JPH10287709A - Catalyst for alpha-olefin polymerization - 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, (B) an organoaluminum compound, (C) an alkylalkoxysilane compound, and (D) MetR _x (Where
Met represents an iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, platinum or palladium metal element, R represents a hydrocarbon-containing group or a halogen atom, and x represents the valency of Met. ) A catalyst for polymerization of α-olefins comprising the compound represented by the formula:

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.

[0003]

Means for Solving the Problems The inventors of the present invention have studied the polymerization catalyst for α-olefins. As a result, the polymerization was carried out in the presence of a specific metal compound to obtain a high stereoregularity and a high MFR. It has been found that a poly (α-olefin) having the following formula can be produced, and the present invention has been completed. That is, the present invention provides (A) a solid component containing magnesium, titanium, a halogen, a metal oxide and an electron donating compound as essential components, (B) an organoaluminum compound, (C) an alkylalkoxysilane compound, and (D) Formula: Met
R _x (where Met is iron, ruthenium, osmium,
Represents a cobalt, rhodium, iridium, nickel, platinum or palladium metal element, R represents a hydrocarbon-containing group or a halogen atom, and x represents a valence of Met. ) Is an α-olefin polymerization catalyst comprising the compound represented by the formula (1):

Preferred embodiments of the present invention are described below. (A) The above-mentioned catalyst wherein the component (B) is selected from trialkylaluminum. As the alkyl, an alkyl having 1 to 18 carbon atoms is preferable. (B) Component (C) 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: (Iii) Met of the component (D) is iron, cobalt, nickel,
The above catalyst, which is a compound of a metal selected from ruthenium, rhodium, osmium, iridium, and platinum metal elements. (D) The catalyst as described above, wherein Met of the component (D) is a compound of a metal selected from iron, cobalt, nickel and platinum metal elements. (E) R of the component (D) is an alkyl group, an alkoxy group,
The above catalyst, which is a compound selected from an alkylamino group and a halogen atom. (F) The above catalyst, wherein R of the component (D) is a compound containing at least one acetylacetonato group. (G) Component (B) per mole of titanium in component (A)
Is 70 to 600 mol, 10 to 30 mol of component (C) and 2 to 200 mol of component (D). (H) The above-mentioned catalyst, wherein the α-olefin is a linear or branched α-olefin having 2 to 10 carbon atoms.

[0005]

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 a general formula of 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.

[0008] 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-mentioned magnesium compound can be prepared from metallic magnesium or another magnesium compound 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 .

Compounds wherein 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 Group 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.

Titanium compounds are divalent, trivalent and tetravalent titanium compounds, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, dichlorodiethoxytitanium, dichlorodiethoxytitanium, and the like. 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 the form of powder. 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 the carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid and crotonic acid, 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 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, 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, any 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, may be carried out by mixing or 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, hexane, heptane, saturated aliphatic hydrocarbons such as octane, cyclopentane, saturated alicyclic hydrocarbons such as cyclohexane, benzene, toluene,
Aromatic hydrocarbons such as xylene can be used.

Preferred methods for preparing the component (A) in the present invention include JP-A-58-162607 and JP-A-58-162607.
-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, and the component (A) may be washed with the above-mentioned inert medium, if necessary, and further dried. In component (A),
Preferably, it contains 2 to 12% of Mg, 1 to 5% of Ti, 10 to 35% by weight of a halogen, 30 to 70% by weight of a metal oxide, and 0 to 20% by weight of an electron donating compound.

Next, the organoaluminum compound will be described. As the component (B) organoaluminum compound, for example, the following formula:

## STR2 ## (R ^k ) _r Al (Y) _3-r (where R ^k is each independently a group selected from an alkyl group and an aryl group, Y is each independently a halogen atom, A group selected from an alkoxy group, an aryloxy group and a hydrogen atom, and r is an arbitrary number in the range of 0 ≦ r ≦ 3), but is not limited thereto. Preferably, one of the following compounds
A single species or a combination of two or more species can be selected and used.

(I) Dialkylaluminum monohalides, such as dimethylaluminum chloride, dimethylaluminum bromide, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum fluoride, dipropylaluminum chloride, di (n-butyl) aluminum chloride, diisobutylaluminum chloride , Di (n-hexyl) aluminum chloride, di (n-octyl) aluminum chloride and the like.

(Ii) alkylaluminum dihalides, such as methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum difluoride, methylaluminum dibromide, ethylaluminum dibromide, propylaluminum dichloride,
Examples include n-butylaluminum dichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride, n-octylaluminum 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) alkylaluminum alkoxy halides such as methylaluminum methoxychloride, ethylaluminum methoxychloride, ethylaluminum ethoxychloride, ethylaluminum ethoxybromide, isobutylaluminum methoxychloride, isobutylaluminum ethoxychloride, isobutylaluminum ethoxybromide, isobutylaluminum isochloride And propoxycyclolide, isobutylaluminum isopropoxybamide and the like. (I
x) Dialkylaluminum monophenoxide, for example, diethylaluminum phenoxide, diisobutylaluminum phenoxide and the like.

(X) Trialkyl aluminum, for example, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, trihexyl aluminum and the like.

The alkyl group preferably has 1 carbon atom.
To 18 alkyl groups, the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and the halide is preferably chloride and bromide. An aryl group is, for example, a phenyl group, and an aryloxy group is
For example, it is a phenoxy group.

Of these, trialkylaluminum is preferred, and triethylaluminum and triisobutylaluminum are particularly preferred. Trialkylaluminum is another organic aluminum compound, for example, industrially available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide,
It can be used in combination with diethyl aluminum hydride or a mixture or complex compound thereof.

Alternatively, it is also possible to use an organic aluminum compound other than those described above, for example, an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Examples of such a compound include (C ₂ H ₅ ) ₂ AlOAl (C
_{2 H 5) 2, (C} 4 H 9) 2 AlOAl (C 4 H 9) 2, (C 2 H
_{5) 2 AlN (C 2 H} 5) Al (C 2 H 5) 2 and the like.

Next, the component (C) alkylalkoxysilane compound will be described. Preferred alkylalkoxysilane compounds include, for example, those of 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.

(D) The following formula: MetR _x (where Met represents a metal element of iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, platinum or palladium, and R represents a hydrocarbon-containing group or a halogen atom. X
Represents the valence of Met. )) Will be described.

Met is iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium or platinum. R may be the same or different, and examples of the hydrocarbon-containing group include an alkyl group, an alkoxy group, an acetylacetonato group, and an alkylamino group. The alkyl group is an alkyl group having 1 to 10 carbon atoms, and specific examples include methyl, ethyl, propyl, butyl, hexyl, and octyl. As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms,
Specific examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, t-butoxy, phenoxy and the like. The amino group is
—NR ¹ R ² , wherein R ¹ and R ² are an alkyl group or hydrogen, and the alkyl groups may be the same or different and have the same or different alkyl groups having 1 to 8 carbon atoms. , Propyl, butyl, hexyl, octyl and the like. Halogen atoms are fluorine, chlorine, bromine,
Iodine.

Preferably, Met is iron, nickel, cobalt, platinum or the like, and specific compounds include nickel (II) chloride, nickel (II) acetylacetonate, cobalt (II) chloride, cobalt ( II) Acetylacetonate, platinum chloride and the like.

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

In the present invention, the component (A) may or may not be subjected to prepolymerization. When the prepolymerization is performed, the olefin is added in the presence of an organoaluminum (component E) and an organosilicon compound (component F). This is done by contacting with. The organoaluminum (component E) can be used by selecting one or more kinds from the compounds described in the component (B). Among them, trialkyl aluminum,
Particularly, triethylaluminum and triisobutylaluminum are preferable. As the organosilicon compound (component F), 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 silicon atoms 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, dimethyl Diphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diphenyldimethoxysilane,
Examples include diphenyldiethoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane, and chlorophenyldiethoxysilane. Preferred organosilicon compounds (component F) 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.

Component (E) 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 (F) 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 α-olefin is polymerized in the presence of the catalyst comprising the components (A), (B), (C) and (D) which are prepolymerized or not prepolymerized as described above. As the α-olefin, carbon atoms of 2 to 10
Are preferred, and examples thereof include ethylene, propylene, butylene, pentene, hexene, heptene, and octene. The catalyst of the present invention can be used not only for homopolymerization of α-olefins but also 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.

[0060]

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)
BEM) 20% -n-heptane solution (manufactured by Texas Alkyls, trade name: MAGALA BEM) 20
Then, the mixture was stirred at 90 ° C. for 1 hour. After cooling the obtained suspension to 0 ° C., it was added with tetraethoxysilane 1
A solution in which 1.2 g was dissolved in 20 ml of n-heptane was dropped from the dropping funnel over 30 minutes. After dropping, 2
The temperature was raised to 50 ° C over time, and stirring was continued at 50 ° C for 1 hour. After completion of the stirring, the supernatant was removed by decantation, and the resulting solid was washed with 60 ml of n-heptane at room temperature, 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 to the suspension from a dropping funnel for 25 minutes. 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%. Solid component I obtained above
10 ml of n-heptane and 40 ml of titanium tetrachloride
Was added, and the temperature was raised to 90 ° C., and 0.6 g of di-n-butyl phthalate dissolved in 5 ml of n-heptane was added over 5 minutes. Thereafter, 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, 15 ml of n-heptane and 40 ml of titanium tetrachloride were added,
The reaction was performed at 115 ° C. for 2 hours. After completion of the reaction, the obtained solid substance was washed eight times with 60 ml of n-hexane at room temperature. Next, drying was performed at room temperature under reduced pressure for 1 hour,
8.3 g of a solid component (component A) was obtained. As a result of analysis, it was confirmed that this component A contained 3.1% by weight of Ti, and also contained Si, Mg, Cl and di-n-butyl phthalate.

(2) Polymerization of propylene In a 1.5-liter stainless steel autoclave equipped with a stirrer, 11.9 mg of the component A obtained in the above (1), 0.4 mmol of triethylaluminum, and isopropoxy were placed under a nitrogen atmosphere. 0.08 mmol of cyclopentyldimethoxysilane, 0.16 mmol of nickel (II) chloride and 7 ml of n-heptane were mixed, and the mixture kept for 5 minutes was added. Next, hydrogen 80 as a molecular weight controlling agent is used.
After pressurizing 00 ml (normal temperature, normal pressure) and 1 liter of liquid propylene, the temperature of the reaction system was raised to 70 ° C., and propylene polymerization was performed for 1 hour. After completion of the polymerization, unreacted propylene and hydrogen were purged, and the polymer was taken out and dried.

The total amount of the obtained polymer was 215 g,
Its melt flow rate (MFR) is 105.1 g / 1
At 0 minutes, the heptane insoluble matter (HI) was 95.7%.
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 5 Propylene was polymerized in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of nickel (II) chloride in (2) of Example 1. . Table 1 shows the results.

Example 6 Propylene polymerization was carried out in the same manner as in Example 1 except that triisobutylaluminum was used instead of triethylaluminum 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 nickel (II) chloride was not used in (2) of Example 1. Table 1 shows the results.

Comparative Example 2 Propylene polymerization was carried out in the same manner as in Example 1 except that triisobutylaluminum was used instead of triethylaluminum and nickel (II) chloride was not used. Was done. Table 1 shows the results.

[0068]

[Table 1]

[0069]

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 comprising (A) magnesium, titanium, a halogen, a metal oxide and an electron donating compound as essential components, (B) an organoaluminum compound, (C) an alkylalkoxysilane compound, and (D) a compound represented by the following formula: : Met
R _x (where Met is iron, ruthenium, osmium,
Represents a cobalt, rhodium, iridium, nickel, platinum or palladium metal element, R represents a hydrocarbon-containing group or a halogen atom, and x represents a valence of Met. ) A catalyst for polymerization of α-olefins comprising the compound represented by the formula: