JPH048708A - Catalyst component for alpha-olefin polymerization - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

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

BACKGROUND OF THE INVENTION Catalyst components for alpha-olefin polymerization containing metal oxides, magnesium, titanium, halogens and electron-donating compounds are known. This metal oxide supported catalyst has good polymerization performance such as high activity and high stereoregularity, as well as excellent particle properties such that the resulting polymer has a narrow particle size distribution and a uniform particle shape such as a spherical shape. .

If the particle strength of the catalyst component is low, the polymer produced by polymerization will be destroyed and pulverized. A typical method for preventing this is so-called prepolymerization, in which the catalyst component is brought into contact with the olefin in advance, and the resulting polymer is incorporated into the catalyst component to increase the strength of the catalyst component particles. By adding an electron-donating compound such as a silicon compound during this prepolymerization, the particle strength is improved and the final polyα-
Attempts have also been made to increase the stereoregularity of olefins.

However, the addition of an electron-donating compound during prepolymerization usually
This brings about effects such as a decrease in catalyst activity or deterioration of catalyst performance during storage.

In addition, as silicon compounds used during prepolymerization, compounds with aromatic groups are often used from the viewpoint of performance, but silicon compounds with aromatic groups are harmful depending on the intended use of the polymer.

It may become.

Problems to be Solved by the Invention The present invention aims to increase the strength of catalyst particles, improve the stereoregularity of the obtained polymer, maintain high catalyst activity, and prevent deterioration of catalyst performance during storage.

Means for Solving the Problem The present inventors conducted extensive research and found that if a specific compound is used as the silicon compound added during prepolymerization, the performance is equivalent to or better than that of an organic silicon compound having an aromatic group. The present invention was completed based on the discovery that a poly-α-olefin can be obtained using the method described above, and that the object of the present invention can be achieved.

Summary of the invention That is, the summary of the present invention is as follows: (A) a solid component containing a metal oxide, magnesium, titanium, halogen, and an electron-donating compound as essential components, (B) an organoaluminum compound, and (C) a general formula [ However, R', R'# and R5 are the same or different hydrocarbon groups having 1 to 10 carbon atoms, R2 is a hydrocarbon group having 1 to 10 carbon atoms, or R'0, R' is a hydrocarbon group having 1 to 10 carbon atoms. hydrocarbon groups or R'0, X is 2 or 3,
R6 and R7 are the same or different hydrocarbon groups having 1 to 10 carbon atoms. ] In the presence of an organosilicon compound represented by
(D) A catalyst component for α-olefin polymerization which is brought into contact with an olefin.

Solid component The solid component used in the present invention (hereinafter referred to as component A) contains a metal oxide, magnesium, titanium, halogen, and an electron-donating compound as essential components. compound, a titanium compound, an electron-donating compound, and if each of the above compounds does not have a halogen, it is prepared by contacting each with a halogen-containing compound.

(1) Metal oxide The metal oxide used in the present invention is an oxide of an element selected from the group of elements of Groups 1 to 2 of the Periodic Table of Elements,
To illustrate them, B, 05, MgO1^120s
5iOz, Can Ti[lz, ZnO12r
Examples include O*, SnO2, BaOTh[]z, and the like. Among these, B2O5, MgO1A1203.5ins
, Ti0i, and Zr0z are preferable, and 5102 is particularly preferable. Furthermore, composite oxides containing these metal oxides, such as 5102 MgO1S102-A1203.5102
-T102, 5i02-V2O, SiO, -Cr2
0. , SiO□-TiOz-MgO, etc. may also be used.

These metal oxides are usually in the form of powder. The size and shape of the powder often affect the shape of the obtained olefin polymer, so it is desirable to adjust it appropriately. For the purpose of removing poisonous substances before use, it is desirable to sinter metal oxides at as high a temperature as possible, and to handle them in a manner that prevents them from coming into direct contact with the atmosphere.

(2) Magnesium Compound Magnesium compounds are generally represented by MgR'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, as the hydrocarbon group for R1 and R2, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group, and as an OR group, R has 1 to 12 carbon atoms. The alkyl group, cycloalkyl group, aryl group, and aralkyl group are halogen atoms such as chlorine,
These include bromine, iodine, and fluorine.

Specific examples of these compounds are shown below, and in the chemical formula, Me dimethyl, Bt: ethyl, Pr: propyl, Bu
Nibutyl, He: hexyl, Oct: octyl, Ph
: phenyl, cy)le dichlorohexyl, respectively.

MgMe2. MgHt2. Mg1-Pr2. Mg
Bu2. MgHt, .

Mg0ctz, MgBtBu, MgP
h2, MgcyHe2.

Mg(OMe)z, Mg(OBt)z, Mg(
OBu)a, Mg(OHe)*.

Mg(00ct)a, Mg(OPh)i, Mg
(OcyHe)z.

BtMgCl, BuMgCl, HeMgCl,
i-BuMgCl, t-BuMgCl, PhM
gC1, PhCLMgCl, BtMgBr.

BuMgBr, PhMgBr, BuMgl,
BtOMgCI.

BuOMgCI, He0MgCl, Ph0Mg
Cl, BtOMgBr.

BuOMgBr, BtOMgl, MgCL,
MgBr2. MgIz.

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

Examples include metallic magnesium, halogenated hydrocarbons, and compounds containing alkoxy groups such as , M is a boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is the valence of M, and man≧0. ] is mentioned. The hydrocarbon groups represented by X and R in the general formula of the alkoxy group-containing compound include methyl (Me
) Ethyl (at), Propyl (Pr), i-Propyl (1-Pr) Butyl (Bu) i-Butyl (1-
Bu) Alkyl groups such as hexyl (He), octyl (0ct), cyclohexyl (cyHe) cycloalkyl groups such as methylcyclohexyl, alkenyl groups such as allyl, propenyl, butenyl, phenyl (Ph)
)! J, aryl group of xylyl group, phenethyl,
Examples include aralkyl such as 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(OMeL, C(O
Et)4゜C(OPr)*, C(OBuL, C
(Di-BuL, C(OHe)4°C(00ct)
4' Formula XC(OR)3
) 3゜HC(OBt)s, HC(OPr)s,
)IC(OBu)3. HC(OHe)3゜HC(O
Ph)s; MeC(OMe)s, MeC(OB
t)3. BtC(OMe)s.

BtC(OBt)s, cyHeC(OBt)s,
PhC(OMe)s.

PhC(OBt)s, CH2C'IC(0ct),
, MeCHBrC(OBt),.

MeCHCIC(OBt); CIC(OMe)s
, CIC(OBt)s.

CIC(Oi-Bu)s, BrC(OBt)s;
Formula LC(OR)2 contains MeCH(OMe)2.
MeC)I(OBt)2. CH2 (OMERI2°C
Ha((]Bt)z, C)12clcH(OBt)
z, CHCl2CH(OBt)2゜CC1,CI(
(OBt)z, ['HzBr['H(Oat)2.
PhCH(OBt)a.

Si(OMe)i included in the compound formula Si(OR)n when 0M is silicon,
5i(OBt)4゜3i(OBu)a, 5i(Di
-Bu)4.5i(OHe)*.

S+(00ct)*, 5i(OPh)*' H3i(OBt)s contained in formula X5i(OR)-d,
H3i(OBu)3. H3i(OHe)a.

H3i(OPh), ; MeSi(OMe)-,
MeSi(mouthBt)s.

MeSi(OBuL, BtSi(OEt)s,
Ph5i(OBt)s, BtSi(OPh)+;
CIStCl5t(O,Cl5i(OBt)s.

Cl5i(OBu)s, Cl5i(OPh)s,
Br5i(Oat)s; Formula % Formula %) B(OBt)s, B(
OBu)3゜B(OHe)= , B(OPh),.

When 0M is aluminum, the compound formula ^1 (OR) is included in ^1 ([]Me)
s, ^1(OBt)s.

^1 (OPr)8. ^1(Di-Pr)s, AI(
OBu)s.

^1(Ot-Bu)s, AI(OHe)a, A
I(OPh)s.

When 0M is phosphorus, P(OMe)s, P(
OBt)s.

P(OBu)s, 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 1IIa of the periodic table can also be used. The complex is a general MgR'R'・n (MR
', ). The metal includes aluminum,
Zinc, calcium, etc., and R' is an alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms.

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 ^
IMes, AIBts, A11-Bus, ^
lPh3゜ZnMez, ZnBt2. ZnBuz
, ZnPhz, CaBta +CaPhz, etc.

(3) Titanium compounds Titanium compounds are compounds of divalent, trivalent, and tetravalent titanium, 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.

(4) Electron-donating compounds Examples of electron-donating compounds include carboxylic acids, carboxylic anhydrides, carboxylic esters, carbonic acid halides, alcohols, ethers, ketones, amines,
Examples include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to organic groups via carbon or oxygen, phosphoamides, thioethers, thioesters, carbonic 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-cyclohexane Sandicarboxylic acid,
Alicyclic forces such as cis-4-methylcyclohexene-1,2-dicarboxylic acid JL/phonic acid, benzoic acid, toluic acid, anisic acid, p-tert-butylbenzoic acid, naphthoic acid,
Examples include aromatic monocarboxylic acids such as cinnamic acid, and aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellidic acid, hemimellitic acid, trimesic acid, pyromellitic 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, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, terephthalate Examples include dibutyl acid, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, and tetrabutyl pyromellitate.

As the carboxylic acid halide, acid halides of the above-mentioned carboxylic acids can be used, and specific examples include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride, butyric acid chloride, butyric acid bromide, butyric acid iodide, and pivalin. Acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide,
Acrylic acid iodide, methacrylic acid chloride, methacrylic acid iodide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid promide,
Conoacyl chloride, succinic acid chloride, glutaric acid chloride, glutaric acid chloride, adipic acid chloride, T
Dipic acid chloride, sebacyl chloride, sebacic acid chloride, maleic acid chloride, maleic acid chloride, fumaric acid chloride, fumaric acid chloride, 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 bromide, benzoyl chloride, benzoyl bromide, p-)ruyl acid chloride, p-toluic acid Bromide, p-anisyl chloride, p-anisyl chloride, α-
Examples include naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. 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 diallyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl ether, butyl allyl ether, diphenyl ether, anisole, ethylphenyl ether, and the like.

The method for preparing component A is as follows: ■Metal oxide (component 1), magnesium compound (component 2), titanium compound (component 3)
and an electron-donating compound (component 4) in that order. ■After bringing component 1 and component 2 into contact, component 4 and component 3
in that order. ■Ingredients 1. After contacting component 2, component 3 and component 4 are brought into contact simultaneously; ■After contacting component 2 and component 3, component 4 and component 1 are brought into contact in that order;■Component 2 and component 4. Component 3 and Component 1 are brought into contact in that order after contacting Component 2. A method such as bringing component 3 and component 4 into contact at the same time and then contacting component 1 may be adopted. It is also possible to contact with a halogen-containing compound before contacting with component 3.

Examples of halogen-containing compounds include halogenated hydrocarbons, halogen-containing alcohols, halogenated silicon compounds having a hydrogen-silicon bond, halides of elements of group Ua, group IVa, and group Va of the periodic table (hereinafter referred to as metal halides). 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-) dichloroethylene, 1.1.
2-) Libromoethylene, 1.1.2°2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1.
2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane, and chlorinated paraffins are used as aliphatic compounds, chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, and hexachlorocyclohexane are used as aromatic compounds. Examples include chlorobenzene, bromobenzene, O-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, pencitrichloride, p-chloropencitrichloride, and the like. Not only one kind but also two or more kinds of these compounds 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, 1
-chlor-2-propatol, 3-chlor-1-propatol, 1-chloro-2-methyl-2-propatol,
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-chloro-α-
Methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorthymol, 4-chlorresorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol, 1-bromo-2
-butanol, 2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (
m,○,p)-bromophenol, 4-bromoresorcin, (m,o,p)fluorophenol, p-iodophenol: 2゜2-dichloroethanol, 2,3-dichloro-1-propatol, 1,3-dichloro-2-propatur, 3-chloro-1-(α-chloromethyl)-1-
Propertool, 2.3-dibrome-1-propertool,
1.3-dibromo-2-propatol, 2.4-dibromophenol, 2.4-dibromo-1-naphthol: 2
．． 2゜2-Trichloroethanol, 1.1.1-) Lichlor-2-propertool, β, β, β-trichloro-t
ert-butanol, 2.3.4-trichlorophenol, 2.4.5-)lichlorphenol, 2,4.6-
) Lichlorphenol, 2.4.6-) Ribromophenol, 2.3゜5-tribromo-2-hydroxytoluene, 2゜3.5-) Ribromo-4-hydroxytoluene, 2.2.2-) Refluoroethanol, α, α.

α-Trifluoro-m-cresol, 2.4°6-doliiodphenol: 2,3,4.6-titrachlorophenol, tetrachlorohydroquinone, tetrachlorbisphenol A1 tetrabromobisphenol A, 2.
2.3.3-tetrafluoro-1-propertool, 2.
Examples include 3°5.6-titrafluorophenol and tetrafluororesorcin.

Examples of halogenated silicon compounds having a hydrogen-silicon bond include HSICI, Hzsic12. )l, 5i
c1.

HCll5SiC12, HC211sSiC1s,
H(t-C4Hs)SiC1z.

HCll5SiC12,f((CHsLSiCl,
H(i-CsLLSiCl)12C2H5SIC1, H
2(n-C4Hs)SICI, )Ia(CsLCL
) SICI HSICI (C,) Is) 2, etc.

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

TI, Si, Ge, Sn, Pb, As, S
b, Bi chloride, fluoride, bromide, iodide, especially BCl3, BBrs, BI3,
AlCl3, AlBr3°Ga113. GaBr
5, InC15, TlCl3, 5IC14.

5nCI4. SbC]s, 5bFs, etc. are suitable.

Ingredient 1. Ingredient 2. Contact with component 3 and component 4, and a halogen-containing compound that can be brought into contact as necessary, is carried out by mixing and stirring in the presence or absence of an inert medium, but by mechanical co-pulverization. Ru. 40 contacts
It can be carried out under heating at ~150°C.

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

Specific examples of the method for preparing component A in the present invention include JP-A-58-162607, JP-A-55-94909, and JP-A-5.
No. 5-115405, No. 57-108107, No. 61
-21109, 61-174204, 61-1
No. 74205, No. 61-174206, No. 62-77
Examples include the method disclosed in Japanese Patent No. 06 and the like. More specifically, ■ A method in which a reaction product of a metal oxide and a magnesium dialkoxide is brought into contact with an electron-donating compound and a tetravalent titanium halide (JP-A-58-162607). A method of contacting a reaction product with a magnesium hydrocarbyl halide compound with a Lewis base compound and titanium tetrachloride (JP-A-55-94909) ■ A reaction product between a porous carrier such as silica and an alkylmagnesium compound, Method of contacting with an electron donating compound and a silicon halide compound before contacting with a titanium compound (JP-A-55-115405, JP-A No. 57-1081)
07 Publication), ■ A method of bringing a metal oxide, an alkoxy group-containing magnesium compound, an aromatic polycarboxylic acid having a carboxyl group at the ortho position or a derivative thereof, and a titanium compound into contact (Japanese Unexamined Patent Publication No. 174204/1982). Metal oxides, alkoxy-containing magnesium compounds,
A method of bringing a silicon compound having a hydrogen-silicon bond, an electron-donating compound, and a titanium compound into contact (Unexamined Japanese Patent Publication No. 61-17
4205 Publication) ■ Method of bringing metal oxide, alkoxy-containing magnesium compound, halogen element or halogen-containing compound, electron donating compound, and titanium compound into contact (JP-A-61-174206 Publication) ■ Metal oxide, dihydrocarbyl magnesium A method of contacting a reaction product obtained by contacting a halogen-containing alcohol with an electron-donating compound and a titanium compound (JP-A-61-21109) ■ Metal oxide, hydrocarbylmagnesium, and hydrocarbyloxy group-containing compound A method in which a solid obtained by contacting a solid (corresponding to the alkoxy group-containing compound) with a norogen-containing alcohol, and further with an electron-donating compound and a titanium compound (Japanese Patent Publication No. 62-7706) It is. Among these ■〜■
Methods (1) and (2) are particularly preferred.

Component A is prepared as described above, but Component A may optionally be washed with the inert medium described above and may be further dried.

Organoaluminum compound The organoaluminum compound (hereinafter referred to as component B) is:
General formula RnAlX3-0 (wherein, R is an alkyl group or an aryl group, and X is an atom), an alkoxy group, or a hydrogen atom, and n is an arbitrary number in the range of 1≦n≦3. ) having 1 to 18 carbon atoms, preferably carbon, such as trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum civalide, alkyl aluminum sesquihalide, dialkylaluminum monoalkoxide, and dialkylaluminum monohydride. number 2 to 6
Alkylaluminum compounds or mixtures or complexes thereof are particularly preferred. Specifically, trialkyl aluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum,
Dialkyl aluminum monohalides such as dimethyl aluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminium iodide, diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dichloride, ethyl aluminum dichloride, ethyl aluminum diiodide, Monoalkylaluminum dino-1rides such as isobutylaluminum dichloride, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, dimethylaluminum methoxide, diethylaluminum ethoxide, diethylaluminum phenoxide,
Examples include dialkyl aluminum monoalkoxides such as dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, and diisobutyl aluminum phenoxide, and dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, and diisobutyl aluminum hydride. Among these, trialkylaluminum is preferred, particularly triethylaluminum and triisobutylaluminum.

Organosilicon Compound The organosilicon 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 this formula, the hydrocarbon groups of R' to R5 and OR', OR'
R6, R? Examples of hydrocarbon groups include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups,
Examples include aralkyl groups.

Alkyl groups include methyl, ethinobepropyl, 1-
Propyl, butyl, i-butyl, S-butyl, t-butyl, amyl, 1-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, decyl, etc., and alkenyl groups include vinyl, allyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-octenyl, 1-dekenyl, 1-methyl-1-pentynyl, 1-methyl-1-heptenyl, etc.; cycloalkyl groups include cyclopentyl, cyclohexyl, methyl Examples of the aryl group include pheninopetryl and xylyl groups; examples of the aralkyl group include benzyl, phenethyl, and 3-phenylpropyl groups. Among these, aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups are preferred, and alkyl groups are particularly preferred.

Furthermore, among the hydrocarbon groups for R4, methyl and ethyl groups are most desirable.

Component C can usually be synthesized by reacting a compound represented by the general formula R'R"R'5iOH and a compound represented by the general formula (R'0)X+l5iR's- in the presence of an amine compound. can.

Specific examples of component C will be listed below. In addition, in the following, Me=methyl, Et=ethyl, Pr=propyl, Bu
=butyl, Amy=amyl, and Hex=hexyl, respectively.

OR'R2R'5iOSi<OR') s,
R2t When R3 is a hydrocarbon group (R'/R'/R'1
Indicated as 0R'.

However, when R', R' or R3 are the same, R1.

It is displayed as R'2/R' etc. ) MesloMe, Me, /(lBt, Bt
, /()Me, Bt.

/OBt, Me2/n-Pr/OMe,
Me2/n-Pr/OBt.

ME! 2/t-Bu/OMe, Me2/t
-Bu/OBt, Bt2/Me/OMe,
Eta/ Me/ OBt 00R'R2R'5I
O3t (OR') 2R', R2,R
When 3 is a hydrocarbon group (R'/R2/R'10R'/
Denoted as R'. However, when R', R2, or R3 are the same, they are displayed as R's, R'27R3, etc. )Me3
10Me/Me, Me310Bt/Me, M
esloMe/Bt, MesloBt/B
t, MesloMe/1-Pr.

Me310Et/1-Pr, Me310Me
/1-Bu, Me,, 10Bt /1-Bu
, Me, 10Me/n-Bu, Me310B
t/n-Bu, Me310Me/5-Bu
, MesloBt/5-Bu.

Bt310Me/Me, Ht3/[lBt/M
e, Bts/[1Me/ 1-Pr, a
t310at/1-Pr, Mez/n-n-
Pr1O/Me, Mez/n-Pr10Bt
/Me, Me2/l-BuloMe /Bt,
Mez/1-BuloBt/at, Me
2/n-BuloBt/Me, Mez/n-
BuloBt/Me, Me2/n-tlex
10Me/Me, Mez/n-flex 10
Bt/Me.

Me2/s-Amy 10Me/Me, Me2/
s-Amy 10Bt/Me ○R'R'R35iO3i(OR')-, R
When 2 is a hydrocarbon group and R3 is R'0 (R'/R2/R
It is indicated as '010R'. However, when R' and R2 are the same, it is displayed as lli 12. ) Me2/MeO10Me, Me2/Men 10
Bt, Men/BtO10Me, Me2/Bt
O10Bt, Me2/1-PrO10Me,
M82/1-PrD/DBt, Mez/t
-BuOloMe, Me,/t-BuO1
0Bt, Me2/n-Hewn/,
.

OMe, Mea/n-)1axn10Bt,
Bt2/MeO10Me.

Bta/MeO108t, Me/1-Bu/1le
O10Me, Me/1-Bu/MeO10Bt,
(i-Pr)z/MeO10Me.

(i-PrL /Men 10Bt, Me/s-
Amy /Men /Due, Me/s-Amy
/MeO10Bt 00R'R"R'5iO5x (
OR') zR', where R2 is a hydrocarbon group,
If R3 is R'[] (R'/R2/R'010R'
/R'. However, when R' and R2 are the same, lit,
is displayed. ) Me2/MeO10Me/Me, 1
lea/noodles aO10Bt/Me, Mez/B
tO10Me/Me, 1lez/BtO10
Bt/Me, Men/1-PrO10Me/
Me, Me, / 1-Pr.

10[jt/Me, Ma2/s-BuOloMe
/Me, Mez/5-BuO10Bt/Me
, M82/t-AIIIyO/OMe/M
e.

Mez/t-AmyO/Oat/Me,
M82/n-)1exO10Me/Me, M6
2/ n-HexOloBt/Me, Bh/
MeO10Me/Me, Btz/MeO1
0Bt/Me, Me/n-Pr/
MeO/OMe/Bt, Me/n-P
r/Men 10Et/at, Me/1-
Bu/Men 10Me/Me, Me/1-B
u/Men 10Bt/Me, Mez/MeO10
Me/Bt.

Me2 /MeO10Bt /Bt, ME! 2/
MeO10Me/1-Pr, Mez/Men
10Et /1-Pr, M+, /Men 10
Me /1-Bu, Me2/Men 10Bt /
It is represented by 1-BuOR'R2R35iO3i(OR')s, where R2 is R'O.

R3MR70 (D case (R'/R60/R'(]
/ []R' c! : show. However, when R6 and R7 are the same, (displayed as R60L) Me/ (MeO)2/ OMe, Me/ (Me
n) 2/OEt, Bt/(MeO)210Me
, St/ (MeO)zloBt, Me/ (
BtOL/ OMe, Me/ (Btu) 2/
Oat, Me/(n-PrO)210Me,
Me/ (n-PrO) 10Bt, Me/ (
Men) / (tBu[l)/()Me, Me/
(Me[]) / (t-BuO) / ()Bt 0
OR'R2R35iO3i(OR')zR5, and when R2 is R1l01R3 is R70 (R'/R'0
/R'O10R'/R'. However, R6 and R7
When are the same, (displayed as R'OL) Me/ (Men), / OMe/ Me, Me
/ (MeO) 2/ OBt/Me, Bt/(M
en)210Me/Me, Bt/(BtO)z/D
Bt/Me, 1-Pr/(MeD)z10Me
/Me, i-Pr/ (MeO)2/ΩBt/M
e, n-Bu/ (Men), /OMe/
Me.

n-Bu/(MeO)a/OBt/Me,
Me/ (n-PrO) 2/ OMe/ Me
, Me/ (n-PrO)2/ OBt/ M
e, Me/ (s-BUO)210Me/
Me, Me/ (s-BuOL 10Bt/Me
.

Me/ Men/ n-)1exO/ OMe/ Me
, Me/ Men/ n-HexO/ Oat/
Me, Bt/ (Me[]) 2/ OMe/
Bt, Et/(Men) 2/OBt/B
t, vinyl/(Men), /OMe/vinyl,
vinyl/(t+to)2/oat/vinyl prepolymerization The prepolymerization of the solid component (component A) is carried out by contacting it with an olefin in the presence of an organoaluminum compound (component B) and an organosilicon compound (component C). .

In addition to ethylene, the olefins include propylene, 1-
α-olefins such as butene, 1-hexene, 4-methyl-1-pentene can be used.

The prepolymerization is preferably carried out in the presence of the above-mentioned inert medium. Prepolymerization is usually carried out at a temperature of 100°C or lower, preferably -30°C to +30°C, more preferably -20°C to +1°C.
It is carried out at a temperature of 5°C. The polymerization method may be either a batch method or a continuous method, or may be carried out in multiple stages of two or more stages. When carrying out multi-stage polymerization, it is natural that the polymerization conditions can be changed in each stage.

Component B is used so that the concentration in the prepolymerization system is 50 to 500 mmol/l, preferably 80 to 200 mmol/l, and per gram atom of titanium in component A, 4
~50,000 mol, preferably 6 to 1.000 mol.

Component C has a concentration in the prepolymerization system of 1 to 100 mmol/
f, preferably 5 to 50 mmol/l.

Olefin polymer is incorporated into component A through prepolymerization, and the amount of polymer is 0.1 to 2 per 1 g of component A.
00 g, especially 0.5 to 50 g.

The catalyst component of the present invention prepared as described above can be diluted or washed with the above-mentioned inert medium, but washing is particularly desirable from the viewpoint of preventing storage deterioration of the catalyst component. After washing, it may be dried if necessary.

In addition, when storing catalyst components, it is desirable to store them at as low a temperature as possible, between -50°C and +30°C, especially between 20°C and +30°C.
A temperature range of 5°C is recommended.

Polymerization of α-olefins The catalyst component of the present invention obtained as described above can be combined with an organometallic compound and, if necessary, an electron-donating compound, for homopolymerization of α-olefins having 3 to 10 carbon atoms. It is useful as a catalyst for copolymerization with other monoolefins or diolefins having 3 to 10 carbon atoms, but especially α-olefins having 3 to 6 carbon atoms, such as propylene, 1-butene, 4-methyl- It exhibits extremely excellent performance as a catalyst for the homopolymerization of 1-pentene, 1-hexene, etc., or the random and block copolymerization of the above α-olefins and/or with ethylene.

The organometallic compound that can be used is an organic compound of a metal from Group 1 to Group II of the periodic table. As such compounds, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly suitable. The organoaluminum compound that can be used is appropriately selected from compounds used in the prepolymerization of the solid component (component A), and trialkylaluminum, particularly triethylaluminum and triisobutylaluminum, are preferred. 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. Examples of such compounds include (C2)1s)2
Al[]Al(C'J5)2.

(C4H9)2^10^1(C,L)2 , (C
JS)2AINAI(C2H5)2C, )15, etc. can be exemplified.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc, etc., as well as LIAI(C2H5)4, LiA1(CJ+s)1
Compounds such as

Examples of electron-donating compounds that can be combined with the catalyst component and organometallic compound of the present invention as needed include the compound used in preparing the component A and the organosilicon compound ( In addition to being appropriately selected from component C), it is also possible to use electron-donating compounds made of organic silicon compounds other than the silicon compounds mentioned above, and electron-donating compounds containing heteroatoms such as nitrogen, sulfur, oxygen, and phosphorus. .

Specific examples of organosilicon compounds include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra(p-methylphenoxy)silane, tetrabenzyloxysilane, methyltrimethoxysilane, and methyl. Triethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltriphenoxysilane Sisilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexyloxysilane, dimethyldiphenoxysilane, diethyljethoxysilane, diethyldiisobutoxysilane , diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyljethoxysilane, diisobutyldiisobutoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, diphenyldibutoxysilane, dibenzyljethoxy Silane, divinyldiphenoxysilane, diallyldipropoxysilane, diethylzinclyloxysilane, methylphenyldimethoxysilane, chlorophenyldiethoxysilane, and the like.

Specific examples of electron-donating compounds containing a petero atom include:
Compounds containing a nitrogen atom include 2.2.6.6-titramethylpiperidine, 2.6-dimethylpiperidine, 2.
6-diethylpyrrolidine, 2.6-diitubrobilbiperidine, 2.6-diitubutyl-4-methylpiperidine, 1.2.2.6.6-pentamethylpiperidine, 2.
2.5.5-Tetramethylpyrrolidine, 2゜5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, 2.5-
Diisopropylpyrrolidine, 1.2.2.5.5-pentamethylpyrrolidine, 2.2.5-)dimethylpyrrolidine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-dimethylpiperidine, 2 .6-
Butylpyridine, 1,2,4-trimethylpiperidine, 2,5-dimethylpiperidine, methyl nicotinate, ethyl nicotinate, nicotinamide, benzoic acid amide, 2-methylpyrrole, 2,5-dimethylvirol,
Imidazole, toluic acid amide, benzonitrile, acetonitrile, aniline, para-toluidine, ortho-toluidine, meta-toluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine, etc. are compounds containing two atoms,
Thiophenol, thiophene, ethyl 2-thiophenecarboxylate, ethyl 3-thiophenecarboxylate, 2-methylthiophene, methylmercaptan, ethylmercaptan, isopropylmercaptan, butylmercaptan,
Diethyl thioether, diphenyl thioether, methyl benzenesulfonate, methyl sulfide, ethyl sulfite, etc. are compounds containing an oxygen atom such as tetrahydrofuran, 2-methyltetrahydrofuran, 3-
Methyltetrahydrofuran, 2-methyltetrahydrofuran, 2,2.5.5-tetraethyltetrahydrofuran, 2,2.5゜5-tetramethyltetrahydrofuran, 2.2゜6.6-tetraethyltetrahydropyran,
2゜2.6.6-tetrahydrobilane, dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, anisole, acetophenone, acetone, methyl ethyl ketone, acetylacetone, 〇-tri-t-butyl ketone,
Methyl-2,6-di-t-butylphenylketone, ethyl 2-furalate, isoamyl 2-furalate, methyl 2-furalate, propyl 2-furalate, etc., as compounds containing a phosphorus atom, include triphenylphosphine, Examples include tributylphosphine, triphenylphosphite, tribenzylphosphite, diethylphosphate, diphenylphosphate, and the like.

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

The amount of organometallic compound used for the catalyst component of the present invention is:
Usually 1 to 2.0% per gram atom of titanium in the catalyst component.
000 gmol, especially 20 to 500 gmol.

The ratio of the organometallic compound to the electron donating compound is selected within the range of 0.1 to 40, preferably 1 to 25 gram atoms of the organometallic compound based on aluminum per mole of the electron donating compound.

The polymerization reaction of α-olefins may be performed in either a gas phase or a liquid phase. When polymerizing in a liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane,
It can be carried out in inert hydrocarbons such as heptane, octane, cyclohexane, benzene, toluene, xylene and in liquid monomers. Polymerization temperature is usually -80℃~+
The temperature is 150°C, preferably in the range of 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 is
The reaction may be carried out continuously or batchwise, and the conditions may be those commonly used. Moreover, the copolymerization reaction may be carried out in one step,
It may be done in two or more stages.

Effects of the Invention By adopting the above-mentioned configuration, the present invention can improve the strength of the catalyst component, and the catalyst component maintains high activity in the (co)polymerization of α-olefin.
A catalyst component that exhibits high stereoregularity and is particularly washed exhibits an excellent effect of suppressing deterioration of performance during storage of the catalyst.

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 abbreviated as HI), which indicates the proportion of crystalline polymer in the polymer, is the residual amount when extracted with boiling n-hebutane for 6 hours using a modified Soxhlet extractor.

Example 1 Preparation of Ingredients A 200-cm flask equipped with a dropping funnel and a stirrer was purged with nitrogen gas. In this flask, silicon oxide (D
G-952 (manufactured by AVISON Co., Ltd., trade name) was calcined in a nitrogen stream at 200°C for 2 hours and then at 700°C for 5 hours, and 5g and 40 bottles of n-hebutane were added. Furthermore n
-Butylethylmagnesium (hereinafter referred to as BBM)
20% n-hebutane solution (manufactured by Texas Alkyls Co., Ltd.,
Add 20 ml of product name (GALA BBM), 9
The mixture was stirred at 0°C for 1 hour.

After cooling the above suspension to 0°C, 11.2 g of tetraethoxysilane was added to it for 20 mj! A solution of 7'l-heptane was added dropwise from the dropping funnel over 30 minutes. After the dropwise addition was completed, the temperature was raised to 50°C over 2 hours, and stirring was continued at 50°C for 1 hour. After the reaction was completed, the supernatant liquid was removed by decantation, and the produced solid was washed with 60 d of n-hebutane at room temperature, and the supernatant liquid was further removed by decantation. This washing treatment with n-hebutane was further repeated four times.

Add 50-n-hebutane to the above solid to make a suspension, and add 8.0 g of 2.2.2-)lichloroethanol to this.
A solution of 10-heptane dissolved in n-heptane was added dropwise from the dropping funnel at 25° C. over 15 minutes. After the dropwise addition was completed, stirring was continued for 30 minutes at 25°C. After the reaction is completed, at room temperature, 60mj? twice with n-hebutane at 60 mf
! Washing was performed three times with toluene. When the obtained solid (solid component I) was analyzed, it was found that SiO□36.
6%, magnesium 5.1%, and chlorine 38.5%.

10-n-heptane and 40 mf2 of titanium tetrachloride were added to the solid component I obtained above, and the temperature was raised to 90°C.
Hebutane 5mj! Di-n-butyl phthalate dissolved in 0.
6g was added over 5 minutes.

Thereafter, the temperature was raised to 115° C., and the mixture was reacted for 2 hours.

After lowering the temperature to 90°C, the supernatant was removed by decantation, and 70rnI of n-hebutane was added. Washed twice with

Furthermore, 15-mf of n-hebutane and 40 mf of titanium tetrachloride were added, and the mixture was reacted at 115°C for 2 hours. After the reaction was completed, the obtained solid material was washed 8 times with 60-n-beef saline at room temperature.

Next, drying was performed at room temperature under reduced pressure for 1 hour to obtain 8.3 g of catalyst component (component A). This component A contains 361%
of titanium, as well as silicon oxide, magnesium, chlorine and di-n-butyl phthalate.

Component A obtained above was placed in a 500 m1' reactor equipped with a prepolymerization stirrer under a nitrogen gas atmosphere.2. 280 ml of Og and n-hebutane were added, and the mixture was cooled to 0° C. without stirring. Then, a solution of n-hebutane (2.0 mol/J) of ethylaluminum (hereinafter abbreviated as TBAL) and 1
．． 1.1-) Liethoxy 3.3.3-) A solution of limethyldisiloxane (SOTES) in n-hebutane (2.0 mol/f) was added to a reaction system in which the concentrations of TEAL and silane were each 200 m! J mol/l and 20 mmol/l
and stirred for 5 minutes.

Next, after reducing the pressure in the system, propylene gas is supplied,
Propylene was allowed to polymerize for 30 minutes. After the polymerization was completed, the propylene in the gas phase was purged with nitrogen gas, and n-hebutane at 5° C. was added to dilute it five times. A slurry of catalyst components was thus prepared. A portion of the slurry was taken out, dried, and the amount of magnesium contained in the catalyst component was measured. As a result, the amount of prepolymerization was 2.4 g per 1 g of the component.

Naoko\5OTES was prepared as follows. That is, 0.452 mol of trimethylsilanol, 0.450 mol of tetraethoxysilane and 20.6 mm IJ mol of n-butylamine were placed in a 300 ml three-lough flask, heated and stirred at 80°C for 1 hour under a nitrogen atmosphere, and after the reaction was completed,
5OTES was obtained by distillation. The boiling point was 172°C.

Examples 2 and 3 In the prepolymerization of Example 1, the organosilicon compounds shown in Table 1 were used instead of 5OTES, and the organic silicon compounds shown in Table 1 were used instead of TEAL.
Component A was prepolymerized in the same manner as in Example 1, except that the organoaluminum compounds shown in the table were used at the concentrations shown in Table 1, and the prepolymerization conditions were as shown in Table 1. was prepared.

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

Comparative Example 2 Component A was prepolymerized in the same manner as in Example 1, except that 5OTES was not used and the prepolymerization conditions were as shown in Table 1 in the prepolymerization of Example 1, and the catalyst component was Prepared.

Comparative Example 3 Prepolymerization of component A was carried out in the same manner as in Example 1, except that dimethyldimethoxysilane was used instead of 5OTES in the prepolymerization of Example 1, and the prepolymerization conditions were as shown in Table 1. A catalyst component was prepared.

Reference Example 1 Preparation of component A was carried out in the same manner as in Example 1, except that phenyltriethoxysilane was used instead of 5OTES in the prepolymerization of Example 1, and the prepolymerization conditions were as shown in Table 1. Polymerization was carried out to prepare catalyst components.

Example 4 Preparation of component A Silicon oxide and BEM were brought into contact with each other in the same manner as in Example 1, except that the stirring time at 90°C was changed to 2 hours, and then the supernatant liquid was removed by decantation, and the resulting solid was was washed with 50 mg of n-heptane at room temperature, and the supernatant was removed by decantation. This washing treatment with n-hebutane was further repeated four times.

Add 20-n-heptane to the above solid to make a suspension, and add 2.2.2-) IJ dichlorotanol 9.6
A solution prepared by dissolving 10 g of n-hebutane was added dropwise from the dropping funnel at 0° C. over 30 minutes. 1 at 0℃
After stirring for an hour, the temperature was raised to 80°C over 1 hour, and the temperature was increased to 80°C.
Stirring was continued for 1 hour at 0°C. After completion of the reaction, washing was performed at room temperature twice with 50 rnl of n-hebutane and three times with 50 rnl of toluene to obtain a solid (solid component I).

20-toluene and 0.6 g of di-n-butyl phthalate were added to the solid component I obtained above, and the reaction was carried out at 50° C. for 2 hours. Next, 30 parts of titanium tetrachloride was added and heated to 90°C.
After reacting for 2 hours at
Washing was performed 8 times with n-hexane at room temperature. Drying was performed at room temperature under reduced pressure for 1 hour to obtain 7.7 g of component A. In addition to 3.0% titanium, this component A contained silicon oxide, magnesium, chlorine, and di-n-butyl phthalate.

Prepolymerization Using the component A obtained above, and changing the prepolymerization conditions to the first
A catalyst component was prepared by prepolymerizing component A in the same manner as in Example 1, except that the procedure was as shown in the table.

Comparative Example 4 A catalyst component was prepared in the same manner as in Example 4, except that in the prepolymerization of Example 4, no electron-donating compound was used and the prepolymerization conditions were as shown in Table 1.

Reference-2 In the prepolymerization of Example 4, 1.1-dimethoxy-1
- Component A was prepared in the same manner as in Example 4, except that diphenyldimethoxysilane was used instead of methyl-3,3,3-)limethyldisiloxane, and the prepolymerization conditions were as shown in Table 1. Preliminary polymerization was performed to prepare catalyst components.

Table 1 Organoaluminum compound prepolymerization Example 1 〃 2 〃 3 〃 4 MesS+O3i (0[!t) s MesSiO3i (OMe)si-PrMesSiO3
i (OMe) s MesSiO9i (OMe) *MeEAL TIBAL BAL BAL Comparative Example 2 〃 3 〃 4 MeaSi (OMe) x EAL T[! AL EAL Reference example 1 〃 2 CsHsSi (OEt) 5 (C-H=) -Si (OMe) 2 (Note) TI
BAL:) Liisobutylaluminum IBAL EAL Application Example 1 Polymerization of propylene A solution of TEA 1 in n-heptane (
0.1 mol/1) 4- and 1゜1-dimethoxy-1-methyl-3,3,3-)limethyldisiloxane in n-heptane solution (0.01 mol/i) (2 ml) were mixed and mixed for 5 minutes. I put in what I kept. Next, hydrogen gas 11 and liquid propylene 11 as molecular weight control agents were injected under pressure, and then the temperature of the reaction system was raised to 70°C. Catalyst component 4 obtained in Example 1
After charging 0.0 mm into the reaction system, propylene polymerization was carried out for 1 hour. After completion of polymerization, purge unreacted propylene,
HI yielded 97.8% white polypropylene powder. Polypropylene production amount (CE) per 1g/hour of component A
was 21.5 kg.

Application Examples 2 to 5 The catalyst components obtained in Examples 2 to 4 were used in place of the catalyst components obtained in Example 1, and 1゜1-dimethoxy-1
Polymerization of propylene is carried out in the same manner as in Application Example 1, except that the electron-donating compound shown in Table 2 is used or not in place of methyl-3,3,3-trimethyldisiloxane,
The results are shown in Table 2.

Application Examples 6 to 11 In place of the catalyst component obtained in Example 1, the catalyst components in Comparative Examples 1 to 4 were used, and 1,1-dimethoxy-1-methyl-3,3,3-)limethyldi Polymerization of propylene was carried out in the same manner as in Application Example 1, except that the electron-donating compound shown in Table 2 was used instead of siloxane, or the electron-donating compound was not used. The results are shown in Table 2. .

Application Example 12.13 The catalyst component obtained in Reference Example 1.2 was used instead of the catalyst component obtained in Example 1, and 1゜1-dimethoxy-1
- Polymerization of propylene was carried out in the same manner as in Application Example 1, except that the electron-donating compound shown in Table 2 was used instead of methyl-3,3,3-trimethyldisiloxane, or the electron-donating compound was not used. The results are shown in Table 2.

Application example Catalyst component Example 1 2 2 2 3 4 Comparative example 1 2 2 3 3 4 Reference example 1 2 Second surface Electron-donating compound Me+5iO3i (Okle) zMeMesSiO
3i (OBt) 3 Me*Si (OMe) 2 (n-Bu) Si (OBt) 5 (n-Bu) S 1(O(it) sMesSiOS
i (OMe) aMe(n-Bu) Si (OEt
) 5 i1ess+Os+ (flat) sMe2Si (
[]Me) 2 Cg) IsSi (flat) s CE HI (g/g・Component A) (%) 21.5 20.2 12.6 13.4 11.6 15, 1" 20.4 19. 9 14.4 9.5 12, B 13.0 10.4 97.8 97.6 95.3 96.1 94.7 92.4 93.8 93.1 95.1 87.1 73.0 96 .2 92.3 Note) 1.8% of fine powder polymer of 150 μm or less was generated.

[Brief explanation of the drawing]

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

Claims (1)

[Scope of Claims] (A) A solid component containing a metal oxide, magnesium, titanium, halogen, and an electron-donating compound as essential components, (B) an organoaluminum compound, and (C) a general formula ▲ mathematical formula, chemical formula, table etc. ▼ [However, R^1, R^4 and R^5 are the same or different hydrocarbon groups having 1 to 10 carbon atoms, and R^2 is a hydrocarbon group having 1 to 10 carbon atoms.
hydrocarbon groups or R^6O, R^3 has 1 or more carbon atoms
10 hydrocarbon groups or R^7O, x is 2 or 3, R^6 and R^7 are the same or different carbon numbers 1 to 1
There are 10 hydrocarbon groups. ] A catalyst component for α-olefin polymerization, which is brought into contact with (D) an olefin in the presence of an organosilicon compound represented by the following.