JPH0472305A - Catalyst for polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain the subject catalyst for polymerization giving a polymer having high stereoregularity in high yield comprising a solid catalyst component containing magnesium, titanium, halogen and an electron-donating compound as essential components, an organometallic compound and a specific organosilicon compound. CONSTITUTION:A monomer of alpha-olefin is polymerized by using a catalyst composed of (A) a solid catalyst component containing magnesium, titanium, halogen and an electron-donating compound (e.g. n-butyl ether) as essential components, (B) an organometallic compound (e.g. triethylaluminum) and (C) an organosilicon compound (e.g. 1,1-dimethoxy-1,2,2,2-tetramethyldisilane) expressed by the formula [R<1> is 1-10C hydrocarbon or R<7>3Si (R<7> is same species as R<1>); R<2> is 1-10C hydrocarbon or R<8>O (R<8> is same species as R<1>); R<3> is 1-10C hydrocarbon or R<9>O (R<9> is same species as R<1>); R<4> and R<5> are 1-10C hydrocarbon; R<6> is 1-10C hydrocarbon or R<10>O (R<10> is same species as R<1>), etc.].

Description

[Detailed description of the invention] Industrial applications The present invention relates to a catalyst for α-olefin polymerization.

Prior Art When producing polyα-olefins using catalyst components containing magnesium, titanium, chlorine and electron-donating compounds, they contain 5i-0-C bonds together with organoaluminum compounds, or the general formula % formula % organic It is known that the use of silicon compounds improves the stereoregularity of the resulting polymer (for example,
No. 1-94690, No. 5636203, No. 5'l-6
No. 3310, No. 58-83016, No. 62-1170
5 etc.).

However, contrary to the improvement in stereoregularity, the polymerization activity may decrease by half or more when no organosilicon compound is used, and the relationship between the improvement in stereoregularity and the decrease in polymerization activity is Depends on the type of compound.

Problems to be Solved by the Invention An object of the present invention is to provide a polymerization catalyst that maintains high stereoregularity and exhibits high polymerization activity in the polymerization of α-olefins.

Means for Solving the Problems The inventors of the present invention have conducted intensive research on catalyst components containing magnesium, titanium, halogens, and electron-donating compounds, and organosilicon compounds to be combined with organoaluminum compounds, and have found that 5i- The present invention was completed by discovering that the object of the present invention can be achieved by using a specific organosilicon compound having 3i and 5i-0-C bonds.

Summary of the invention That is, the summary of the present invention is as follows. is a hydrocarbon group having 1 to 10 carbon atoms or R:Si, R' is a hydrocarbon group having 1 to 10 carbon atoms or R80, R3 is a hydrocarbon group having 1 to 10 carbon atoms or R90, R' and R5 is the same or different carbon number 1-10
R6 is a hydrocarbon group having 1 to 10 carbon atoms, 0R10 or Si[+, and R7 to R1+ are the same or different hydrocarbon groups having 1 to 10 carbon atoms. ] An α-olefin polymerization catalyst comprising an organosilicon compound represented by the following.

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, and such components usually include a magnesium compound, It is prepared by contacting a titanium compound, an electron-donating compound, and a halogen-containing compound when each of the above compounds does not have a halogen.

(],) Magnesium Compound A magnesium compound is represented by the general formula Mg11'R2. In the formula, R1 and R2 represent the same or different hydrocarbon group, OR group (R is a hydrocarbon group), or a halogen atom. More specifically, the hydrocarbon groups of R1 and R2 are:
An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group; However, examples of halogen atoms include chlorine, bromine, iodine, and fluorine.

Specific examples of these compounds are shown below. In the chemical formula, Me = methyl, Bt: ethyl, Pr propyl, B
U Nibutyl, He: Hexyl, Oct: Octyl, P
h: phenyl and cyHe dichlorohexyl, respectively.

MgMe2. MgEtz, Mg1-Pr, ,
MgBu, , MgHe2゜Mg0ct2. MgE
tBu, MgPha, MgcyHez.

Mg(OMe)z, Mg(OBt)z, Mg(
DBu)z, Mg(OHe)z.

Mg(ODct)2, Mg([1Ph)z, Mg
(OcyHe)z.

εtMgc], BuMgC], H
eMgCl, i-BuMg[:l,
tBuMgCl, PhMg[l:I,
PhCtlJgC], HtMgBrBuJB
r, PhMgBr, BuMgl,
BtOMgCI.

BuOMgCI, He0MgCl, P
h0MgCl, Et[]MgBrBuOMg
Br, EtOMgl, MgClz
, MgBrz, Mg12.

The above magnesium compound can also be prepared from metallic magnesium or other magnesium compounds when preparing component Δ.

Examples thereof include magunium metal, halogenated hydrocarbons, and alkoxy group-containing compounds of the general formula Hydrocarbon group, M is boron, carbon, aluminum, silicon or phosphorus atom, R has 1 to 2 carbon atoms
0 hydrocarbon groups, m represents the valence of M, and m>n≧O. ] is mentioned. The hydrocarbon groups represented by X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Bt), propyl (P
r), ]-propyl (1-Pr), butyl (Bu),
Alkyl groups such as i-butyl (i-Bu), hexyl (He), octyl (Oct), cyclohexyl (cy
He), cycloalkyl groups such as methylcyclohexyl, noalkenyl groups such as allyl, propenyl, butenyl, aryl groups such as phenyl (Ph), )lyl and xylyl groups,
Examples include aralkyl such as phenethyl and 3-phenylpropyl.

Among these, alkyl groups having 1 to 10 carbon atoms are particularly desirable. Specific examples of alkoxy group-containing compounds are listed below.

When 0M is carbon, C(OMe) contained in the compound formula C(OR) = , C
(Oat) 4.

C(OPr)1. C(OBu), , C(Oi-B
u)-, C(OHe)4゜C(00ct)4' Formula
XC(OR), included in) Ic (OMe) 3°HC(Oat)3. HC(OPr)*, HC(O
Bu)3. HC(OHe)3°f(C(OPh)3;
MeC(OMe)3. MeC(OBt)s, B
tC(OMe>+.

Btc(OBt)3. cyHeC(OEtt)3.
PhC(OMe)s.

PhC(OEtt)s, CH2C]C(OEt)a
, MeCHBrC(OBt)3゜MeCHCIC(
OBt)s; CIC(OMe), , CIC(O
Et)a.

CIC(Oi-Bu)+, BrC(OEtt)s
;MeCH(OMe)2 contained in formula X2C(OR),
．． MeCH(OBt)2. CL(OMe)2゜CL
(OEtt)z , CH, CICH(OBt)i
,C)IcLcH(0εt)2゜CC1,C)I(OB
t)2, CHJrCH(OBt)z, PhCII(O
Bt)2.

S+ (OMe) contained in compound formula S+ (OR) 4 when 0M is silicon
4, S+ (OBt),.

5i(OBu)4.5i(Oi-Bu), , 5i(
OHe) 4゜5i (00ct) < , 5i (OPh)
,: Formula X5i(OR)-2 containing 1(Si(OB
t)3. 1(Si(OBu)+ , H81(OH
e)+.

)ISi(OPh)s;MeSi(OMe)+,
MeSi(0εt)3゜MeSi(OBu)+,
E! tsi(OBt)3. Ph5i(OEt)+.

EtSi(OPh)3; CISiCl5i(O, Cl
5i(OBt)3°Cl5i(OBu)3. Cl5i
(OPh)3. Br5i(OBt)*; Formula % Formula %) B(OEt) s contained in the compound 2B (OR) when 0M is boron,
B(OBu) 3゜口(OHe)s, B(OPh)
*.

AI(OMe)s contained in the compound formula ^1 (OR) 3 when 0M is aluminum,
AI (OBt)3゜A1 (OPr) s, ^]
(Oi-Pr)s, AI(OBu)+.

AI(Ot Bu)s, AI(0)1e)s, A
I (OPh)s.

P(OMe) 3 contained in the compound 2P (OR> s when 0M is phosphorus,
P(OBt) 3゜P(OBu)*, P(OHe)
s, P(OPh)s.

Further, as the magnesium compound, a complex with an organic compound of a metal (M) of Group 1 or Group Ma of the periodic table can also be used. The complex has the general formula MgR'R'.n (MR'
, ). Examples of the metal include aluminum, zinc, calcium, etc., and R3 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 a number from 0.1 to 10. A specific example of a compound represented by MR' is ^
IMe, , AI [! t3. A11-Bu+ , ^l
Ph3゜ZnMez, ZnBt2. ZnBuz
, ZnPh2. CaBtz.

Examples include CaPh2.

(2) Titanium compounds Titanium compounds are divalent, trivalent, and tetravalent titanium compounds, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, and dichlorjetoxytitanium. , dichlordibutoxytitanium, dichlordiphenoxytitanium, chlortriethoxytitanium, chlortributoxytitanium, tetrabutoxytitanium, titanium trichloride, and the like. Among these, tetravalent titanium halides such as titanium tetrachloride, trichlorethoxytitanium, dichlorodibutoxytitanium, and dichlordiphenoxytitanium are preferred, and titanium tetrachloride is particularly preferred.

(3) Electron-donating compounds Examples of electron-donating compounds include carboxylic acids, carboxylic anhydrides, carboxylic esters, carbonic acid halides, alcohols, ethers, ketones, amines, amides, and nitriles. , aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to organic groups via carbon or acid S, phosphoamides, thioethers, thioesters, carbonate esters and the like. Among these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carbonic acid halides, alcohols, and ethers are preferably used.

Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, and crotonic acid, malonic acid, and succinic acid. , aliphatic dicarboxylic acids such as glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid, cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid ,
Alicyclic carboxylic acids such as cis-4-methylcyclo-can-1,2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, p-tert-butylbenzoic acid, naphthoic acid, cinnamic acid, etc. Examples include aromatic polycarboxylic acids such as aromatic monocarboxylic acids, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellidic acid, hemimellitic acid, trimesic acid, pyronoIJ) acid, and mellitic acid.

As the carboxylic acid anhydride, acid anhydrides of the above-mentioned 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, isobutyl pivalate, acrylic. Ethyl acid, 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-)rulyate, ethyl p-tert-butylbenzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, phthalic acid Monomethyl, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, di-sulfur phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, terephthalic acid Examples include diethyl, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, tetrabutyl pyromellitate, and the like.

As the carboxylic acid halide, acid halides of the above-mentioned carboxylic acids can be used, and specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, acetic acid chloride, butyric acid bromide, acetic acid iodide, and pivalin. Acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide,
Acrylic acid iodide, methacrylic acid chloride, methacrylic acid iodide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid promide,
Succinic acid chloride, succinic acid bromide, glutaric acid chloride, glutaric acid bromide, adipic acid chloride, adipic acid bromide, sebacic acid chloride, sebacic acid chloride, maleic acid chloride, maleic acid chloride, fumaric acid chloride, fumaric acid bromide, tartaric acid chloride , tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid chloride, 1-cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, benzoyl chloride, benzoyl bromide, p- Toluic acid chloride, p-toluic acid bromide,
p-Anisyl chloride, p-anisyl bromide, α-naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, naphthalic acid Dichloride is mentioned.

Monoalkyl halides of dicarboxylic acids such as monomethyl adipate chloride, monoethyl maleate chloride, monomethyl maleate, and butyl phthalate chloride may also be used.

Alcohols are represented by the general formula ROH.

In the formula, R is alkyl, alkenyl, cycloalkyl, aryl, or aralkyl having 1 to 12 carbon atoms.

Specific examples include methanol, ethanol, propatool, isoproptool, butanol, isobutanol, pentanol, hexanol, octatool, 2-
These include ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol, and the like. Ethers have the general formula ROR
' In the formula, R and R' have 1 to 12 carbon atoms.
alkyl, alkenyl, cycloalkyl, aryl, and aralkyl, and R and R1 may be the same or different. Specific examples include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethylphenyl ether, and the like.

The preparation method for the components is as follows: ■ Magnesium compound (component 1), titanium compound (component 2), and electron-donating compound (component 2).
Component 3) is contacted in that order. (2) Component 1 and Component 3 are brought into contact with each other, and then Component 2 is brought into contact with each other. ■Ingredients 1. Ingredient 2
A method such as bringing Component 3 and Component 3 into contact at the same time can be adopted.

It is also possible to contact with a halogen-containing compound before contacting with component 2.

Examples of halogen-containing compounds include halogenated hydrocarbons, halogen-containing alcohols, halogenated silicon compounds having a hydrogen-silicon bond, halides of Group 11a, IVa, and Va elements of the periodic table (hereinafter referred to as metal halides), and the like. can be mentioned.

Examples of halogenated hydrocarbons include mono- and polyhalogen-substituted saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. Specific examples of these compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, Carbon iodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-short ethane,
Methyl chloroform, methyl bromoform, methyl iodoform, 1,1,2-trichloroethylene, 1.1.
2-) Libromoethylene, 1,1,22-tetrachloroethylene, pentachloroethane, hexachloroethane,
Hexabromoethane, n-propyl chloride, 1.2
- dichloroethane, hexachloropropylene, octachloropropane, decabromobutane, chlorinated paraffins; alicyclic compounds such as chlorochloropropane, tetrachloroethylenetane, hexachloroclopentadiene, hexachlorocyclohexane; aromatic compounds such as chlorobenzene, bromobutane; Benzene, 0-dichloropentene, p
Examples include dichlorobenzene 1, hexachlorobenzene, hexabromobenzene, pencitrichloride, p-chloropencitrichloride, and the like. These compounds are
Not only one type but also two or more types may be used.

A halogen-containing alcohol refers to a compound in which one or more hydrogen atoms other than the hydroxyl group in a mono- or polyhydric alcohol having one or more hydroxyl groups in the molecule are substituted with a halogen atom. do. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine atoms, with chlorine atoms being preferred.

Examples of these compounds include 2-chloroethanol, ■
-chloro-2-propertool, 3-chloro-1-propertool, 1-chloro-2-methyl-2-propertool,
4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 3-chloro-1.
2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m, o, p)-
Chlorbenzyl alcohol, 4-chlorcatechol, 4
-chloro-(m,o)-cresol, 6-chloro-(m
, o)-cresyl, 4-chloro-3,5-dimethylphenol, chlorohydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m,
o, p) -Chlorphenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorthymol, 4-chlorresorcin,
2-bromoethanol, 3-bromo-1-propatol, 1-bromo-2-7' lovanol, 1-bromo-2-butanol, 2-bromo-p-cresol, 1-bromo-2
゛-naphthol, 6-bromo-2-naphthol, (m, o
, p)-bromophenol, 4-bromoresorcin, (
m, o, p) Fluorophenol, p-iodophenol 22-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3
-chloro-1-(α-chloromethyl)-1-propatur, 2,3-dibromo1-propatur, 1,3-dibromo-2propatur, 2,4-dibromophenol,
2.4-dibromo-1-naphthol: 2.2゜2-trichloroethanol, 1,1.1-trichloro-2-propatol, β, β, β-trichloro-tert-butanol, 2,3.4-) Dichlorophenol, 2,4.5
-) Dichlorophenol, 2,4.6-trichlorophenol, 2.4.6-tribromophenol, 2,3°5-) U-bromo-2-hydroxytoluene, 23.
5-) U-bromo-4-hydroxytoluene, 2.2.2
-) Rifluoroethanol, α,αα-trifluoro-m-cresol, 2,4°6-doliodophenol:
2.3,4.6=tetrachlorophenol, tetrachlorohydroquinone, tetrachlorbisphenol A1 tetrabromobisphenol A, 2,2,3.3tetrafluoro-1-propatol, 2.3゜5.6-thitra Examples include fluorophenol and tetrafluororesorcinol.

Examples of the halogenated silicon compound having a hydrogen-silicon bond include HSiCl3. H2SiCl2. LSiCl
.

11cH3slc12, HC2H5SICI2,
8 (t-Cntls) SIC12°H mouth. H2SiCl
2, H(CLLSiCI, H(i-C3
L) 2sicl.

H20JsSiC], L(n-c4L)sic
l, L(CaH-CL)SiC1,1lsic
l(Cslls)z, etc.

Examples of metal halides include B, AI, Ga, and In.

TI, Si, Ge, Sn, Pb, As,
Examples include chlorides, fluorides, bromides, and iodides of Sb and Bi, especially BC+3. BBr3. B+3, ^
l[:L, AlBr3°Ga[, l+, GaB
r3.1ncL, TI[:13, 3ick<.

SnC], Sb[:Is, 5bFs, etc. are suitable.

Ingredient 1. Components 2 and 3, and the halogen-containing compound that can be brought into contact as necessary, are brought into contact by mixing and stirring in the presence or absence of an inert medium, and by mechanical co-pulverization. Ru. 40-150 contacts
It can be carried out under heating at ℃.

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 preferred method for preparing component A in the present invention is disclosed in Japanese Patent Application Laid-open No. 63
-264607, 58-198503, 62-
This method is disclosed in Japanese Patent No. 146904 and the like. More specifically, ■ (a) metallic magnesium, (b) halogenated hydrocarbon, (c) general formula X, , M (OR) *
The magnesium-containing solid obtained by contacting -r+ compound (same as the alkoxy group-containing compound) is (d) brought into contact with a halogen-containing alcohol, and then (v) an electron-donating compound and (h) a titanium compound. Contact method (Japanese Unexamined Patent Publication No. 63-264607), ■ (a) Magnesium dialkoxide and (b) hydrogen.
After contacting a halogenated silicon compound having a silicon bond, (c) contacting a halogenated titanium compound, and then (
d) A method of contacting with an electron-donating compound (further contacting with a halogenated titanium compound if necessary) (Unexamined Japanese Patent Publication No. 6
2-146904), ■ (a) Magnesium dialkoxide and (b) hydrogen-
After contacting a halogenated silicon compound having a silicon bond, (c) contacting with an electron-donating compound, and then (:) contacting with a titanium compound (JP-A-58-19850
Publication No. 3).

Among these, method (2) is particularly desirable.

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

In addition, component A further comprises, in the presence of an organoaluminum compound,
Olefin polymers formed in component A upon contact with olefins may also be included. The organoaluminum compound is selected from the organometallic compounds described below that are one of the components of the catalyst of the present invention.

Examples of olefins include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, etc.
-Olefins may be used.

Contact with the olefin is preferably carried out in the presence of the inert medium described above. The contact is usually carried out at a temperature of 100°C or less, preferably -10°C to +50°C. The amount of olefin polymer contained in component A is usually 0 per gram of component A.
．． It is 1-100g.

Contacting the olefin with the component may include the presence of an electron donating compound along with the organoaluminum compound. The electron-donating compound is selected from among the compounds used in preparing the components. Component A that has been in contact with the olefin can be washed with the above-mentioned inert medium, if necessary, or further dried.

Organometallic compoundsOrganometallic compounds (hereinafter referred to as component B) are found in the first part of the periodic table.
It is an organic compound of a group metal to a group II metal. As component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly suitable. As the organoaluminum compound that can be used, the general formula R, A]X3
, (wherein, R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group, or a hydrogen atom, and n is an arbitrary number in the range of 1≦n≦3), for example. Trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum civalide, alkylaluminum sesquino\ride,
Particularly preferred are alkyl aluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as dialkyl aluminum monoalkoxides and dialkyl aluminum monohydrides, or mixtures or complexes thereof. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride, etc. dialkylaluminum monohalides, methylaluminum dichloride, ethylaluminum cyclolide, methylaluminum dibromide, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum dichloride, monoalkylaluminum cybarides, alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, etc. halide, dialkyl aluminum monoalkoxides such as dimethyl aluminum methoxide, diethylaluminum ethoxide, diethylaluminium phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, Dialkyl aluminum hydrides such as diisobutyl aluminum hydride are mentioned. Among these, trialkylaluminum is preferred, particularly triethylaluminum and triisobutylaluminum. In addition, these trialkylaluminums may be combined with other organoaluminum compounds such as industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminium hydride, or mixtures or complex compounds thereof. Can be used in combination with etc.

Furthermore, an organic aluminum compound in which two or more pieces of aluminum are bonded via an oxygen atom or a nitrogen atom can also be used. Such compounds include, for example (C2H5)
2AI[lA] (C, 115) 2 .

(C4119)2^10AI(C,R9)2, (
An example is C2115>2AINAI([:,R5)2Js.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc, etc., as well as LiAl([:zHs)n, LIA+(CJ, 5)
Examples include compounds such as , and the like.

The organic silicon compound (hereinafter referred to as component C), which is one component of the catalyst of the present invention, is represented by the above general formula. In the linear formula, the hydrocarbon group of R'-R'' is an alkyl group,
Examples include an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkagenyl group, an aryl group, and an aralkyl group.

Alkyl groups include methyl, ethyl, propyl, 1-
Propyl, butyl, 1-butyl, S-butyl, t-butyl, amyl, ]-amyl, hexyl, octyl, 2-ethylhexyl, decyl, etc., and alkenyl groups include vinyl, allyl, propenyl, etc. , 1-butenyl, 1-pentenyl, 1-hexenyl, ■-octenyl, 1-butenyl, 1-methyl-1-pentynyl, ■=methyl-1-hebutenyl, etc., cycloalkyl groups include cyclopentyl, cyclohexyl, Methylcyclohexyl group etc., cycloalkenyl group such as cyclopentenyl, cyclohexenyl, methylcyclohexenyl group etc., cycloalkagenyl group such as cyclopentagenyl, methylcyclopentadienyl, indenyl group etc. However, examples of the aryl group include phenyl, tolyl, and xylyl groups, and examples of the aralkyl group include benzyl, phenethyl, and 3-phenylpropyl groups. For R4 and R5, methyl and ethyl groups are particularly desirable.

Specific examples of component C will be listed below. Note that the general formula is expressed as R'/R2/R310R'/OR5/R'.

In addition, in the following, Me=methyl, Bt-ethyl, Pr
-Propyl, Bu-butyl, Any-amyl, Hey,
-Hexyl respectively.

■R', R' and R3 are hydrocarbon groups, and R6 is [l[
CR' if R2 and R3 are the same, R1 if R2 and R3 are the same
, when R and R2 are the same, R'2/R' and OR',
[lI[15 and 0R10 are the same, OR' and O
When R'' and []R5 are the same, they are displayed as (OR')210R10.]Me/OMe, Ma
/ Omit, Bt/DMe, Bt/ 01
Et, Mez/n-Pr/OMe, M
ez/n-Pr/OBt.

Mez/t-Bu/OMe, Mez/t-
Bu/OEt, Bt2/Me10Me,
Btz/Me10[Et SMe/ (OMe)alo
Bt.

Me/ (OMe) 2/ Di-Pr, Me/
(OMe) 2/ 0t-Bu, Me/(OB
t)alon-Hex, Et/(OMe)210
i-Pr.

MP! 2/ t-Bu/ (OMe)2/ 0t-Bu
, Bt2/ Me/ (OMe)zlon-He
x 0 ■R' is R:iS+, R2 and R3 are hydrocarbon groups and R
When 6 is 0R10, when CR2 and R3 are the same, R; Si/R: and OR'
When OR5 and OR'° are the same, when OR' and OR5 are the same, (OR'>210RIO is displayed respectively.)
Me*Si/ Me, /OMe, IJe+Si/
Me,/OEt.

Bt+Si/Met10Me, Et+Si/Mez
101Et, MesSi/8t2/OMe,
Me3S+/Etz/OBt, εt3st/B
ti10Me, Mi t3s+/ Btz/ OBt
, MesS+/Me/BtloMe, B
t3S+/Me/Bt/OBt, Me3Sl
/ Bt/1-Pr10Bt, BtsSi/Me/
t-BuloMe, Me3Si/ Me2/ (
OMe) 2/0t-Bu-, Me3Si/Me
2/ (OBt) 2/ 0n-Hex, Bt
sSi/ Mez/ (OMe)2/ Us-8my
.

Me3Si/ Me/ Bt/ (OMe) 2/ 0
t-Bu, EtsSi/Me/Et/(O
Et) 2/0n-)lex, BtsSi/
Me/1-Pr/(Oat)2/t-Bu,
Bt3Si/ Me/ t-Bu/ (OMe) 2
10s-Amy.

■When R+, R2 and R3 are hydrocarbon groups, and R6 is a hydrocarbon group [When R', R2 and R3 are the same, R1, R2 and R
When 2 are the same, it is displayed as R4/R'', and when OR' and OR5 are the same, it is displayed as (OR') 2/R6.]
Me/ (OMe) 2/ Me, Me/ (0
8t) 2/ Me, Me/(mouth Me) 2/ B
t, Me/ (Oat)2/ Bt, Me/
(OMe)2/ iPr, Me/ (0 巳t
)2/ 1-Pr, Me/ (OMe)2/
t-Bu.

Me/ (OEt) 2/ t-Bu, Me/
(OMe) 2/ n-Bu, Me/ (OBt
) 2/ n-Bu, Me/ (OMe) 2/
5-BLI, Me/(OBtL/5-Bu
, Et/ (OMe)2/ Me , Et/ (0
[Et)2/Me, Bt/(OMeL/1-Pr,
Et/(OEt)2/iPr, Me2/n-
Pr/(OMe)2/Me, Me2/n-P
r/(OEt) 2/Me, Mez/t-Bu
/ (OMe) 2/ Bt, Me2/1-Bu/
(OBt) 2/ Bt, M[! 2/ n-Bu
/ (OBt) 2/ Me.

Me2/ n-Bu/ (OEt) 2/ Me,
Me2/ n-Hex/ (OMEri 2/ Me,
Me2/ n-Hex/ (OBt) 2/ Me
, Me2/ s-Amy/ (OMe) 2/
Me, Me2/ s-Amy/ (OBt) 2
/Me.

Me/ (OMe) 2/cyclopentyl, Me/
(OM!ri 2/cyclopentadienyl.

OR1 is R; isi, R' and R3 are hydrocarbon groups,
When R6 is a hydrocarbon group [When R2 and R3 are the same, R; Si/R↓ and OR'
When and OR5 are the same, each is displayed as (OR') 2/R6. ] Me+Si/ME! 2/ (OMe) 2/ Me
, Me3Si/Me, /(OBt)=/Me
, 巳t3si/ Me2/ ([]Me)2/
1-Pr.

Bt3Si/ Mez/ (OMe> 2/ n-He
x a ■ When R', R' and R3 are hydrocarbon groups and R6 is SiR-occupied 1 [When R', R2 and R3 are the same, R1, R2 and R3
When OR' and OR5 are the same, R:/R3 is displayed, and (OR')=/5iR4' is displayed when OR' and OR5 are the same.

]Me/ (OMe) 2/ SiMe3. Me/
(OBt) 2/ SiMe3゜Me/ (OMe)i
/ SrBt3. Bt/ (OMe)2/ SrMe
s, Bt/(OBt)2/SiMes, Et
/ (OMe)z/5iBta, Bt/(OEt)
2/5ifts, Mez/ n-Pr/ (
OMe)2/SiMes.

Me, /1-Bu/ (OMe)2/SiMes,
Bt2/ 1-Pr/(OBt)2/S+Bts
.

■R' is R:Sr, R'' and R3 are hydrocarbon groups, and R
When 6 is S, i RM l [When R' and R3 are the same, R arrangement Si/R: and [lR
When ' and OR5 are the same, (OR') 2/SiR 1 is displayed. ] Me+Si/ Mez/ (OMe) 2/ SiMe
+, 'Me+Si/ Eit2/(OMe) 2/
SiMes, Me3Si/ Me2/ (OEt
) 2/ SiMe3゜Me+Si/ Mez/ (O
Me) 2/ 5iEt+, Me3Si/ Me/
Et/ (OBt)2/ SrMea, [! t
3s+/Etz/ (OEt)2/SrMei,
EtsS+/ Et2/ (OBtL/ SrEts
, Me3S+/ Me/ n-Bu/ (OEt)
2/ SiMe3゜■R' and R2 are hydrocarbon groups,
If R3 is R9[) and R6 is 0R10, [When R' and R2 are the same, R↓/R90 and OR'O
When R5 and 0R10 are the same (1R4 and OR' and O
When R5 is the same, it is displayed as (OR'), /OR'' respectively.] Mez/ Men/ OMe, Me2/ M
en/ 0巳t, Mez/εto/ OMe
, Me2/ Eta/ DEt , Mez/
1-Pr[IloMe, Me2/ 1-PrO/
DEt, Me2/t-BuO/[]MeM
ez/1-BuO10Bt, Me;+/n
-11ex[IloMa, Me2/n-He
xO/OBt, Bt2/Men/OM
e, Mitz/Men/ OEt Me/
t-Bu/ Me[ll/ []Me, Me/
t-Bu/MenloBt, (i-Pr)
z/MeD/f1Me, (i-Pr)2/Ma0
10, Me/ s-Amy/ Men/ O
Me, Me/s-Amy/Men10Et
Mea/MeO/ ([]Me)210Bt,
Me2/ Met]/ (OBt) 2/ 0t
-Bu, Mez/Eta/ (OMe) 21
0n-11ex Mez/ Btu/ (O[Et
) 2/ 0i-Pr, [it2/Men/ (
OMe) 2/ OBt, Et2/ Men/
(Oat)2/ 0tBu, Et2/ Btu/
(OMe)2/0n-Hex, Et2/B
tu/(OEt) 2/ Di-Pr, Me/t
-Bu/ Men/ OMe/ OBt/Old-Pr
, Bt/1-Pr/Eta/DMe/On Amy.

■R1 is RsSi, R2 is a hydrocarbon group, R3 is R”O
Then, when R6 is 0R10, [OR', OR5 and [1R10 are the same, mouth R
When 4 and OR' and OR5 are the same, (OR'), 10R
9 is displayed respectively. ] Me+Si/ Me/ Men/ []Me, M
e3Si/Me/MenloBt, Me
3Si/Me/Btu/OMe, Et
sSi/ Et/Men/ OMe, Bt+Si
/Me/Eta/OMe, Et3Si/M
e/ Men/ 0εt, 8t+S+/ Et/
Eta/ [lEtMe3Si/ t-Bu/ Me
n/OMe, tit3si, /1-Pr/
1EtO/ 0IEt, Me3Si/ Me/
Men/ ([]Me) 2/ Dt-BuMe+Si
/ Bt/ MeO/ (OEt) 2/ 0n-Pr
, Me3Si/ Et/ Eta/ (OBt)
2/ Di-Pr, Bt3Si/Me/M
en/(OEt) 2/ Di-Pr, Bt,,
Si/ Et/ Eta/ (OBt) 2/Di-P
r, Et3Si/ Me/ [EtO/ ([]
Me) 2/Os-Amy.

■When R1 and R2 are hydrocarbon groups, R3 is R90, and R6 is a hydrocarbon group [When R' and R2 are the same, R4/Rs [l, OR'
When and (]R5 are the same, they are respectively displayed as (OR') 2/ R'.] Me2/ Men/ (OMe) 2/ Me,
Me2/ Me口/ (OIEt) 2/ Me,
Me2/ Btu/ (OMe) 2/ Me,
Mea/EtO/(mouthBt)z/Me, M
e2/ 1-PrO/ (OMe)z/ Me,
Mez/ 1-Pro/ (OBt) 2/ Me,
Mez/ 5-Bun/ (OMe) 2/Me
, Me2/ 5-Bu mouth/ (OBt) 2/ M
e, Mez/ t-Amy0/(OMe) 2/
Me, Mez/t-AmyO/ (OEt)
2/Me.

Mez/ n-HexO/ (OMe) 2/ Me
, Me2/n-HexO/(OEt) =/M
e, 巳t2/ Men/ (DMe)z/ Me
, Etz/Men/ (OEt) 2/ Me
, Me/ n-Pr/ Men/ ([]Me)
2/ Et, Me/ n-Pr/ Men/ (
[1lEt) 2/ Bt , Me/1-Bu/
Me mouth/ (DMe) 2/'Me, Me
/ t-Bu/ Men/(OEt), /Me,
Me2/Men/(OMe)2/Et, Me2/
Men/ ([1Et)2/ Et, Me, /
Men/ (OMe)2/ i-PrMe2/ Me
Mouth/ (OEt)2/ 1-Pr, Me
2/ Men/ (OMe)2/ t-Bu,
M82/ Men/ (OEt) 2/ t-Bu,
Me2/ MeO/ (OMe) 2/cyclohexyl, Mez/MeO10Me10t/Et
, Mez/ Eta/ OMe/ OBt/ t
-Bu, Bt2/ Men/ OMe/ Oa
t/ 1-Pr, Me/ t-Bu/ Me[l
/DMe/DEt/Me, Et/ 1-Pr/
Eta10Me10Et/n-Hex.

■When R' is RaSi, R2 is a hydrocarbon group, R3 is R90, and R6 is a hydrocarbon group [: When OR' and OR5 are the same, (OR'), /It
Display as 6. ] Me3Si/ Me/ Men/ (OMe) 2/
Me, MesSi/ Bt/Men/ (OMe)
2/Me, Me3Si/Et/Et[] / ([)
Me)z/Me Me:+Si/Bt/Eta/
([]Et)2/Et, EtaSi/Me/
Men/(DMe)z/Me, BtsSi/Et/
Men/(OMe)2/Me, Et3Si/Et/E
ta/ (OMe:12/Meet3sl/Et/1E
to/ (OBt)2/Et, Me*S+/B
t/Men/ (O[Et)2/ t-Bu,
Et3Si/ Me/MitO/ (DMe)2/5-B
u, Me+Si/Me/Men10Me/DEt/
Memit3Si/ Et/ Men/ OMe/ []
Et/i-Pr.

111) R' and R2 are hydrocarbon groups, R3 is l'19
0 and R6 is 5illi11 [When R' and R2 are the same, R↓/R90 is displayed, and when OR'' and OR5 are the same, it is displayed as (OR') 2/SiR;'.] Mep/ Men/(OMe)2/SiMe3,
Mep/ Et[]/(OMe) 2/ 5iix
e3, Mez/ MeO% ([]Et) 2/
SiMe3Me2/ MeO/ (OMe)2/ Si
Snake t3, Et2/ Men/ (OMe)z/
S+Mei, Bt2/ Btu/ (OMe)2/
SIMe++, Et2/Men/ (OMe)
2/ S+Et+, E! t2/ Btu/ (OE
t) 2/5iHt3. Me/ Et/ Men/
(OEt)z/SiMe+, Me/Bt/Et
a/ (OMe) 2/ 5ift3. Me/t-
8r/Et[:l/(OMe)2/SiMe3,
Bt/s-Amy/&leO/(OFft)2/SiM
e+, 1-Pr/n-day u/Men/ (
OMe) 2/5iBt3.

Me/εt/Men10Me10[! t/SiMes
, Et/1-Bu/Men10Me10at/5
iBt+.

OR' is R:S+, R' is a hydrocarbon group, R3 is R90
So, if R6 is 5iRA' [When OR4 and OR5 are the same (OR') 2/S
+RA is displayed. ] MesSi/ Me/ Men/ (OMe) 2/
SiMes, Me+Si/ Et/ Men/ (O
Me) 2/ SiMe+, Me+Si/ Me/
BtO/(OMe) 2/ SiMes, Bt+
Si/ Me/ Men/ (OMe) 2/SiMe
3. BtsSi/ Bt/ Men/ (OMe)
x/SiMes.

Et3Si/ Et/ Btu/ (OMe) 2/
SiMes, Bt3Si/Me/Men/ (
OMe) 2/5ilEt3. Bt3Si/ Bt
/ )EtO/ (Oat) 2/ 5iBts,
Me+Si/ Me/ Men/ OMe10Et/
SiMe3. Et+Si/ Et/ Btu/ O
Me/OBt/S+Bts.

When OR1 is a hydrocarbon group, R2 is R'0, R3 is R90, and R6 is 0R10 [R'0 and RsO are the same (7), then R'/(R''O
)2t, OR', OR' when OR5 and OR50 are the same, and (OR') when OR' and OR' are the same.
, /OR” respectively.] Me/ (Men), 10Ma, Me/ (Men
), 10Bt, Bt/(Men) 2/OMe
, εt/ (MeO)z/ OEt , Me/ (B
tO)-10Me, Me/(BtO)210Et
, Me/ (n-Pro)210Me, Me/
(n-PrO)10Bt, Me/ (Men)/
(tBun)10Me, Me/ (Men) /
(t-BuO)10Et.

Me/ (Men) 2/ (DMe) 2/ 0t-
Bu, Me/ (Men) 2/(0εt) 2/
0i-Pr, Me/Men/t-BuO/
(OMe) 2/0nHex, Et/εtO/
1-PrO/(OBt)z/0i-Bu, M
e/ Eta/ n-Bun/ OMe/ Btu/
0n-Hex.

■ R1 is R:Si, R2 is R'0, R3 is R90
So, if R6 is 0R10 [When R80 and R'O are the same, R; St/ (R80
)2, OR', OR' when OR' and 0R10 are the same, and (OR') when OR' and OR5 are the same,
10R” respectively.] Me3Si/ (MeO)zloMe, Me3S
i/(EtO)zloMe.

MesS+/ (Men)z/ OBt, Bt3S
+/(EtO)z/OMe.

Bt3Si/ (Men)210Bt, Bt3
Si/ (BtO)z10EtMe+Si/ (n-P
ro)210Me, Bt+Si/Btu/1-
PrOloEt, MesSi/Men/n-
BunloMa, MeiSi/(Men)2/
(OMe>210t-Bu, MesS+/
(Btu)2/(OMe)210n-Hex,
Bt+Si/ (Men)2/ (01Et)210i
Pr, MeaSi/Men/1-BuO/
(OMe)2/Us-Amy.

Et3Si/Eta/i-PrOloMeloBtl
-Pr0l0 0■1lil is a hydrocarbon group, R2 is R8
0, When R3 is R90 and R6 is a hydrocarbon group [When R110 and R90 are the same, R'/ (R80)
, and when OR' and OR5 are the same, (OR')2/
Each is displayed as R6. ] Me/ (Men> 2/ ([]Me) 2/ Me
, Me/ (Men) 2/(OEt)2/ M
e, at/ (MeO)2/ (OMe)z/
Me.

Bt/ (Eta) −/ (OBt) 2/ Me
, 1-Pr/ (Men) 2/(OMeL/ M
e, 1-Pr/ (MeO)z/ (OEt)2
/Me.

n-Bu/ (Men) 2/ (DMe) 2/ M
e, n-Bu/ (MeO) 2/(OEt)2/
Me, Me/ (n-PrOL/ (OMe)z
/Me.

Me/ (n-PrO)2/ (O[1t)z/ Me
, Me/ (S-BLIO)2/ (OMe)
2/ Me , Me/ (s-BuO) x/ (
OBt) 2/Me.

Me/Men/n-)1exO/ (OMe)2/Me
, Me/Men/n-HexO/(OFft)
2/Me, Et/ (Men)2/(OMe)2
/Bt, Et/ (Men) 2/ (DBt)
2/Et, vinyl/(MeO) 2/(DMe
) 2/vinyl, vinyl/ (Eta) 2/(OBt
) 2/Vinyl, Me/ (Men) 2/ OM
e/OBt/Me, Me/(BtO)210
Me10Bt/Bt, Et/ (EtOL10Me
10Bt/Me, Bt/ (Btu) 210M
e10Et/Et, Me/Men/Eta10
Me10Et/Et, Bt/MeO/[Et
O10Me10Et/Bt 0■R1 is a hydrocarbon group,
R2 is R"0, R3 is R90, and R6 is SiR'J'
In the case of [When R80 and R'0 are the same, II'/ (l18[
])2, and when OR' and OR5 are the same, (OR')2
/ SIRM' are displayed respectively. ] Me/ (Men) 2/ (OMe) 2/ SiM
e+, Me/ (Men) 2/(OEt) 2/
SiMe+ , Me/ (Men> 2/ (OM
e) 2/ Siεt3゜Eit/ (Men) 2/
(OMe) 2/ S+Me+ , Bt/ (Et
a) 2/(OMe) 2/ SiMe+, Bt/
(Men) 2/ (OEt) 2/ SiMe3゜Et/(Men)2/(OMe)2/5iEt*,
Et/(EtO)2/(OBt) 2/ 5iBt+
, Me/ Men/ Eta/ DMe/ OBt/
SiMe3, fEt/Men/EtO/QMe/
[]Et/5iBtzi-Pr/ (MeO)i/ (
OMe)z/SiMe,, n-Bu/ (MeO)
2/ (OMe)2/5iEt,, Me/ (S-
BLIO)2/ (OBt)2/SiMe3, Vinyl/ (Men)2/ IBMs/ DBt/S
iMe3゜OR1 is R distribution S1, R2 is R80, R' is R
90, when R6 is S+RA' [when R80 and ll'0 are the same, R:iSi/ (R
60) When 2, OR' and OR5 are the same, (OR'
) 2/5iRj' respectively. ] MeaSi/ (MeD)2/ (DMe)s/ Si
Me3. Me3Si/(lEto)2/ (OMe)
2/ S+Me3. Me3S1/(Men)2/(
OEt) 2/ SiMe+, MeaSi/ (
Men) 2/ (OMe) 2/ 5iBts,
Me3Si/ (Btu) 2/ (OBt) 2/
5iEti.

Et3S+/ (MeO)2/ (OMe)2/ S+
Bt3. Bt3sl/(EtO), /(OEt)2
/5iEt3. Me+Si/Men/Btu/(O
Me) 2/SiMe+, Me+Si/ (B
tu) 2/ OMe/ []Et/S+Me+,
Bt+S+/ MeO/ Eta/ (DMe)z/
S1Me+Et3Si/ Men/ Btu/ OM
e/ OEt/ 5iBt+.

The catalyst of the present invention is composed of component A, component B, and component C, and the composition ratio thereof is such that component B is 1 to 2.000 g mol, preferably 2.00 g mol per 1 gram atom of titanium in component A.
Component C is used in an amount of 1 to 10 moles of O,OO, preferably 0.01 to 1.0 moles, per mole of component B.

Polymerization of α-olefins The catalyst of the present invention can be used for the homopolymerization of α-olefins having 3 to 10 carbon atoms or other monoolefins or other monoolefins having 3 to 10 carbon atoms.
It is particularly useful as a catalyst for copolymerization with C3 to C6 α-olefins, such as propylene, 1-butene, 4-methyl-1-pentene, I
It shows extremely excellent performance as a catalyst for the homopolymerization of hexene, etc., or the random and block copolymerization of the α-olefins mentioned above and/or with ethylene.

The polymerization reaction may be performed in either a gas phase or a liquid phase. When polymerizing in a liquid phase, inert carbonization of normal butane, isobutane, normal pentane, isopenkune, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. It can be carried out in hydrogen and in liquid monomers. The polymerization temperature is usually in the range of -80°C to +150°C, preferably 40 to 120°C. The polymerization pressure may be, for example, 1 to 60 atmospheres. The molecular weight of the resulting polymer can also be controlled by the presence of hydrogen or other known molecular weight regulators. Further, the amount of other olefin to be copolymerized with the α-olefin in the copolymerization is usually selected within the range of 30% by weight, particularly from 0.3 to 15% by weight based on the α-olefin. The polymerization reaction using the catalyst system according to the present invention is carried out in a continuous or batchwise reaction, and the conditions may be those commonly used. Further, the copolymerization reaction may be carried out in one stage, or may be carried out in two or more stages.

Effects of the Invention The catalyst of the present invention can produce a highly stereoregular polymer in high yield in the polymerization of α-olefins.

EXAMPLES The present invention will be specifically explained by examples and application examples. Note that percentages (%) in the examples are based on weight unless otherwise specified.

The heptane-insoluble content (hereinafter H1, !: abbreviated as abbreviation), which indicates the proportion of crystalline polymer in the polymer, is the residual amount when extracted with boiling n-hebutane for 6 hours using an improved Soxhlet extractor.

Example 1 Preparation of ingredients 1 with reflux condenser! In a reaction vessel under a nitrogen gas atmosphere, chip-shaped metallic magnesium (purity 995%, average particle size 1.6n+m>8.3 g and 7']-hexane 250 WIf!) was placed and stirred at 68°C for 1 hour. rear,
Magnesium metal was taken out and dried under reduced pressure at 65°C to obtain preactivated magnesium metal.

Next, n-butyl ether 1
A suspension of 0.5 ml of n-butyl ether solution (175 mol/liter) of n-butylmagnesium chloride and 0.5 ml of n-butylmagnesium chloride was kept at 55°C, and further 50 ml of n-butyl ether was added.
A solution of 38.5 rnl of n-butyl chloride dissolved in - was added dropwise over 50 minutes. After carrying out the reaction at 70°C for 4 hours with stirring, the reaction solution was maintained at 25°C.

Then, to this reaction solution) IC (OC2H5), 55
7- was added dropwise over 1 hour. After dropping, heat at 60℃ for 15 minutes.
The reaction was carried out for 30 minutes, and the reaction product solid was mixed with 30% each of n-hexane.
0-6 times and dried under reduced pressure at room temperature for 1 hour to recover 31.6 g of a magnesium-containing solid containing 19.0% magnesium and 28.9% chlorine.

300m equipped with reflux condenser, stirrer and dropping funnel
6.3 g of a magnesium-containing solid and 50 g of n-hebutane were placed in a reaction vessel under a nitrogen gas atmosphere to form a suspension.
While stirring at room temperature, 2.2.2-) A mixed solution of 20-(0.02 mmol) of dichloroethanol and 11 mmol of n-hebutane was added dropwise from the dropping funnel over 30 minutes, and then heated to 80°C.
The mixture was stirred for 1 hour. The resulting solid was filtered off and stored in room temperature n-
Wash 4 times with 100ml each of hexane, and then 1x each of toluene.
A solid component was obtained by washing twice with 00d.

To the above solid component was added 40% of toluene, further titanium tetrachloride was added so that the volume ratio of titanium tetrachloride/toluene was 372, and the temperature was raised to 90°C. Under stirring, diphthalate n
A mixed solution of -butyl 2- and toluene 5- was added dropwise over 5 minutes, and then stirred at 120°C for 2 hours. The obtained solid substance was filtered at 90°C and diluted twice with 100°C of toluene at 90°C.
Washed at °C. Furthermore, titanium tetrachloride was newly added so that the titanium tetrachloride/toluene volume ratio was 372, and 1
The mixture was stirred at 20°C for 2 hours. The obtained solid substance was heated to 110℃
The mixture was filtered and washed seven times with each 100-hexane solution at room temperature to obtain 5.5 g of component A.

Component A 11 obtained above was placed in a stainless steel autoclave No. 1, 51 equipped with a propylene polymerization stirrer under a nitrogen gas atmosphere.
．． Solution 4 containing 0.1 mol of triethylaluminum (referred to as TEAL under D) in 0■, n-hebutane 1β
A solution l- containing 0.04 mol of 1,1-dimethoxy1,2,2,2-tetramethyldisilane (hereinafter referred to as XMMS) in i- and n-heptane 11 was mixed and held for 5 minutes. I put it in. Next, 600d of hydrogen gas and 1! of liquid propylene were added as a molecular weight control agent. After press-fitting the
The reaction system was heated to 70°C, and propylene was polymerized for 1 hour. After completion of polymerization, purge unreacted propylene,
A white polypropylene powder with HI$97, s% was obtained. The polymerization activity of 1 catalyst was 25.0 kg/g・Component A.

Examples 2 to 5 Propylene polymerization was carried out in the same manner as in Example 1, except that the organosilicate metal shown in Table 1 was used instead of XMMS, and the results are shown in Table 1.

Comparative Example I Polymerization of propylene was carried out in the same manner as in Example 1, except that XMMS was not used. The results are shown in Table 1.

Example 6 Preparation into components 170 g of commercially available magnesium jetoxide was
Proof stainless steel (SIJS 316) If, -9400
1.2A stainless steel (SIIS)
316) in a nitrogen gas atmosphere, the mill pot was attached to a shaker, and the mixture was shaken for 2 hours at an amplitude of 10 and a rotation speed of 1420 rpm to perform contact, and a pulverized product (+) was obtained. .

200- equipped with reflux condenser, dripper and stirrer
The glass reactor is sufficiently purged with nitrogen gas. In this reactor, 8.3 g of pulverized material (I) and 42 ml of n-heptane were added.
After adding trichlorosilane 14 while stirring at room temperature.
．． A mixed solution of 9 g and 7'l -'' + 30 mf of butane was added dropwise from the dropping funnel over 30 minutes, and then heated at 65°C for 4 hours.
Stir for hours. The resulting solid was filtered off at 65°C and diluted twice each with 100 w n heptane at room temperature and 100 w toluene at room temperature.
, 183 times for 10 minutes under stirring to obtain a toluene slurry of the reaction solid N).

TlC1251 was added to a toluene slurry consisting of 8.5 g of reaction solid (1) and 26 ml of toluene, and the internal temperature was raised to 80°C over 20 minutes. After raising the temperature, di-n-butyl phthalate], A mixed solution consisting of 7 g and 8 d of toluene was added dropwise over 15 minutes using a dropping funnel. Thereafter, the temperature was further raised to 115°C, and the mixture was stirred at the same temperature for 2 hours. After removing the supernatant liquid by decantation, washing was performed twice by stirring at a temperature of 90° C. for 10 minutes using 100 ml of toluene. Next, add 21mf of new toluene.
, Tl[:1251m were added thereto, and the mixture was stirred at 115°C for 2 hours.

The obtained solid substance was filtered at 115°C and washed eight times with 100 bottles of n-hebutane at room temperature each time to obtain a hebutane slurry.

Polymerization of propylene Propylene was produced in the same manner as in Example 1, except that component A obtained above, the organosilicon compound shown in Table 1, and triisobutylaluminum were used in place of TEΔL, and the polymerization temperature was 80°C. The results are shown in Table 1.

Example 7 Propylene was polymerized in the same manner as in Example 6, except that the compounds shown in Table 1 were used as organosilicon compounds, and the results are shown in Table 1.

Comparative Example 2 Propylene was polymerized in the same manner as in Example 6 except that no organosilicon compound was used. The results are shown in Table 1.

Examples Example 1 〃 2 〃 3 〃 4 〃 5 // 6 〃 7 Comparative Example 1 Table Organosilicon Compound Me3Si-3i (Me) Je Me3Si-5i (OMe> 3 EtsSi-3i (DMe)3 Me+5i-3i (OEt)3 Me3Si-3i (OMe)2 cyclopentyl Me3
Si-3i (OMe)2(Ot-Bu)(MeD)M
e2S+ Sr (DMe) Tripolymerization activity T (Kg/g・Component A) (%) 25.0 21.4 27.4 17.1 26.4 31.2 28.4 97.8 97.5 97.3 97.4 97.5 32.8 59.1 〃 2 40.4 58.3

[Brief explanation of the drawing]

Figure 1 shows A diagram showing the preparation process of the catalyst of the present invention. It is a low chart diagram.

Claims (1)

[Claims] (A) Solid catalyst component containing magnesium, titanium, halogen, and an electron-donating compound as essential components, (B) Organometallic compound, and (C) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, R^1 is a hydrocarbon group having 1 to 10 carbon atoms or R^7_3Si, R^2 is a hydrocarbon group having 1 to 10 carbon atoms or R^8O, and R^3 is a hydrocarbon group having 1 to 10 carbon atoms. or R^9O, R^4 and R^5 are the same or different hydrocarbon groups having 1 to 10 carbon atoms, R^6 is a hydrocarbon group having 1 to 10 carbon atoms, OR^1 ^0 or SiR
^1^1_3, and R^7 to R^1^1 are the same or different hydrocarbon groups having 1 to 10 carbon atoms. ] An α-olefin polymerization catalyst comprising an organosilicon compound represented by: