JP2775507B2 - Method for producing poly-α-olefin - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for producing a poly-α-olefin, and particularly to a high melt flowable poly-α-olefin having a melt flow rate of 50 or more.
It relates to a method for producing an olefin.

2. Description of the Related Art When a poly-α-olefin is produced using a component containing magnesium, titanium, a halogen and an electron-donating compound as a main catalyst, the use of an organosilicon compound together with an organoaluminum compound improves the stereoregularity of the resulting polymer. . However, at the same time, the polymerization activity of the catalyst is reduced. The degree of improving the stereoregularity and the rate of decreasing the polymerization activity vary greatly depending on the type of silicon compound used. Generally, a silicon compound having an aromatic group exhibits good performance, but an undesirable substance may be formed from the silicon compound having an aromatic group depending on the intended use of the polymer.

On the other hand, in order to improve the melt fluidity of the polymer, a method of increasing the melt flow rate of the polymer with hydrogen is generally employed, but this method generally reduces the stereoregularity of the polymer.

Recently, (A) a solid titanium catalyst component containing magnesium, titanium, halogen and a polycarboxylic acid ester as essential components formed by contacting a magnesium compound, a titanium compound and a polycarboxylic acid ester, and (B) an organic compound Aluminum compound catalyst component, (C)
MFR is 10 g / 1 in the presence of a catalyst system formed from an organosilicon compound catalyst component represented by the general formula SiR ¹ _m (OR ² ) _4-m.
A method for producing a propylene block copolymer for more than 0 minutes has been proposed (JP-A-63-27517).

However, this method is a method for producing a specific propylene block copolymer, and the MFR of the obtained copolymer is also 40 g / 10
There are only examples up to less than a minute.

Further, the components (A), (B) and (C) of the general formula SiR ¹ R ² (OR ³ ) ₂ described in JP-A-63-27517.
Also known is a method of polymerizing or copolymerizing an olefin in the presence of a catalyst formed from an organosilicon compound catalyst component represented by the following formula (JP-A-63-223008).
In this method, even if the melt flow rate of the polymer is changed by hydrogen, the decrease in the tacticity of the polymer is small. However, in this method, the organosilicon compound substantially used is a methoxy group-containing silicon compound, and the resulting polymer also has an MFR of less than 40 g / 10 minutes.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention uses a catalyst that combines an organosilicon compound that has a good effect on the melt flow rate by hydrogen (that is, hydrogen response) and that causes a small decrease in the stereoregularity of a polymer. It is an object of the present invention to provide a method for obtaining a poly-α-olefin having high melt fluidity in high yield.

Means for Solving the Problems The present inventors have conducted intensive studies on a polymerization method of α-olefin using a polymerization catalyst containing an organosilicon compound as a component, and as a result, the volume of the molecule is somewhat large, and A specific polymerization catalyst in which the ethoxy group-containing silane compound in which the electron density of the oxygen atom of the ethoxy group is in a specific range is one component,
The present invention has been found to exhibit high activity and to be able to produce a poly-α-olefin having a high stereoregularity, to have a good hydrogen response, and to have a small decrease in the stereoregularity even when a large amount of hydrogen is used. completed.

SUMMARY OF THE INVENTION That is, the present invention provides (A) a solid catalyst component comprising 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 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 R _n Si (OC ₂ H ₅ ) _{4-n wherein} R is 5 to 10 carbon atoms.
Aliphatic hydrocarbon groups, n and 1 or 2. Represented by], quantum chemical calculation volume 240～500A ³ calculated in the electron density of oxygen atoms in the ethoxy group likewise 0.680～0.800A.
A method for producing a poly-α-olefin, comprising polymerizing an α-olefin in the presence of a catalyst comprising an ethoxy group-containing silane compound of U. (atomic unit).

Solid Catalyst Component The solid catalyst component (hereinafter referred to as component A), which is one component of the catalyst used in the present invention, contains magnesium, titanium, halogen and an electron donating compound as essential components. In the case where the compound, the titanium compound, the electron donating compound, and each of the compounds has no halogen, the compound is prepared by contacting the compound with a halogen.

(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, and examples of the halogen atom include chlorine, bromine, iodine and fluorine.

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 , Mg-Pr ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgE
tBu, MgPh 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, B
uMgCl, HeMgCl, i-BuMgCl, t-BuMgCl, PhMgCl, PhCH ₂ MgCl,
EtMgBr, BuMgBr, PhMgBr, BuMgI, EtOMgCl, BuOMgCl, HeOMgC
l, PhOMgCl, EtOMgBr, BuOMgBr, EtOMgI, MgCl ₂ , MgBr ₂ , Mg
I _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, N 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 represented by X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Bt), propyl (Pr), i
-Propyl (i-Pr), butyl (Bu), i-butyl (i
-Bu), 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 And aralkyl groups such as phenethyl and 3-phenylpropyl. 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 (O) contained in the formula C (OR) _{4
Bu) 4, C (Oi-} Bu) 4, C (OHe) 4, C (OOct) 4: Formula XC (OR) HC contained in the _{3 (OMe) 3, HC (} OEt) 3, HC (OPr) 3 , HC (OBu) ₃ , HC (OBu
He) ₃ , HC (OPh) ₃ ; MeC (OMe) ₃ , MeC (OEt) ₃ , EtC (OMe) ₃ , E
tC (OEt) ₃ , cyHeC (OEt) ₃ , PhC (OMe) ₃ , PhC (OEt) ₃ , CH ₂ Cl
C (OEt) ₃ , MeCHBrC (OEt) ₃ , MeCHClC (OEt) ₃ ; ClC (OMe) ₃ ,
_{ClC (OEt) 3, ClC (} Oi-Bu) 3, BrC (OEt) 3; wherein X ₂ C MeCH contained in _{(OR) 2 (OMe) 2} , MeCH (OEt) 2, CH 2 (OMe) 2, CH ₂ (OE
t) ₂ , CH ₂ ClCH (OEt) ₂ , CHCl ₂ CH (OEt) ₂ , CCl ₃ CH (OEt) ₂ , C
_{H 2 BrCH (OEt) 2,} PhCH (OEt) 2.

Compound where M is silicon Si (OMe) ₄ , Si (OEt) ₄ , Si (OB) contained in formula Si (OR) ₄
u) ₄ , Si (Oi-Bu) ₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (OPh) ₄ : Formula
HSi (OEt) ₃ , HSi (OBu) ₃ , HSi (OH) contained in XSi (OR) ₃
e) ₃ , HSi (OPh) ₃ ; MeSi (OMe) ₃ , MeSi (OEt) ₃ , MeSi (OB
u) ₃ , EtSi (OEt) ₃ , PhSi (OEt) ₃ , EtSi (OPh) ₃ ; ClSi (OMe)
₃ , ClSi (OEt) ₃ , ClSi (OBu) ₃ , ClSi; (OPh) ₃ , BrSi (OE
t) ₃ ; Me ₂ Si (OMe) ₂ , Me ₂ Si (OE) contained in the formula X ₂ Si (OR) ₂
t) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (OEt) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CC
l ₃ SiH (OEt) ₂ ; MeBrSi (OEt) ₂ : Me ₃ SiOM contained in X ₃ SiOR
e, Me ₃ SiOEt, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ SiOEt, Ph ₃ SiOE
t.

B where M is contained in the compound formula B (OR) ₃ in the case of boron _{(OEt) 3, B (OBu} ) 3, B (OHe) 3, B (O
Ph) ₃ .

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

Compound when M is phosphorus P (OMe) ₃ , P (OEt) ₃ , P (OBu) ₃ , P (O) contained in the formula P (OR) ₃
He) 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 represents the valence of the metal M, and n represents a number of 0.1 to 10. M
Specific examples of the compound represented by R ³ _m include AlMe ₃ , AlEt
_{3, Ali-Bu 3, AlPh} 3, ZnMe 2, ZnEt 2, ZnBu 2, ZnPh 2, CaE
t 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. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutylate, propyl pivalate, isobutyl pivalate, and acrylic. 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, an acid halide of the above carboxylic acids can be used. 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 pivalic 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,
Examples include isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, naphthalic acid dichloride and the like. Further, monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride and phthalic acid butyl chloride can 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 of an element of Groups IIIa, IVa, and Va of the periodic table (hereinafter, referred to as metal halide).

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 , 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 paraffin, etc., chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, hexachlorocyclohexane, etc. in alicyclic compounds, chlorobenzene, bromobenzene, o-dichlorobenzene in aromatic compounds, 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-bromoresorcinol, (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.

Examples of the silicon halide compound having a hydrogen-silicon bond include HSiCl ₂ , H ₂ SiCl ₂ , H ₃ SiCl, HCH ₃ SiCl ₂ , HC ₂ H ₅ SiC
l ₂ , H (tC 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 and Bi chlorides, fluorides, bromides and iodides are mentioned, especially BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ , AlBr ₃ , GaCl ₃ and GaBr
₃ , InCl ₃ , TlCl ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF _{5 and the} like are suitable.

Contact with component 1, component 2 and component 3, and optionally with a halogen-containing compound that can be brought into contact, if necessary, by mixing and stirring or mechanically co-milling in the presence or absence of an inert medium 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 contacted with (d) a halogen-containing alcohol and then with (e) an electron-donating compound and (f) a titanium compound (JP-A-63-2646).
No. 07), after contacting (a) magnesium dialkoxide with (b) a silicon halide compound having a hydrogen-silicon bond,
(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 (ii) silicon halide compound having a hydrogen-silicon bond,
(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 organoaluminum compound is selected from the below-mentioned organometallic compounds which are one component of the catalyst used in the present invention.

As the olefin, propylene other than ethylene, 1-
Alpha-olefins such as butene, 1-hexene, 4-methyl-1-benthene 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 1 g of the component A.

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 the compounds used when preparing component A. Component A in contact with the olefin can be optionally washed with the inert medium described above,
It can be further dried.

Organoaluminum compound As the organoaluminum compound, 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 represents 1
Any number in the range of n3. And C1 to C18 such as trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide and dialkylaluminum monohydride.
Preferably, an alkylaluminum compound having 2 to 6 carbon atoms or a mixture or complex compound thereof is particularly preferred. Specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trialkylaluminum such as trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride and the like Monoalkylaluminum dihalides such as dialkylaluminum monohalide, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride, and alkylaluminum sesquichloride such as ethylaluminum sesquichloride Dialkylaluminum monoalkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, diethylaluminum phenoxide, dipropylaluminum ethoxide, diisobutylaluminum ethoxide, diisobutylaluminum phenoxide, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutyl Dialkyl aluminum hydrides such as aluminum hydride may be mentioned. Among these, trialkyl aluminum, particularly triethyl aluminum and triisobutyl aluminum are desirable. Further, these trialkylaluminums are other organoaluminum compounds, for example, industrially available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or mixtures or complex compounds thereof Etc. can be used in combination.

Ethoxy Group-Containing Silane Compound The ethoxy group-containing silane compound (hereinafter, referred to as component C) used in the present invention is represented by the general formula R _n Si (OC ₂ H ₅ ) _4-n and calculated by quantum chemical calculation. The volume of the molecule is 240-500Å
³ , the electron density of oxygen atom of ethoxy group is 0.680 ~ 0.800A.
U. (Atomic Unit).

The quantum chemical calculation is performed by the following method. The volume of a molecule is
The MNDO method (semi-empirical molecule) of MOPAC, a molecular orbital method program (purchased from QCPB (Quantum Chemistry Program Exchange Organization), a non-profit organization that aims to disseminate various programs for chemistry at Indiana University, USA) Orbital method) [J. Am. Chem. Soc., Journal of American Chemical Society] 99 , 4899, 4907 (1977)
100 ), p. 3607, (1978)] and Vander Waals
From the radius [J. Phys. Chem., (Journal of Physical Chemistry), vol. 68 , pp. 441-451 (1964)], and the electron density of the oxygen atom of the ethoxy group is
This was calculated by the MOPAC MNDO method. In addition,
The calculation is made by DEC (DIGITAL BQUIPMENT CORPORATION).
VAX 11/785 was used.

R in the general formula of Component C is an aliphatic hydrocarbon group having 5 to 10 carbon atoms, that is, an alkyl group and an alkenyl group.

Component C, the volume of 240～500A ³ obtained by the above calculation method, but those having an electron density of the oxygen atoms of 0.680～0.800AU, especially the volume of 240～350A ³ and 0.685~0.700AU
The one having the above electron density is desirable.

Specific examples of the component C that satisfies the above volume and electron density are illustrated below by chemical formulas. In the formula, Me: CH ₃ , E
_{t: C 2 H 5, Pr} : C 3 H 7, Bu: C 4 H 9, Pe: C 5 H 11, He: shows the C ₆ H _13, respectively.

[(N-Pr) (Me) CH] ₂ Si (OEt) ₂ , (t-Pe) ₂ Si (OEt) ₂ , [(tB
u) CH _{2] 2} Si (OEt) _2, [(Et) (Me) CH · CH 2 ] _{2 Si (OEt) 2, (} n
-He) ₂ Si (OEt) ₂ , [(Et) (Me) ₂ CCH ₂ ] ₂ Si (OEt) ₂ , [(tB
u) (CH ₂ ) ₂ ] ₂ Si (OEt) ₂ ; (n-Pe) Si (OEt) ₃ , (t-Pe) Si (OEt)
_{3, (n-Pr) (} Me) CH · Si (OEt) 3, (t-Bu) CH 2 · Si (OE
t) ₃ , (Et) (Me) CHCH ₂ .Si (OEt) ₃ , (n-He) Si (OEt) ₃ , [(E
t) (Me) ₂ C ・ CH ₂・ Si (OEt) ₃ , (t, Bu) (CH ₂ ) ₂ Si (OEt) ₃ : CH ₂
= CH (CH ₂ ) ₃ · Si (OEt) ₃ , CH ₂ = CH (CH ₂ ) ₄ · Si (OEt) ₃ , CH ₂
= CH (CH ₂ ) ₅ · Si (OEt) ₃ , CH ₂ = CH (CH ₂ ) ₆ · Si (OEt) ₃ , (M
e) CH = CH (CH ₂ ) ₃ .Si (OEt) ₃ ; [CH ₂ = CH (CH ₂ ) ₄ ] ₂ Si (OE
t) ₂ , and the like.

The catalyst used in the present invention comprises Component A, Component B and Component C.
The component ratio of component B is from 1 to 2,000 gmol, preferably from 20 to 500 gmol, and preferably from 20 to 500 gmol, per mole of titanium in component A.
It is used in an amount of 0.001 to 10 mol, preferably 0.01 to 1.0 mol.

Polymerization of α-olefin The present invention is to produce a polyα-olefin by polymerizing an α-olefin using the above catalyst. The α-olefin has 3 to 10 carbon atoms, and specific examples thereof include propylene, 1-butene, 1-hexene,
-Methyl-1-pentene and the like. The polymerization is α-
In addition to olefin homopolymerization, random copolymerization of α-olefin with ethylene or other α-olefin is also included.

The polymerization reaction may be any of a gas phase and a liquid phase.When the polymerization is performed in a liquid phase, an inert carbon such as normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, or xylene is used. 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.

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 is carried out by a continuous or batch-type reaction, and the condition may be a commonly used condition. Further, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.

The present invention particularly has a melt flow rate (MFR) of 50 g / 10
MFR is suitable for the production of
Can be adjusted with a known molecular weight regulator, particularly hydrogen.

Advantageous Effects of the Invention The present invention particularly has an MFR of 50 g / 10 min or more, preferably 70 g / 1
In the production of poly-α-olefins having a high MFR of 0 minutes or more, more preferably 100 g / 10 minutes or more, even when a large amount of hydrogen is used as a molecular weight regulator, a high steric compound having a heat heptane insoluble content (HI) of 96% or more is obtained. A poly-α-olefin can be produced in high yield while maintaining regularity. Moreover, the silane compound used in the present invention exhibits catalytic performance equal to or higher than that of the case where the silane compound having an aromatic group is used, though it does not have an aromatic group.

Examples The present invention will be specifically described with reference to Examples and Comparative 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. The measurement of MFR followed ASTM-D1238.

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

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 the completion of the dropwise addition, the reaction was carried out at 60 ° C. for 15 minutes. The solid produced by the reaction was washed six times with 300 ml each of n-hexane, dried under reduced pressure at room temperature for 1 hour, and 19.0% of magnesium and 28.9% of chlorine.
% 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. In addition, a new titanium tetrachloride / toluene volume ratio of 3 /
Titanium tetrachloride was added so as to obtain 2, and the mixture was stirred at 120 ° C. for 2 hours. The solid substance obtained was 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 A 1.5-liter stainless steel equipped with a stirrer was placed in an autoclave, and under a nitrogen gas atmosphere, the component A 9.7 mg obtained above,
4 ml of a solution containing 0.8 mol of triethylaluminum (hereinafter referred to as TEAL) in n-heptane 1 and 1 ml of a solution containing 0.08 mol of t-amyltriethoxysilane in n-heptane 1 and kept for 5 minutes Was put.
Then, after injecting 2.0 l of hydrogen gas and liquid propylene 1 as a molecular weight controlling agent, the reaction system was heated to 70 ° C.
Propylene was polymerized for 1 hour. After completion of the polymerization, unreacted propylene was purged to obtain 97.2% HI white polypropylene powder. The polymerization activity (R _c ) of the catalyst is 25.3 kg / g
Component A. hours. The MFR of the polymer was 75.9 g / 10 minutes.

The volume of t-amyltriethoxysilane and the electron density of oxygen atoms of the ethoxy group were calculated according to the above, and the results are shown in Table 1.

Further, propylene was polymerized in the same manner as above except that the amount of hydrogen used was changed as shown in Table 1, and the results are shown in Table 1.

Examples 2 to 8 Polymerization of propylene in the same manner as in Example 1 except that the silane compounds shown in Table 1 were used instead of t-amyltriethoxysilane and the amount of hydrogen used was as shown in Table 1. And the results are shown in Table 1. Further, the volumes of these compounds and the electron density were calculated, and the results are shown in Table 1.

Comparative Examples 1 to 7 Propylene was polymerized in the same manner as in Example 1 except that the compounds shown in Table 2 were used as the silane compounds, and the amounts of hydrogen used were as shown in Table 2. 2
It is shown in the table. The calculated values of the volume of the compound and the electron density are as shown in Table 2.

Reference Examples 1 to 5 Except that the aromatic group-containing compounds shown in Table 3 were used as the silane compound, and the amount of hydrogen used was as shown in Table 3,
Propylene was polymerized in the same manner as in Example 1, and the results are shown in Table 3. Further, the calculated values of the volumes and the electron densities of these compounds are as shown in Table 3.

[Brief description of the drawings]

FIG. 1 is a flowchart showing the method of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroyuki Furuhashi 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Inside the Tonen Research Laboratory (72) Inventor Masahide Murata 1 Nishi-Tsurugaoka, Oi-machi, Iruma-gun, Saitama Chome 3-1, Tonen Co., Ltd. (72) Inventor Satoshi Ueki 1-3-1, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. (56) References JP-A-2-229806 ( JP, A) JP-A-2-283703 (JP, A) (58) Fields investigated (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 wherein} R is an alkyl group or an aryl group; 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 R _n Si (OC ₂ H ₅ ) _{4-n wherein} R is 5 to 10 carbon atoms.
Aliphatic hydrocarbon groups, n is 1 or 2. Represented by], quantum chemistry volume calculated in calculations 240～500A ^3, the electron density of oxygen atoms in the ethoxy groups is also 0.680~0.800AU
(Atomic unit) A method for producing a poly-α-olefin comprising polymerizing an α-olefin in the presence of a catalyst comprising an ethoxy group-containing silane compound.