JP2873055B2 - α-Olefin polymerization catalyst - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an α-olefin polymerization catalyst.

2. Description of the Related Art When a poly-α-olefin is produced using a catalyst component containing magnesium, titanium, chlorine and an electron-donating compound, the poly-α-olefin has a Si-OC bond together with an organoaluminum compound, or has a general formula SiR ¹ R ² _n ( It is known that when an organosilicon compound represented by OR ³ ) _3-n (n = 0 to 2) is used, the stereoregularity of the resulting polymer is improved (for example, see JP-A-54-94690, No. 56-36203, No. 57-63310,
Nos. 58-83016 and 62-11705).

However, contrary to the improvement in stereoregularity, the polymerization activity may be reduced to half or less as compared with the case where the organosilicon compound is not used. Depends on the type.

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

Means for Solving the Problems The present inventors have conducted extensive studies on a catalyst component containing magnesium, titanium, a halogen and an electron donating compound, and an organic silicon compound combined with an organoaluminum compound. The inventors have found that the object of the present invention can be achieved by using a cyclic organic silicon compound having an O bond, and completed the present invention.

SUMMARY OF THE INVENTION That is, the gist of the present invention includes (A) a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound as essential components, (B) a general formula R _n AlX _3-n (where R is an alkyl A group or an aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom, and n is an arbitrary number in the range of 1 ≦ n ≦ 3.) And (C) a general formula [However, R ¹ and R ² are identical or different numbers 1-10 hydrocarbon group having a _{^{carbon, OR 4, ▲ OSiR 5 3}} ▼ or ▲ SiR ^{6 ₃} ▼, R ₃ is 1-10 divalent carbon atoms Wherein R ⁴ , R ⁵ and R ⁶ are each a hydrocarbon group having 1 to 10 carbon atoms. ] An organosilicon compound represented by the formula:

Solid catalyst component The solid catalyst component (hereinafter referred to as component A), which is one component of the catalyst of the present invention, contains magnesium, titanium, halogen and an electron donating compound as essential components, and such components are usually magnesium compounds, In the case of a titanium compound, an electron donating compound, and a compound having no halogen, the compound is prepared by contacting a halogen-containing compound.

(1) Magnesium compound The magnesium compound is represented by the general formula MgR ¹ R ² .
In the formula, R ¹ and R ² represent the same or different hydrocarbon groups, OR groups (R is a hydrocarbon group), and halogen atoms. More specifically, as the hydrocarbon group of R ¹ and R ² , an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group, Twelve alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups include chlorine, bromine, iodine, and fluorine as halogen atoms.

Specific examples of these compounds are shown below.In the chemical formula, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl,
He: Hexyl, Oct: Octyl, Ph: Phenyl, cyHe: Cyclohexyl.

MgMe ₂ , MgEt ₂ , Mgi-Pr ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgEtBu, Mg
Ph ₂ , MgcyHe ₂ , Mg (OMe) ₂ , Mg (OEt) ₂ , Mg (OBu) ₂ , Mg (OHe) ₂ , Mg
(OOct) ₂ , Mg (OPh) ₂ , Mg (OcyHe) ₂ , EtMgCl, BuMgCl, HeMgCl, i
-BuMgCl, t-BuMgCl, PhMgCl, PhCH ₂ MgCl, EtMgBr, BuMgBr, Ph
MgBr, BuMgI, EtOMgCl, BuOMgCl, HeOMgCl, PhOMgCl, EtOMgB
_{r, BuOMgBr, EtOMgI, MgCl 2} , MgBr 2, MgI 2.

When preparing the component A, the magnesium compound
It is also possible to prepare from metallic magnesium or other magnesium compounds. Examples thereof include metal magnesium, halogenated hydrocarbons and an alkoxy group-containing compound of the general formula X _n M (OR) _mn , wherein X is a hydrogen atom,
A halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, M is boron, carbon, aluminum, silicon or a phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is a valence of M, m> n ≧ 0. ] Is contacted. Examples of the hydrocarbon group of X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl (Pr), i
-Propyl (i-Pr), butyl (Bu), i-butyl (iB
u), alkyl groups such as hexyl (He) and octyl (Oct), cycloalkyl groups such as cyclohexyl (cyHe) and methylcyclohexyl, alkenyl groups such as allyl, propenyl and butenyl, phenyl (Ph), tolyl and xylyl groups. Aryl groups, phenethyl, aralkyls such as 3-phenylpropyl and the like. Among these, an alkyl group having 1 to 10 carbon atoms is particularly desirable. Hereinafter, specific examples of the alkoxy group-containing compound will be described.

Compound when M is carbon C (OMe) ₄ , C (OEt) ₄ , C (OPr) ₄ , C (OBu) contained in formula C (OR) _4
4 , C (Oi-Bu) ₄ , C (OHe) ₄ , C (OOct) ₄ : H contained in the formula XC (OR) ₃
C (OMe) ₃ , HC (OEt) ₃ , HC (OPr) ₃ , HC (OBu) ₃ , HC (OHe) ₃ , HC (OP
h) ₃ ; MeC (OMe) ₃ , MeC (OEt) ₃ , EtC (OMe) ₃ , EtC (OEt) ₃ , cyHeC
(OEt) ₃ , PhC (OMe) ₃ , PhC (OEt) ₃ , CH ₂ ClC (OEt) ₃ , MeCHBrC (OE
t) ₃ , MeCHClC (OEt) ₃ ; ClC (OMe) ₃ , ClC (OEt) ₃ , ClC (Oi-B
u) ₃ , BrC (OEt) ₃ ; MeCH (OMe) ₂ , MeCH contained in formula X ₂ C (OR) ₂
(OEt) ₂ , CH ₂ (OMe) ₂ , CH ₂ (OEt) ₂ , CH ₂ ClCH (OEt) ₂ , CHCl ₂ CH (O
Et) ₂ , CCl ₃ CH (OEt) ₂ , CH ₂ BrCH (OEt) ₂ , PhCH (OEt) ₂ .

Compound where M is silicon Si (OMe) ₄ , Si (OEt) ₄ , Si (OBu) ₄ , Si contained in formula Si (OR) ₄
(Oi-Bu) ₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (OPh) ₄ : HSi (OEt) ₃ , HSi (OBu) ₃ , HSi (OHe) contained in the formula XSi (OR) _{3 3} , HSi (OPh) ₃ ; M
eSi (OMe) ₃ , MeSi (OEt) ₃ , MeSi (OBu) ₃ , EtSi (OEt) ₃ , PhSi (OE
t) ₃ , EtSi (OPh) ₃ ; ClSi (OMe) ₃ , ClSi (OEt) ₃ , ClSi (OBu) ₃ , C
lSi (OPh) ₃ , BrSi (OEt) ₃ ; Me ₂ Si (O) contained in the formula X ₂ Si (OR) _{2
Me) 2, Me 2 Si (} OEt) 2, Et 2 Si (OEt) 2; MeClSi (OEt) 2; CHCl 2 S
iH (OEt) ₂ ; CCl ₃ SiH (OEt) ₂ ; MeBrSi (OEt) ₂ : Me ₃ SiOMe, Me ₃ SiOEt, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ SiOE contained in X ₃ SiOR
t, Ph ₃ SiOEt.

Compound where M is boron B (OEt) ₃ , B (OBu) ₃ , B (OHe) ₃ , B (OPh) contained in formula B (OR) _3
3 .

Compound when M is aluminum Al (OMe) ₃ , Al (OEt) ₃ , Al (OPr) ₃ , Al contained in formula Al (OR) ₃
(Oi-Pr) ₃ , Al (OBu) ₃ , Al (Ot-Bu) ₃ , Al (OHe) ₃ , Al (OPh) ₃ .

Compound when M is phosphorus P (OMe) ₃ , P (OEt) ₃ , P (OBu) ₃ , P (OHe) contained in formula P (OR) _3
3 , P (OPh) ₃ .

Further, as the magnesium compound, a complex with an organic compound of a metal (M) of Group II or Group IIIa of the periodic table can also be used. The complex is represented by the general formula MgR ¹ R ² .n (MR ³ _m ). Examples of the metal include aluminum, zinc, and calcium, and R ³ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
M is the valence of the metal M, and n is a number from 0.1 to 10 MR ³
Specific examples of the compound represented by _m include AlMe ₃ , AlEt ₃ , A
Li-Bu ₃ , AlPh ₃ , ZnMe ₂ , ZnEt ₂ , ZnBu ₂ , ZnPh ₂ , CaEt ₂ , CaPh _{2 and the} like.

(2) Titanium compound The titanium compound is a compound of trivalent and tetravalent titanium, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, dichlorodiethoxytitanium, and dichlorodichlorotitanium. Butoxytitanium, dichlorodiphenoxytitanium, chlorotriethoxytitanium, chlorotributoxytitanium, tetrabutoxytitanium, titanium trichloride and the like. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxytitanium, dichlorodibutoxytitanium and dichlorodiphenoxytitanium are desirable, and titanium tetrachloride is particularly desirable.

(3) Electron-donating compound Examples of the electron-donating compound include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, ethers, ketones, amines, amides, nitriles, Aldehydes, alcoholates, phosphorus bonded to an organic group via carbon or oxygen,
Examples include arsenic and antimony compounds, phosphoamides, thioethers, thioesters, carbonate esters and the like. Of 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, crotonic acid, malonic acid, and succinic acid. , Glutaric acid, adipic acid, sebacic acid, maleic acid, aliphatic dicarboxylic acids such as fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid,
Cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexane dicarboxylic acid,
Aromatic carboxylic acids such as cis-4-methylcyclohexene-1,2-dicarboxylic acid, aromatic monocarboxylic acids such as benzoic acid, toluic acid, anisic acid, p-tert-butyl benzoic acid, naphthoic acid, and cinnamic acid Carboxylic acid, phthalic acid, isophthalic acid,
Aromatic polycarboxylic acids such as terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid, and melitic acid are exemplified.

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

As the carboxylic acid ester, mono- or polyvalent esters of the above carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutylate, propyl pivalate, isopropyl pivalate, and acrylic acid. Ethyl acrylate, 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, ditartrate Chill, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-tert-butyl benzoate, ethyl p-anisate, ethyl α-naphthoate, α-naphthoate Isobutyl, 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, dibutyl terephthalate, diethyl naphthalate,
Examples include dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, tetrabutyl pyromellitate, and the like.

As the carboxylic acid halide, acid halides of the above 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 bromide, butyric acid iodide, and pivalin. Acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride,
Methacrylic acid 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 bromide, maleic acid chloride, maleic acid bromide,
Fumaric acid chloride, fumaric acid bromide, tartaric acid chloride, tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, 1-cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid bromide Benzoyl chloride, benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid chloride, p-anisic acid bromide,
α-naphthoic acid chloride, cinnamate chloride, cinnamate bromide, phthalic dichloride, phthalic dibromide,
Isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, naphthalic acid dichloride. Also, adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride,
Monoalkyl halides of dicarboxylic acids such as butyl phthalate chloride may also be used.

Alcohols are represented by the general formula ROH. In the formula, R is an alkyl, alkenyl, cycloalkyl, aryl, aralkyl having 1 to 12 carbon atoms. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol,
Allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p
-Tert-butylphenol, n-octylphenol and the like. Ethers represented by the general formula ROR ^1. In the formula, R and R ¹ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R and R ¹ may be the same or different. Specific examples thereof 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, and ethylphenyl ether. .

As a method for preparing Component A, a magnesium compound (Component 1), a titanium compound (Component 2), and an electron donating compound (Component 3) are contacted in that order. Component 1 and component 3
And then contact component 2. Component 1, Component 2
And the method of contacting the component 3 simultaneously.
It is also possible to contact with a halogen-containing compound before contacting with component 2.

Halogen-containing compounds include halogenated hydrocarbons,
Examples thereof include a halogen-containing alcohol, a silicon halide compound having a hydrogen-silicon bond, and a halide (hereinafter, referred to as a metal halide) of a Group IIa, IVa, or Va element of the periodic table.

Examples of the halogenated hydrocarbon include mono- and polyhalogen-substituted saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. Specific examples of those 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 tetraiodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methyl chloroform, methyl bromoform, methyl iodoform, 1,1 1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-di Chlorpropane, hexachloropropylene, octachloropropane,
Decabromobutane, chlorinated paraffins, alicyclic compounds chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, hexachlorocyclohexane, aromatic compounds chlorobenzene, bromobenzene, o-dichlorobenzene, p -Dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloride and the like. These compounds may be used alone or in combination of two or more.

As the halogen-containing alcohol, a mono- or polyhydric alcohol having one or two or more hydroxyl groups in one molecule means a compound in which any one or two or more hydrogen atoms other than a hydroxyl group are substituted with a halogen atom. I do. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and a chlorine atom is preferable.

Illustrating those compounds are 2-chloroethanol,
1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1 -Hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-
Chlor- (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-chlorothymol, 4-chlororesorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-
2-propanol, 1-bromo-2-butanol, 2-
Brom-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-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-chloro-1- (α-chloromethyl) -1-propanol, 2 , 3-Dibromo-1
-Propanol, 1,3-dibromo-2-propanol,
2,4-dibromophenol, 2,4-dibromo-1-naphthol: 2,2,2-trichloroethanol, 1,1,1-trichloro-2-propanol, β, β, β-trichloro-tert
-Butanol, 2,3,4-trichlorophenol, 2,4,5-
Trichlorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,3,5-tribromo-2-hydroxytoluene, 2,3,5-tribromo-4-
Hydroxytoluene, 2,2,2-trifluoroethanol, α, α, α-trifluoro-m-cresol, 2,4,
6-triiodophenol: 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,
Examples include 3,3-tetrafluoro-1-propanol, 2,3,5,6-tetrafluorophenol, tetrafluororesorcin and the like.

Hydrogen - The halogenated silicon compound having _{silicon-bonded, HSiCl 3, H 2 SiCl 2} , H 3 SiCl, HCH 3 SiCl 2, HC 2 H 5 SiCl 2, H (t
-C ₄ H ₉ ) SiCl ₂ , HC ₆ H ₅ SiCl ₂ , H (CH ₃ ) ₂ SiCl, H (iC ₃ H ₇ ) ₂ SiCl,
H ₂ C ₂ H ₅ SiCl, H ₂ (nC ₄ H ₉ ) SiCl, H ₂ (C ₆ H ₄ CH ₃ ) SiCl, HSiCl (C ₆
H ₅ ) _{2 and the} like.

As metal halides, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb,
As, Sb, Bi include chloride, fluoride, bromide, iodide, especially BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ , AlBr ₃ , GaCl ₃ , GaBr ₃ , InCl
₃ , TlCl ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF _{5 and the} like are preferred.

Component 1, Component 2 and Component 3, and contact with a halogen-containing compound that can be contacted as necessary, are mixed and stirred in the presence or absence of an inert medium, but are mechanically co-ground. This is done by: The contact can be performed under heating at 40 to 150 ° C.

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

A desirable method for preparing Component A in the present invention is described in
-264607, 58-198503, 62-146904 and the like. More specifically, it can be obtained by contacting (a) metal magnesium, (b) a halogenated hydrocarbon, and (c) a compound of the general formula X _n M (OR) _mn (the same as the above-mentioned alkoxy group-containing compound). A method in which a magnesium-containing solid is brought into contact with (d) a halogen-containing alcohol and then with (e) an electron-donating compound and (f) a titanium compound (JP-A-63-26460).
No. 7), (b) after contacting a magnesium dialkoxide with a silicon halide having a hydrogen-silicon bond (b)
(C) a method of contacting with a titanium halide compound and then (d) contacting with an electron donating compound (and further contacting with a titanium halide compound if necessary)
62-146904), (b) after contacting a magnesium dialkoxide with a silicon halide compound having a hydrogen-silicon bond (b)
(C) A method of contacting with an electron donating compound and then (d) contacting with a titanium compound (JP-A-58-198503)
It is.

 Of these, the particular method is most desirable.

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

Further, the component A may further contain an olefin polymer formed in the component A by being brought into contact with an olefin in the presence of an organoaluminum compound. The organic aluminum compound is selected from the following organic aluminum compounds which are one component of the catalyst of the present invention.

As the olefin, propylene other than ethylene, 1-
Alpha-olefins such as butene, 1-hexene, 4-methyl-1-pentene can be used. Contact with the olefin is
It is desirable to carry out in the presence of the above-mentioned inert medium. Contact is
Usually, it is carried out at a temperature of 100 ° C. or less, preferably -10 to + 50 ° C. The amount of the olefin polymer contained in the component A is usually 0.1 to 100 g per component Alg.

The contact between the component A and the olefin may cause the electron donating compound to be present together with the organoaluminum compound. The electron donating compound is selected from compounds used for preparing the component A and organic silicon compounds having a Si—OC bond or a Si—NC bond. Component A, which has come into contact with the olefin, can be optionally washed with the above-mentioned inert medium and further dried.

Organoaluminum Compound Organoaluminum compound (hereinafter referred to as component B)
It is represented by the general formula R _n AlX _3-n (where R represents an alkyl group or an aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom, and n is an arbitrary number in the range of 1n3). Yes, for example, having 1 carbon atom such as trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide and dialkylaluminum monohydride.
Particularly preferred are alkyl aluminum compounds having from 18 to 18, preferably 2 to 6 carbon atoms, or mixtures or complex compounds thereof. Specifically, trimethyl aluminum,
Triethyl aluminum, tripropyl aluminum,
Trialkylaluminums such as triisobutylaluminum and trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, dialkylaluminum monohalides such as diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum Monoalkylaluminum dihalide such as dibromide, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride, alkylaluminum sesquihalide such as ethylaluminum sesquichloride, dimethylaluminum methoxide, diethylaluminum ethoxide,
Examples thereof include dialkylaluminum monoalkoxides such as diethylaluminum phenoxide, dipropylaluminum ethoxide, diisobutylaluminum ethoxide, diisobutylaluminum phenoxide, dimethylaluminum hydride, diethylaluminum hydride, and dialkylaluminum hydrides such as dipropylaluminum hydride and diisobutylaluminum hydride. Among these, trialkyl aluminum, particularly triethyl aluminum and triisobutyl aluminum are desirable. Further, these trialkylaluminums are other organic aluminum compounds, for example, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride, or mixtures or complex compounds thereof, which are easily available industrially. Etc. can be used in combination.

Organic silicon compound An organic silicon compound (hereinafter, referred to as one component of the catalyst of the present invention)
Component C. ) Is represented by the above general formula. In formula, R ^1, R ² hydrocarbon groups and _{^{OR 4, ▲ OSiR 5 3 ▼}} , ▲ Si
Examples of the hydrocarbon group R ^4, R ^5, R ⁶ in R ⁶ ₃ ▼, alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, cycloalkadienyl group, and aryl group, an aralkyl group or the like .

Examples of the alkyl group include methyl, ethyl, propyl, i
-Propyl, butyl, i-butyl, s-butyl, t-butyl, amyl, i-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, decyl group and the like, and alkenyl groups such as vinyl, allyl and propenyl , 1-butenyl, 1-pentenyl, 1-hexenyl, 1-octenyl, 1-decenyl, 1-methyl-1-pentynyl, 1-
Methyl-1-heptenyl and the like, as a cycloalkyl group, cyclopentyl, cyclohexyl, methylcyclohexyl group and the like, as a cycloalkenyl group, cyclopentenyl, cyclohexenyl, methylcyclohexenyl group and the like, and as a cycloalkadienyl group. , Cyclopentadienyl, methylcyclopentadienyl, indenyl group, etc., the aryl group is phenyl, tolyl, xylyl group, etc., and the aralkyl group is benzyl, phenethyl, 3-phenylpropyl group, etc. .

R ³ in the above general formula is a divalent hydrocarbon group, and specific examples include a group represented by the following general formula.

In the above, m is 1 to 10, and n, p, and q are 2 to 8, respectively.

 Specific examples of the above groups are as follows.

Component C is usually prepared by reacting a compound represented by the general formula R ¹ R ² SiX ₂ (X is a halogen atom) with a compound represented by the general formula HOR ³ OH in the presence of a dehydrohalogenating agent such as pyridine and quinoline. Reacting or reacting a compound represented by the general formula R ¹ R ² Si (OR ⁷ ) ₂ (R ⁷ is a hydrocarbon group) with a compound represented by the general formula HOR ³ OH in the presence of an acid or base catalyst Can be synthesized.

The catalyst of the present invention is composed of Component A, Component B and Component C.
1-2,000 gram moles per gram atom, preferably 20-5
00 g mol, component C is 0.001 to 10 per mol of component B.
Mole, preferably 0.01 to 1.0 mole.

Polymerization of α-olefin The catalyst of the present invention is useful as a catalyst for homopolymerization of an α-olefin having 3 to 10 carbon atoms or copolymerization with another monoolefin or a diolefin having 3 to 10 carbon atoms,
In particular, α-olefins having 3 to 6 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene, 1-
It shows extremely excellent performance as a catalyst for homopolymerization of hexene or the like or random and block copolymerization with the above-mentioned α-olefin and / or ethylene.

The polymerization reaction may be either a gas phase or a liquid phase, and when polymerizing in the liquid phase, an inert carbon such as 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 -80C to + 150C, preferably 40 to 120C. The polymerization pressure is, for example, 1 to 60
Atmospheric pressure is fine. Adjustment of the molecular weight of the resulting polymer is performed by the presence of hydrogen or other known molecular weight regulators. In the copolymerization, the amount of the other olefin to be copolymerized with the α-olefin is usually selected up to 30% by weight, especially in the range of 0.3 to 15% by weight, based on the α-olefin. The polymerization reaction by the catalyst system according to the present invention is carried out by a continuous or batch reaction, and the conditions may be those usually used. Further, the copolymerization reaction may be performed in one stage, or may be performed in two or more stages.

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

Examples The present invention will be specifically described with reference to examples and application examples.
The percentages (%) in the examples are by weight unless otherwise specified.

The heptane-insoluble matter (hereinafter abbreviated as HI), which indicates the proportion of the crystalline polymer in the polymer, is the remaining amount when extracted with boiling n-heptane for 6 hours using an improved Soxhlet extractor.

Example 1 Preparation of Component A In a single reaction vessel equipped with a reflux condenser, 8.3 g of chip-shaped metallic magnesium (purity 99.5%, average particle size 1.6 mm) and 250 ml of n-hexane were placed under a nitrogen gas atmosphere. , 68 ℃
After stirring for 1 hour, magnesium metal was taken out and dried under reduced pressure at 65 ° C. to obtain preactivated metal magnesium.

Next, n-butyl ether was added to the metallic magnesium.
A suspension obtained by adding 140 ml and 0.5 ml of an n-butyl ether solution (1.75 mol / l) of n-butylmagnesium chloride was added to the suspension.
While maintaining the temperature at 5 ° C., 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 conducting the reaction at 70 ° C. for 4 hours with stirring, the reaction solution was kept at 25 ° C.

Then, 55.7 ml of HC (OC ₂ H ₅ ) _{3 was} added dropwise to the reaction solution over 1 hour. After completion of the dropwise addition, the reaction was carried out at 60 ° C. for 15 minutes, and the solid produced by the reaction was washed six times with 300 ml each of n-hexane, and dried under reduced pressure at room temperature for 1 hour.
% Of the solid containing magnesium was recovered.

300ml equipped with reflux condenser, stirrer and dropping funnel
In a reaction vessel, a solid containing magnesium under a nitrogen gas atmosphere
6.3 g and 50 ml of n-heptane were put into a suspension, and a mixed solution of 20 ml (0.02 mmol) of 2,2,2-trichloroethanol and 11 ml of n-heptane was dropped from the dropping funnel over 30 minutes while stirring at room temperature. The mixture was further stirred at 80 ° C. for 1 hour. The obtained solid was separated by filtration, washed four times with 100 ml each of n-hexane at room temperature, and twice with 100 ml each of toluene to obtain a solid component.

40 ml of toluene was added to the above solid component, and titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. Under stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, followed by stirring at 120 ° C. for 2 hours. The obtained solid substance is 90
It was filtered off at 90 ° C. and washed at 90 ° C. twice with 100 ml each of toluene. Furthermore, a new volume ratio of titanium tetrachloride / toluene
Titanium tetrachloride was added to 3/2, and the mixture was stirred at 120 ° C for 2 hours. The solid material obtained is filtered off at 110 ° C.
After washing 7 times with 00 ml of n-hexane, 5.5 g of component A was obtained.

Polymerization of Propylene In a 1.5-liter stainless steel autoclave equipped with a stirrer, under a nitrogen gas atmosphere, 10.8 mg of the component A obtained above,
4 ml of a solution containing 0.1 mol of triethylaluminum (hereinafter referred to as TEAL) in n-heptane 1 and 0.04 mol of 2-cyclohexyl-2-methyl-2-sila-1,3-dioxane in n-heptane 1 ( 1 ml of a solution containing CMRS) was mixed and kept for 5 minutes. Next, 600 ml of hydrogen gas as a molecular weight controlling agent and liquid propylene 1 were injected under pressure, and then the temperature of the reaction system was raised to 70 ° C. to polymerize propylene for 1 hour. After completion of the polymerization, unreacted propylene was purged to obtain 96.8% HI white polypropylene powder.

 The polymerization activity of the catalyst was 18.6 kg / g · Component A.

Here, CMRS was prepared as follows. 150 ml of dry ether was placed in a reaction vessel and cooled with ice. To this, 47.5 g of cyclohexylmethyldichlorosilane and dry ether 1
A mixture of 00 ml and a mixture of 18.8 g of 1,3-propanediol, 40 g of pyridine and 100 ml of dry ether were simultaneously added dropwise with stirring. After the addition, the mixture was stirred at room temperature for 16 hours. The precipitate formed was separated by filtration, and the filtrate was distilled to obtain 19.9 g of CMRS.
I got The boiling point was 83 ° C / 0.1 mmHg.

Examples 2 to 7 Propylene was polymerized in the same manner as in Example 1 except that the organosilicon compounds shown in Table 1 were used instead of CMRS, and the results are shown in Table 1.

Comparative Example 1 Propylene was polymerized in the same manner as in Example 1 except that CMRS was not used, and the results are shown in Table 1.

Example 8 Preparation of Component A An internal volume of 170 g of commercially available magnesium diethoxide containing 400 stainless steel (SUS 316) balls having a diameter of 12 mm 1.
A nitrogen-gas atmosphere was placed in a 2 l stainless steel (SUS 316) mill pot, and the mill pot was mounted on a shaker, shaken at an amplitude of 10 mm and a rotation speed of 1420 rpm for 2 hours to make contact, and the crushed material (I) I got

200ml equipped with reflux condenser, dropping funnel and stirrer
Is sufficiently replaced with nitrogen gas. After 8.3 g of the pulverized product (I) and 42 ml of n-heptane were put into this reactor, 14.9 g of trichlorosilane and n-heptane were stirred at room temperature.
A mixed solution of 30 ml of heptane was dropped from the dropping funnel over 30 minutes, and the mixture was further stirred at 65 ° C. for 4 hours. 65
The mixture was filtered at 200C and washed with 100 ml of n-heptane at room temperature twice and 100 ml of toluene at room temperature three times with stirring for 10 minutes to obtain a toluene slurry of the reaction solid (I).

51 ml of TiCl ₂ was added to a toluene slurry composed of 8.5 g of the reaction solid (I) and 26 ml of toluene, and the internal temperature was raised to 80 ° C. over 20 minutes. After the temperature was raised, di-n-butyl phthalate was added.
A mixed solution consisting of 1.7 g and 8 ml of toluene was added dropwise over 15 minutes using a dropping funnel. Thereafter, the temperature was further raised to 115 ° C., and the mixture was stirred at the same temperature for 2 hours. After removing the supernatant liquid by decantation, the mixture was washed twice with 100 ml of toluene at a temperature of 90 ° C. for 10 minutes. Next, 21 ml of fresh toluene and 51 ml of TiCl ₂ were added, and the mixture was stirred at 115 ° C. for 2 hours.

The obtained solid substance was separated by filtration at 115 ° C., and washed eight times with 100 ml of n-heptane at room temperature to obtain a heptane slurry of the component A.

Polymerization of propylene Example 1 was repeated except that component A obtained above, the organosilicon compound shown in Table 1 and triisobutylaluminum were used instead of TEAL and the polymerization temperature was set to 80 ° C.
The polymerization of propylene was performed in the same manner as in
It is shown in the table.

Examples 9 and 10 Propylene was polymerized in the same manner as in Example 8, except that the compounds shown in Table 2 were used as the organosilicon compound.
The results are shown in Table 2.

Comparative Example 2 Propylene was polymerized in the same manner as in Example 8 except that the organosilicon compound was not used, and the results are shown in Table 2.

[Brief description of the drawings]

FIG. 1 is a flowchart showing the preparation process of the catalyst of the present invention.

Continuing from the front page (72) Inventor Sachi Usui 1-3-1, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama Prefecture Inside the Tonen Research Laboratory (72) Inventor Hiroyuki Furuhashi 1-3-3, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama No. 1 Tonen Research Laboratory (72) Inventor Satoshi Ueki 1-3-1 Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture 1 Tonen Research Laboratory (58) Fields surveyed (Int. Cl. ⁶ , DB name ) C08F 4/60-4/70

Claims (1)

(57) [Claims] 1. A solid catalyst component comprising (A) magnesium, titanium, a halogen and an electron donating compound as essential components, (B) a general formula R _n AlX _3-n (where R is an alkyl group or an aryl group, X Represents a halogen atom, an alkoxy group or a hydrogen atom, and n is an arbitrary number in the range of 1 ≦ n ≦ 3); and (C) a general formula [However, R ¹ and R ² are identical or different numbers 1-10 hydrocarbon group having a carbon, OR ^4, OSiR ⁵ ₃ or SiR ^{6 _3,} R ₃ is 1-10 divalent hydrocarbon group having a carbon number And R ⁴ , R ⁵ and R ⁶ are each a hydrocarbon group having 1 to 10 carbon atoms. ] An organosilicon compound represented by the formula:? -Olefin polymerization catalyst.