu)₃.

(2) When x = 1, y = 1, z = 2 VC₂H_Four-Si (Me) (Oi-Pr)₂, V-C
₂H_Four-Si (Me) (Ot-Bu)₂, V-C₂H_Four
-Si (Et) (Oi-Pr)₂, V-C₂H _Four-Si
(N-Pr) (Ot-Bu)₂, V-C₂H_Four-Si
(Ot-Bu) (Oi-Pr)₂, V-C_FourH₈-Si
(Me) (Oi-Pr)₂, V-C_FourH₈-Si (E
t) (Ot-Bu)₂, V-C_FourH₈-Si (n-P
r) (Oi-Pr)₂, V-C_FourH₈-Si (i-P
r) (Ot-Bu)₂, V-C_FourH₈-Si (Ot-B
u) (Oi-Pr)₂, V-C₆H₁₂-Si (Me)
(Oi-Pr)₂, V-C₆H₁₂-Si (Me) (Ot
-Bu)₂, V-C₆H₁₂-Si (Ot-Bu) (Oi
-Pr)₂, V-C₆H₁₂-Si (Oi-Pr) (Ot
-Bu)₂, V-C₂H_Four-Si (Ph) (Oi-P
r)₂, V-C₂H_Four-Si (cyHex) (Oi-P
r)₂, V-C_FourH₈-Si (Ph) (Oi-P
r)₂, V-C_FourH₈-Si (cyHex) (Oi-P
r)₂, V-C₆H₁₂-Si (Ph) (Oi-P
r)₂, V-C₆H₁₂-Si (cyHex) (Oi-P
r)₂, V-C₆H_Four-Si (Me) (Oi-P
r)₂, V-C₆H_Four-Si (Me) (Ot-B
u)₂.

(3) When x = 2, y = 0, z = 2 (VC₂H_Four)₂Si (Oi-Pr)₂, (VC₂
H_Four)₂Si (On-Bu)₂, (VC₂H_Four)₂S
i (Os-Bu)₂, (VC₂H_Four)₂Si (Ot-
Bu)₂, (VC₂H_Four)₂Si (On-Pe)₂，
(VC₂H_Four)₂Si (On-Hex)₂, (VC
₂H_Four)₂Si [OC (= CH₂) Me]₂, (VC
₂H_Four)₂Si [OC (= CH₂) Et]₂, (VC
₃H₆)₂Si (Oi-Pr)₂, (VC₃H₆)₂
Si (On-Bu)₂, (VC₃H₆)₂Si (Os
-Bu)₂, (VC₃H₆)₂Si (Ot-B
u)₂, (VC₃H₆)₂Si (On-Pe)₂，
(VC₃H₆)₂Si (On-Hex)₂, (VC
₃H₆)₂Si [OC (= CH₂) Me]₂, (VC
₃H₆)₂Si [OC (= CH₂) Et]₂, (VC
_FourH₈)₂Si (Oi-Pr)₂, (VC_FourH₈)₂
Si (On-Bu)₂, (VC_FourH₈)₂Si (Os
-Bu)₂, (VC_FourH₈)₂Si (Ot-B
u)₂, (VC_FourH₈)₂Si (On-Pe)₂，
(VC_FourH₈)₂Si (On-Hex)₂, (VC
_FourH₈)₂Si [OC (= CH₂) Me]₂, (VC
_FourH₈)₂Si [OC (= CH₂) Et]₂, (VC
_FiveH_Ten)₂Si (Oi-Pr)₂, (VC_FiveH_Ten)₂
Si (On-Bu)₂, (VC_FiveH_Ten)₂Si (Os
-Bu)₂, (VC_FiveH_Ten)₂Si (Ot-B
u)₂, (VC_FiveH_Ten)₂Si (On-Pe)₂，
(VC_FiveH_Ten)₂Si (On-Hex)₂, (VC
_FiveH_Ten)₂Si [OC (= CH₂) Me]₂, (VC
_FiveH_Ten)₂Si [OC (= CH₂) Et]₂, (VC
₆H₁₂)₂Si (Oi-Pr)₂, (VC₆H₁₂)₂
Si (On-Bu)₂, (VC₆H₁₂)₂Si (Os
-Bu)₂, (VC₆H₁₂)₂Si (Ot-B
u)₂, (VC₆H₁₂)₂Si (On-Pe)₂，
(VC₆H₁₂)₂Si (On-Hex)₂, (VC
₆H₁₂)₂Si [OC (= CH₂) Me]₂, (VC
₆H₁₂)₂Si [OC (= CH₂) Et]₂, (VC
₆H₁₂) ₂Si (OPh)₂, (VC₆H₁₂)₂Si
(OcyHex)₂.

(4) When x = 2, y = 1, z = 1 (VC₆H₁₂)₂Si (Me) (Ot-Bu), (V
-C₆H₁₂)₂Si (Me) (On-Pe), (VC)
₆H₁₂)₂Si (Et) (On-Hex), (VC)₆
H₁₂)₂Si (Ot-Bu) (Oi-Pr), (VC)
₆H₁₂)₂Si (On-Hex) (Ot-Bu), (V
-C₆H₁₂)₂Si (Ph) (OPh) ₂, (VC₆
H₁₂)₂Si (cyHex) (OcyHex).

The contact between the prepolymerized solid component (component A) and the organosilicon compound (component C) is carried out in the presence of the organoaluminum compound (component B). The polymer of the component C is incorporated into the component A by this catalyst (hereinafter referred to as prepolymerization).

The prepolymerization is preferably carried out 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 + 50 ° C., more preferably −30 ° C.
It is carried out at a temperature of 5 ° C to + 30 ° C. The polymerization method may be a batch method or a continuous method, or may be a multi-step polymerization of two or more steps. When carrying out in multiple stages, it goes without saying that the polymerization conditions can be changed. Component B is used so that the concentration in the prepolymerization system is 50 to 500 mmol / liter, preferably 80 to 200 mmol / liter, and 4 to 50
It is used in an amount of 000 mol, preferably 6 to 1,000 mol.

The prepolymerization may be carried out in the presence of an electron donating compound. The electron-donating compound is appropriately selected from the above-mentioned compounds used when preparing the component A, and also includes an electron-donating compound composed of an organosilicon compound and a hetero atom such as nitrogen, sulfur, oxygen or phosphorus. An electron donating compound containing can also be used.

The organic silicon compound may be an organic silicon compound having a Si--O--C bond or a Si--N--C bond, and is preferably a compound having a Si--O--C bond. Such compounds include those represented by the general formula R _n Si
(OR ¹ ) _4-n [wherein R represents a hydrocarbon group or a halogen atom, R ¹ represents a hydrocarbon group, and 0 ≦ n ≦ 3 is shown. ] The compound represented by these is mentioned. Examples of the hydrocarbon group represented by R in the above general formula include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkadienyl group, a cycloalkenyl group and a cycloalkazinyl group. Examples of the halogen atom of R include chlorine, bromine, iodine and the like. Examples of the hydrocarbon group for R ¹ include an alkyl group, a cycloalkyl group, an aryl group and an alkenyl group. Furthermore, n hydrocarbons of R and (4-
n) The hydrocarbon groups of R ¹ of OR ¹ may be the same or different.

Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane, methyltrimethoxysilane and methyl. Triethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltriphenoxysilane, Isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexadiene Syloxysilane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane, Examples thereof include diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane, and chlorophenyldiethoxysilane.

Specific examples of the electron-donating compound containing a hetero atom include compounds containing a nitrogen atom:
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, Two
4-trimethylpiperidine, 2,5-dimethylpiperidine, methyl nicotinate, ethyl nicotinate, nicotinic acid amide, benzoic acid amide, 2-methylpyrrole, 2,5
-Dimethylpyrrole, imidazole, toluic acid amide, benzonitrile, acetonitrile, aniline, paratoluidine, orthotoluidine, metatoluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine, etc., as a compound containing a sulfur atom, thiol Phenol, thiophene,
Ethyl 2-thiophenecarboxylate, Ethyl 3-thiophenecarboxylate, 2-Methylthiophene, Methylmercaptan, Ethylmercaptan, Isopropylmercaptan, Butylmercaptan, Diethylthioether, Diphenylthioether, Methylbenzenesulfonate, Methylsulfite, Ethylsulfite Etc., as a compound containing an oxygen atom, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran,
2-methyltetrahydrofuran, 2,2,5,5-tetraethyltetrahydrofuran, 2,2,5,5-tetramethyltetrahydrofuran, 2,2,6,6-tetraethyltetrahydropyran, 2,2,6,6-tetrahydropyran , 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-butylphenyl ketone, 2- Ethyl fullerate, isoamyl 2-furate, methyl 2-furate, propyl 2-furate and the like are compounds containing a phosphorus atom, such as triphenylphosphine, tributylphosphine, triphenylphosphite and triben. Ruhosufaito, diethyl phosphate, and diphenyl phosphate and the like.

The electron-donating compound used as necessary is used so that the concentration in the prepolymerization system is 1 to 100 mmol / liter, preferably 5 to 50 mmol / liter.

The polymer of the component C incorporated in the component A by the prepolymerization is added in an amount of 0.05 to 500 g per 1 g of the component A,
In particular, it is desirable that the amount is 0.2 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, but from the viewpoint of preventing storage deterioration of the catalyst component,
It is particularly desirable to wash. After washing, it may be dried if necessary. When the catalyst component is stored, it is desirable to store it at a low temperature as much as possible, and a temperature range of -50 ° C to + 30 ° C, particularly -20 ° C to + 5 ° C is recommended.

Polymerization of α-Olefin The catalyst component of the present invention obtained as described above is used in combination with an organometallic compound and, if necessary, an electron donating compound, an α-olefin having 3 to 10 carbon atoms. Are useful as catalysts for the homopolymerization of 1 or of other mono-olefins or copolymers with other mono-olefins or di-olefins having 3 to 10 carbon atoms, in particular α-olefins having 3 to 6 carbon atoms, such as propylene, 1-butene, 4 -Methyl-1-pentene, homopolymerization of 1-hexene or the like or the above α-olefins and / or
Alternatively, it exhibits extremely excellent performance as a catalyst for random and block copolymerization with ethylene.

Organometallic compounds that can be used are organic compounds of metals of groups I to III of the periodic table. As the compound, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are 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), but trialkylaluminum, particularly triethylaluminum and triisobutylaluminum are preferable. Further, these trialkylaluminums are other organoaluminum compounds, for example, industrially readily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or complex compound thereof. Etc. can be used together.

Also, two or more via an oxygen atom or a nitrogen atom.
Organo-aluminum compound with aluminum
It can be used. Examples of such compounds include (C
₂H_Five)₂AlOAl (C₂H_Five)₂, (C_FourH₉)₂
AlOAl (C_FourH ₉)₂,

[Chemical 3] Etc. can be illustrated.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc and the like, and LiAl (C
Examples thereof include compounds such as ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

The electron donating compound which can be optionally combined with the catalyst component of the present invention and the organometallic compound is selected from electron donating compounds which may be used in the prepolymerization of the component A. It is selected appropriately. Two or more kinds of these electron donating compounds may be used. Further, these electron donating compounds may be used when an organometallic compound is used in combination with a catalyst component, or may be used after being brought into contact with the organometallic compound in advance.

The amount of the organometallic compound used with respect to the catalyst component of the present invention is, based on 1 gram atom of titanium in the catalyst component,
Usually 1 to 2,000 gram moles, especially 20 to 500 gram moles are desirable.

The ratio of the organometallic compound to the electron-donating compound is 0.1 to 40, preferably 1 to 40, preferably 1 to 10 moles of the electron-donating compound.
Selected in the range of 25 gram atoms.

The polymerization reaction of the α-olefin may be either a gas phase or a liquid phase. When the polymerization is carried out in the liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane,
It can be carried out in an inert hydrocarbon such as benzene, toluene, xylene and in a liquid monomer. The polymerization temperature is usually -80 ° C to + 150 ° C, preferably 40 to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atmospheres.
Further, the molecular weight of the obtained polymer is controlled by the presence of hydrogen or other known molecular weight regulator. The amount of the other olefin to be copolymerized with the α-olefin in the copolymerization is usually 3 with respect to the α-olefin.
It is selected up to 0% by weight, especially in the range 0.3 to 15% by weight. The polymerization reaction is carried out by a continuous or batch reaction, and the conditions therefor may be those usually used. Further, the copolymerization reaction may be carried out in one step or in two or more steps.

[0061]

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 flexural modulus in the polymer was measured according to JIS K 7203-1982. Example 1 Preparation of component A In a 1 liter reaction vessel equipped with a reflux condenser, under a nitrogen gas atmosphere, chip-shaped metallic magnesium (purity 99.5) was prepared.
%, Average particle size 1.6 mm) 8.3 g and n-hexane 25
After adding 0 ml and stirring at 68 ° C for 1 hour, metallic magnesium was taken out and dried under reduced pressure at 65 ° C to obtain preactivated metallic magnesium.

Next, 140 ml of n-butyl ether and 0.5 ml of an n-butyl ether solution of n-butyl magnesium chloride (1.75 mol / liter) were added to this metallic magnesium, and the suspension was kept at 55 ° C. n-
N-butyl chloride 38.5 in 50 ml of butyl ether
The solution in which ml was dissolved was added dropwise over 50 minutes. 70 ° C under stirring
After carrying out the reaction for 4 hours, the reaction solution was kept at 25 ° C.

Next, HC (OC ₂ H ₅ ) was added to this reaction solution.
The ₃ 55.7 ml was added dropwise over 1 hour. After the dropping, 60 ℃
The reaction product solid was washed 6 times with 300 ml each of n-hexane and dried under reduced pressure at room temperature for 1 hour to obtain a magnesium-containing solid containing magnesium 19.0% and chlorine 28.9% 31. 6 g was recovered.

A 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel was charged with 6.3 g of magnesium-containing solid and 50 ml of n-heptane under a nitrogen gas atmosphere to form a suspension, which was stirred at room temperature for 2,2. A mixed solution of 20 ml (0.02 mmol) of 2-trichloroethanol and 11 ml of n-heptane was added dropwise from a dropping funnel over 30 minutes,
Furthermore, it stirred at 80 degreeC for 1 hour. The solid obtained is filtered off,
The solid component was obtained by washing 4 times with 100 ml of n-hexane at room temperature and 2 times with 100 ml of toluene.

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

In a 500 ml reactor equipped with a prepolymerization stirrer, 2.3 g of the component A obtained above and n-heptane 1 were added under a nitrogen gas atmosphere.
80 ml was added and cooled to 0 ° C. with stirring. Next, n of triethylaluminum (hereinafter abbreviated as TEAL)
-Heptane solution (2.0 mol / l) was added so that the TEAL concentration in the final reaction system would be 100 mmol / l, and the mixture was stirred for 5 minutes. Then 100 ml of 1-hexenyltriisopropoxysilane was added and 4
Polymerized for hours. After completion of the polymerization, the solid phase portion was washed with 100 ml of n-hexane three times at room temperature. Further, the solid phase portion was dried under reduced pressure at room temperature for 1 hour to prepare a catalyst component. As a result of measuring the amount of magnesium contained in the catalyst component, the amount of preliminary polymerization was 1.4 g per 1 g of component A.

Examples 2 to 6 In the prepolymerization of Example 1, 1-hexenyltriisopropoxysilane was replaced with an organosilicon compound shown in Table 1, and TEAL or TEAL was replaced with triisobutylaluminum (TIBAL). Were used at the concentrations shown in Table 1 and the prepolymerization conditions were changed as shown in Table 1 to polymerize Component C in the same manner as in Example 1 to prepare a catalyst component. In Examples 3 to 5, the electron-donating compounds shown in Table-1 were used at the concentrations shown in Table-1.

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

Comparative Examples 2 to 4 In the same manner as in Example 1, except that propylene or an organosilicon compound shown in Table 1 was used in place of 1-hexenyltriisopropoxysilane in the prepolymerization of Example 1. A catalyst component was prepared.

[Table 1]

Application Example 1 4 ml of a TEAL n-heptane solution (0.1 mol / l) and n-diphenyldimethoxysilane were added to a 1.5 liter stainless steel autoclave equipped with a propylene polymerization stirrer under a nitrogen gas atmosphere. 2 ml of a heptane solution (0.04 mol / l) was mixed and held for 5 minutes. Then, 1 liter of hydrogen gas as a molecular weight control agent and 1 liter of liquid propylene were injected under pressure, and then the reaction system was heated to 70 ° C. After 40 mg of the catalyst component obtained in Example 1 was charged into the reaction system, propylene was polymerized for 1 hour. After completion of the polymerization, unreacted propylene was purged to obtain white polypropylene powder. Ingredient A (1 g) · Polypropylene production amount (CE) per hour was 21.3 kg. The flexural modulus of the obtained polymer is 13,600 kgf / cm.
^{Was 2} .

Application Examples 2 to 10 Instead of the catalyst components obtained in Example 1, the catalyst components obtained in Examples 2 to 6 and Comparative Examples 1 to 4 were used, and diphenyldimethoxysilane was used instead of the catalyst. Polymerization of propylene was carried out in the same manner as in Application Example 1 except that the electron-donating compound shown in 2 was used. The results are shown in Table-2.

[Table 2] Table-2 Application example Catalyst component Electron donating compound CE Bending elastic modulus (kg / g · component A) (kgf / cm ² ) 1 Example 1 Ph ₂ Si (OMe) ₂ 21.3 13,600 2 〃 2 〃 19.5 13,800 3 〃 3 〃 18.6 14,100 4 〃 4 〃 25.2 14,600 5 〃 5 PhSi (OEt) ₃ 20.7 14,300 6 〃 6 6 〃 22.1 13,400 7 Comparative example 1 Ph ₂ Si (OMe) ₂ 25.6 11,300 8 Si 〃 2 Ph ₃ 18.9 11,900 9 〃 3 〃 10.7 11,700 10 〃 4 Ph ₂ Si (OMe) ₂ 13.1 12,000

[0072]

EFFECTS OF THE INVENTION According to the present invention, by adopting the above constitution, the obtained catalyst component can be used for the polymerization of α-olefin to produce a highly rigid polymer in a high yield, and the organosilicon Since the compound is pre-polymerized, the catalyst particles have high strength, and therefore, it is possible to prevent pulverization of the polymer.

[Brief description of drawings]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadanao Ohara 1-3-1, Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Co., Ltd.

Claims (1)

[Claims] 1. A solid component comprising (A) magnesium, titanium, a halogen and an electron donating compound as essential components,
(B) In the presence of the organoaluminum compound, (C) the general formula: [However, R ¹ is an alkylene group or arylene group having 1 to 10 carbon atoms, R ² is an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 10 carbon atoms or R ⁴ O and R ³ are carbon atoms. An aliphatic, alicyclic or aromatic hydrocarbon group having 3 to 10 carbon atoms, R ⁴ is an aliphatic, alicyclic or aromatic hydrocarbon group having 3 to 10 carbon atoms which is the same as or different from R ³ . x is 1 or 2, y is 0 or 1, and z is 4-xy. ] Α formed by contacting with an organosilicon compound represented by
-Olefin polymerization catalyst component.