JP2709627B2 - 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—O—C bond together with an organoaluminum compound, or has a general formula SiR ¹ R ² _n (OR) ³ _3-n (n = 0 to
It is known that the use of the organosilicon compound represented by 2) improves the stereoregularity of the resulting polymer (for example, JP-A-54-94690, JP-A-56-36203, and JP-A-57-36203).
63310, 58-83016, 62-11705, etc.).

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. In general, silicon compounds having an aromatic group are known to exhibit good performance in the polymerization of α-olefins, but silicon compounds having an aromatic group may be harmful depending on the purpose of use of the polymer. .

Problems to be Solved by the Invention The present invention is less harmful even if contained in a polymer, an organosilicon compound having no aromatic group,
It is an object of the present invention to provide an α-olefin polymerization catalyst containing, as a component, an organosilicon compound having performance equal to or higher than that of an aromatic group-containing organosilicon compound.

Means for Solving the Problems In general, it is considered that there are two types of α-olefin polymerization catalysts, an active species for producing an isotactic polyolefin and an active species for producing an atactic polyolefin. The polymerization activity (R _I ) of the isotactic polyolefin and the polymerization activity (R _A ) of the atactic polyolefin are calculated using the total polymerization activity (R _T ) and stereoregularity (HI: heptane-insoluble matter,%) as follows. It is expressed by an equation.

The present inventors conducted polymerization of α-olefin using dimethoxydialkylsilane in combination with a magnesium-containing solid component and an organometallic compound obtained by a specific treatment method,
R _I and R _A and result of intensive studies the relationship between properties of the silane have a volume of 230～500A ^3, and the electron density of oxygen methoxy group be used dimethoxy group-containing silane compound 0.685~0.800AU A poly-α- having high activity and high stereoregularity equivalent to or higher than the organic silicon compound having an aromatic group.
The inventors have found that the object of the present invention that olefin can be produced can be achieved, and completed the present invention.

SUMMARY OF THE INVENTION That is, the gist of the present invention is to provide (A) (a) a metal magnesium, (b) a halogenated hydrocarbon, and (c) an alkoxy group-containing compound of the general formula X _n M (OR) _mn wherein X is Hydrogen atom, halogen atom or carbon number 1
~ 20 hydrocarbon groups, M is boron, carbon, aluminum,
A silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m
Represents the valence of M and m> n ≧ 0. The magnesium-containing solid obtained by contacting is contacted with (d) a halogen-containing alcohol, and then (e) an electron-donating compound and (f) TiX _n (OR) _4-n [where X is A halogen atom and R represent a hydrocarbon group, and 0 <n ≦ 4. ]
Solid component obtained by contacting with in represented by a titanium compound, (B) 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 , N is an arbitrary number in the range of 1 ≦ n ≦ 3], and (C) a general formula R ¹ R ² Si (OCH ₃ ) ₂ [where R ¹ and R ² are respectively in the same or a different number 4-6 branched aliphatic hydrocarbon group having a carbon and the total carbon number of R ¹ and R ² are 9 to 12 amino. ]
The volume calculated by quantum chemical calculation is 230-500Å
^3. Similarly, the electron density of the oxygen atom of the methoxy group is 0.685-
An α-olefin polymerization catalyst comprising 0.800 AU (atomic unit) of a dimethoxy group-containing silane compound.

Raw Materials for Adjustment of Solid Catalyst Component The solid catalyst component (hereinafter referred to as component A), which is one component of the catalyst of the present invention, is described in detail in the following (a) metallic magnesium, (b) halogenated hydrocarbon, (c) ) General formula X _n M
(OR) contacting the magnesium-containing solid obtained by contacting the _mn compound with (c) a halogen-containing alcohol, then (e) an electron-donating compound and (f)
It is adjusted by contacting with a titanium compound.

(A) Metallic magnesium Any type of metallic magnesium may be used, but powdered and chip-shaped ones are particularly suitable.

(Ii) Halogenated hydrocarbons Halogenated hydrocarbons 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 paraffin, chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentagen, hexachlorocyclohexane for alicyclic compounds, chlorobenzene, bromobenzene, o-dichlorobenzene, p-chlorobenzene for aromatic compounds -Dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloride and the like. These compounds may be used alone or in combination of two or more.

(Iii) the general formula X _n M (OR) alkoxy-containing compound of the _mn formula XnM (OR) _mn alkoxy group-containing compound [in the formula, X represents a hydrogen atom, a halogen atom or a C 1 -C 20
Hydrocarbon groups, M is a boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is M
And m> n ≧ 0. ] As the hydrocarbon group for X and R, methyl (Me), ethyl (Et), propyl (Pr), i-propyl (i-Pr), butyl (Bu), i-
Butyl (i-Bu), hexyl (He), octyl (Oct)
Alkyl groups such as cyclohexyl (cyHe) and methylcyclohexyl; alkenyl groups such as allyl, propenyl and butenyl; aryl groups such as phenyl (Ph), tolyl and xylyl; alkenyl groups such as phenethyl and 3-phenylpropyl. And an alkyl group. 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.

_{C (OMe) 4, C (} OEt) 4 in which M is contained in the compound formula C _{(OR) 4} in the case of carbon,
C (OPr) ₄ , C (OBu) ₄ , C (Oi-Bu) ₄ , C (OH
e) ₄ , C (OOct) ₄ : HC (OMe) contained in formula XC (OR) _3
3 , HC (OEt) ₃ , HC (OPr) ₃ , HC (OBu) ₃ , HC (OH
e) ₃ , HC (OPh) ₃ : MeC (OMe) ₃ , MeC (OEt) ₃ , EtC
(OMe) ₃ , EtC (OEt) ₃ , cyHeC (OEt) ₃ , PhC (OM
e) ₃ , PhC (OEt) ₃ , CH ₂ ClC (OEt) ₃ , MeCHBrC (OE
t) ₃ , MeCHClC (OEt) ₃ : ClC (OMe) ₃ , ClC (OE
t) ₃ , ClC (Oi-Bu) ₃ , BrC (OEt) ₃ : Formula X ₂ C (OR) ₂
MeCH (OMe) ₂ , MeCH (OEt) ₂ , CH ₂ (OMe)
_{2, CH 2 (OEt) 2} , CH 2 ClCH (OEt) 2, CHCl 2 CH (OEt)
₂ , CCl ₃ CH (OEt) ₂ , CH ₂ BrCH (OEt) ₂ , PhCH (OEt)
₂ .

Si of M is contained in the compound formula Si _{(OR) 4} in the case of silicon _{(OMe) 4, Si (OEt} ) 4,
Si (OBu) ₄ , Si (Oi-Bu) ₄ , Si (OHe) ₄ , Si (OOc
t) ₄ , Si (OPh) ₄ : HSi (OE) contained in the formula XSi (OR) ₃
t) ₃ , HSi (OBu) ₃ , HSi (OHe) ₃ , HSi (OPh) ₃ : MeS
i (OMe) ₃ , MeSi (OEt) ₃ , MeSi (OBu) ₃ , EtSi (OE
t) ₃ , PhSi (OEt) ₃ , EtSi (OPh) ₃ , ClSi (OM
e) ₃ , ClSi (OEt) ₃ , ClSi (OBu) ₃ , ClSi (OP
h) ₃ , BrSi (OEt) ₃ : Me ₂ Si contained in formula X ₂ Si (OR) _{2
(OMe) 2, Me 2 Si} (OEt) 2, Et 2 Si (OEt) 2, MeClSi
(OEt) ₂ : CHCl ₂ SiH (OEt) ₂ : CCl ₃ SiH (OEt) ₂ : MeBrSi
(OEt) ₂ : Me ₃ SiOMe, Me ₃ SiOEt, Me ₃ Si contained in X ₃ SiOR
OBu, Me ₃ SiOPh, Et ₃ SiOEt, Ph ₃ SiOEt.

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 (OPh) ₃ .

Al which M is contained in the compound formula Al _{(OR) 3} in the case of aluminum _{(OMe) 3, Al (OEt} ) 3,
Al (OPr) ₃ , Al (Oi-Pr) ₃ , Al (OBu) ₃ , Al (Ot-
Bu) ₃ , Al (OHe) ₃ , Al (OPh) ₃ .

P where M is contained in the compound formula P _{(OR) 3} in the case of phosphorus _{(OMe) 3, P (OEt} ) 3,
P (OBu) ₃ , P (OHe) ₃ , P (OPh) ₃ .

(D) Halogen-containing alcohol As a halogen-containing alcohol, in a mono- or polyhydric alcohol having one or more hydroxyl groups in one molecule, any one or two or more hydrogen atoms other than hydroxyl groups are halogen atoms. A substituted compound is meant. 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.

(E) 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, ethers and the like 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. , Glutanic 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, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate,
Diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-tert-butyl benzoate, ethyl p-ethyl anisate, α-ethyl Ethyl naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl phthalate, Diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, 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, 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, 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, isophthalic acid dibromide, terephthalic acid dichloride, and naphthyl acid dichloride. 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 having 1 to 12 carbons,
Alkenyl, cycloalkyl, aryl and aralkyl, wherein 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, ethylphenyl ether and the like.

(F) Titanium compound The titanium compound is represented by the general formula TiX _n (OR) _4-n .
In this formula, X represents a halogen atom of chlorine or bromine, R represents an alkyl group or an aryl group having 1 to 8 carbon atoms, and n is an arbitrary number in the range of 0 <n ≦ 4. Examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxy titanium, trichlorobutoxy titanium, dichlorodiethoxy titanium, dichlorodibutoxy titanium, dichlorodiphenoxy titanium, chlorotriethoxy titanium, chlorotributoxy titanium, and the like. Can be. Among these, titanium tetrachloride, trichloroethoxy titanium, dichlorodibutoxy titanium, and dichlorodiphenoxy titanium are desirable, and titanium tetrachloride is particularly desirable.

Method for Preparing Solid Catalyst Component The method for preparing Component A in the present invention is described in JP-A-63-264607.
This is a method disclosed in Japanese Patent Publication No. More specifically, (a) contacting a metal magnesium, (b) a halogenated hydrocarbon, and (c) an alkoxy group-containing compound of the general formula X _n M (OR) _mn (the same as the above-mentioned alkoxy group-containing compound) Contacting the magnesium-containing solid obtained in (1) with a halogen-containing alcohol, and then contacting (e) an electron donating compound and (f) a titanium compound.

The contact of the components (a) to (f) is performed in the presence of an inert medium.
Alternatively, it is performed by mixing and stirring or mechanically co-milling in the absence. 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.

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 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 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 Organoaluminum compound (hereinafter referred to as component B)
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 1 ≦ n ≦ 3). And 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, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum, 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.

Dimethoxy Group-Containing Silane Compound The dimethoxy group-containing silane compound (hereinafter referred to as component C) used in the present invention has a general formula R ¹ R ² Si (OCH ₃ ) ₂
The volume of the molecule calculated by quantum chemical calculation is 230
, ~ 500 ^3, the electron density of oxygen atoms in the methoxy groups 0.685～
0.8000AU (atomic unit).

The quantum chemical calculation is performed by the following method. The volume of a molecule is
MNDO method (semi-empirical) of MOPAC, a molecular axis method program (purchased from QCPE (Quantum Chemistry Program Exchange Organization), a non-profit institution aiming to disseminate various programs for chemistry at Indiana University, USA) J. Am. Chem. Soc., Journal of American Chemical Society, Vol. 99, p. 4899, p. 4907 (1977)
100), p. 3607 (1978)] and Van der W
aals radius [J. Phys. Chem., (Journal of Physical Chemistry) 68, 441-451 (1964)]
The electron density of the oxygen atom of the methoxy group was calculated by the MNDO method of MOPAC.
The calculation was performed by DEC (DIGITAL EQU-IPMENT CORPORA).
TION) VAX 11/785.

R ¹ and R ² in the above general formula of the component C are those having 4 to 6 carbon atoms.
Branched aliphatic hydrocarbon groups, ie, an alkyl group and an alkenyl group, and preferably an alkyl group.

Component C has an electron density of molecular volume and oxygen atoms of said, is desirable particularly those having an electron density of volume and 0.690~0.740AU of 230~350Å ^3.

The component C satisfying the volume and electron density as described above, the number of carbon atoms of R ¹ and R ² in 4 to 6, and the total number of carbon atoms in R ¹ and R ² are of 9-12 amino .

Hereinafter, specific examples of the component C are listed by chemical formulas. In the formula, Me: CH ₃ , Et: C ₂ H ₅ , Pr: C ₃ H ₇ , Bu: C ₄ H ₉ , Pt: C
₅ H ₁₁ and He: C ₆ H ₁₃ are shown.

(T-Bu) (t-Pt) Si (OMe) ₂ , (t-Bu) (s
_{-Pt) Si (OMe) 2,} (t-Pt) 2 Si (OMe) 2, [(n
-Pr) (Me) CH] _{2 Si (OMe) 2, (} t-Pt) (s-Pt)
Si _{(OMe) 2,} [(t-Bu) CH _{2] 2} Si _{(OMe) 2,} [(E
t) (Me) CH · CH 2 ] _{2 Si (OMe) 2, (} t-Pt) [(t-
Bu) CH _2] Si _{(OMe) 2,} [(n-Pr) (Me) 2 C ] (t-
_Pt) Si (OMe) _{2, [(Et) (Me) 2 C} · CH 2 ] (t-Pt)
_{Si (OMe) 2, (n} -He) 2 Si (OMe) 2, [(n-Pr)
(Me) ₂ C] ₂ Si (OMe) ₂ , [(Et) (Me) ₂ C · CH ₂ ] ₂ Si
(OMe) ₂ , [(t-Bu) · C ₂ H ₄ ] ₂ Si (OMe) ₂ ,
[(N-Pr) (Me) ₂ C] [(Et) (Me) ₂ C · CH ₂ ] Si (O
Me) _{2 and the} like.

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 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. 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 use of a silane compound having an aromatic group does not generate a harmful substance that causes a problem, and a polymerization activity and stereoregularity equivalent to or higher than that of a catalyst containing the silane compound having an aromatic group. The catalyst exhibits the following catalytic performance.

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 1-liter reaction vessel equipped with a reflux condenser, 8.3 g of chip-shaped magnesium metal (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, metallic magnesium was taken out and dried at 65 ° C. under reduced pressure to obtain pre-activated metallic 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.

Next, 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.
31.6 g of a magnesium-containing solid containing 8.9% 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 and washed twice with 100 ml each of n-hexane at room temperature to obtain a solid component.

40 ml of toluene was added to the 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 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 In a 1.5-liter stainless steel autoclave equipped with a stirrer, under a nitrogen gas atmosphere, 10.2 mg of the component A obtained above,
4 ml of a solution containing 0.1 mol of triethylaluminum (hereinafter referred to as TEAL) in 1 l of n-heptane and 1 ml of a solution containing 0.04 mol of di (1-methylbutyl) dimethoxysilane in 1 l of n-heptane are mixed and kept for 5 minutes. I put what I did. Next, after 600 ml of hydrogen gas and 1 l of liquid propylene as a molecular weight controlling agent were injected under pressure, the temperature of the reaction system was raised to 70 ° C., and propylene was polymerized for 1 hour. After polymerization,
Unreacted propylene was purged to obtain a white polypropylene powder of HI 98.2%.

The polymerization activity (R _T ) of the catalyst was 26.7 kg / g · Component A.
As a result, the polymerization activity (R _I ) of isotactic polypropylene was determined to be 26.2 kg / g · component A, and the polymerization activity (R _A ) of atactic polypropylene was found to be 0.41 kg / g · component A.

In addition, the volume of di (1-methylbutyl) dimethoxysilane and the electron density of oxygen atoms of the methoxy group were calculated in accordance with the above, and the results are shown in Table 1 (R ¹ and R ² in the table represent the general formula R ¹ R ² Si (OCH ₃ ) ₂ is shown.

Examples 2,3 Instead of di (1-methylbutyl) dimethoxysilane,
Propylene was polymerized in the same manner as in Example 1 except that the silane compounds shown in Table 1 were used, 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 10, Reference Example 1 Propylene was polymerized in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the silane compounds, and the results are shown in Table 1. Table 1 shows the volumes of these compounds and the calculated values of the electron density.

Examples 4 and 5, Reference Example 2 Instead of di (1-methylbutyl) dimethoxysilane,
Propylene was polymerized in the same manner as in Example 1 except that the silane compounds shown in Table 1 were each replaced by triisobutylaluminum instead of TEAL and the polymerization temperature was set to 80 ° C. It was shown to. The calculated values of the volume of these silane compounds and the electron density are as shown in Table 1.

[Brief description of the drawings]

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

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masahide Murata 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Inside the Toa Fuel Industry Co., Ltd. (72) Inventor Hiroyuki Furuhashi, Oimachi, Iruma-gun, Saitama 1-3-1, Nishi-Tsurugaoka, Research Institute of Toa Fuel Industry Co., Ltd. (72) Inventor Satoshi Ueki 1-3-1, Nishi-Tsurugaoka, Oi-machi, Irima-gun, Saitama Prefecture, Japan Research Institute of Toa Fuel Industry Co., Ltd. (56) References JP-A-63-223008 (JP, A) JP-A-63-264607 (JP, A)

Claims (1)

(57) [Claims] (A) (a) a metal magnesium, (b) a halogenated hydrocarbon and (c) an alkoxy group-containing compound of the general formula X _n M (OR) _mn wherein X is a hydrogen atom, a halogen atom or Carbon number 1
~ 20 hydrocarbon groups, M is boron, carbon, aluminum,
A silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m
Represents the valence of M and m> n ≧ 0. ), The magnesium-containing solid obtained by contacting with (d) a halogen-containing alcohol, then (e) an electron-donating compound and (f) a general formula TiX _n (OR) _4-n [where X is a halogen The atom R represents a hydrocarbon group, and 0 <n ≦ 4. Solid component obtained by contacting with the titanium compound represented by], (B) the general formula R _n AlX _3-n [where, R represents an alkyl group or an aryl group, X is 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 ¹ R ² Si (OCH ₃ ) ₂ [where R ¹ and R ² are in each the same or different number 4-6 branched aliphatic hydrocarbon group having a carbon and the total carbon number of R ¹ and R ² are 9 to 12 amino. ]
The volume calculated by quantum chemical calculation is expressed as 230 to 500
^{３ 3} Similarly, the electron density of the oxygen atom of the methoxy group is 0.685
~ 0.800 AU (atomic unit) dimethoxy group-containing silane compound.