JPH0376708A - Catalyst component for alpha-olefin polymerization - Google Patents

Abstract

PURPOSE:To increase the strengths of catalyst particles by bringing a solid component mainly comprising 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 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 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. trimethylaluminum) 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 230-500Angstrom <3> and an electron density of an oxygen atom in the methoxy group of 0.685-0.800A.U.

Description

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

BACKGROUND OF THE INVENTION Catalyst components for alpha-olefin polymerization containing magnesium, titanium, halogen and electron-donating compounds are known.

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 the so-called prepolymerization method, in which the catalyst component is brought into contact with an olefin in advance, and the polymer produced therein is incorporated into the catalyst component to increase the strength of the catalyst component particles. Attempts have been made to improve the particle strength and stereoregularity of the final polyα-olefin by adding an electron-donating compound such as a silane compound during this prepolymerization.

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 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 can be harmful. Sometimes.

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 have found that the silane compound added during prepolymerization has a volume of 230 to 500 people and has an electron density of 0.685 for the oxygen of the methoxy group. ~
0.800A. U, (7) If a dimethoxy group-containing silane compound is used, a polyα-olefin can be obtained with performance equivalent to or better than that of an organosilicon compound having an aromatic group,
The present invention was completed by discovering 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: (8) A solid component containing magnesium, titanium, halogen, and an electron-donating compound as essential components, (B) trialkylaluminum and (C) general formula R'R'5i (OCHa)2CHowever, R1
and R2 are the same or different aliphatic hydrocarbon groups having 1 to 10 carbon atoms. ], and the volume calculated by quantum chemical calculation is 230 to 500 people3 Similarly, the electron density of the oxygen atom of the methoxy group is 0.685 to 0.80 OA, U,
In the presence of a dimethoxy group-containing silane compound (atomic unit), the catalyst component for α-olefin polymerization is brought into contact with (D) an olefin.

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

(1) Magnesium Compound A magnesium compound is represented by the general formula MgR'R''. 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,
Examples include bromine, iodine, and fluorine.

Specific examples of these compounds are shown below, and in the chemical formula, Me dimethyl, Bt: ethyl, P': propyl, Bu
Nibutyl, He: hexyl, Oct: octyl, Ph
: Represents phenyl and cyHe dichlorohexyl, respectively.

MgMez, MgBt, Mg1-Pra, M
gBu2, MgHe2.

Mg0ct2 + MgBtBu, MgPh
a, MgcyHe2.

Mg(OMe)a, Mg(OBt)z, Mg(
OBu)a, Mg(OHe)2.

Mg(0ct)2, Mg(OPh)z,
Mg(Ocy)leL.

BtMgCI, BuMgCl, HeMgCl,
i-BuMgCI, t-BuMgCl, PhM
gC1, PhC1 (*MgC1, BtMgBr.

Mouth uMgBr, PhMgBr, BuM
gl, BtOMgCI.

BuOMgCI, HeBuMgCI, P
h0MgCl, BtOMgBr.

OuOMgCI, BtOMgCI, MgCl2
, MgBr2, MgL.

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 (Bt) Propyl (P''), i-propyl (1-Pr) Butyl (8u) i-butyl (1-
Bu) Alkyl groups such as hexyl (He), octyl (Oct), cycloalkyl groups such as cyclohexyl (cyHe) methylcyclohexyl, alkenyl groups such as allyl, propenyl, butenyl, phenyl (Ph)
) IJ, aryl group of xylyl group, phenethyl,
Examples include aralkyl such as 3-phenylpropyl.

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

■C(OMe)*, C(O
Bt)n.

C(OPr), , [:(OBLI)4, C
(Di-Bu)< , [:(OHe)4°C(OOc
t)4: IC(O included in the formula XC(OR)3)
MeL.

+1(:(OEt)3.IC(OPrL, HC(
OBu)s, IIc(OHe)3゜8C(OPh)
3; MeC(OMe)s, MeC(OBt)a
, BtC(OMe)s.

BtC(mouthBt)s, cyHec(OBt)3
, PhC([]Me)3.

PhC(OBt)+ , (:HzCIC(OBt)3
, MeCtl2[1rC(OBt)+ .

MeCLCIC(OBt)* ; CIC(OMe
)3, CIC(OBt)3.

(1'1c(Di-Bu)s, BrC(OBt)3
; MeCtl (OMe
L, CLCH(OBtL, C11C112(O
.

CL(OBtL, CHClCH(OBt)2, C
HCl2CH(0[EtL.

CCl5CH(OBt)z, CtlJrC)I
(OBt)2. PhCII((][1t)z■Contained in compound formula 5i(OR)< when M is silicon Si(OMe)< ,
5i(01Et)4゜5i(O[lu)< ,
5i(Oi-RoU)4, St(Otle)<
.

Si (OOct) 4, St (OPh) 4
: 1Isi(OBt) contained in formula X5i(OR)s
)+ , ISi(OBu)a, 1lsi(O
tle)+.

) ISi(OPhL; MeSi(OMe)s,
MeSi(OEt)+.

MeS i (mouthBu)a, BtSt(OBt
)a, PhSt(OBt)+.

BtSi(OPh)+; CISiCl5i(O,C
l5i(OBt)*.

ClSi (Bu) + , Cl5i (OPh)
s, Br5i(OBt)+ ;Formula%Formula%) ): ) ■B(OBt)s, B(O) contained in the compound 2〇(OR) when M is boron
Bu) 3゜B (OHe) 3, 8 (OPh) 3
゜■ To the compound formula when M is aluminum, l (OR), AI(OMe)s contained in l
, Al ([]OBt s .

AI (OPr) 3 , ^1 (Di-Pr)a , A
I(OBu)3゜＾1 (Ot-Bu) 3, AI(
Otle)s, AI(OPh)s.

■P(OMe)s, P(O) contained in compound 2P(OR)3 when M is phosphorus
Bt)+.

P(OBu)+, P(OHe)3. P(OPh)
a.

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 has the general formula MgR'R2.n(MR
3m). Examples of the metal include aluminum, zinc, calcium, etc., and R3 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.

Further, m represents the valence of the metal M, and n represents a number from 0.1 to 1.0. Specific examples of compounds represented by MR3 are:
^IMes, ^1ota, ^11-lowu3
+ AlPh3.

ZnMe2, ZnBt2, ZnBu2, ZnPh
2, CaBtz.

Examples include CaPhz and the like.

(2) Titanium compounds Titanium compounds are divalent, trivalent, and tetravalent titanium compounds, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, and dichlorjetoxytitanium. , dichlordibutoxytitanium, dichlordiphenoxytitanium, chlortriethoxytitanium, chlortributoxytitanium, tetrabutoxytitanium, titanium trichloride, and the like. Among these, tetravalent titanium halides such as titanium tetrachloride, trichlorethoxytitanium, dichlorodibutoxy-f-9, and dichlordiphenoxytitanium are preferred;
Particularly desirable is titanium tetrachloride. .

(3) Electron-donating compounds Examples of electron-donating compounds include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic 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, 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, bilometic 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-toluate, ethyl p-tertiary 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 trimellidate, tributyl trimellidate, tetramethyl hyromellitate, tetraethyl pyromellitate, and tetrabutyl pyromellitate.

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

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

Alcohols are represented by the general formula R.

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 1-12 carbon atoms.
alkyl, alkenyl, cycloalkyl, aryl, and aralkyl, and R and R1 may be the same or different. Specific examples include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethylphenyl ether, and the like.

As for the preparation method of component A, ■ a magnesium compound (component 1), a titanium compound (component 2) and an electron-donating compound (
Component 3) is contacted in that order. (2) After component 1 and component 3 are brought into contact, component 2 is brought into contact. ■Ingredients 1. Ingredient 2
A method such as bringing Component 3 and Component 3 into contact at the same time can be adopted.

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

Examples of halogen-containing compounds include halogenated hydrocarbons, halogen-containing alcohols, halogenated silicon compounds having a hydrogen-silicon bond, halides of Group 11a, IVa, and Va elements of the periodic table (hereinafter referred to as metal halides), etc. 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, ethylchloride, 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-tribromoethylene, 1.1.2゜2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1
．． 2-dichloropropane, hexachlorobrobylene, octachloropropane, decabromobutane, chlorinated paraffin, and alicyclic compounds such as chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, and hexachlorocyclohexane are aromatic. Examples of the group compounds include chlorobenzene, bromobenzene, 0-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, pensitrichloride, p-chlorobencitrichloride, 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, 1-10Jl/-2-methyl-2-propatol, 4-chloro-1-butanol, 5-chloro-l-pentanol, 6-chlor -1-hexanol, 3-chlorotree 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, l-bromo-2-propanol, 1-bromo-2
-butanol, 2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (m
, o, p)-bromophenol, 4-bromoresorcin, (m, o, p) fluorophenol, p-iodophenol = 2゜2-dichloroethanol, 2.3-dichloro1-propatol, l, 3-dichloro-2-propatol, 3-chloro-1-(α-chloromethyl)-1-propatol, 2.3-dibromo-1-propatol, 1.
3-dibromo-2-propatol, 2.4-dibromophenol, 2.4-dibromo-1-naphthol: 2.2
゜2-Trichloroethanol, 1, ■, 1-trichlor-2-propanol, β, β, β-trichlorter
t-butanol, 2.3.4-)lichlorophenol,
2,4.5-trichlorophenol, 2.4.6-)lichlorophenol, 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-doliodophenol: 2. a, 4.6-tetrachlorophenol, tetrachlorno\hydroquinone, tetrachlorbisphenol A, tetrabromobisphenol A, 2
．． 2.3.3 Tetrafluoro-1-propertool; 2.
Examples include 3°5.6-tetrafluorophenol and tetrafluororesorcin.

Examples of halogenated silicon compounds having a hydrogen-silicon bond include H81C1s, H2SiCl2. L, 5iC1
.

HCHaSiClz, HCzHsSiCIa,
II(t-Ca)Is)Si('12゜1-1cs)I
sS+CIz, fl(CHa)zsicl, H
(1-C3Ht)zs+cIH2C211sSiC1,
1(2(n-Calls)SiC1,B2(C6H4C
H3) Sit: ], H3iCI(CaI2)2, etc.

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

TI, Si, Ge, Sn, Pb, ^s, Sb,
Examples include Bi chloride, fluoride, bromide, and iodide,
Especially B[:1. , BBrs, B13, AlC
l3+ AlBr3゜GaC1,,I GaBr3+
InC1a + TlCl3+ 5IC14.

5nC1, 5bCIs, SbF, etc. are preferred.

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

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

A preferred method for preparing component A in the present invention is disclosed in Japanese Patent Application Laid-open No. 63
-264607, 58-198503, 62-
This method is disclosed in Japanese Patent No. 146904 and the like. More specifically, ■ (a) metallic magnesium, (b) halogenated hydrocarbon, (c) general 2X. The magnesium-containing solid obtained by contacting the compound M(OR) (same as the alkoxy group-containing compound described above) with (d)
Method of contacting with a halogen-containing alcohol, and then contacting (e) an electron-donating compound and (h) a titanium compound (JP-A-63-264607) ■ (a) Magnesium dialkoxide and (b) hydrogen-
After contacting a halogenated silicon compound having a silicon bond, contacting a halogenated titanium compound, and then (
d) A method of contacting with an electron-donating compound (further contacting with a halogenated titanium compound if necessary) (Unexamined Japanese Patent Publication No. 6
(No. 2146904) ■ (a) Magnesium dialkoxide and (b) hydrogen-
A method of contacting a halogenated silicon compound having a silicon bond, then (c) contacting an electron-donating compound, and then (d) contacting a titanium compound (JP-A-58-19850)
Publication No. 3).

Among these, method (2) is particularly desirable.

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

Trialkylaluminum Trialkylaluminum (hereinafter referred to as component B) has a -grade formula ^IR5 [wherein R represents an alkyl group having 1 to 12 carbon atoms. ].

Specific examples thereof include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, and the like.

Dimethoxy group-containing silane compound The dimethoxy group-containing silane compound (hereinafter referred to as component C) used in the present invention has the general formula R'R25i (OCH
3) The volume of the molecule represented by z and calculated by quantum chemical calculation is 230 to 500.3 The electron density of the oxygen atom of the methoxy group is 0.685 to 0.800.

U, (atomic unit).

Quantum chemical calculations are performed using the following method. Molecular Volume is a molecular orbital method program. MNDO method (a type of semi-empirical molecular orbital method) of MOPAC [purchased from QCPB (Quantum Chemistry Program Exchange), a nonprofit organization located at Indiana University in the United States that aims to disseminate various chemistry programs] [ J, 8m, Chem, Sa
c, Journal of the American Chemical Society) ± 1 volume.

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

441-452 (1964)], and the electron density of the oxygen atom of the methoxy group is calculated from the above MOPA
It was calculated by the MNDO method of C. In addition, the calculation was carried out by DEC (DIGITAL [!QU-IPMBN
T C0RPORAT10N) (7) VAX 11/
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 the above-mentioned molecular volume and electron density of oxygen atoms, especially a volume of 230-350 and 0.690-0.
It is desirable to have an electron density of 740^0.

The component C that satisfies the above volume and electron density is:
The number of carbon atoms in RI and R2 must be 3 to 8, and the total number of carbon atoms in R' and R2 must be 9 or more, but preferably the total number of carbon atoms in R' and R2 is 10. That's all.

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

In the formula, Me: C)Is, Bt: C2
H5, Pr: C3H7, Bu: C4H! l,
Pt: CsL+, He: C5Ls.

(t-Bu) (t-Pt) Si (OMe) 2
, (t-Bu) (s-Pt) Si (OMe)
2(t-Pt)zsi(OMe)2. [:(n-P
r)(Me)CHI zsi(OMe)z(t Pt)
(s-Pt)Si(OMe)2. [(Me)3cm
Cfl□l zsi(OMe)z, [(Bt)(M
e) C) l-CH2F 2si(OMe)2゜(t-P
t) [(CHa)a C-CH2) asi(OMe
)2゜[(n-Pr)(Me)2c) (t-Pt)S
i(OMe)2. [(Bt)(Me)+C-CH2F
(t-Pt)Si(OMe)z, (n-He)
2si(OMe)z.

C(n-Pr) (Me) 2C″] 2si-(OM
e)z, [(Bt) (Me)2c ・CHz]2
si(OMe)a, ((Me)ac-CzL)
2si(OMe)2C(n-Pr)(Me)2C]
[:(Bt)(Me)2C-C)+2)S i (OM
e) 2 etc.

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-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. Polymerization methods include batch method,
It may be carried out either continuously or 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/1, preferably 80 to 200 mmol/β, and per 1 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/
1, preferably 5 to 50 mmol/β.

The olefin polymer is incorporated into component A by prepolymerization, but the amount of the botamer is 0.1 to 1 g per 1 g of component A.
It is desirable to set it as 200g, especially 0.5-50g.

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, between -50°C and +30°C, especially between -20°C and below.
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 shows extremely excellent performance as a catalyst for the homopolymerization of l-pentene, -hexene, etc., or for 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 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. The organoaluminum compound that can be used has the general formula Rn^IX, (where R is an alkyl group or an aryl group, X is a halogen atom,
Indicates an alkoxy group or a hydrogen atom, n is l −: n≦
Any number in the range of 3. ), and
Alkylaluminum having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as trialkylaluminum, dialkylaluminium monohalide, monoalkylaluminum civalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide, and dialkylaluminum monohydride. Particular preference is given to compounds or mixtures or complexes thereof.

Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride,
Dialkyl aluminum monohalides such as diethylaluminium chloride, diethylaluminum bromide, diethylaluminium iodide, diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum dichloride, etc. monoalkylaluminum civalide, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, dialkylaluminum such as dimethylaluminum methoxide, diethylaluminum ethoxide, diethylaluminum phenoxide, dipropylaluminium ethoxide, diisobutylaluminum ethoxide, diisobutylaluminum phenoxide, etc. Examples include dialkyl aluminum hydrides such as monoalkoxide, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, and diisobutyl aluminum hydride. Among these, trialkylaluminum is preferred, particularly triethylaluminum and triisobutylaluminum. These trialkylaluminums can also be used with other organoaluminum compounds, such as diethylaluminum chloride, which is industrially easy to handle.
It can be used in combination with ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminium hydride, or a mixture or complex compound thereof.

Furthermore, an organic aluminum compound in which two or more pieces of aluminum are bonded via an oxygen atom or a nitrogen atom can also be used. Such compounds include, for example, (CJs)2A1
0A1(CJs)2゜(C,H9)2A10AI(C,
H9)! , (C2H5)2^IN^1 (C2H
s) 2C2I+.

etc. can be exemplified.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc, etc., as well as Li^1(C2H5)4, LiA1(CJ+s)s
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 component A and the silane compound ( In addition to being appropriately selected from component C), electron-donating compounds consisting of organic silicon compounds other than the silane compounds, nitrogen, oxygen,
Electron donating compounds containing heteroatoms such as phosphorous 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 chlorophenyldiethoxysilane.

Specific examples of electron-donating compounds containing heteroatoms include:
Compounds containing a nitrogen atom include 2.2.6.6-titramethylpiperidine, 2.6-dimethylpiperidine, 2.
6-diethylpyrrolidine, 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-)lyntylpyrrolidine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-diitubro Bilviridin, 2.
6-butylpyridine, 1.2.4-trimethylpiperidine, 2.5-dimethylpiperidine, methyl nicotinate, ethyl nicotinate, nicotinamide, benzoic acid amide, 2-methylpyrrole, 2.5-dimethylpyrrole , imidazole, toluic acid amide, benzonitrile, acetonitrile, aniline, para-toluidine, ortho-toluidine, meta-toluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine, etc., as compounds containing a sulfur atom, thiophenol, thiophene , ethyl 2-thiophenecarboxylate, ethyl 3-thiophenecarboxylate, 2-
Methylthiophene, methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, butyl mercaptan, diethyl thioether, diphenyl thioether,
Methyl benzenesulfonate, methyl sulfide, ethyl sulfide, etc. are compounds containing oxygen atoms.
Tetrahydrofuran, 2-methyltetrahydrofuran,
3-Methyltetrahydrofuran, 2-methyltetrahydrofuran, 2.2.5.5-tetraethyltetrahydrofuran, 2.2.5゜5-tetramethyltetrahydrofuran, 2,2゜6.6-tetraethyltetrahydrofuran, 2゜2.6 .6-Tetrahydropyran, 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-butylphenyl Ketone, 2
- Ethyl furalate, isoamyl 2-furalate, methyl 2-furalate, propyl 2-furalate, etc. are compounds containing a phosphorus atom such as triphenylphosphine, tributylphosphine, triphenylphosphine, tribenzylphosphite, diethyl Examples include 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 in soil that has been brought into contact with an organometallic compound in advance.

The amount of organometallic compound used for the catalyst component of the present invention is:
per gram atom of titanium in the catalyst component, usually 1 to 2.
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℃~+
(50°C, preferably in the range of 40 to 120°C. The polymerization pressure may be, for example, 1 to 60 atm. The molecular weight of the resulting polymer pair can be adjusted by adding hydrogen or other known molecular weight regulators. In the copolymerization, the amount of other olefins to be copolymerized with the olefin is usually up to 30% by weight, especially 0.5% by weight, based on the olefin.
It is selected in a range of 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 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 an improved Soxhlet extractor.

Example 1 Preparation of components Chip-shaped metallic magnesium (purity 99.5%) was placed in 11 reaction vessels equipped with a reflux condenser under a nitrogen gas atmosphere.
, average particle size 1,6u+) 8.3g and n-hexane 25
After adding 0 mA' and stirring at 68°C for 1 hour, the metallic magnesium was taken out and dried under reduced pressure at 65°C, thereby obtaining preactivated metallic magnesium.

Next, n-butyl ether 1
40rn1 and n- of n-butylmagnesium chloride
0.5 r of butyl ether solution (1,75 mol/1)
The suspension was kept at 55 DEG C., and a solution of 38.5 ml of n-butyl chloride dissolved in 50 ml of n-butyl ether was added dropwise over 50 minutes. After carrying out the reaction at 70°C for 4 hours with stirring, the reaction solution was maintained at 25°C.

Next, HC ([1C2H5) 355.7
- was added dropwise over 1 hour. After the dropwise addition was completed, the reaction was carried out at 60°C for 15 minutes, and the reaction product solid was mixed with 3001 g of each n-hexane.
n! ! , and dried under reduced pressure at room temperature for 1 hour to recover 31.6 g of a magnesium-containing solid containing 19.0% magnesium and 28.9% chlorine.

300 equipped with reflux condenser, stirrer and dropping funnel
ml of reaction vessel, put 6.3 g of magnesium-containing solid and 50 rnl of n-hebutane under nitrogen gas atmosphere to make a suspension, and add 2.2.2-)lichloroethanol 20-(0, 02 mmol> and n-heptane 1i
A mixed solution of rnl was added dropwise from the dropping funnel for 30 minutes,
The mixture was further stirred at 80°C for 1 hour. The obtained solid was filtered,
100 mj each of beef shank to n- at room temperature! A solid component was obtained by washing four times with 100% of toluene and twice with each 100% of toluene.

To the above solid component, 40% of toluene was added, and further titanium tetrachloride was added so that the titanium tetrachloride/toluene volume ratio was 372, and the temperature was raised to 90°C. Under stirring, diphthalate n
-Butyl 2- and toluene 5d! After dropping the mixed solution over 5 minutes, the mixture was stirred at 120°C for 2 hours. The solid material obtained was filtered off at 90°C and washed twice with 100 rR1 of toluene at 90°C. Furthermore, titanium tetrachloride was newly added so that the titanium tetrachloride/toluene volume ratio was 372, and the mixture was stirred at 120° C. for 2 hours. The obtained solid substance was filtered at 110° C. and washed seven times with each 100-hexane solution at room temperature to obtain 5.5 g of component A.

In a 500-mm reactor equipped with a prepolymerization stirrer, 2.5 g of component A obtained above and 22 g of n-heptane were added under a nitrogen gas atmosphere.
80W11 was added and cooled to -5°C while stirring. Next, triethyl aluminum (hereinafter referred to as TEAL)
A solution of n-hebutane (2.0 mol/1) and a solution of di-n-hexyldimethoxysilane in n-hebutane (1.0 mol/Il) were added to the concentration of TEAL and di-n-hexyldimethoxysilane in the reaction system. is 100 mmol/each
They were added at concentrations of 1 and 10 mmol/l and stirred for 5 minutes. Next, after reducing the pressure in the system to 40 nnHg, propylene gas was continuously supplied to polymerize propylene for 30 minutes. After the polymerization is completed, the propylene gas in the gas phase is purged with nitrogen gas for 100 d each! of n-hexane three times,
The solid phase portion was washed at room temperature. Furthermore, the solid phase portion was dried under reduced pressure at room temperature for 1 hour to prepare a catalyst component.

As a result of measuring the amount of magnesium contained in the catalyst component, the amount of prepolymerization was 2.0 g per 1 g of component A.

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 5 In the prepolymerization of Example 1, the silane compounds shown in Table 1 were used instead of di-n-hexyldimethoxysilane, and T
Using trialkyl aluminum shown in Table 1 instead of EAL or TEAL at the concentration shown in Table 1, respectively,
A catalyst component was prepared by prepolymerizing component A in the same manner as in Example 1, except that the prepolymerization conditions were as shown in Table 1.

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 In the prepolymerization of Example 1, component A was prepolymerized 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. , the catalyst components were prepared.

Comparative Example 2 In the prepolymerization of Example 1, dimethyldimethoxysilane was used instead of di-n-hexyldimethoxysilane,
A catalyst component was prepared by prepolymerizing component A in the same manner as in Example 1, except that the prepolymerization conditions were as shown in Table 1.

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

Reference Example In the prepolymerization of Example 1, diphenyldimethoxysilane was used instead of di-n-hexyldimethoxysilane, and the prepolymerization conditions were as shown in Table 1.
Component A was prepolymerized in the same manner as in Example 1 to prepare a catalyst component.

笈-上一表(人・) (A,U) (mmol/It”) Comparative Example 1 Boiled (n-) 1e) as i ([1Me) *((n-
Pr)(Me)CH) asi(014e)a[(Et
)(Me)zc) aSj(Olle)a((Me)
mc-CHa ] isi(OMe)tC(Et) (
Me) aC-CL E zsi (OMe) 229
0, 4 256, 4 256, 4 256, 2 290, 7 0, 6941 0, 6980 0, 7223 0.6934 0, 6900 (Me)zsi(OMe).

(Csl(s) asi (OMe) a120, 1 0, 6802 5 EAL EAL EAL TIBAL'I IBAL Wash x 3 times dry dilute) x 5 times wash x 1 time dilute x 3 times wash x 3 times TEA and EAL 00 0 3.0 2.1 Wash x 1 time Rare x 3 times EAL 50 0 9 Wash x 1 time! 1) TI8^nitriin butylaluminum 2) Dilute: dilute, wash: clean, dry: dry 3) Application example of dilution with n-hebutane Under gas atmosphere, TEAL n-fuhebutane solution (0.1 mol/l) 2mj! and n-hebutane solution of di-n-hemacyldimethoxysilane (0.01 mol/I
l) 2ml was mixed and held for 5 minutes. Next, 600 ml of hydrogen gas as a molecular weight control agent and 11 liquid propylene were pressurized, and then the temperature of the reaction system was raised to 70°C.

After charging 40 mg of the catalyst component obtained in Example 1 to the reaction system, propylene polymerization was carried out for 1 hour.

After the polymerization is completed, unreacted propylene is purged and HI98
, 4% white polypropylene powder was obtained.

Raw propylene tL amount (CB) per 1g of component A/hour
was 47.6 kg.

Further, the catalyst component obtained in Example 1 was placed in a glass container purged with nitrogen gas, sealed, and stored at 15° 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, 150μ
No fine powder polymer of less than m was observed.

Application Examples 2 to 7 The catalyst components obtained in Examples 2 to 5 were used in place of the catalyst components obtained in Example 1, and the electron-donating compounds shown in Table 2 were used in place of di-n-hexyldimethoxysilane. Polymerization of propylene was carried out in the same manner as in Application Example 1, except that the polymer was used or not, and the results are shown in Table 2.

Application Examples 8 to 13 The catalyst components obtained in Comparative Examples 1 to 3 and Reference Examples were used in place of the catalyst component obtained in Example 1, and the catalyst components shown in Table 3 were used in place of di-n-hexyldimethoxysilane. Polymerization of propylene was carried out in the same manner as in Application Example 1, except that an electron-donating compound was used or not, 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 magnesium, titanium, halogen, and an electron-donating compound as essential components, (B) trialkylaluminium, and (C) general formula R^1R^2Si(OCH_3)_2 [ However, R^1 and R^2 each have the same or different carbon numbers of 1 to
10 aliphatic hydrocarbon groups. ], the volume calculated by quantum chemical calculation is 230 to 500 Å^3, and the electron density of the oxygen atom of the methoxy group is 0.685 to 0.800 A. 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 (atomic unit).