JPH07149812A - Polymerization catalyst for alpha-olefin - Google Patents

Abstract

PURPOSE:To prepare a catalyst which is composed of a specific solid catalyst component, an organometallic compound, an organosilicon compound and a carbonyl compound and is useful for producing alpha-olefin polymer having high stereoregularity and excellent physical properties in a high yield. CONSTITUTION:The catalyst comprises (A) a solid catalyst component containing essentially Mg, Ti halogen and an electron-donating compound, (B) an organometallic compound (preferably organo-aluminum compound, particularly triethylaluminum, tri-i-butyl-aluminum, (C) an organosilicon compound having Si-O-C bonds, and (D) a carbonyl compound, preferably carboxylic ester or ketone. In the catalyst, the amount of component B is 1 to 2,000 gram moles per Ti gram atom in the component A and components C and D are 0.001 to 10 moles per mole of component B, respectively.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, a catalyst comprising (i) a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound as essential components, (ii) an organometallic compound catalyst component and (iii) an electron donating compound catalyst component. A number of methods have been proposed for the polymerization of α-olefins. In particular, (ii
i) Regarding the electron-donating compound catalyst component, carboxylic acid ester, sterically hindered amine, organosilicon compound, etc. have been proposed, and it is said that a polymer having high polymerization activity and high stereoregularity can be obtained (special characteristics Kai 63-6980
4, JP-A-58-138707, JP-A-4
-227707 gazette etc.). However, although the α-olefin polymer obtained by the conventional method shows high stereoregularity as such, it is still insufficient depending on the purpose of use, and further improvement has been desired.

[0003]

SUMMARY OF THE INVENTION Under the circumstances, the present invention provides an α-olefin polymer such as propylene with further high stereoregularity, and is capable of producing it in a high yield. The purpose is to provide a catalyst.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that (i) magnesium, titanium, halogen and electron donating properties as a catalyst for the polymerization of α-olefins such as propylene. A solid catalyst component containing a compound as an essential component, (ii) an organometallic compound catalyst component, and (iii)
By using both an organosilicon compound having a Si—O—C bond and a compound having a carbonyl group as the electron-donating compound, an α-olefin polymer such as polypropylene having extremely high stereoregularity can be produced in high yield. And
The present invention has been completed by finding that the object of the present invention can be achieved.

SUMMARY OF THE INVENTION That is, the gist of the present invention is (A) a solid catalyst component containing magnesium, titanium, a halogen and an electron-donating compound as essential components, (B) an organometallic compound, and (C) Si-O-C. The catalyst for α-olefin polymerization comprises an organosilicon compound having a bond and (D) a compound having a carbonyl group.

Solid Catalyst Component The solid catalyst component (hereinafter referred to as component A), which is one component of the catalyst of the present invention, contains magnesium, titanium, halogen and an electron donating compound as essential components. Usually, a magnesium compound, a titanium compound, and an electron-donating compound, and in the case where each of the above compounds does not have a halogen, a halogen-containing compound is prepared by bringing them into contact with each other.

(1) Magnesium Compound The magnesium compound is represented by the general formula MgR ¹ R ² . In the formula, R ¹ and R ² represent the same or different hydrocarbon groups, OR ³ groups (R ³ 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 ³ group is R ³ having a carbon number. Examples of the halogen atom include 1 to 12 alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups, and examples of the halogen atom include chlorine, bromine, iodine and fluorine.

Specific examples of these compounds are shown below. In the chemical 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 (cyHe), methylcyclohexyl and other cycloalkyl groups, allyl, propenyl, butenyl, etc. Alkenyl group, phenyl (Ph), aryl group such as tolyl and xylyl group, aralkyl group such as phenethyl and 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.

Compounds where M is carbon C (OR)_FourIncluded in C (OMe)_Four, C (OE
t)_Four, C (OPr) _Four, C (OBu)_Four, C (Oi-
Bu)_Four, C (OHe)_Four, C (OOct)_Four: Formula X
C (OR)₃HC (OMe) contained in₃, HC (OE
t)₃, HC (OPr)_3,HC (OBu)₃, HC
(OHe)₃, HC (OPh)₃MeC (OM
e)₃, MeC (OEt)₃, EtC (OMe)₃ , E
tC (OEt)₃, CyHeC (OEt)₃, PhC
(OMe)₃, PhC (OEt)₃, CH₂ClC (O
Et)₃, MeCHBrC (OEt)₃, MeCHCl
C (OEt) ₃; ClC (OMe)₃, ClC (OE
t)₃, ClC (Oi-Bu)₃, BrC (OE
t)₃Formula X₂C (OR)₂Included in MeCH (O
Me)₂, MeCH (OEt)₂, CH₂(OM
e)₂, CH₂(OEt)₂, CH₂ClCH (OE
t)₂, CHCl₂CH (OEt)₂, CCl₃CH
(OEt)₂, CH ₂BrCH (OEt)₂, PhCH
(OEt)₂.

Compound in which 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 (O contained in the formula XSi (OR) ₃
Et) ₃ , HSi (OBu) ₃ , HSi (OHe) ₃ ,
HSi (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 contained in Me ₂ Si (OMe) ₂ and Me ₂ Si (O
Et) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (O
Et) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ S
iH (OEt) ₂ ; MeBuSi (OEt) ₂ : X ₃ S
Me ₃ SiOMe, Me ₃ SiOE contained in iOR
t, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ Si
OEt, 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 .

Compounds where M is phosphorus P (OR)₃Included in P (OMe)₃, P (OE
t)₃, P (OBu) ₃, P (OHe)₃, P (OP
h)₃.

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

(3) Titanium Compound The titanium compound is a compound of divalent, trivalent and tetravalent titanium. 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.

(4) 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 and carbonic acid esters. 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, adipic acid monomethyl chloride,
Monoalkyl halides of dicarboxylic acids such as maleic acid monoethyl chloride, maleic acid monomethyl chloride, phthalic acid butyl chloride may also be used.

Alcohols are represented by the general formula R ⁴ OH. In the formula, R ⁴ is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol,
Examples include isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol. The ethers are represented by the general formula R ⁵ OR ⁶ . In the formula R ⁵ ,
R ⁶ is alkyl, alkenyl, cycloalkyl, aryl or aralkyl having 1 to 12 carbons, and R ⁵ and R
⁶ can be the same or different. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether,
Di-2-ethylhexyl ether, diallyl ether,
Examples include 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 IIIa and 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 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-chloro- (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
-Chlor-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 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) -bromophenol, 4-
Bromresorcin, (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-tribrom-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-tetrafluorophenol, tetrafluororesorcin and the like can be mentioned.

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 SiCl
_{2, H (CH 3) 2} SiCl, H (i-C 3 H 7) 2 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 , TlC
l ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF ₅
Etc. are suitable.

The contact with Component 1, Component 2 and Component 3, and optionally 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, or by mechanical stirring. 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, and 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, it is obtained by bringing (a) metallic magnesium, (b) a halogenated hydrocarbon, and (c) a compound of the general formula X _n M (OR) _mn (the same as the above-mentioned alkoxy group-containing compound) into contact with each other. A method in which a magnesium-containing solid is brought into contact with (d) a halogen-containing alcohol and then (e) an electron-donating compound and (f) a titanium compound (JP-A-63-63).
-264607), (a) magnesium dialkoxide and (b) hydrogen-
After contacting a silicon halide compound having a silicon bond, (c) a titanium halide compound is contacted, and then (d) an electron-donating compound (if necessary, further contacted with a titanium halide compound). (JP-A-62-146904), (a) magnesium dialkoxide and (b) hydrogen-
After contacting with a silicon halide compound having a silicon bond, (c) contact with an electron donating compound, and then (d)
Method of contacting with titanium compound (JP-A-58-1985)
No. 03). 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.

Further, the component A may further contain an olefin polymer produced in the component A by contacting with an olefin in the presence of the organoaluminum compound. The organoaluminum compound is selected from the organometallic compounds described below, which are one component of the catalyst of the present invention.

As the olefin, α-olefins such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene can be used in addition to ethylene. The contact with the olefin is preferably carried out in the presence of the above-mentioned inert medium. Contact is usually 100 ° C or lower, preferably -10 to +
It is carried out at a temperature of 50 ° C. The amount of the olefin polymer contained in the component A is usually 0.1 to 10 per 1 g of the component A.
It is 0 g.

For the contact between the component A and the olefin, an electron donating compound may be present together with the organoaluminum compound. The electron-donating compound is a compound used in preparing the component A and a Si—O—C bond or Si—N—
It is selected from organic silicon compounds having a C bond and the like, and preferably S which is one component of the catalyst of the present invention described later.
Organosilicon compound having i-O-C bond (component (C))
Alternatively, it is a compound having a carbonyl group (component (D)). Two or more kinds of these electron donating compounds can be used. The component A contacted with the olefin can be washed with the above-mentioned inert medium, if necessary, and can be further dried.

Organometallic compounds Organometallic compounds (hereinafter referred to as component B) are represented by I in the periodic table.
Organic compounds of Group III to Group III metals. As component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly preferable. Organoaluminum compounds that can be used include those represented by the general formula R ⁷ _{n ′} A
lX ¹ _{3-n ′} (wherein R ⁷ is an alkyl group or an aryl group,
X ¹ represents a halogen atom, an alkoxy group or a hydrogen atom, and n ^′ is an arbitrary number within the range of 1 ≦ n ^′ ≦ 3. ), For example, a trialkylaluminum, a dialkylaluminum monohalide, a monoalkylaluminum dihalide, an alkylaluminum sesquihalide, a dialkylaluminum monoalkoxide and a dialkylaluminum monohydride, and the like, preferably 1 to 18 carbon atoms Particularly preferred are alkylaluminum compounds of the number 2 to 6 or mixtures or complex compounds thereof. Specifically, such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, diisobutyl aluminum chloride, etc. Alkyl aluminum sesquihalides such as dialkyl aluminum monohalide, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, isobutyl aluminum dichloride, etc., and alkyl aluminum sesquichloride. , Dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, dialkylaluminum mono alkoxides 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.
Further, these trialkylaluminums are other organic aluminum compounds, for example, industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or complex compound thereof. Etc. can be used together. Further, an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can also be used. Examples of such compounds include

[Chemical 1] Etc. can be illustrated.

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 .

Organosilicon Compound The organosilicon compound, which is one component of the catalyst of the present invention (hereinafter referred to as component C), has the general formula R ⁸ _{n "} i (OR ⁹ ) _4-n" [where 0≤n ^“ ≦ 3, R ⁸ is a hydrocarbon group, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a haloalkenyl group, an aminoalkenyl group, or halogen, and R ⁹ is a hydrocarbon group, for example, an alkyl group, cyclo Examples thereof include an alkyl group, an aryl group, an alkenyl group and an alkoxyalkenyl group, and n "R
R ⁸ and (4-n ") pieces of OR ⁹ groups R ⁹ is represented by may be the same or different.]. More preferably the general formula _{^{(R 10 O) X R 11}} y Si (OR 12 ) Z [In the formula, R ¹⁰ is preferably an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group having 3 to 10 carbon atoms or an aromatic hydrocarbon group, and particularly preferably an alkyl group. As for the group, a branched alkyl group often shows good results, and R ¹¹ has 1 to 1 carbon atoms.
They are 10 aliphatic, alicyclic hydrocarbon groups or aromatic hydrocarbon groups. The hydrocarbon group is preferably an alicyclic hydrocarbon group such as a cycloalkyl group, a cycloalkenyl group and a cycloalkadienyl group. R ¹² is preferably a methyl group or an ethyl group. In the formula, x + y + z
= 4 and 0≤x≤2, 1≤y≤2, 1≤z≤3.
R ¹⁰ x number of R ¹⁰ O group, y-number of R ^11, R ¹² in the z-number of OR ¹² groups may be the same or different. ] Is the case.

Specific examples of the component C are listed below. In addition,
In the following, Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Amy = amyl, Hex = hexyl Oct = octyl, Dec = decyl, CyPe = cyclopentyl, CyHe = cyclohexyl, CyPy =
Cyclopentenyl, CyPt = cyclopentadienyl,
CyHy represents a cyclohexenyl group, respectively. In addition,
The following specific examples are only for the case where R ¹² is a methyl group in the above general formula, and are omitted when R ¹² is an ethyl group. Compounds in which some or all of the methyl groups of R ^{12 in} these specific examples are replaced with ethyl groups can also be mentioned as specific examples.

Compound of (R ¹⁰ O) R ¹¹ Si (OR ¹² ) ₂ (i-PrO) MeSi (OMe) ₂ , (i-PrO)
n-PrSi (OMe) ₂ , (n-PrO) t-Amy
Si (OMe) ₂ , (i-PrO) n-HexSi (O
Me) ₂ , (n-BuO) MeSi (OMe) ₂ , (t
-BuO) MeSi (OMe) ₂ , (s-BuO) Et
Si (OMe) ₂ , (i-BuO) i-PrSi (OM
e) ₂ , (t-BuO) t-BuSi (OMe) ₂ ,
(N-BuO) s-BuSi (OMe) ₂ , (t-Bu
O) n-AmySi (OMe) ₂ , (t-BuO) t-
Amy (SiCOMe) ₂ , (n-AmyO) i-Pr
Si (OMe) ₂ , (t-AmyO) t-BuSi (O
Me) ₂ , (t-AmyO) t-AmySi (OMe)
₂ , (t-AmyO) MeSi (OMe) ₂ , (n-A)
myO) EtSi (OMe) ₂ , (n-HexO) Me
Si (OMe) ₂ , (n-HexO) EtSi (OM
e) ₂ , (n-HexO) i-PrSi (OMe) ₂ ,
(N-HexO) t-BuSi (OMe) ₂ , (n-H
exO) n-HexSi (OMe) ₂ , (n-Hex
O) n-OctSi (OMe) ₂ , (n-OctO) M
eSi (OMe) ₂ , (n-OctO) n-OctSi
(OMe) ₂ , (i-PrO) CyPeSi (OMe)
₂ , (n-PrO) CyPeSi (OMe) ₂ , (n-
BuO) CyPeSi (OMe) ₂ , (i-BuO) C
yPeSi (OMe) ₂ , (s-BuO) CyPeSi
(OMe) ₂ , (t-BuO) CyPeSi (OMe)
₂ , (n-AmyO) CyPeSi (OMe) ₂ , (t
-AmyO) CyPeSi (OMe) ₂ , (n-Hex)
O) CyPeSi (OMe) ₂ , (n-OctO) Cy
PeSi (OMe) ₂ , (i-PrO) CyHeSi
(OMe) ₂ , (n-PrO) CyHeSi (OMe)
₂ , (n-BuO) CyHeSi (OMe) ₂ , (i-
BuO) CyHeSi (OMe) ₂ , (s-BuO) C
yHeSi (OMe) ₂ , (t-BuO) CyHeSi
(OMe) ₂ , (n-AmyO) CyHeSi (OM
e) ₂ , (t-AmyO) CyHeSi (OMe) ₂ ,
(N-HexO) CyHeSi (OMe) ₂ , (n-O)
ctO) CyHeSi (OMe) ₂ , (n-PrO) C
yPySi (OMe) ₂ , (i-PrO) CyPySi
(OMe) ₂ , (n-BuO) CyPySi (OMe)
₂ , (i-BuO) CyPySi (OMe) ₂ , (s-
BuO) CyPySi (OMe) ₂ , (t-BuO) C
yPySi (OMe) ₂ , (n-AmyO) CyPyS
i (OMe) ₂ , (t-AmyO) CyPySi (OM
e) ₂ , (n-HexO) CyPySi (OMe) ₂ ,
(N-OctO) CyPySi (OMe) ₂ , (n-P
rO) CyPtSi (OMe) ₂ , (i-PrO) Cy
PtSi (OMe) ₂ , (n-BuO) CyPtSi
(OMe) ₂ , (i-BuO) CyPtSi (OMe)
₂ , (s-BuO) CyPtSi (OMe) ₂ , (t-
BuO) CyPtSi (OMe) ₂ , (n-AmyO)
CyPtSi (OMe) ₂ , (t-AmyO) CyPt
Si (OMe) ₂ , (n-HexO) CyPtSi (O
Me) ₂ , (n-OctO) CyPtSi (OM
e) ₂ , (n-PrO) CyHySi (OMe) ₂ ,
(I-PrO) CyHySi (OMe) ₂ , (n-Bu)
O) CyHySi (OMe) ₂ , (i-PrO) CyH
ySi (OMe) ₂ , (s-BuO) CyHySi (O
Me) ₂ , (t-BuO) CyHySi (OMe) ₂ ,
(N-AmyO) CyHySi (OMe) ₂ , (t-A
myO) CyHySi (OMe) ₂ , (n-HexO)
CyHySi (OMe) ₂ , (n-OctO) CyHy
Si (OMe) ₂ , (CyPeO) MeSi (OMe)
₂ , (CyPeO) EtSi (OMe) ₂ , (CyPe
O) n-PrSi (OMe) ₂ , (CyPeO) i-P
rSi (OMe) ₂ , (CyPeO) n-BuSi (O
Me) ₂ , (CyPeO) i-BuSi (OMe) ₂ ,
(CyPeO) s-BuSi (OMe) ₂ , (CyPe
O) t-BuSi (OMe) ₂ , (CyPeO) n-A
mySi (OMe) ₂ , (CyPeO) t-AmySi
(OMe) ₂ , (CyPeO) n-HexSi (OM
e) ₂ , (CyPeO) n-OctSi (OMe) ₂ ,
(CyHeO) MeSi (OMe) ₂ , (CyHeO)
EtSi (OMe) ₂ , (CyHeO) n-PrSi
(OMe) ₂ , (CyHeO) i-PrSi (OMe)
₂ , (CyHeO) n-BuSi (OMe) ₂ , (Cy
HeO) i-BuSi (OMe) ₂ , (CyHeO) s
-BuSi (OMe) ₂ , (CyHeO) t-BuSi
(OMe) ₂ , (CyHeO) n-AmySi (OM
e) ₂ , (CyHeO) t-AmySi (OMe) ₂ ,
(CyHeO) n-HexSi (OMe) ₂ , (CyH
eO) n-OctSi (OMe) ₂ , (CyPyO) M
eSi (OMe) ₂ , (CyPyO) EtSi (OM
e) ₂ , (CyPyO) n-PrSi (OMe) ₂ ,
(CyPyO) i-PrSi (OMe) ₂ , (CyPy
O) n-BuSi (OMe) ₂ , (CyPyO) i-B
uSi (OMe) ₂ , (CyPyO) s-BuSi (O
Me) ₂ , (CyPyO) t-BuSi (OMe) ₂ ,
(CyPyO) n-AmySi (OMe) ₂ , (CyP
yO) t-AmySi (OMe) ₂ , (CyPyO) n
-HexSi (OMe) ₂ , (CyPyO) n-Oct
Si (OMe) ₂ , (CyPtO) MeSi (OMe)
₂ , (CyPtO) EtSi (OMe) ₂ , (CyPt)
O) n-PrSi (OMe) ₂ , (CyPtO) i-P
rSi (OMe) ₂ , (CyPtO) n-BuSi (O
Me) ₂ , (CyPtO) i-BuSi (OMe) ₂ ,
(CyPtO) s-BuSi (OMe) ₂ , (CyPt)
O) t-BuSi (OMe) ₂ , (CyPtO) n-A
mySi (OMe) ₂ , (CyPtO) t-AmySi
(OMe) ₂ , (CyPtO) n-HexSi (OM
e) ₂ , (CyPtO) n-OctSi (OMe) ₂ ,
(CyHyO) MeSi (OMe) ₂ , (CyHyO)
EtSi (OMe) ₂ , (CyHyO) n-PrSi
(OMe) ₂ , (CyHyO) i-PrSi (OMe)
₂ , (CyHyO) n-BuSi (OMe) ₂ , (Cy
HyO) i-BuSi (OMe) ₂ , (CyHyO) s
-BuSi (OMe) ₂ , (CyHyO) t-BuSi
(OMe) ₂ , (CyHyO) n-AmySi (OM
e) ₂ , (CyHyO) t-AmySi (OMe) ₂ ,
(CyHyO) n-HexSi (OMe) ₂ , (CyH
yO) n-OctSi (OMe) ₂ , (CyPeO) C
yPeSi (OMe) ₂ , (CyPeO) CyHeSi
(OMe) ₂ , (CyPeO) CyPySi (OMe)
₂ , (CyPeO) CyPtSi (OMe) ₂ , (Cy
PeO) CyHySi (OMe) ₂ , (CyHeO) C
yPeSi (OMe) ₂ , (CyHeO) CyHeSi
(OMe) ₂ , (CyHeO) CyPySi (OMe)
₂ , (CyHeO) CyPtSi (OMe) ₂ , (Cy
HeO) CyHySi (OMe) ₂ , (CyPyO) C
yPeSi (OMe) ₂ , (CyPyO) CyHeSi
(OMe) ₂ , (CyPyO) CyPySi (OMe)
₂ , (CyPyO) CyPtSi (OMe) ₂ , (Cy
PyO) CyHySi (OMe) ₂ , (CyPtO) C
yPeSi (OMe) ₂ , (CyPtO) CyHeSi
(OMe) ₂ , (CyPtO) CyPySi (OMe)
₂ , (CyPtO) CyPtSi (OMe) ₂ , (Cy
PtO) CyHySi (OMe) ₂ , (CyHyO) C
yPeSi (OMe) ₂ , (CyHyO) CyHeSi
(OMe) ₂ , (CyHyO) CyPySi (OMe)
₂ , (CyHyO) CyPtSi (OMe) ₂ , (Cy
HyO) CyHySi (OMe) ₂ .

○ R¹¹Si (OR¹²)₃Compound of n-PrSi (OMe)₃, I-PrSi (OM
e)₃, T-BuSi (OMe)₃, S-BuSi (O
Me)₃, N-BuSi (OMe)₃, T-AmySi
(OMe)₃, CyPeSi (OMe)₃, CyHeS
i (OMe)₃, N-AmySi (OMe)₃, CyP
ySi (OMe)₃, CyPtSi (OMe) ₃, Cy
HySi (OMe)₃, N-HexSi (OMe)₃，
n-OctSi (OMe)₃, N-DecSi (OM
e)₃.

Compound of R ¹¹ ₂ Si (OR ¹² ) ₂ n-Pr ₂ Si (OMe) ₂ , i-Pr ₂ Si (OM
e) _2, t-Bu ₂ Si (OMe) ₂ , s-Bu ₂ Si
(OMe) ₂ , n-Bu ₂ Si (OMe) ₂ , t-Am
y ₂ Si (OMe) ₂ , CyPe ₂ Si (OMe) ₂ ,
CyHe ₂ Si (OMe) ₂ , n-Amy ₂ Si (OM
e) ₂ , CyPy ₂ Si (OMe) ₂ , CyPt ₂ Si
(OMe) ₂ , CyHy ₂ Si (OMe) ₂ , n-He
x ₂ Si (OMe) ₂ , n-Oct ₂ Si (OM
e) ₂ , n-Dec ₂ Si (OMe) ₂ , Me (t-B)
u) Si (OMe) ₂ , Me (t-Amy) Si (OM
e) ₂ , Me (CyPe) Si (OMe) ₂ , Me (C
yHe) Si (OMe) ₂ , Me (i-Pr) Si (O
Me) ₂ , Et (t-Bu) Si (OMe) ₂ , Et
(T-Amy) Si (OMe) ₂ , Et (CyPe) S
i (OMe) ₂ , Et (CyHe) Si (OMe) ₂ ,
Et (i-Pr) Si (OMe) ₂ .

○ (R^TenO)₂R¹¹Si (OR¹²) Compound
Thing (i-PrO)₂i-PrSi (OMe), (i-Pr
O)₂t-BuSi (OMe), (i-PrO)₂s-
BuSi (OMe), (i-PrO)₂t-AmySi
(OMe), (i-PrO)₂CyPeSi (OM
e), (i-PrO)₂CyHeSi (OMe), (n
-PrO)₂i-PrSi (OMe), (n-PrO)
₂t-BuSi (OMe), (n-PrO)₂s-Bu
Si (OMe), (n-PrO)₂t-AmySi (O
Me), (n-PrO)₂CyPeSi (OMe),
(N-PrO)₂CyHeSi (OMe), (n-Bu
O)₂i-PrSi (OMe), (n-BuO)₂t-
BuSi (OMe), (n-BuO)₂s-BuSi
(OMe), (n-BuO)₂t-AmySi (OM
e), (n-BuO)₂CyPeSi (OMe), (n
-BuO)₂s-BuSi (OMe). Out of these
(R^TenO) R¹¹Si (OMe)₂, (R^TenO) R¹¹Si
(OEt) ₂Compounds represented by are particularly preferable.

Compound Having Carbonyl Group As the compound having a carbonyl group (hereinafter referred to as component D) which is one component of the catalyst of the present invention, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halogens, etc. Compounds, ketones, aldehydes, carboxylic acid amides (R ¹³ —CO—NR ¹⁴ R ¹⁵ ) and the like. Of these, carboxylic acid esters and ketones are particularly preferably used. These compounds may be the same as or different from the electron-donating compound used when preparing the component A.

Specific examples of the carboxylic acid ester include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, isobutyl pivalate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and isobutyl methacrylate. Diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, diisobutyl adipate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, maleic acid Diisobutyl, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate Ethyl benzoate, methyl p-triylate, ethyl p-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, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, naphthalic acid Examples thereof include diethyl, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitic acid, tetraethyl pyromellitic acid, and tetrabutyl pyromellitic acid.

Specific examples of the ketone include acetone,
Diethyl ketone, i-propyl methyl ketone, cyclohexanone, methylbenzyl ketone, ethylbenzyl ketone, diphenyl ketone, dibenzyl ketone, dicyclohexyl ketone, di i-butyl ketone, di n-butyl ketone, di t-butyl ketone, di t-amyl ketone, etc. Can be mentioned.

The catalyst of the present invention comprises a component A, a component B and a component C.
And component D, the composition ratio of component B is 1 to 2,000 gram moles per gram atom of titanium in component A, preferably 20 to 500 gram moles, and component C and component D relative to 1 mole of component B. 0.001 to 1 each
It is used in an amount of 0 mol, preferably 0.01 to 1.0 mol.

Polymerization of α-Olefin The catalyst of the present invention is a homopolymerization of α-olefin having 3 to 10 carbon atoms or another monoolefin or 3 to 10 carbon atoms.
Useful as a catalyst for the copolymerization with diolefins, especially α-olefins having 3 to 6 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene,
It exhibits extremely excellent performance as a catalyst for homopolymerization of 1-hexene or the like or for random and block copolymerization with the above α-olefins and / or ethylene.

The polymerization reaction may be carried out in 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, benzene, toluene, xylene, etc. It can be carried out in inert hydrocarbons and in liquid monomers. The polymerization temperature is usually -80 ° C to +1.
It is in the range of 50 ° 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. Further, the amount of the other olefin to be copolymerized with the α-olefin in the copolymerization is usually selected in the range of up to 30% by weight, particularly 0.3 to 15% by weight based on the α-olefin. The polymerization reaction by the catalyst system according to the present invention is carried out in a continuous or batch reaction,
The conditions may be those usually used. Further, the copolymerization reaction may be carried out in one step or in two or more steps.

The preferred embodiments of the present invention will be summarized below. (1) The α-olefin polymerization catalyst according to claim 1, wherein the solid catalyst component is prepared by bringing a magnesium compound, a titanium compound and an electron donating compound into contact with each other. (2) The catalyst for α-olefin polymerization as described in (1) above, wherein when each of the compounds is a compound containing no halogen, a halogen-containing compound is further present and contacted. (3) The catalyst for α-olefin polymerization as described in (1) or (2) above, wherein the magnesium compound is represented by the general formula MgR ¹ R ² (R ¹ and R ² are as defined above). (4) The magnesium compound is prepared by contacting metallic magnesium, a halogenated hydrocarbon and an alkoxy group-containing compound of the general formula XnM (OR) _mn (X, M, R, m and n have the same meanings as described above). The catalyst for α-olefin polymerization according to the above (1) or (2). (5) The magnesium compound has the general formula MgR ¹ R ² · n
(R ¹ , R ² , M ′, represented by (M′R ³ m)
R ³ , n, m are as defined above) (1) or (2)
The catalyst for α-olefin polymerization described in 1.

(6) The electron-donating compound is a carboxylic acid, a carboxylic acid anhydride, a carboxylic acid ester, a carboxylic acid halide, an alcohol, an ether, a ketone, an amine, an amide, a nitrile, or an aldehyde. Any of one or all selected from the group consisting of compounds, alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group through carbon or oxygen, phosphoamides, thioethers, thioesters and carbonic acid esters. The catalyst for α-olefin polymerization according to any one of (1) to (5) above. (7) After contacting each of the components with a magnesium compound (component 1), a titanium compound (component 2) and an electron donating compound (component 3) in that order, or after contacting components 1 and 3 The α-olefin according to the above (1), (3), (4), (5) or (6), which is carried out by contacting the component 1, component 2 or component 1, component 2 and component 3 simultaneously. Polymerization catalyst. (8) The catalyst for α-olefin polymerization according to the above (2), which is brought into contact with a halogen-containing compound before being brought into contact with a titanium compound. (9) The halogen-containing compound is a halogenated hydrocarbon, a halogen-containing alcohol, a silicon halide compound having a hydrogen-silicon bond, and Group IIIa, IVa, or Va of the periodic table.
The catalyst for α-olefin polymerization according to any one of (1) to (8) above, which is any one kind or all kinds selected from the group consisting of halides of group elements. (10) The organometallic compound is represented by the general formula R ⁷ _{n ′} AlX ¹ _{3-n ′} (R ⁷ , X ¹ , n ′ has the same meaning as above) (1)
The catalyst for α-olefin polymerization according to any one of to (9).

(11) The organosilicon compound has the general formula R ⁸ _{n "} S
i (OR ⁹ ) _{4-n "} (R ⁸ , R ⁹ and n" have the same meanings as defined above) α- according to any one of (1) to (10) above
Olefin polymerization catalyst. (12) The organosilicon compound has the general formula (R ¹⁰ O) xR ¹¹ yS.
i (OR ¹² ) z (R ¹⁰ , R ¹¹ , R ¹² , x,
y and z have the same meaning as above) The catalyst for α-olefin polymerization according to any one of (1) to (11) above. (13) The compound having a carbonyl group is one or all selected from the group consisting of carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, ketones, aldehydes and carboxylic acid amides. The α-olefin polymerization catalyst according to any one of (1) to (12) above. (14) Component A, component B, component C and component D are component B
1 to 2,000 per 1 gram atom of titanium in component A
The catalyst for α-olefin polymerization according to claim 1, wherein gram mol, component C and component D are mixed in an amount of 0.001 to 10 mol with respect to 1 mol of component B, respectively.

[0052] specifically described by examples and comparative examples Example invention. The percentages (%) in the examples are by weight unless otherwise specified. The heptane-insoluble content (hereinafter abbreviated as HI), which represents the proportion of the crystalline polymer in the polymer, is the remaining amount when extracted with boiling n-heptane in a modified Soxhlet extractor for 6 hours. The physical properties of the polymer were measured by adding BHT (2,6-di-tertiarybutyl-4) to the polymer powder.
-Methylphenol) 0.18% by weight, DSTDP
(Distearyl thiodipropionate) 0.08% by weight, IRGANOX 1010 [tetrakis- {methylene- (3,5-di-sha-butyl-4-hydroxyhydro-cinnamate) methane}] 0.04% by weight, Calcium stearate was added in an amount of 0.06% by weight, melted and kneaded into pellets, and then test pieces were prepared by injection molding. Flexural modulus: JIS K 7
According to 203-1982. Also, the polymer MFR is AS
It was measured according to TM D-1238.

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%, average particle size 1.6 mm) 8.3 g and n-hexane 2
After adding 50 ml and stirring at 68 ° C. for 1 hour, metallic magnesium was taken out and dried under reduced pressure at 65 ° C. to obtain pre-activated 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 / l) were added to this metallic magnesium at 55 ° C.
A solution of 38.5 ml of n-butyl chloride dissolved in 50 ml of n-butyl ether was added dropwise over 50 minutes. After reacting at 70 ° C. for 4 hours with stirring, the reaction solution was mixed with 2
Hold at 5 ° C. Then, HC (OC ₂ H
₅ ) 35.7 ml of _{3 was} added dropwise over 1 hour. After the dropping is completed,
The reaction was carried out at 60 ° C. for 15 minutes, the reaction product solid was washed 6 times with 300 ml of n-hexane each and dried under reduced pressure at room temperature for 1 hour to obtain a magnesium-containing solid containing 19.0% magnesium and 28.9% chlorine. 31.6 g was recovered. In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, magnesium-containing solid 6.3 in a nitrogen gas atmosphere.
g and n-heptane (50 ml) were added to form a suspension, and 2,2,2-trichloroethanol (20 ml) was stirred at room temperature.
A mixed solution of (0.02 mmol) and 11 ml of n-heptane was added dropwise from the dropping funnel over 30 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The obtained solid was filtered, washed with 100 ml of n-hexane at room temperature 4 times each, and further washed with 100 ml of toluene twice each to obtain a solid component. 40 ml of toluene was added to the above solid component, titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. With stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, and then 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 solid material obtained was filtered off at 110 ° C. and 100 at room temperature.
It was washed 7 times with ml of n-hexane to obtain 5.5 g of component A.

Component A obtained above was placed in a 1.5-liter stainless steel autoclave equipped with a propylene polymerization stirrer under a nitrogen gas atmosphere.
9.5 mg, 4 ml of a solution containing 0.4 mol of triethylaluminum (hereinafter TEAL) in 1 l of n-heptane and 0.08 mol of t-butoxy t-butyldimethoxysilane in 1 l of n-heptane. And 0.0
1 ml of a solution containing 2 mol of ethyl benzoate was mixed and held for 5 minutes. Then, 600 ml of hydrogen gas as a molecular weight controlling agent and 1 liter of liquid propylene were injected under pressure, and then the reaction system was heated to 70 ° C. to polymerize propylene for 1 hour. After completion of the polymerization, unreacted propylene was purged to obtain white polypropylene with HI 98.3% MFR 1.7. The polymerization activity was 29.4 kg / g-component A · hr. The flexural modulus of this polypropylene molding was 15200 kg / cm ² .

Examples 2 to 4 Instead of t-butoxy t-butyldimethoxysilane,
Polymerization of propylene was carried out in the same manner as in Example 1 except that the organosilicon compound (component C) and the compound having a carbonyl group (component D) shown in Table 1 were used, and the results are shown in Table 1.

Comparative Examples 1 to 4 Polymerization of propylene was carried out in the same manner as in Examples 1 to 4 except that the compound having a carbonyl group (component D) was not used, and the results are shown in Table 1.

[0057]

[Table 1]

Example 5 Preparation of component A 170 g of commercially available magnesium diethoxide were added with a diameter of 12 mm.
Of stainless steel (SUS316) with an internal volume of 1.2 liters (SUS31
6) Put in a mill pot made of nitrogen gas under a nitrogen gas atmosphere, and after mounting the mill pot on a shaker, the amplitude is 10 mm and the rotation speed is 1
Contact was performed by shaking at 420 rpm for 2 hours to obtain a pulverized product (I). A 200 ml glass reactor equipped with a reflux condenser, dropping funnel and stirrer is thoroughly replaced with nitrogen gas. After putting 8.3 g of pulverized product (I) and 42 ml of n-heptane into this reactor, a mixed solution of 14.9 g of trichlorosilane and 30 ml of n-heptane was added dropwise from a dropping funnel over 30 minutes while stirring at room temperature. Furthermore, at 65 ℃ 4
Stir for hours. The solid obtained was filtered off at 65 ° C., 100 ml of n-heptane at room temperature twice each, and 100 ml of toluene at room temperature.
After washing by contacting three times with stirring for 10 minutes, a toluene slurry of reaction solid (I) was obtained. Reaction solid (I)
51 ml of TiCl ₄ was added to a toluene slurry composed of 8.5 g and 26 ml of toluene, the internal temperature was raised to 80 ° C. over 20 minutes, and after the temperature was raised, 1.7 g of di-n-butyl phthalate and 8 ml of toluene. The mixed solution consisting of was added dropwise for 15 minutes using a dropping funnel. Then 115 more
The temperature was raised to ° C and the mixture was stirred at the same temperature for 2 hours. After removing the supernatant liquid by decantation, 100 ml of toluene was stirred at a temperature of 90 ° C. for 10 minutes and washed twice. Next, 21 ml of new toluene and 51 ml of TiCl ₄ were added, and the mixture was stirred at 115 ° C. for 2 hours. The obtained solid substance was filtered off at 115 ° C. and washed with 100 ml of room temperature n-heptane 8 times to obtain a heptane slurry of component A.

Polymerization of Propylene Example 1 except that the component A obtained above, the organosilicon compound shown in Table 2, the compound having a carbonyl group and the organoaluminum compound were used and the polymerization temperature was 80 ° C.
Polymerization of propylene was carried out in the same manner as in, and the results are shown in Table 2.
It was shown to.

Example 6 Propylene was polymerized in the same manner as in Example 5 except that the organosilicon compound and the compound having a carbonyl group shown in Table 2 were used, and the results are shown in Table 2.

Polymerization of propylene was carried out in the same manner as in Example 5 except that the compounds shown in Comparative Example 5 and Table 2 were used, and the results are shown in Table 2.

[0062]

[Table 2]

[0063]

The catalyst for α-olefin polymerization capable of producing an α-olefin polymer such as polypropylene having high stereoregularity and excellent physical properties in a high yield is provided.

[Brief description of drawings]

FIG. 1 is a flow chart showing the steps for preparing a catalyst of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasushi Nomura Nishitsurugaoka 1-3-1, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Corporation Research Institute (72) Masahide Murata Nishitsurugaoka, Oi-cho, Saitama-ken 3-3-1 Tonen Co., Ltd. Research Institute (72) Inventor Satoshi Ueki 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Research Institute

Claims (1)

[Claims] 1. A solid catalyst component comprising (A) magnesium, titanium, a halogen and an electron donating compound as essential components,
A catalyst for α-olefin polymerization comprising (B) an organometallic compound, (C) an organosilicon compound having a Si—O—C bond, and (D) a compound having a carbonyl group.