JPH0480210A - Alpha-olefin polymerization catalyst - Google Patents

Abstract

PURPOSE:To keep stereoregularity high and improve polymn. activity by compounding a solid catalyst component contg. a metal oxide, Mg, Ti, a halogen, and an electron donating compd. with an organometallic compd. and a specific organosilicon compd. CONSTITUTION:A metal oxide comprising an oxide of an element of the groups II to IV, an Mg compd., a Ti compd., an electron donating compd., and, if necessary, a halogen compd. are brought into contact with each other to give a solid catalyst component contg. the metal oxide, Mg, Ti, the halogen, and the electron donating compd. as the essential components. The catalyst component is compounded with an organometallic compd., pref. an organoaluminum compd., in an amt. of 1-2,000 gram molecule per gram atom of Ti in the catalyst component and an organosilicon compd. of the formula (wherein R<1> and R<2> are each a 1-10C hydrocarbon group, OR<4>, OSiR3<5>, or OSiR3<6>; R<3> is a 1-10C divalent hydrocarbon group; and R<4>, R<5>, and R<6> are each a 1-10C hydrocarbon group) in an amt. of 0.001-10mol per mol of the organometallic compd.

Description

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

Prior Art When producing polyα-olefins using catalyst components containing magnesium, titanium, chlorine and electron-donating compounds, they contain 5i-D-C bonds together with organoaluminum compounds, or the general formula % formula % organic It is known that the use of silicon compounds improves the stereoregularity of the resulting polymer (for example,
No. 4-94690, No. 5636203, No. 57-63
No. 310, No. 58-83016, No. 62-11705
However, despite the improvement in stereoregularity, the polymerization activity may be reduced to less than half of that when no organosilicon compound is used, and the relationship between the improvement in stereoregularity and the decrease in polymerization activity is unclear. , depends on the type of organosilicon compound.

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

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

Summary of the invention That is, the summary of the present invention is as follows: (A) a solid catalyst component containing a metal oxide, magnesium, titanium, halogen, and an electron-donating compound as essential components; (B) an organometallic compound; and (C) a general formula [ However, R' and R2 are the same or different hydrocarbon groups having 1 to 10 carbon atoms, OR'05iRH or 1tSiRH1
R3 is a divalent hydrocarbon group having 1 to 10 carbon atoms;
4, R5 and R6 are each a hydrocarbon group having 1 to 10 carbon atoms. ] An α-olefin polymerization catalyst comprising an organosilicon compound represented by the following.

Solid catalyst component The homogeneous catalyst component (hereinafter referred to as component A), which is a component of the catalyst of the present invention, contains metal oxides, magnesium, titanium, halogen, and electron-donating compounds as essential components. Usually, it is prepared by contacting a metal oxide, a magnesium compound, a titanium compound, an electron-donating compound, and, if each of the above-mentioned compounds does not have a halogen, 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 of them are B2O3, MgO1AI-03S
ID□, [:aOTiO2, Zn[], Z"02.5n
02, BaOTh[]2, etc. Among these, B2O3, MgO1AI203.5in2, TlO2
, ZrO2 are preferred, and 5102 is particularly preferred. Furthermore, composite oxides containing these metal oxides, such as 5I02
MgO1S102 Al2O3, 5102TlO2,
5102V2O5S+0z-Cr20:+, 5102
TlO2MgO and 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'R2. In the formula, R1 and R2 represent the same or different hydrocarbon group, OR group (R is a hydrocarbon group), or a halogen atom.

More specifically, as the hydrocarbon group for R' 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. In particular, the alkyl group, cycloalkyl group, aryl group, and aralkyl group include chlorine, bromine, iodine, fluorine, etc. as the halogen atom.

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

MgMe2. MgBt2. Mg1-Pr2. Mg
Bu2. MgHe2゜h [1ct2. Mg[1! t
Bu, JPh2. MgcyHe2Mg(OMe)
2. Mg(OBt)2. Mg([]Bu)2. M
g(OHeLMg(OOct)2. Mg(OPh)2
．． Mg(OcyHe)2゜EtMgC], BuM
gCl, HeMgCl, i-BuMgCl, t
BuMgC], PhMgBr, PhCH2Mg
Cl, BtMgBr.

BuMgBr, PhMgBr, BuMgl,
BtOMgCIBuOMgCl, He[]M
gCl, Ph[1MgCl, EtDMgBr.

BuOMgBr, BtOMgl, MgCl
z, MgBrz, 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 alkoxy group-containing compounds of the general formula group, M is boron, carbon,
An aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is the valence of M, and m>n≧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 (Et), propyl (Pr),
, ]-Propyl (1-Pr) Butyl (Bu) i-Butyl (1-Bu) Hexyl (He) Octyl (
Alkyl groups such as 0ct), cyclohexyl (cyHe
) cycloalkyl groups such as methylcyclohexyl, norylkenyl groups such as allyl, propenyl, butenyl, phenyl (Ph)) aryl groups such as IJ and xylyl groups,
Examples include aralkyl such as phenethyl and 3-phenylpropyl.

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

When 0M is carbon, C(OMe) contained in the compound formula [:(OR),4. C(
OBt), .

C(OPr)4. C(OBu), , C(Di-B
u)4. [: (Offle) 4°C (ODct),
: tic(OMe) contained in the formula XC(Orl)3
)3°HC(OBt)3. HC(OPr)3. H.C.
(OBu)3. HC(OHe)3゜HC(DPh)s
; MeC (DMe)3. Me[:(OBt)3.
[! tC(DMe)3Bt[l:(DBt)3. c.
yHeC(DBt)+, PhC(DMe)a.

PhC(OBt)3. [:H2CIC(OEt)3.
MeCHBr[:(OEt)3゜MeCtlC]C(
DEL)3; Cl[': (OMe), +, CIC
(OEt)3゜CI[: (old-BLI)3, BrC
(OEt)3: MeCH contained in formula X2C(OR)2
(OMe)2. MeCt((OBt)2.Cl12
C112 (O.

CH, ([]Et)2. [)12i1'1C)I(O
Bt)2. CII[I□[:H(DE!t)2゜CC
+3Cll(OBt)2. [:H2BrCH(OBt
)2. Si(OMe) contained in the compound formula Si (OR) when PhCH(OEt)2゜■M is silicon,
, 5i(OEt)<.

5i(OBu), 5i(Di-Bu)4, 5i(
Dlle),.

S+ (00ct) 4, 31 (OPh) a'
H3i (OBt
)a, H3i(OBu)s, H3i(OHe)
3゜H3i(OPh); MeSi(OMe)+
, MeSi(OBt)3.

MeSi(OBu)s, BtSi(OEt)3,
Ph5i(OEt)3.

BtSi(OPh)+; CISiCl5i(O
, Cl5i(OBt)3.

Cl5i(OBu)a, Cl5i(OPh)3.
Br5i(OBt)+; Formula% Formula% B ([]Bt)3 contained in compound 2B(OR)3 when 0M is boron. B(D
Bu)3゜B (OHe) 3,8 (DPh) 3
AI(OMe) + contained in the compound formula AI (OR) 9 when ゜0M is aluminum,
AI(OEt):, .

AI (OPr)s, 81 (Di-Pr)3
, 8] (OBu)3.

AI (Ot-Bu) 3. AI (Kana e) 3,
AI(OPh)3.

P(OMe)3 contained in the compound formula P(OR)3 when 0M is phosphorus. P(OB
t)3゜P(OBu)3, P(Olle)3,
P(OPh)3.

Further, as the magnesium compound, a complex with an organic compound of a metal (M) of Group 1 or Group 111a of the periodic table can also be used. The complex has a Gohan style MgR'R”・n (M
R', ). Examples of the metal include aluminum, zinc, calcium, etc., and R3 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.

Further, m represents the valence of the metal M, and n represents a number from 0.1 to 10. Specific examples of compounds represented by MR3 include A
]M83, AIBt3. A11-Bu+,
8] Ph3゜ZnMe2. ZnBt2. ZnB
u2′, ZnPh2. 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, titanium trichloroethquine, titanium trichlorobutoxy, and titanium dichlorjetoxy. Titanium, dichlordibutoxytitanium, dichlordiphenoxytitanium, chlortriethoxytitanium, chlortributoxytitanium, tetrabutoxytitanium, titanium trichloride and the like can be mentioned. Among these, tetravalent titanium halides such as titanium tetrachloride, trichlorethoxytitanium, dichlorodibutoxytitanium, and dichlordiphenoxytitanium are preferred, and titanium tetrachloride is particularly preferred.

(4) Electron-donating compounds Examples of electron-donating compounds include carboxylic acids, carboxylic anhydrides, carboxylic esters, 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, carbonic acid halides, alcohols, and ethers are preferably used.

Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, and crotonic acid, malonic acid, and succinic acid. , aliphatic dicarboxylic acids such as glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid, cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexane Sandicarboxylic acid,
Alicyclic 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 thereof include aromatic polycarboxylic acids such as carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellidic acid, hemimellitic acid, trimesic acid, pyromellitic acid, and methacrylic acid.

As the carboxylic acid anhydride, acid anhydrides of the above-mentioned carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above-mentioned carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, isobutyl pivalate, acrylic. Ethyl acid, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate,
Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, Methyl benzoate, ethyl benzoate, methyl p-)rulyate, ethyl p-tert-butylbenzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, phthalic acid Monomethyl, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, terephthalate Examples include dibutyl acid, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, triphytyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, and tetrabutyl pyromellitate.

As the carboxylic acid halide, acid halides of the above-mentioned carboxylic acids can be used, and specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride, butyric acid promide, butyric acid iodide, Pivalic acid chloride, pivalic acid promide, acrylic acid chloride, acrylic acid promide,
Acrylic acid iodide, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid bromide,
Succinic acid chloride, succinic acid bromide, glutaric acid chloride, glutaric acid bromide, adipic acid chloride, adipic acid bromide, sebacic acid chloride, sebacic acid 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 ROH.

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

Specific examples include methanol, ethanol, propatool, isoproptool, butanol, isobutanol, pentanol, hexanol, octatool, 2-
These include ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol, and the like. Ethers have the general formula ROR
' In the formula, R and R' have 1 to 12 carbon atoms.
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, etc. .

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

Examples of the halogen-containing compound include halogenated hydrocarbons, halogen-containing alcohols, halogenated silicon compounds having a hydrogen-silicon bond, and halides of elements of group 1 [a, IVa, and Va of the periodic table (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, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, carbon, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-short ethane,
Methyl chloroform, methyl bromoform, methyl iodoform, 1.1.2-) dichloroethylene, 1.1.
2-tribromoethylene, 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-chloropencitrichloride, and the like. Not only one kind but also two or more kinds of these compounds may be used.

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

Examples of these compounds include 2-chloroethanol, 1
-chlor-2-propertool, 3-o-1-propertool, 1-10-2-methyl-2-propertool, 4-
Chlor-1-butanol, 5-chloro-1-pentanol, 6-90-1-hexanol, 3-chlor-1.2-
Propanediol, 2-chlorocyclohexanol, 4
-Chlorbenzhydrol, (m,o,p)-chlorobenzyl alcohol, 4-chlorcatechol, 4-chloro-(m,o)-cresol, 6-chloro-(m,o
)-cresol, 4-chloro-3,5-dimethylphenol, chlorhydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m,
o, p)-Chlorphenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-90 luthymol, 4-chlorresorcin, 2
-bromoethanol, 3-bromo-1-propertool,
1 bromo 2-propatol, ■-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-dichlor-1-propatur, 1,3-dichloro-2-propatur, 3-chloro-1-(α-chloromethyl)-1-7′ lovanol,
2.3-dibromo1-propatol, 1.3-dibromo-2-propatol, 2.4-dibromophenol, 2
．． 4-dibromo-1-naphthol: 2.2゜2-trichloroethanol, 1.1.1-)lichlor-2-propatol, β, β, β-trichlor-tert-butanol, 2,3.4-)ribrome Phenol, 2,4.5-
)! J Chlorphenol, 2,4.6-trichlorophenol, 2.4.6-)ribromophenol, 2,3゜5-tribromo-2-hydroxytoluene, 2゜3.5
-) Ribromo-4-hydroxytoluene, 2.2.1-
) Refluoroethanol, α, α.

α-triple oro m-cresol, 2,4゜6-triiodophenol: 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 H3iC1s, LSiCl2. LSiCl)I
CLSiCI2. HC211sSiCh, H(t
-C4Hs)SiCl2°HCsH5Si[:1. ,
H(CL)zsicI, H(i-1,Ht)zs
icIH2CJsSiC1,L(n C1Hs)SiC
1, H2 (C6H4C) 13) SICI, H3+C
I (CsHs) 2 and the like.

Metal halides include B, AI, Ga, I
n.

TI, Si, Ge, Sn, Pb,
As, Sb, Bi chloride, fluoride, bromide,
Mention may be made of iodides, especially BCl2, BBr3.
BI3, AlCl2, AlBr3゜GaC15
, GaBr+ , InCl+ , TlC1! ,
Si[:1<.

5nC1, 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, bean alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic M2 hydrocarbons such as benzene, toluene and xylene can be used.

Specific examples of the preparation method for the components in the present invention include JP-A-58-162607, JP-A-55-94909, JP-A-5
No. 5-115405, No. 57-108107, No. 61
-21109, 61-174204, 61-1
No. 74205, No. 61-174206, No. 62-77
Examples include the method disclosed in Japanese Patent No. 06 and the like. More specifically, ■ A method in which a reaction product of a metal oxide and a magnesium dialkoxide is brought into contact with an electron-donating compound and a tetravalent titanium halide (JP-A-58-162607). A method of contacting a reaction product with a magnesium hydrocarbyl halide compound with a Lewis base compound and titanium tetrachloride (JP-A-55-94909) ■ A reaction product between a porous carrier such as silica and an alkylmagnesium compound, Method of contacting with an electron-donating compound and a silicon halide compound before contacting with a titanium compound (JP-A-55115405, JP-A No. 57-10810)
7) ■ A method of bringing a metal oxide, an alkoxy group-containing magnesium compound, an aromatic polycarboxylic acid having a carboxyl group at the ortho position or a derivative thereof, and a titanium compound into contact (Japanese Patent Application Laid-open No. 17420.11/1982) ■ Metal oxides, alkoxy-containing magnesium compounds,
A method of bringing a silicon compound having a hydrogen-silicon bond, an electron-donating compound, and a titanium compound into contact (Unexamined Japanese Patent Publication No. 61-17
4205 Publication) ■ Method of bringing metal oxide, alkoxy-containing magnesium compound, halogen element or halogen-containing compound, electron donating compound, and titanium compound into contact (JP-A-61-174206 Publication) ■ Metal oxide, dihydrocarbyl magnesium A method of contacting a reaction product obtained by contacting a halogen-containing alcohol with an electron-donating compound and a titanium compound (JP-A-61-21109) ■ Metal oxide, hydrocarbylmagnesium, and hydrocarbyloxy group-containing compound This is a method (Japanese Unexamined Patent Publication No. 627706) in which a solid obtained by contacting a solid (corresponding to the aforementioned alkoxy group-containing compound) with a halogen-containing alcohol, and further with an electron donating compound and a titanium compound. 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.

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

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

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

In the contact between component A and the olefin, an electron-donating compound may be present together with the organoaluminum compound. The electron-donating compound is selected from compounds used in preparing the components and organosilicon compounds having a 5i-0-C bond or a 5i-N-C bond. Component A that has been in contact with the olefin can be washed with the above-mentioned inert medium, if necessary, or further dried.

Organometallic compoundsOrganometallic compounds (hereinafter referred to as component B) are found in the first part of the periodic table.
It is an organic compound of a group metal to a group II metal. As component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly suitable. As the organoaluminum compound that can be used, the general formula R,, to 1X
3-. ．． (However, R is an alkyl group or an alkyl group, X is a halogen atom, an alkoxy group, or a hydrogen atom, and n is an arbitrary number in the range of 1≦η≦3.) 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxy)', and dialkyl aluminum monohydride. Alkylaluminum compounds or mixtures or complexes thereof are particularly preferred. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride, etc. dialkylaluminium monohalides, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, isobutyl aluminum dichloride, and alkylaluminum sesquihalides such as ethylaluminum sesquichloride. , dimethylaluminum methoxide, diethylaluminum ethoxide, diethylaluminum phenoxide, dipropylaluminum ethoxide, diisobutylaluminum ethoxide, diisobutylaluminum phenoxide, dialkylaluminum monoalkoxide, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutyl Examples include dialkyl aluminum hydrides such as aluminum hydride. Among these, trialkylaluminum is preferred, particularly triethylaluminum and triisobutylaluminum. In addition, these trialkylaluminums may be combined with other organoaluminum compounds such as industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminium hydride, or mixtures or complex compounds thereof. Can be used in combination with etc.

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

([:, H9) 2A10A1 (C4Hs) 2 ,
(C2115) 2AINAI (C211s)
Examples include 2[:, H5, etc.

Examples of organic compounds of metals other than aluminum include diethylmagnesium, ethylmagnesium chloride, diethylzinc, etc., as well as LiA1(C2Hs)4. LiA1(C7H,s)4
Compounds such as

Organosilicon Compound The organosilicon compound (hereinafter referred to as component C), which is one component of the catalyst of the present invention, is represented by the above general formula. In the chain formula, R', the hydrocarbon group of R2 and OR', 03
Examples of the hydrocarbon groups for R', R5, and R6 in iR8 and SiR include alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkagenyl groups, aryl groups, aralkyl groups, and the like.

Alkyl groups include methyl, ethyl, propyl, ]-
Propyl, butyl, i-butyl, S-butyl, t-butyl, methyl, 1-amyl, hexyl, octyl, 2-ethylhexyl, decyl, etc. are alkenyl groups such as ha, hinyl, allyl, Propenyl 1.1-7”7
-: L, 1-pentenyl, 1-hexenyl, 1-octenyl, 1-dekenyl, 1-methyl-1-pentynyl, 1
-Methyl-1-heptenyl, cycloalkyl groups include cyclopentyl, cyclohexyl, methylcyclohexyl groups, etc. cycloalkenyl groups include cyclopentenyl, cyclohexenyl, methylcyclohexenyl groups, cycloalkagenyl groups, etc. Examples of aryl groups include phenyl, tolyl, xylyl groups, etc.; examples of aralkyl groups include benzyl, phenethyl, 3-phenylpropyl groups, etc. Can be mentioned.

Further, R3 in the above general formula is a divalent hydrocarbon group, and specific examples include groups represented by the following general formula.

In the above, m is 1 to 10, n, p.

q is 2 to 8, respectively.

Specific examples of the groups (1) to (2) above are as follows.

2H5 CH3 Component C is usually a compound represented by the general formula R'R''5IX2 (X ha halogen atom) and the general 2H[1R3
0) A compound represented by 1 is reacted in the presence of a dehydrohalogenating agent such as pyridine or quinoline, or a compound represented by the general formula R'R2S+ (OR7) 2 (R' is a hydrocarbon group) and a general 2 The catalyst of the present invention, which can be synthesized by reacting a compound represented by HOR''DH in the presence of an acid or base catalyst, is composed of component A, component B, and component C, and their constituent proportions are is 1 to 2.0% of component B per gram atom of titanium in component A.
Component C is used in an amount of 0.001 to 10 mol, preferably 0.01 to 1.0 mol, per mol of component B.

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

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

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

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

The heptane-insoluble content (hereinafter abbreviated as H1), which indicates the proportion of crystalline polymer in the polymer, is the remaining amount when extracted with boiling ILt n-hebutane for 6 hours using a modified Soxhlet extractor.

Example 1 Preparation of Ingredients A 200rd flask equipped with a dropping funnel and a stirrer was purged with nitrogen gas. In this flask, 5 g of silicon oxide (manufactured by DAVISON, trade name G-952) calcined in a nitrogen stream at 200°C for 2 hours and 1, near 00°C for 5 hours and 40rr1 of n-hebutane were added. . Furthermore, η-butylethylmagnesium (hereinafter, BIE
It's called M. ) in 20% n-hebutane solution (manufactured by Texas Alkyls, trade name: MAGALA BBM) 2 D-
was added and stirred at 9D°C for 1 hour.

After the suspension was cooled to 0° C., a solution of 11.2 g of tetraethoxysilane dissolved in 20 mf 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-heptane at room temperature, and the supernatant liquid was further removed by decantation. This washing treatment with n-heptane was further repeated four times.

Add 50 ml to the above solid. n-hebutane was added to form a suspension, and to this was added 2.2.2-trichloroethanol8.
A solution of 0 g dissolved in 10-helbutane 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, 60 ml. twice in n-hebutane, 60
Washing was performed three times with rd toluene. When the obtained solid (solid component ■) was analyzed, it was found that 510236
．． 6%, magnesium 5.1%, and chlorine 38.5%.

To the solid component (1) obtained above, 10-heptane and 40 d of titanium tetrachloride were added, the temperature was raised to 90°C, and 0.6 g of di-n-butyl phthalate was dissolved in 5 mf of n-hebutane.
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 supernatant was removed by decantation and washed twice with 70 rnl of n-hebutane. Furthermore, 15-n-heptane and 40-titanium tetrachloride were added,
The reaction was carried out at 115°C for 2 hours. After the reaction is completed, 60al! Washing was performed 8 times with n-hexane at room temperature.

Next, drying was performed at room temperature under reduced pressure for 1 hour to obtain 8.3 g of catalyst component (component A). This component A contains 3.1%
of titanium, as well as silicon oxide, chlorine and di-n-butyl phthalate.

Component A 12 obtained above was placed in a stainless steel autoclave No. 1 and 51 equipped with a propylene polymerization stirrer under a nitrogen gas atmosphere.
．． 3 mg, 4 ml of a solution containing 0.8 mol of triethylaluminum (hereinafter referred to as TEAL) in 1 liter of n-hebutane. and 0.08 mol of 2 in n-heptane 11
- Cyclohexyl 2-methyl-2-silar A solution 1- containing 1,3-dioxane (hereinafter referred to as CMR3) was mixed and held for 5 minutes. Next, after 600°C of hydrogen gas and 1β liquid propylene were injected as a molecular weight control agent, the temperature of the reaction system was raised to 70°C, and propylene was polymerized for 1 hour. After the polymerization was completed, unreacted propylene was purged to obtain a white polypropylene powder with an HI of 96.5%. The polymerization activity of the catalyst was 13.3 kg/g/component A.

Note that CMR3 was prepared as follows. 150 ml of dry ether was placed in a reaction vessel and cooled on ice. to this,
A mixture of 47.5 g of cyclohexylmethyldichlorosilane and 100 ml of dry ether and a mixture of 18.8 g of 1,3-propanediol, 40 g of pyridine and 100 mf of dry ether were simultaneously added dropwise with stirring. After the dropwise addition, the mixture was stirred at room temperature for 16 hours. The formed precipitate is filtered,
By distilling the filtrate, 319.9 g of CMR was obtained.

The boiling point was 83°C/0.1 mmHg.

Examples 2 to 6 Propylene was polymerized in the same manner as in Example 1, except that the organosilicon compounds shown in Table 1 were used instead of CMR3, and the results are shown in Table 1.

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

Comparative Example 1 Table H3 H3 H3 H3 Heavy activity (kg/g・Component A) 13.3 12.3 15.0 12.4 60.7 12.7 12.7 I (%) 96.5 96. 6 97.2 96.0 95.5 97.5 Example 7 Preparation of Component A Silicon oxide and BEM were brought into contact in the same manner as in Example 1 except that the stirring time at 90°C was 2 hours. The supernatant liquid was removed by decantation, and the resulting solid was collected in 50ml. The supernatant was washed with n-hebutane at room temperature, and the supernatant was removed by decantation. This washing treatment with n-hebutane was further repeated four times.

20 mI to the above solid! of n-hebutane was added to form a suspension, and to this was added 2.2.2-MJ dichlorotanol9.
6g to 10rn1. A solution of n-hebutane of
The mixture was added dropwise from the dropping funnel at 0° C. over 30 minutes.

After continuing stirring at 0°C for 1 hour, the temperature was raised to 80°C over 1 hour, and stirring was continued at 80°C for 1 hour. After the reaction was completed, the solids (solid component
) was obtained.

20rrt of toluene and 0.6g of di-n-butyl anti-hyphthalate were added to the solid component I obtained above, and the mixture was heated at 50℃ for 2 hours.
A time reaction was performed. Next, 30% of titanium tetrachloride was added and reacted at 90°C for 2 hours, and the obtained solid substance was washed 8 times with 50rd n-hexane at room temperature. Drying was carried out under reduced pressure at room temperature for 1 hour to obtain 7.7 g of the component.

Polymerization of propylene 13.5 mg of component A obtained above, 2-t-butoxy-2-cyclopentadienyl-2-sila-1,3-dioxane (hereinafter referred to as BCR3).

0.08 mol/l n-heptane solution 1rd and triisobutylaluminum 0.8 mol/β n-heptane solution 1mf! , at 80°C in the same manner as in Example 1.
Polymerization of propylene was carried out for 1 hour, and the results are shown in Table 2.

Example 8.9 Propylene was polymerized in the same manner as in Example 7, except that the organosilicon compound shown in Table 2 was used instead of BCR3, and the results are shown in Table 2.

Comparative Example 2 Propylene was polymerized in the same manner as in Example 7 except that no organosilicon compound was used, and the results are shown in Table 2.

[Brief explanation of drawings]

No. Figure 1 is A diagram showing the preparation process of the catalyst of the present invention. Rocha This is a diagram.

Claims (1)

[Scope of Claims] (A) A solid catalyst component containing a metal oxide, magnesium, titanium, halogen, and an electron-donating compound as essential components, (B) An organometallic compound, and (C) General formula ▲ Numerical formula, chemical formula, table etc. ▼ [However, R^1 and R^2 are the same or different carbon numbers 1 to 1
0 hydrocarbon groups, OR^4, OSiR^5_3 or S
iR^6_3 and R^3 are divalent hydrocarbon groups having 1 to 10 carbon atoms, and R^4, R^5 and R^6 are each hydrocarbon groups having 1 to 10 carbon atoms. ] An α-olefin polymerization catalyst comprising an organosilicon compound represented by: