JPH0376709A - Catalyst component for alpha-olefin polymerization - Google Patents

Abstract

PURPOSE:To increase the strengths of catalyst particles by bringing a solid component mainly comprising a metal oxide, Mg, Ti, a halogen, and an electron- donating compd. into contact with an olefin in the presence of a trialkylaluminum and a specific dimethoxysilane compd. CONSTITUTION:An oxide of a metal of the group II-IV of the periodic table, an Mg compd. (e.g. MgCl2), a di- to tetravalent Ti compd. (e.g. TiCl4), and an electron-donating compd. (e.g. acetyl chloride) are brought into contact with each other to give a solid component mainly comprising a metal oxide, Mg, Ti, a halogen, and an electron-donating compd., which is then brought into contact with an olefin at 100 deg.C or lower in the presence of a trialkylaluminum (e.g. trimethylalminum) and a dimethoxysilane compd. of the formula (wherein R<1> and R<2> are each a 1-10C aliph. hydrocarbon group) having a quantum- chemically calculated volume of 170-500Angstrom <3> and an electron density of an oxygen atom in the methoxy group of 0.690-0.800A.U. or having the volume of 200-500Angstrom <3> and the electron density of 0.685-0.800A.U.

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 silane 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.

Furthermore, as silane compounds used during prepolymerization, compounds with aromatic groups are generally used from the viewpoint of performance, but depending on the purpose of the polymer, silane compounds with aromatic groups may be harmful. There is.

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 Problems As a result of intensive research, the present inventors found that the silane compound added during prepolymerization has a volume of 170 to 500 A', and the electron density of oxygen in the methoxy group is 0.690 to 0.
If the dimethoxy group-containing silane compound of , g o o^4+ is used, a poly-α-olefin can be obtained with performance equivalent to or better than that of an organic silicon compound having an aromatic group, and the object of the present invention can be distantly related. They discovered this and completed the present invention.

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) a trialkylaluminium, and (C) a compound of the general formula R 'R'5i (OCR-)2 [However, R1
and R2 are aliphatic hydrocarbon groups having 1 to 10 carbon atoms, respectively. ], the volume calculated by quantum chemical calculation is 170-500A', and the electron density of the oxygen atom of the methoxy group is 0.690-0.800^, U, (
atomic unit) or the volume is 200 to 500 Å3
,, the electron density force 0.685-0.80 OA, U, (
7) A catalyst component for α-olefin polymerization which is brought into contact with an olefin in the presence of a dimethoxy group-containing silane compound.

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,
Examples include B2O3, MgO1AI2a, 5
iOz, Can TlO2, ZnO1ZrL, 5n
o2, Ban Thaw, etc. Among these, B20.3, Mg0, ^1203.5102, T
1O2 and ZrO2 are preferable, and 5I02 is particularly preferable. Furthermore, composite oxides containing these metal oxides, such as S
i[12-MgD, 5iD2-81203.5102
TlO2,510a-V2ns 3102 [:r
Z[]3.5iO2-TI[12-Mg or the like 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 A magnesium compound is represented by the general formula MgR'R'. In the formula, R' 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 a mialalkyl group, and as an OR group, R is an alkyl group having 1 to 12 carbon atoms. group, cycloalkyl group, aryl group, aralkyl group, the halogen atom is chlorine,
These include bromine, iodine, and fluorine.

Specific examples of these compounds are shown below. In the chemical formula, Me = methyl, Bt: ethyl, Pr: propyl, Bu
Nibutyl, He: hexyl, Oct: octyl, Ph
: Represents phenyl and cyHe dichlorohexyl, respectively.

MgMe2. MgBtz, Mg1-Prz,
MgBu2. MgHez.

Mg[1ct2. MgBtBu, MgPhz,
MgcyHe2゜Mg(OMe)z, Mg(OB
t)2. Mg(OBu)z, Mg(OHe)2゜M
g(00ct)z, Mg(OPh)s+, Mg
(OcyHe)2゜FltMg[:1, BuMgC
I, HeMgC1, i-BuMg['l, t-
BuMg(:I, PhMgCl, PhCHJg
Cl, BtMgBr.

BuMgBr, PhMgBr, BuMgl,
BtOMgCI.

OuOMgCI, He0MgCl, Ph0Mg
Cl, BtOMgBr.

[1uOMg[”l, BtOMgCI,
MgC1z, MgBr2, Mg12 The above magnesium compounds can also be prepared from metallic magnesium or other magnesium compounds when preparing component A.

Examples include metallic magnesium, halogenated hydrocarbons, and alkoxy group-containing compounds of the general formula group, M is a boron, carbon, aluminum, silicon or phosphorus atom, R is a carbon number of 1 to 20
m represents the valence of M, m>n≧0. ] is mentioned. As the hydrocarbon groups of X and R in the general formula of the alkoxy group-containing compound,
Methyl (Me) Ethyl (Bt) Propyl (P
), i-propyl (1-Pr) butyl (Bu) i-
Alkyl groups such as butyl (i-Bu), hexyl (He), octyl (Oct), cyclohexyl (cyHe)
) Cycloalkyl groups such as methylcyclohexyl, alkenyl groups such as allyl, propenyl, and butenyl, aryl groups such as phenyl (Ph) tolyl and xylyl groups, and aralkyl groups such as phenethyl and 3-7 enylpropyl.

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

■C(OMe) s , C contained in the compound formula C(OR) when M is carbon
(OBt) 4.

C(OPr)< , C(OBu)n, C(Oi-
Bu) < , C(OHe)n.

C((l[1ct)s' Formula XC([lR) 3
IC included in ([]Me) 3゜IIc(OBt)s
, IIc(OPr)3. , tlc(OBu)3.
HC(OHe)3゜HC(OPh)3; MeC(O
Me)3. MeC(OBt)3. BtC(OMe)
3゜BtC(OBt)a, cyt(eC(OBt)
:+, PhC(OMe)i.

PhC(OBt)3. CIIzCIC([]Bt)3
．． MeCLBrC(OBtL.

MeCH2CIC(OBt), + ; CIC(OMe
)3. CIC(Oat)a.

CIC (old-Bud3. BrC(OBt)s; Formula X
2C (OR), MeCH (Due) contained in 2. (
'H3CI([1Bt)z, C1lzC11z(D
.

Ctlz (Oat) 2, CILCICH (OB
t) 2, C) IcI□CH(OBt)2゜CCl
5CH(OBt)2. CCl5CH(OBt)2.
St(OMe)a included in the compound formula 5i(OR)= when PhCl1(OBt)2■M is silicon,
5i(OBt)4゜5i(OBu)n, 5i(O
i-Bu)4.3i(OHe)4°St (00ct)
4, St (OPh) 4: Formula XS i
1si(DBt)s, tls included in (OR)3
i(DBu)s, tlsi(OHe)*.

ll5i(OPh)+; MeS+(OMe)s,
MeSi(OBt)3゜MeSi(OBu)3,B
tSi(OBt)a, Ph5i(Out)s.

RtSi(OPh)s; Cl5i(mouthMe),
, Cl5i(OBt)3.

Cl5i(OBu)s, Cl5i(OPh)a
, Rrs+(OBt)3 ;Formula%Formula%) ) ): ■B(OBt)a, B(O) contained in compound 2〇(OR)3 when M is boron
Bu)*.

B (Olle) -, B (mouth Ph) 3.

■AI(OMe)s contained in the compound formula AI ((]R) when M is aluminum
, ^+(oBtL.

^1(OPrL, AI(Ot-Pr)a, AI(
OBu)s.

^+(ot-Bu)s, AI(OHe)+, A
I(OPh)s.

■When M is phosphorus, compound 2 P (OR) P (Due) a contained in s, P
(OBt)s.

1' (OBll) 3, P (Olle) 3
, P (OPh) 3° Furthermore, as the magnesium compound, a complex with an organic compound of a metal (M) of group Ⅰ or group ma of the periodic table can also be used. The complex has the general formula M
It is expressed as gR'R''・n(MR',).The metals include aluminum, zinc, calcium, etc.
'' is an alkyl group, a cycloalkyl group, an aryl group, or an 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. Specific examples of compounds represented by MR' include A
IMe= , A]Bta , A11-Buz l
^IPh, .

ZnMez, ZnBtz, ZnBuz, Z
nPh2. Examples include CaBt2°CaPh2.

(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, triethoxytitanium, 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, etc. Among these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, and ethers are preferably used.

Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, 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-methylcyclohexene-1,2-dicarboxylic acid, aromatic monomers such as benzoic acid, toluic acid, anisic acid, p-tert-butylbenzoic acid, naphthoic acid, and cinnamic acid. Examples include aromatic polycarboxylic acids such as carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellidic acid, hemimellitic acid, trimesic acid, viromeIJ) acid, meIJ) acid, and the like.

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 include butyl formate, ethyl acetate, butyl acetate, isobutyl isoacetate, propyl pivalate, isobutyl pivalate, and acrylic. Ethyl acid, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl di-1succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, adipine Diisobutyl acid, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, benzoin Methyl acid, ethyl benzoate, methyl p-)rulyate, ethyl p-tert-butylbenzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate , monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, terephthalic acid Examples include dibutyl, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellidate, 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, acetic acid chloride, acetic 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 chloride, glutaric acid chloride, glutaric acid chloride, adipic acid chloride, adipic acid chloride, 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, ■-cyclohexenecarboxylic acid chloride, cis-4,-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, benzoyl chloride, benzoyl bromide, p -) Tolyic acid chloride, p-toluic acid bromide, p-anisic acid chloride, p-anisic acid bromide, 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 R011.

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

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'7-shari-butylphenol, n-octylph4nol, and the like. Ethers have the general formula RO
It is represented by R'. In the formula, R and R' have 1- carbon atoms.
12 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 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. ■After contacting components 1 and 2, components 3 and 4 are brought into contact simultaneously.■After bringing components 2 and 3 into contact, component 4 and component 1 are brought into contact in that order.■Components After contacting component 2 with component 4, bringing component 3 and component 1 into contact with each other, ■component 2
．． A method such as bringing Component 3 and Component 4 into contact at 9 o'clock and then bringing Component 1 into contact may be employed. 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, Group 1Ia of the periodic table, group rVa, Va
Halides of group elements (hereinafter referred to as metal halides)
etc.

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 methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride,
Carbon tetrabromide, carbon tetraiodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-short ethane, methylchloroform, methylbromoform, methyliodoform, 1. 1.2-) Lichlorethylene, 1.1
．． 2-) Libromoethylene, 1.1.2゜2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1
2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane, and chlorinated paraffins; alicyclic compounds such as chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, and hexachlorocyclohexane; Examples include benzene, bromobenzene, 0-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, pencitrichloride, p-chlorobencitrichloride, and the like. These compounds may be used not only in one type but also in two types.

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-propatur, 3-chlor-1-propatol, 1-chlor-2-methyl-2-propatur,
4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 3-chloro-1
, 2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m, 0.p)
-Chlorbenzyl alcohol, 4-chlorcatechol,
4-chloro-(m,o)-cresol, 6-chloro-(
m,o)-cresol, 4-chloro-3,5-dimethylphenol, chlorohydroquinone, 2-benzyl-4
-Chlorphenol, 4-chloro-l-naphthol, (
m, o, p)-Chlorphenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorthymol, 4-chlorresorcin, 2-bromoethanol, 3-bromo-1- Proper tool, 1-bromo 2-proper tool, l-bromo-2-
Butanol, 2-bromo-p-cresol, l-bromo-
2-naphthol, 6-bromo-2naphthol, (m, o
, p)-bromophenol, 4-bromoresorcin, (
m, o, p) Fluorophenol, p-iodophenol = 2゜2-dichloroethanol, 2.3-dichloro-1
-propertool, 1,3-dichloro-2-propertool, 3-chloro-1-(α-chloromethyl)-1-propertool, 2,3-dibromo-1-propertool, 1.3
-Dibrome-2propanol, 2,4-dibromophenol, 2.4-dibrome-■-naphthol: 2.2゜2
-Trichlorethanol, 1.1, ■-Trichlorethanol 2
-Proper tool, β, β, β-triclo router
-Butanol, 2.3.4-) Lichlorphenol, 2
, 4.5-) Lichlorphenol, 2,4.6-) Lichlorphenol, 2.4.6-) Ribromophenol,
2,3゜5-tribromo-2-hydroxytoluene, 2
゜3.5-tribromo-4-hydroxytoluene, 2.
2.2-) Refluoroethanol, α, α.

α-Trifluoro-m-cresol, 2,4゜6-doliiodphenol: 2,3.4.6 Tetrachlorophenol, Tetrachlorohydroquinone, Tetrachlorbisphenol A1 Tetrabromobisphenol A, 2.2
, 3.3-tetrafluoro-1-propertool, 2,3
Examples include 5.6-tetrafluorophenol and tetrafluororesorcin.

Examples of halogenated silicon compounds having a hydrogen-silicon bond include )lsjcls, )+2slc12, LSi
C.I.

11cHssich, lIC2HsSiC12,1
1(t-CJs)SiCIz.

11cJ, 5iC1゜, H(C)i3)2sic1
, H(i-C31(,), 5iCILc2115si
cl L (n-CJs) SICI L (CeLCL
) SiCI, H3iC1(CeHs) 2, etc.

Metal halides include Ni, AI, Ga, In
.

TI, Si, Ge, Sn, Pb, As,
Examples include chlorides, fluorides, bromides, and iodides of Sb and Bi, especially BCI, , BBra, 813
, AICIa, AlBr3゜GaC1a,
GaBra, InC15t TIC]3
, 5ICI4.

5nC1a, 5bC1s, 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-5594909, and JP-A-55
-115405, 57-108107, 61-
No. 21109, No. 61-174204, No. 61-17
No. 4205, No. 61-174206, No. 62-770
Examples include the method disclosed in Publication No. 6 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)
(No. 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 its derivative, and a titanium compound into contact (Japanese Unexamined Patent Publication No. 1771204/1984) ■ Metal A method of contacting an oxide, an alkoxy-containing magnesium compound, a silicon compound having a hydrogen-silicon bond, an electron-donating compound, and a titanium compound (JP-A-61-1
74205 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 (corresponding to the alkoxy group-containing compound) is brought into contact with a halogen-containing alcohol, and further brought into contact with an electron-donating compound and a titanium compound (JP-A No. 6
2-7706). Among these methods, methods ① to ① are particularly desirable, and methods ① and ② are particularly preferable.

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.

TrialkylaluminiumTrimethylaluminum (hereinafter referred to as component B) is represented by the general formula AlR3 (where R represents an alkyl group having 1 to 12 carbon atoms). Specific examples include trimethylaluminum , triethylaluminum,
Examples include tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, trihexyl aluminum, and the like.

The dimethoxy group-containing silane compound (hereinafter referred to as component C) used in the present invention has the general formula R' R2S i (
OCH3) 2, the volume of the molecule calculated by quantum chemical calculation is 170-500 Å3, and the electron density of the oxygen atom of the methoxy group is 0.690-0.80 OA, tl, (
atomic unit), or the volume is 200 to 50
0 Å3, the electron density is 0,685~0.800^, u
,belongs to.

Quantum chemical calculations are performed using the following method. The volume of the molecule was purchased from QCPB (Quantum Chemistry Program Exchange Board), a non-profit organization that aims to disseminate various chemistry programs at Indiana University in the United States, to MUP8C, a molecular orbital method program. MNDO method (a type of semi-empirical molecular orbital method) [J, 8m, Chem, Soc,
, Journal of the American Chemical Society), Volume 99.

4899 pages, 4907 pages (1977); Volume 100,
3607, (1978)] and Van der W.
aals radius [J, Phys, Chem, (Journal of Physical Chemistry) Volume 68.

441-452 (1964)], and the electron density of the oxygen atom of the methoxy group is calculated from the above MOPA
It is calculated by Mlli[l[l method of C'.

The calculations were made using DEC (DIGITAL 801PM)
BNT C0RPOR8Tl0N) made (7) V to X 1
1/785 was used.

R1 and R2 in the above general formula of component C have 1 to 1 carbon atoms.
10 aliphatic hydrocarbon groups, namely alkyl groups and alkenyl groups, preferably alkyl groups.

Component C has a volume of 170-500 Å3 and a volume of 0.690-0
．． 800 The electron density of the oxygen atom of 8, U, or 200
~500 Å3, with a volume of 0.685~0,800 8,
It has an electron density of an oxygen atom of U, but both have an electron density of 2
0,690~0.760A with a volume of 00~400Å3,
, υ, and especially one having an electron density of 0.690 to 0.740 8U in a volume of 230 to 350 Å3 is desirable.

As described above, the component C that satisfies the volume and electron density is one in which the total number of carbon atoms in R1 and R2 is 5 or more, preferably 7 or more, and particularly preferably 9 or more.

Specific examples of component C will be listed below using chemical formulas.

In the formula, Me: CHs, Bt: C2t
ls, Pr: CpH1, Bu: Cs1ls
, Pt: CsL+, He: C6HI3
shows.

(t-Bu)(Me)Si(OMe)z, (i-
Pr)2si(UMe)2゜(t-Bu)'(Bt)S
i(OMe)z, (t-Bu)(i-Pr)Si
(OMe)2゜(n-11c)(Me)Si(OMe)
z, (t-Bu)(Et)Si(OMe)2゜[
(n-Pr)(Me)2c] (Me)Si(OMe)
z, (n-Bu)2si([]UMe2.(
i-Bu)2si(OMe)2. (s-Bu)2S
i(OMe),.

(t-Ru)2si(OMe)2, (t-Pt)
(i-Pr)Si(OMe>2.

[(n-Pr)(Me)JIBt-3+(OMe)z,
I: (Bt) + C] (Me) S i (mouth Me)
2, (t-Bu)(s-Bu)Si(OMe)z
, (t-Bu)(L-Pt)Si(OMe)2. [
:(n-Pr)(Me)2c] (i-Pr)Si(O
Ale)2. E (Bt)J〕(Bt)Si(DMe
)z, (L-Bu)[(nPr)(Me)CHI
S+ (OMe)z, (tPt)2si(O
Me)2. [(n-Pr)(Me)CH:l,5i
(Ole)z.

[(Me)3cmCH2:] 2si(OMe)z,
[:(at)(Me)zC・C11z]zsi(O
Me)z, (n-tle)zsi(OMe)2゜[(Me)3('-C2H4] 2Si(OMe)2
, [(Bt)(Me)2C'C)Iz] *Si(
[]Me)z, [(n-Pr)(Me)2c]
Examples include zsi(OMe) 2 and the like.

Prepolymerization The prepolymerization of the solid component (component A) is carried out by contacting it with an olefin in the presence of a trialkyl aluminum compound (component B) and a dimethoxy group-containing silane compound (component C).

In addition to ethylene, the olefins include propylene, 1-
α of 1f, 1-hexene, 4-methyl l-pentene, etc.
-Olefins may 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 higher, 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 multiple injections, it is natural that the polymerization conditions can be varied.

Component B is used so that the concentration in the prepolymerization system is 50 to 500 mmol/Il, preferably 80 to 200 mmol/I, and per gram atom of titanium in component A,
It is used in an amount of 4 to 50,000 mol, preferably 6 to t, ooo mol.

Component C has a concentration in the prepolymerization system of 1 to 100 mmol/
It is preferably used in an amount of 5 to 50 mmol/l.

Olefin polymer is incorporated into component A by prepolymerization, and the amount of polymer is 001 to 2 per component Atg.
00g, particularly preferably 0.5 to 50g.

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, from -50°C to +30°C, especially from 20°C to
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 also 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, ■-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 α-olefins mentioned above with each other and/or with ethylene.

The organometallic compound that can be used is an organic compound of a metal from Group 1 to Group 2 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. As the organoaluminum compound that can be used, general formula RnAlX3. ．． ．． ．． ．． (
However, >R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group, or a hydrogen atom, ir, and n is an arbitrary number in the range of l≦n≦3. ) having 1 to 18 carbon atoms, such as trialkylaluminium, dialkylaluminum monohalide, monoalkylaluminum civalide, alkylaluminum sesquihalide, di-γ-alkylaluminum monoalkoxide, and dialkylaluminum monohydride; Particularly preferred are alkyl aluminum compounds having preferably 2 to 6 carbon atoms, or mixtures or complexes thereof. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum, dimethylaluminum chloride, diethylaluminium chloride, diethylaluminum bromide, diethylaluminium iodide, diisobutylluminium Dialkyl aluminum monohalides such as chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dichloride, ethyl aluminum dichloride,
Monoalkylaluminum cibarides such as ethylaluminum diiodide, isobutylaluminum dichloride, alkyl°fluminium sesquihalides such as ethylaluminum sesquichloride, dimethylaluminum methoxide, diethylaluminum ethoxide, diethylaluminum phenoxide, dipropylaluminium ethoxide, Examples include dialkyl aluminum monoalkoxides such as diisobutyl aluminum ethoxide and diisobutyl aluminum phenoxide; dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, dialkyl aluminum hydride, and dialkyl aluminum hydride. Among these, trialkylaluminum is especially triethylaluminum,
Triisobutylaluminum is 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 (C-11s)
2^10^1 (CJs) a.

(C4L)2^lO^+(C,H9)2, (
C2H5)2AIN8I ([:2H5)2C2II
Examples include S.

Examples of organic compounds of metals other than aluminum include diethylmagnesium, ethylmagnesium chloride, diethylzinc, etc., as well as LiA1 (CJs)1. LiA1(CtH+s)4
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 Δ and the silane compound (component) used in the prepolymerization. In addition to being appropriately selected from C), electron-donating compounds made of organic silicon compounds other than the silane compounds, and electron-donating compounds containing heteroatoms such as nitrogen, sulfur, oxygen, and phosphorus can also be used.

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 Examples include silane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane, and lylorophenyldiethoxysilane.

Specific examples of electron-donating compounds containing heteroatoms include:
Compounds containing a nitrogen atom include 2゜2.6.6-tetramethylpiperidine, 2.6dimethylpiperidine, 2,6
-ethylbiperidine, 2,6-diisopropylpyrrolidine, 2,6-dibutyl-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-diitubrobilpyridine, 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, paratoluidine, orthotoluidine, metatoluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine,
Tributylamine is a compound containing a sulfur atom, such as thiophenol, thiophene, ethyl 2-thiophenecarboxylate, ethyl 3-thiophenecarboxylate, 2-methylthiophene, methylmercaptan, ethylmercaptan, isopropylmercaptan, butylmercaptan, diethylthioether. , diphenylthioether, methyl benzenesulfonate, methyl sulfide, ethyl sulfide, etc., as compounds containing an oxygen atom, tetrahydrofuran, 2-methyltetrahydrofuran, 3
-Methyltetrahydrofuran, 2-methyltetrahydrofuran, 2.2.5.5tetraethyltetrahydrofuran, 2.2,5゜5-tetramethyltetrahydrofuran, 2,2゜6.6-tetraethyltetrahydropyran,
2.2.6.6-Tetrahydropyran, dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, anisole, acetophenone, acetone, methyl ethyl ketone, acetylacetone, o-tolyl-t-butyl ketone, methyl2. 6-di-t-butylphenylketone, ethyl 2-furalate, isoamyl 2-furalate, methyl 2-furalate, propyl 2-furalate, etc. are examples of compounds containing a phosphorus atom, such as triphenylphosphine, tributylphosphine, and triphenylphosphine. Examples include phenyl phosphite, tribenzyl phosphite, diethyl phosphate, diphenyl phosphate 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,
The reaction can be carried out in an inert hydrocarbon such as heptane, octane, cyclohexane, benzene, toluene, xylene, or in a liquid aqueous solution. Polymerization temperature is usually -80℃~
+150°C, preferably in the range of 40-120°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. In addition, the amount of other olefin to be copolymerized with the α-olefin in the copolymerization is usually up to 30% by weight based on the α-olefin.
In particular, it is selected within the range of 0.3 to 15% by weight. The polymerization reaction may be carried out continuously or batchwise, 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 By adopting the above-mentioned structure, the present invention can improve the strength of the catalyst component, and the catalyst component has α-
In the (co)polymerization of olefins, catalyst components that maintain high activity, exhibit high stereoregularity, and are particularly washed are
It has the excellent effect of suppressing deterioration of performance and performance during catalyst storage.

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 H1), which indicates the proportion of crystalline polymer in the polymer, was measured using a modified Soxhlet extractor at boiling point 11! This is the residual amount after extraction with n-heptane for 6 hours.

Example 1 Preparation of Ingredients A 200 ml flask equipped with a dropping funnel and a stirrer was purged with nitrogen gas. In this flask, add silicon oxide (
5 g of VISON (trade name, -952) calcined in a nitrogen stream at 200°C for 2 hours and then at 700°C for 5 hours and 40% of n-hebutane were added. 20 rd of a 20% n-hebutane solution of ethylmagnesium (hereinafter referred to as BBM) (manufactured by Texas Alkyls, trade name: MAGALA BBM) was added, and the mixture was stirred at 90°C for 1 hour.

After the suspension was cooled to 0° C., a solution of 11.2 g of tetraethoxysilane dissolved in 201 nl of n-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, the produced solid was washed with 60-n-hebutane at room temperature, and the supernatant liquid was further removed by decantation. This washing treatment with n-hebutane was continued for 4 more times.
I went twice.

To the above solid, 50 ml of n-hebutane was added to make a suspension, and to this was added 8.0 ml of 2.2.2-trichloroethanol.
A solution prepared by dissolving G in 10 ml of n-hebutane 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, 60 mj! twice in n-hebutane, 60
Washing was performed three times with ml of toluene. When the obtained solid (solid component I) was analyzed, it was found that 810□36
．． 6%, magnesium 5.1%, and chlorine 38.5%.

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

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

After the temperature was lowered to 90° C., the clear solution was removed by decantation, and the solution was washed twice with 70 rnl of n-heptane.

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

Next, drying was carried out for 1 hour in a vacuum chamber, and 8:3
A catalyst component (component Δ) of g was obtained. This component A contains 3
．． It contained 1% titanium as well as silicon oxide, magnesium, chlorine and di-n-butyl phthalate.

In a 500 d reactor equipped with a prepolymerization stirrer, 1.9 g of component A obtained above and 280 rnl of n-heptane were placed under a nitrogen gas atmosphere, and the mixture was cooled to 5° C. while stirring. Next, a n-heptane solution (2.0 mol/f) of triethylaluminum (hereinafter abbreviated as TB Yari) and di-n
-hexyldimethoxysilane in n-hebutane solution (1,
0 mol/A'), and the concentrations of TEAL and di-n-hexyldimethoxysilane in the reaction system were each 80
The mixture was added at a concentration of 1J mol/l and 8 mmol/1, and stirred for 5 minutes. Next, after reducing the pressure in the system to 40 mmHH, propylene gas was supplied and propylene was polymerized 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 3.0 g per 1 g of the component.

Further, the volume of di-n-hexyldimethoxysilane and the electron density of the oxygen atom of the methoxy group were calculated as described above, and the results are shown in Table 1.

Examples 2 to 6 In the prepolymerization of Example 1, the silane compounds shown in Table 1 were used instead of di-n-hexyldimethoxysilane, and T
Preparation of the components was carried out in the same manner as in Example 1, except that the trialkyl aluminum shown in Table 1 was used in place of EAL at the concentration shown in Table 1, and the prepolymerization conditions were as shown in Table 1. Polymerization was carried out to prepare catalyst components.

Further, Table 1 shows the calculated values of the volume of each silane compound and the electron density of the oxygen atom of the methoxy group.

Comparative Example 1 Prepolymerization of component A was carried out in the same manner as in Example 1, except that di-n-hexyldimethoxysilane was not used and the prepolymerization conditions were as shown in Table 1. and prepared the catalyst component.

Comparative Example 2 The components were prepared in the same manner as in Example 1, except that in the prepolymerization of Example 1, dimethoxysilane was used instead of di-n-hexyldimethoxysilane, and the prepolymerization conditions were as shown in Table 1. A was prepolymerized to prepare a catalyst component.

Comparative Example 3 A catalyst component (component A) was prepared in the same manner as in Example 1, except that prepolymerization was not performed.

Example 7 Preparation of components 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 ml of n-hebutane at room temperature, and the supernatant was removed by decantation. This washing treatment with n-hebutane was further repeated four times.

To the above solid, 20-n-heptane was added to make a suspension, and to this was added 9.6 g of 2.2.2-)lichloroethanol.
A solution prepared by dissolving . After continuing stirring at 0°C for 1 hour, the temperature was raised to 80°C over 1 hour.
Stirring was continued at 80°C for 1 hour. After completion of the reaction, washing was performed at room temperature twice with 50 ml of n-hebutane and three times with 50 ml of toluene to obtain a solid (solid component I).

To the solid component I obtained above, 20-toluene and 0.6 g of di-n-butyl phthalate were added, and the reaction was carried out at 50°C for 2 hours. Next, 30 ml of titanium tetrachloride was added, and 9
After reacting for 2 hours at 0°C, the resulting solid material was
Washing was performed 8 times at room temperature with m1 of n-hexane. Dry for 1 hour at room temperature under reduced pressure to obtain 7.7 g of component A.
I got it. In addition to 3.0% titanium, Component A contained silicon oxide, magnesium, chlorine, and di-n-butyl phthalate.

Prepolymerization of component A using the component A obtained above and prepolymerization of component A was carried out in the same manner as in Example 1, except that the polymerization conditions were as shown in Table 1. was prepared.

Comparative Example 4 In the prepolymerization of Example 7, the catalyst components were prepared in the same manner as in Example 7, except that bis(2,2dimethylpropyl)dimethoxysilane was not used and the prepolymerization conditions were as shown in Table 1. Prepared.

Reference Example Example 7 except that in the prepolymerization of Example 7, diphenyldimethoxysilane was used instead of bis(2,2-dumethylpropyl)dimethoxysilane, and the prepolymerization conditions were as shown in Table 1. Preliminary polymerization of component Δ was carried out in the same manner as in Example 7 to prepare a catalyst component.

(A, Ll) (mmol/1) (n-He) asi (OMe) z ((Et) (M
e) ic) 2si(OMe)a(n-Bu) as
i (OMe) z(t-Bu) as i (OMe
) 2((n-Pr)(Me)CHI aSi(OMe
)z(([it)(Me)2C-CHa ]zsi(O
Me)2((lie)sC' CH2) asi(OM
e) z290, 4 256, 4 222, 1 222, 4 256, 5 290, 7 256, 2 0, 6941 0.7223 0, 6892 0, 7300 0, 6980 0, 6900 0, 6934 TI! ^L Tε^L TE.

I TIBAL EAL Tε^L 0 0 00 0 00 5 0 00 5 0 00 20 (Me)aSi(OMe)a 120, 1 0, 6802 EAL EAL ^LL Cliff 1) TIBAL: Triisobutyl aluminum 3
) loO+m! Wash 3 times with n-hexane 2) Dilute: Dilute, Wash: Clean, Dry: Dry for 1 hour under reduced pressure at room temperature Dilute x 5 times wash x 1 wash x 3 times Dry wash x 3 washes x 3 times Dry wash x 1 time Dilute x 3 wash x 3 times Dry wash x 1 Application example 1 In a stainless steel autoclave No. 1 and 51 equipped with a propylene polymerization stirrer, a solution of TEA l in n-heptane (0,1 4 ml of n-hebutane solution of di-t-amyldimethoxysilane (0.01 mol/Il〉2rn
1 was mixed and held for 5 minutes. Next, hydrogen gas 11 and liquid propylene If as a molecular weight control agent
After pressurizing the reaction system, the temperature of the reaction system was raised to 70°C. After charging 40 cm of the catalyst component obtained in Example 1 to the reaction system, propylene polymerization was carried out for 1 hour. After the polymerization was completed, unreacted propylene was purged to obtain a white polypropylene powder with an HI of 97.4%. The amount of polypropylene produced (C) per 1"g of component A/hour was 23.4 kg.

Further, the catalyst component obtained in Example 1 was placed in a glass container purged with nitrogen gas, sealed, and stored at 5° C. for 4 days, 10 days, and 20 days, and then subjected to propylene polymerization.

Polymerization of propylene was carried out in the same manner as above. The results are shown in Table 2. From the description in Table 2, it can be seen that storage deterioration is slight. In addition, in these polymerizations, 150 μm
The following fine powder polymers were not observed at all.

Application Examples 2 to 7 In place of the catalyst component obtained in Example 1, the catalyst components obtained in Examples 2 to 6 were used, and in Application Examples 4 and 7, di-t-
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 amyldimethoxysilane, and the results are shown in Table 2.

Application Examples 8 to 11 In place of the catalyst component obtained in Example 1, the catalyst components obtained in Comparative Examples 1 to 3 were used, and in Application Example IO, the catalyst components shown in Table 3 were used instead of di-t-amyldimethoxysilane. Polymerization of propylene was carried out in the same manner as in Application Example 1, except that the electron-donating compound shown was used, and the results are shown in Table 3.

In place of the catalyst component obtained in Example 1, Example 7. Using the catalyst components obtained in Comparative Example 4 and Reference Example, triisobutylaluminum was used instead of TEAL, the polymerization temperature was 80°C, and the electron-donating compounds shown in Table 3 were used instead of di-t-amyldimethoxysilane. using chemical compounds or
Polymerization of propylene was carried out in the same manner as in Application Example 1 except that no electron-donating compound was used, and the results are shown in Table 3.

[Brief explanation of drawings]

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) a trialkylaluminium, and (C) a compound having the general formula R^1R^2Si( OCH_3)_2 [However, R^1 and R^2 are the same or different carbon numbers 1 to
10 aliphatic hydrocarbon groups. ], the volume calculated by quantum chemical calculation is 170 to 500 Å^3, and the electron density of the oxygen atom of the methoxy group is 0.690 to 0.800 A. U. (atomic unit) or the volume is 200 to 500 Å^3 and the electron density is 0
．． 685-0.800A. U. A catalyst component for α-olefin polymerization, which is brought into contact with (D) an olefin in the presence of a dimethoxy group-containing silane compound.