JPH10237122A - Catalyst for polymerizing alpha-olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerization catalyst capable of producing poly (α-olefin) having high stereoregularity and good fluidity. SOLUTION: (A) a solid component containing Mg, Ti, a halogen, a metal oxide and an electron donating compound as essential components, and (B-1) a charge on an Al atom in an aluminum compound obtained by molecular orbital calculation. An organoaluminum compound having an amount of less than +0.7, (B-2) an aluminum compound having a charge on an Al atom in the aluminum compound determined by molecular orbital calculation of +0.7 or more, and (C) an alkylalkoxysilane An α-olefin polymerization catalyst comprising a compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

An α-olefin polymerization catalyst comprising a catalyst component containing Mg, Ti, a halogen and an electron donating compound as essential components, an organoaluminum compound and a silane compound is well known. At this time, the stereoregularity of the resulting poly (α-olefin) can be changed by changing the silane compound (Japanese Patent Application Laid-Open No. 7-109309). However, in general, when the silane compound is changed to improve the stereoregularity of poly (α-olefin), the melt flow rate (MFR) of the polymer tends to decrease. Therefore, development of a polymerization catalyst capable of producing poly (α-olefin) having high stereoregularity and high MFR, that is, good fluidity, has been desired.

An object of the present invention is to provide a polymerization catalyst capable of producing poly (α-olefin) having high stereoregularity and good fluidity.

[0004]

Means for Solving the Problems The inventors of the present invention have studied the polymerization catalyst of α-olefin, and as a result, when a specific aluminum compound is used in combination with a specific component, a high stereoregularity and a high stereoregularity are obtained. Poly (α-
Olefin), and completed the present invention.

That is, the present invention relates to (A) magnesium,
A solid component containing titanium, a halogen, a metal oxide and an electron-donating compound as essential components, and (B-1) an organic compound having a charge amount on an Al atom in an aluminum compound of less than +0.7 determined by molecular orbital calculation. Aluminum compounds,
(B-2) an α-olefin polymerization catalyst comprising an aluminum compound having a charge amount on an Al atom in an aluminum compound obtained by molecular orbital calculation of +0.7 or more, and (C) an alkylalkoxysilane compound. .

Preferred embodiments of the present invention are described below. (A) The above catalyst wherein the component (B-1) is selected from trialkylaluminum. (B) The above catalyst, wherein the component (B-2) is selected from the group consisting of dialkylaluminum monochloride, alkylaluminum dichloride, alkylaluminum sesquichloride, dialkylaluminum monoalkoxide and alkylaluminum dialkoxide. (C) Component (C) an alkylalkoxysilane compound,
The following formula:

Embedded image R ¹ Si (OR ² ) (OCH ₃ ) ₂ (In the above formula, R ¹ is a branched or cyclic alkyl group having 3 to 6 carbon atoms, and R ² is a 3 to 6 carbon atoms. Is a branched alkyl group, alkenyl group or alkynyl group)
The above catalyst, which is an alkyltrialkoxysilane represented by the formula: (D) Component (B-) per mole of titanium in component (A)
1) 70 to 600 mol, component (B-2) 2 to 200
The above-mentioned catalyst, wherein 10 to 30 mol of the mol and the component (C) are mixed. (E) The above-mentioned catalyst, wherein the α-olefin is a linear or branched α-olefin having 2 to 10 carbon atoms.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A) in the catalyst of the present invention
Contains magnesium, titanium, halogen, metal oxide and electron donating compound as essential components. Component (A)
It is a component known per se. Such components are usually prepared by contacting a magnesium compound, a titanium compound, a metal oxide, and an electron-donating compound, and, in the case where each of the compounds has no halogen, a halogen-containing compound.

The magnesium compound has the general formula MgR ^a R ^b
It is represented by Here, ^Ra and ^Rb 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 ^a and R ^b ,
An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group, and the OR group is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine.

Specific examples of these compounds are shown below. In the following chemical formula, Me: methyl, Et: ethyl, Pr:
Propyl, i-Pr: isopropyl, Bu: butyl, i
-Bu: isobutyl, t-Bu: tertiary butyl,
He: hexyl, Oct: octyl, Ph: phenyl,
cyHe: represents cyclohexyl.

[0010] MgMe ₂ , MgEt ₂ , Mg (i-Pr)
₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgEtB
u, MgPh ₂ , MgcyHe ₂ , Mg (OMe) ₂ , M
g (OEt) ₂ , Mg (OBu) ₂ , Mg (OHe) ₂ ,
Mg (OOct) ₂ , Mg (OPh) ₂ , Mg (OcyH
e) ₂ , EtMgCl, BuMgCl, HeMgCl,
i-BuMgCl, t-BuMgCl, PhMgCl,
PhCH ₂ MgCl, EtMgBr, BuMgBr, P
hMgBr, BuMgI, EtOMgCl, BuOMg
Cl, HeOMgCl, PhOMgCl, EtOMgB
r, BuOMgBr, EtOMgI, MgCl ₂ , Mg
Br ₂ , MgI ₂ .

The above magnesium compound can be prepared from metallic magnesium or other magnesium compounds when preparing component A. Examples thereof include metallic magnesium, halogenated hydrocarbons and alkoxy group-containing compounds 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 a boron, carbon, aluminum, 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. ) Is contacted.

The hydrocarbon group of X and R in the general formula of the alkoxy group-containing compound includes methyl (Me), ethyl (Et), propyl (Pr), i-propyl, (i-P
r), alkyl groups such as butyl (Bu), i-butyl (i-Bu), hexyl (He), octyl (Oct), cycloalkyl groups such as cyclohexyl (cyHe) and methylcyclohexyl, allyl, propenyl, butenyl, etc. And an aryl group such as phenyl (Ph), tolyl, and xylyl, and an aralkyl group 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.

Compounds wherein M is carbon C (OMe) ₄ , C (OEt) contained in formula C (OR) _4
4 , C (OPr) ₄ , C (OBu) ₄ , C (Oi-B
u) ₄ , C (OHe) ₄ , C (OOct) ₄ : Formula XC (O
R) ₃ contained in HC (OMe) 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 (OE
t) ₃ , cyHeC (OEt) ₃ , PhC (OMe) ₃ ,
PhC (OEt) ₃ , CH ₂ ClC (OEt) ₃ , MeC
HBrC (OEt) ₃ , MeCHClC (OEt) ₃ ; C
1C (OMe) ₃ , ClC (OEt) ₃ , ClC (Oi-
Bu) ₃ , BrC (OEt) ₃ ; MeCH (OMe) ₂ , MeCH (OEt) ₂ , CH contained in the formula X ₂ C (OR) _2
2 (OMe) ₂ , CH ₂ (OEt) ₂ , CH ₂ ClCH (O
Et) ₂ , CHCl ₂ CH (OEt) ₂ , CCl ₃ CH (O
Et) ₂ , CH ₂ BrCH (OEt) ₂ , PhCH (OE
t) ₂ .

Compound when M is silicon Si (0Me) ₄ , Si (O) contained in the formula Si (OR) ₄
Et) ₄ , Si (OBu) ₄ , Si (Oi-Bu) ₄ , S
i (OHe) ₄ , Si (OOct) ₄ , Si (OP
h) ₄ : HSi (OEt) contained in the formula XSi (OR) _3
3 , HSi (OBu) ₃ , HSi (OHe) ₃ , HSi
(OPh) ₃ ; MeSi (OMe) ₃ , MeSi (OE
t) ₃ , MeSi (OBu) ₃ , EtSi (OEt) ₃ ,
PhSi (OEt) ₃ , EtSi (OPh) ₃ ; ClSi
(OMe) ₃ , ClSi (OEt) ₃ , ClSi (OB
u) ₃ , ClSi (OPh) ₃ , BrSi (OEt) ₃ ;
Me ₂ Si (OMe) ₂ in an expression X ₂ Si (OR) _2,
Me ₂ Si (OEt) ₂ , Et ₂ Si (OEt) ₂ ; MeC
1Si (OEt) ₂ ; CHCl ₂ SiH (OEt) ₂ ; C
Cl ₃ SiH (OEt) ₂ ; MeBuSi (OEt) ₂ :
Me ₃ SiOMe, Me ₃ SiO contained in X ₃ SiOR
Et, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ Si
OEt, Ph ₃ SiOEt.

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

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

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

Further, as the magnesium compound, a complex with an organic compound of a metal (M ') of Group II or IIIa of the periodic table can be used. The complex has the general formula MgR
represented by ^{a R b · p (M'R c} q) (R a and R ^b are as defined above). As the metal (M '), aluminum, zinc, and calcium, and the like, R ^C is alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group. Also, q is the valence of the metal M 'and p is 0.
The number of 1-10 is shown. Specific examples of the compound represented by M′R ^C _q include AlMe ₃ , AlEt ₃ , Al (i-B
u) ₃ , AlPh ₃ , ZnMe ₂ , ZnEt ₂ , ZnB
_{u 2, ZnPh 2, CaEt 2} , CaPh 2 , and the like.

The titanium compound is a divalent, trivalent or tetravalent titanium compound, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, dichlorodiethoxytitanium, and dichlorodiethoxytitanium. Butoxytitanium, dichlorodiphenoxytitanium,
Examples thereof include chlorotriethoxytitanium, chlorotributoxytitanium, tetrabutoxytitanium, and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxytitanium, dichlorodibutoxytitanium and dichlorodiphenoxytitanium are desirable, and titanium tetrachloride is particularly desirable.

The metal oxide is an oxide of an element selected from the group II to IV of the periodic table, and examples thereof include B ₂ O ₃ , MgO, Al ₂ O ₃ , and SiO _2. , C
aO, TiO ₂ , ZnO, ZrO ₂ , SnO _2, BaO, T
hO _{2 and the} like. Among them, B ₂ O ₃ , Mg
O, Al ₂ O ₃ , SiO ₂ , TiO ₂ and ZrO ₂ are preferred, and SiO ₂ is particularly preferred. Further, composite oxides containing these metal oxides, for example, SiO ₂ —MgO, SiO ₂
—Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , S
iO ₂ -Cr ₂ O _3, it is also possible to use SiO ₂ -TiO ₂ -MgO and the like.

These metal oxides are usually used in powder form. Since the form such as the size and shape of the powder often affects the form of the obtained olefin polymer, it is desirable to appropriately adjust the form. It is desirable that the metal oxide be fired at as high a temperature as possible for the purpose of removing poisonous substances when used, and that the metal oxide be handled so as not to come into direct contact with the atmosphere.

Examples of the electron donating compound include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes,
Examples include alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group via carbon or oxygen, phosphoamides, thioethers, thioesters, carbon 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, and malonic acid. , 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- Cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,
Alicyclic carboxylic acids such as 2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, p-tert-butyl benzoic acid, naphthoic acid, aromatic monocarboxylic acids such as cinnamic acid, phthalic acid, isophthalic acid, Terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid,
And aromatic polycarboxylic acids such as melitic acid.

As the carboxylic anhydride, anhydrides of the above-mentioned 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, adipic acid Diisobutyl, dibutyl sebacate, diisobutyl sebacate,
Diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, p-toluic acid Methyl, p-tert-butyl, ethyl benzoate, p
-Ethyl anisate, α-ethyl naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-phthalate di- 2-ethylhexyl, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, pyromellitic And tetrabutyl pyromellitate.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used.
Specific examples thereof include acetate chloride, acetate bromide, acetate iodide, propionate chloride, butyrate 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 chloride, succinic 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, cinnamic acid chloride,
Examples include cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. Also, adipic acid monomethyl chloride,
Monoalkyl halides of dicarboxylic acids such as monoethyl maleate chloride, monomethyl maleate chloride, butyl phthalate chloride may also be used.

Alcohols are represented by the general formula R ^d OH. In the formula, R ^d is alkyl, alkenyl, cycloalkyl, aryl, aralkyl having 1 to 12 carbon atoms. Specific examples 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.

The ether is represented by the general formula R ^e OR ^f. In the formula, R ^e , R ^f is alkyl, alkenyl, cycloalkyl, aryl, aralkyl having 1 to 12 carbon atoms, and R ^e and R ^f 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 metal oxide (component 1), a magnesium compound (component 2), a titanium compound (component 3) and an electron donating compound (component 4) are brought into contact in that order. After contacting Component 1 and Component 2, contact Component 4 and Component 3 in that order. After contacting Component 1 and Component 2, contact Component 3 and Component 4 simultaneously. Component 2 and Component 3 After the contact, the components 4 and 1 are brought into contact in that order. After the components 2 and 4 are brought into contact, the components 3 and 1 are brought into contact in that order. The components 2, 3 and 4 are simultaneously brought into contact. After contact
A method such as contacting the component 1 can be employed. Also, the contact with the halogen-containing compound can be carried out before the contact of the component 3.

Examples of the halogen-containing compound include halogenated hydrocarbons, halogen-containing alcohols, silicon halide compounds having a hydrogen-silicon bond, and Periodic Table IIIa.
And halides of Group IVa, Group Va and Group Va elements (hereinafter referred to as metal halides).

Halogenated hydrocarbons include those having 1 to 1 carbon atoms.
Mono- and polyhalogen substituents of 12 saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbons are used.
Specific examples of such compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, Carbon iodide, 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-dichloropropane, hexachloropropylene, octachloropropane,
Decabromobutane, chlorinated paraffin and the like.
Examples of the alicyclic compound include chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, and hexachlorocyclohexane. For 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, one or two or more hydrogen atoms other than a hydroxyl group in a mono- or polyhydric alcohol having one or more hydroxyl groups in one molecule are substituted with a halogen atom. Compounds can be used. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine atoms, and a chlorine atom is preferable.

Examples of these compounds include 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-chloro- (m, o) -cresol,
6-chloro- (m, o) -cresol, 4-chloro-
3,5-dimethylphenol, chlorohydroquinone,
2-benzyl-4-chlorophenol, 4-chloro-1
-Naphthol, (m, o, p) -chlorophenol, p
-Chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-
Chlororesorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol,
1-bromo-2-butanol, 2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-
Naphthol, (m, o, p) -bromophenol, 4-
Bromoresorcin, (m, o, p) -fluorophenol, p-iodophenol: 2,2-dichloroethanol, 2,3-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: 2,2,4,6-
Tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,3,3-tetrafluoro-1-
And propanol, 2,3,5,6-tetrafluorophenol, tetrafluororesorcin and the like.

Examples of the silicon halide compound having a hydrogen-silicon bond include HSiCl ₃ , H ₂ SiCl ₂ , H ₃ S
iCl, H (CH ₃ ) SiCl ₂ , H (C ₂ H ₅ ) SiCl
_{2, H (t-C 4} H 9) SiCl 2, H (C 6 H 5) SiCl
_{2, H (CH 3) 2} SiCl, H (i-C 3 H 7) 2 SiC
_{l, H 2 (C 2 H} 5) SiCl, H 2 (n-C 4 H 9) Si
Cl, H ₂ (C ₆ H ₄ CH ₃ ) SiCl, HSiCl (C ₆
H ₅ ) _{2 and the} like.

As the metal halide, B, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, As, Sb, B
i chlorides, fluorides, bromides, iodides,
In particular, BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ , AlB
r ₃ , GaCl ₃ , GaBr _3, InCl ₃ , TlCl ₃ , S
iCl ₄ , SnCl ₄ , SbCl ₅ , SbF _{5 and the} like are preferred.

The contact with the component 1, the component 2, the component 3 and the component 4, and optionally the halogen-containing compound which can be brought into contact with each other may be carried out by mixing and stirring in the presence or absence of an inert medium or by mechanical stirring. This is done by co-milling. 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. .

Preferred methods for preparing component (A) in the present invention are described in JP-A-58-162607 and JP-A-55-162607.
-94909, 55-115405, 57-108107, 61-21109, 61-174204, and 61-17420.
No. 5, No. 61-174206, No. 62-77
No. 06 publication and the like. More specifically, a method in which a reaction product of a metal oxide and a magnesium dialkoxide is brought into contact with an electron-donating compound and a tetravalent titanium halide (JP-A-58-162607); A method in which a reaction product of a hydrocarbyl halide compound is contacted with a Lewis base compound and titanium tetrachloride (Japanese Patent Application Laid-Open No. 55-94909), a reaction product of a porous carrier such as silica and an alkylmagnesium compound is treated with titanium. A method of contacting with an electron donating compound and a silicon halide compound before contacting with a compound (Japanese Patent Application Laid-Open Nos. 55-115405 and 57-1)
08107), metal oxides, alkoxy-containing magnesium compounds,
A method of contacting an aromatic polycarboxylic acid having a carboxyl group at the ortho position or a derivative thereof and a titanium compound (JP-A-61-174204), a metal oxide, an alkoxy group-containing magnesium compound,
A method of contacting a silicon compound having a hydrogen-silicon bond, an electron donating compound, and a titanium compound
-174205), a metal oxide, an alkoxy group-containing magnesium compound,
A method of contacting a halogen element or a halogen-containing compound, an electron-donating compound and a titanium compound (JP-A-6
No. 1-174206), a method of contacting a reaction product obtained by contacting a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron-donating compound and a titanium compound (JP-A-61-21109). ), Contacting a solid obtained by contacting a metal oxide, hydrocarbylmagnesium and a hydrocarbyloxy group-containing compound (in charge of the alkoxy group-containing compound) with a halogen-containing alcohol, and further with an electron-donating compound and a titanium compound (Japanese Patent Laid-Open No. Sho 62-7706). Among these ~
The above method is particularly preferable.

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

In component (A), Mg is preferably 2 to 2.
It contains 12%, 1 to 5% of Ti, 10 to 35% by weight of halogen, 30 to 70% by weight of metal oxide, and 0 to 20% by weight of an electron donating compound.

Next, the organometallic component will be described. Component (B-1) is an organoaluminum compound in which the charge on Al atoms in the aluminum compound determined by molecular orbital calculation is less than +0.7.

The molecular orbital calculation is performed by the following method. MNDO method (semi-empirical molecule) of MOPAC, a molecular orbital 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) SC of various aluminum compounds using orbital method)
F (Self consistent field) calculation and energy minimization calculation were performed to obtain an optimum structure and a charge amount on aluminum atoms. The calculation conditions are the default ground state, RHF (Restrictive Hav).
tree Fock) calculation. Note that the calculation uses D
EC Company (Digital Equipment COR)
VAX11 / 785 manufactured by PORATION).
The larger the value of the amount of charge on the aluminum atom of the aluminum compound obtained by this calculation, the stronger the Lewis acidity of the aluminum compound molecule.

Examples of the organoaluminum compound in which the charge on the Al atom in the aluminum compound determined by molecular orbital calculation is less than +0.7 include the following compounds. One of these can be used alone or in combination of two or more.

Formula AlR ₃ (where R is a carbon number of 1 to 1)
2 represents an alkyl group. ), For example, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum and the like. Particularly, triethylaluminum and triisobutylaluminum are preferable.

The component (B-2) has a charge on the Al atom in the aluminum compound determined by molecular orbital calculation of +
The aluminum compound is 0.7 or more. Examples of the aluminum compound in which the charge on the Al atom in the aluminum compound obtained by the molecular orbital calculation is +0.7 or more include, for example, the following compound group. One of these can be used alone or in combination of two or more.

(I) dialkylaluminum monohalides such as dimethylaluminum chloride, dimethylaluminum bromide, ditylaluminum chloride,
Examples thereof include diethylaluminum bromide, diethylaluminum fluoride, dipropylaluminum chloride, di (n-butyl) aluminum chloride, diisobutylaluminum chloride, di (n-hexyl) aluminum chloride, and di (n-octyl) aluminumchloride.

(Ii) alkylaluminum dihalide,
For example, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum difluoride, methylaluminum dibromide, ethylaluminum dibromide, propylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride, n-octyl aluminum dichloride and the like.

(Iii) alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide, propylaluminum sesquichloride, n-butylaluminum sesquichloride, isobutylaluminum sesquichloride, n-hexylaluminum sesquichloride , N-octyl aluminum sesquichloride, ethyl aluminum sesquifluoride and the like.

(Iv) dialkylaluminum monoalkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dipropylaluminum ethoxide, diisopropylaluminum ethoxide, diisobutylaluminum ethoxide, di (n-butyl) aluminum ethoxide, di ( n-hexyl) aluminum ethoxide, di (n-octyl) aluminum ethoxide and the like.

(V) alkylaluminum dialkoxides, for example methylaluminum diethoxide, ethylaluminum diethoxide, propylaluminum diethoxide, n-butylaluminum diethoxide, isobutylaluminum diethoxide, n-hexylaluminumdiethoxyd And n-octyl aluminum diethoxide.

(Vi) Trialkoxy aluminums such as trimethoxy aluminum and triethoxy aluminum.

(Vii) Alkyl aluminoxanes such as methylaluminoxane and ethylaluminoxane.

(Viii) alkyl aluminum alkoxy halides such as methyl aluminum methoxy chloride, ethyl aluminum methoxy chloride, ethyl aluminum ethoxy chloride, ethyl aluminum ethoxy bromide, isobutyl aluminum methoxy chloride, isobutyl aluminum ethoxy chloride, isobutyl aluminum ethoxy bromide, isobutyl aluminum iso Propoxycyclolide, isobutyl aluminum isopropoxy bromide and the like can be mentioned.

(Ix) dialkylaluminum monophenoxides, for example diethylaluminum phenoxide,
Diisobutylaluminum phenoxide and the like.

(X) Aluminum trihalide, for example, aluminum trichloride, aluminum tribromide and the like.

Particularly preferably, component (B-2) comprises dialkylaluminum monochloride, dialkylaluminum monobromide, alkylaluminum dichloride, alkylaluminum dibromide, alkylaluminum sesquichloride, alkylaluminum sesquibromide, dialkylaluminum alkoxide and alkylaluminum It is selected from the group consisting of dialkoxides.

Next, the component (C) alkylalkoxysilane compound will be described. Preferred alkylalkoxysilane compounds include, for example, those represented by the general formula

Embedded image R ¹ Si (OR ² ) (OCH ₃ ) ₂ (wherein R ¹ is a branched or cyclic alkyl group having 3 to 6 carbon atoms, and R ² is a C 3 to C 6 alkyl group) , A branched alkyl group, an alkenyl group, or an alkynyl group).
R ¹ is, for example, an isopropyl group, a t-butyl group,
Examples include an s-butyl group, a t-amyl group, a cyclopentyl group, a cyclohexyl group, and the like. R ² is, for example, isopropyl, t-butyl, s-butyl, t-amyl, 2-methyl-3-butenyl, 3-methyl-2-butenyl, 2-methyl-3-butynyl, etc. Is mentioned. Specific compounds include, for example, t-butoxycyclopentyldimethoxysilane, isopropoxycyclopentyldimethoxysilane, s-butoxycyclopentyldimethoxysilane, t-amyloxycyclopentyldimethoxysilane, (2-methyl-3-butene-2-oxy) cyclopentyldimethoxy Silane, (3-methyl-
2-butene-1-oxy) cyclopentyldimethoxysilane, (2-methyl-3-butene-2-oxy) cyclopentyldimethoxysilane, t-butoxycyclohexyldimethoxysilane, isopropoxycyclohexyldimethoxysilane, s-butoxycyclohexyldimethoxysilane, t -Amyloxycyclohexyldimethoxysilane, (2-methyl-3-butene-2-oxy) cyclohexyldimethoxysilane, (3-methyl-2-butene-1-oxy) cyclohexyldimethoxysilane,
(2-methyl-3-butene-2-oxy) cyclohexyldimethoxysilane and the like.

As the alkylalkoxysilane compound,
In addition to the above, an alkylalkoxysilane containing a lactone group or a carboxyl group, an alkylalkoxysilane having a heterocyclic substituent having a silicon atom or a nitrogen atom as a ring-constituting atom, and the like can also be preferably used.

The catalyst of the present invention comprises the above-mentioned components. Preferably, 70 to 600 mol of the component (B-1) and 70 to 600 mol of the component (B-
2) 2 to 200 mol and 10 to 30 mol of the component (C) are blended. More preferably, 90 to 400 mol of the component (B-1) per 1 mol of titanium in the component (A),
-2) is blended in an amount of 9 to 45 mol and the component (C) in an amount of 15 to 25 mol.

In the present invention, the component (A) may or may not be subjected to prepolymerization. In the case of performing the prepolymerization, an olefin containing an organoaluminum (component D) and an organosilicon compound (component E) is used. This is done by contacting with. The organoaluminum (component D) is the same as the component (B-
1) One or more compounds selected from the compounds described in component (B-2) can be used. Among these, trialkyl aluminum, especially triethyl aluminum,
Triisobutylaluminum is preferred. As the organosilicon compound (component E), any of the compounds described in the above-mentioned component (C) can be used, but any other compounds having a total of four alkyl groups and alkoxy groups bonded to a silicon atom can be used. It is possible. For example, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane ethyltriisobutoxy Silane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane,
Dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane , Diphenyldiallyloxysilane, methylphenyldimethoxysilane, chlorophenyldiethoxysilane and the like. Preferred organosilicon compounds (component E) are t-butoxycyclopentyldimethoxysilane, isopropoxycyclopentyldimethoxysilane or S-butoxycyclopentyldimethoxysilane.

Examples of the olefin used for the prepolymerization include, in addition to ethylene, α-olefins such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene. Prepolymerization is normal butane, isobutane,
Normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene,
It is preferably carried out in an inert hydrogen such as xylene. The prepolymerization is usually carried out at a temperature of 100 ° C or lower, preferably -30 ° C to +
The reaction is performed at a temperature of 30 ° C, more preferably -20 ° C to + 20 ° C. The polymerization system may be either a batch system or a continuous system, and may be performed in two or more stages.

The component (D) has a concentration of 10 to 10 in the prepolymerized system.
It is used in an amount of 500 mmol / l, preferably 30 to 200 mmol / l, and 1 to 50,000 mol per 1 mol of titanium in the component (A).
It is preferably used in an amount of 2 to 1,000 mol. Component (E) has a concentration of 1 to 1,000 in the prepolymerized system.
Mmol / liter, preferably 5-200 mmol /
Used to be liters. The olefin polymer is incorporated into the component (A) by the prepolymerization, and the amount of the polymer is 0.1 to 200 / g of the component (A).
g, especially 0.5 to 50 g. The catalyst component thus prepared can be diluted or washed with the above-mentioned inert medium, but it is particularly preferable to wash it from the viewpoint of preventing catalyst deterioration. After washing, it may be dried if necessary. When storing the catalyst, it is preferable to store it at a temperature as low as possible.
° C, especially the temperature range of -20 ° C to + 5 ° C is recommended.

The components (A), (B-1), and (B-
2) The polymerization of the α-olefin is carried out in the presence of the catalyst comprising the component (C). As the α-olefin, a linear or branched α-olefin having 2 to 10 carbon atoms is preferable, and examples thereof include ethylene, propylene, butylene, pentene, hexene, heptene, and octene. The catalyst of the present invention can be used for homopolymerization of α-olefin,
It can also be used for copolymerization of two or more α-olefins. The catalyst of the present invention is particularly preferably used for propylene homopolymerization and copolymerization thereof (which may be either random copolymerization or block copolymerization).

As the reaction conditions in the polymerization of α-olefin, conventional conditions can be used. For example, -20 to +15
At 0 ° C., preferably 0-100 ° C. and 1-60 atm.
Performed for 5-7 hours. The polymerization reaction may be performed in a gas phase or a liquid phase. When the reaction is carried out in a liquid phase, the reaction can be carried out in the above-mentioned inert medium or in a liquid monomer. Also,
The polymerization may be carried out either batchwise or continuously. The polymerization reaction may be performed in one stage, or may be performed in two or more stages by changing the polymerization conditions or changing the type of monomer used.

In order to control the molecular weight of the produced polymer, a known molecular weight controlling agent such as hydrogen can be present in the polymerization reaction system.

[0065]

The present invention will be described in more detail with reference to the following examples. The percentages are by weight unless otherwise specified. Example 1 (1) Preparation of Component (A) A 200 ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. In this flask, 5 g of silicon oxide (trade name: G-952, manufactured by DAVISON) and 40 ml of n-heptane, which were calcined at 200 ° C. for 2 hours and further at 700 ° C. for 5 hours in a nitrogen stream, were put. Further, n-butylethylmagnesium (hereinafter, referred to as n-butylethylmagnesium)
20% n-heptane solution (named BEM) (manufactured by Texas Alkyls, trade name: MAGALA BEM) 20 m
and stirred at 90 ° C. for 1 hour.

After the obtained suspension was cooled to 0 ° C., 11.2 g of tetraethoxysilane was added to 20 ml of n-
The solution dissolved in heptane was dropped from the dropping funnel over 30 minutes. After completion of the dropwise addition, the temperature was raised to 50 ° C. over 2 hours, and stirring was continued at 50 ° C. for 1 hour. After the completion of the stirring, the supernatant was removed by decantation, and the generated solid was washed with 60
Washing at room temperature with ml of n-heptane, and the supernatant was removed by decantation. This washing treatment with n-heptane was further performed four times.

To the above solid, 50 ml of n-heptane was added to form a suspension, and a solution of 8.0 g of 2,2,2-trichloroethanol dissolved in 10 ml of n-heptane was added from a dropping funnel to a suspension. The mixture was added dropwise at 15 ° C over 15 minutes. After completion of the dropwise addition, stirring was continued at 25 ° C. for 30 minutes. After completion of the stirring, 2 ml of n-heptane was added at room temperature.
Washing was performed three times each with 60 ml of toluene. When the obtained solid (referred to as solid component I) was analyzed, SiO ₂ : 36.6%, Mg: 5.1%, Cl:
38.5%.

To the solid component I obtained above, 10 ml of n-heptane and 40 ml of titanium tetrachloride were added.
Then, 0.6 g of di-n-butyl phthalate dissolved in 5 ml of n-heptane was added over 5 minutes. afterwards,
The temperature was raised to 115 ° C, and the reaction was performed for 2 hours. After the temperature was lowered to 90 ° C., the supernatant was removed by decantation, and the mixture was washed twice with 70 ml of n-heptane. Further n-heptane 1
5 ml and 40 ml of titanium tetrachloride were added and reacted at 115 ° C. for 2 hours. After the reaction is completed, the obtained solid substance is
Washing was performed 8 times at room temperature with 1 n-hexane. Then, drying was performed at room temperature under reduced pressure for 1 hour to obtain 8.3 g of a solid component (component A). As a result of the analysis, this component A contains:
Contains 3.1% by weight of Ti, and Si, M
It was confirmed that g, Cl and di-n-butyl phthalate were contained.

(2) Polymerization of propylene In a 1.5-liter stainless steel autoclave equipped with a stirrer, under a nitrogen atmosphere, 10.2 mg of the component A obtained in the above (1), 0.4 mmol of triethyl aluminum, diethyl aluminum 0.16 mmol of ethoxide, 0.08 mmol of isopropoxycyclopentyldimethoxysilane and 7 ml of n-heptane were mixed,
The one held for 5 minutes was placed. Next, 8000 ml of hydrogen (normal temperature, normal pressure) as a molecular weight control agent and 1 liter of liquid propylene were injected, and then the temperature of the reaction system was increased to 70 ° C., and polymerization of propylene was performed for 1 hour. After polymerization,
Unreacted propylene and hydrogen were purged, and the polymer was taken out and dried.

The total amount of the obtained polymer was 203 g,
Its melt flow rate (MFR) is 80.4 g / 10
And the heptane insoluble matter (HI) was 95.8%.
The MFR is calculated according to ASTM D1238.
Measured under the condition of 230 ° C. and 2160 g load, HI is
This is the remaining amount when extracted with boiling n-heptane for 6 hours using a modified Soxhlet extractor. These measuring methods are the same in the following.

Examples 2 to 4 Propylene was polymerized in the same manner as in Example 1 except that the aluminum compounds shown in Table 1 were used instead of diethylaluminum ethoxide in (2) of Example 1. . Table 1 shows the results.

Example 5 Propylene polymerization was carried out in the same manner as in Example 1 except that triisobutylaluminum and ethylaluminum sesquichloride were used in place of triethylaluminum and diethylaluminum ethoxide in (2) of Example 1. Table 1 shows the results.

Comparative Example 1 Propylene was polymerized in the same manner as in Example 1 except that triethylaluminum was used as the organoaluminum compound and diethylaluminum ethoxide was not used in (2) of Example 1. . Table 1 shows the results.

Comparative Example 2 Propylene was polymerized in the same manner as in Example 1 except that triisobutylaluminum was used as the organoaluminum compound and no diethylaluminum ethoxide was used in (2) of Example 1. . Table 1 shows the results.

[0075]

[Table 1]

[0076]

When the polymerization reaction of an α-olefin is carried out using the catalyst of the present invention, poly (α-olefin) having high stereoregularity, good fluidity and high rigidity can be obtained.

[Brief description of the drawings]

FIG. 1 is a flowchart schematically showing a preparation process of an α-olefin polymerization catalyst of the present invention.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Issei Akira 1-3-1 Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Inside the Tonen Co., Ltd. 1-3-1 Kaoka Inside Tonen Research Institute

Claims (1)

[Claims] 1. A solid component containing (A) magnesium, titanium, a halogen, a metal oxide and an electron-donating compound as essential components, and (B-1) an aluminum atom in an aluminum compound obtained by molecular orbital calculation. The charge amount is +0.7
Α comprising an organoaluminum compound having a charge of less than +0.7, (B-2) an aluminum compound having a charge amount on an Al atom in the aluminum compound determined by molecular orbital calculation of +0.7 or more, and (C) an alkylalkoxysilane compound. -An olefin polymerization catalyst.