JPH1180237A - Alpha-olefin polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerization catalyst which can realize the production of a poly(α-olefin) having high stereoregularity and good flowability. SOLUTION: This catalyst consists of a solid component (A) comprising essentially magnesium, titanium, halogen atoms and an electron-donating compound, trimethylaluminum (B), an alkylalkoxysilane compound (C) and a boron compound (D) represented by the formula: BX3 (wherein X is Br, I, alkyl, alkoxy, aryl or aryloxy, provided that at least one of X's is Br or I).

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.

[0003]

SUMMARY OF THE INVENTION 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 for α-olefins and found that the polymerization was carried out in the presence of a co-catalyst comprising a combination of trimethylaluminum, a boron bromide compound and a boron iodide compound. By doing
The present inventors have found that a poly (α-olefin) having a high stereoregularity and a high MFR can be produced, and completed the present invention.

That is, the present invention provides (A) a solid component comprising magnesium, titanium, a halogen and an electron donating compound as essential components, (B) trimethylaluminum,
(C) an alkylalkoxysilane compound and (D) a general formula BX _{3 wherein} X is Br, I, an alkyl group, an alkoxy group, an aryl group or an aryloxy group, provided that at least one is Br or I ) Is an α-olefin polymerization catalyst comprising a boron compound represented by the formula:

An embodiment of the present invention will be described below. (A) Component (A) is magnesium, titanium, halogen,
The above catalyst, which is a solid component containing a metal oxide and an electron donating compound as essential components. (B) Component (C) alkylalkoxysilane compound,
General formula: 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)
The above catalyst, which is an alkyltrialkoxysilane represented by the formula: (C) Component (D) is represented by the general formula BX ₃ (where X is Br,
I or an alkyl group. However, at least one is B
r or I. The above catalyst selected from the group consisting of boron compounds represented by the formula (1): (D) The catalyst as described above, wherein the component (D) is selected from the group consisting of boron compounds represented by the general formula BX ₃ (where X is Br or I). (E) The above catalyst, wherein the component (D) is selected from the group consisting of tribromoboron, ethyldibromoboron, triiodoboron, and ethyldiiodoboron. (F) The catalyst as described above, wherein the component (D) is selected from the group consisting of ethoxydibromoboron, phenyldibromoboron, phenoxydibromoboron, ethoxydiiodoboron, phenyldiiodoboron and phenoxydiiodoboron. (G) Component (B) per mole of titanium in component (A)
Is 70 to 600 mol, 10 to 30 mol of the component (C) and 2 to 200 mol of the component (D). (H) 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

1. Solid component (A) essentially containing Ti, Mg, halogen and an electron donating compound The component (A) in the catalyst of the present invention contains magnesium, titanium, a halogen and an electron donating compound as essential components, and optionally contains a metal. An oxide can be included. Component (A) is a component known per se. Such components are usually prepared by contacting a magnesium compound, a titanium compound, an electron donating compound, and, in the case where each of the compounds does not have a halogen, a halogen-containing compound. Hereinafter, each component will be described.

(1) Magnesium A magnesium compound is represented by the general formula MgR ^{a Rb} .
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, Tansomoto 20
Alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups are OR groups, and R is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group is a halogen atom. Chlorine, bromine, iodine, fluorine and the like.

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.

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

(3) Electron-donating compounds The electron-donating compounds 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, and carbon esters. Of these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, and ethers are preferably used.

(A) Carboxylic acids 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 and crotonic acid. Carboxylic acids, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, aliphatic dicarboxylic acids such as fumaric acid, and aliphatic oxycarboxylic acids such as tartaric acid;
Cycloaliphatic carboxylic acids such as cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,2-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, hemimeltic acid, trimesic acid, pyromellitic acid, And aromatic polycarboxylic acids such as melitic acid.

(B) Carboxylic anhydride As the carboxylic anhydride, anhydrides of the above-mentioned carboxylic acids can be used.

(C) Carboxylic acid ester As the carboxylic acid ester, mono- or polyhydric esters of the above carboxylic acids can be used. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, and the like. Propyl pivalate, isobutyl pivalate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, glutaric acid Dibutyl, diisobutyl glutarate,
Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, Methyl benzoate, ethyl benzoate, methyl p-toluate, p-tert-butyl,
Ethyl benzoate, ethyl p-anisate, ethyl α-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, trimellitic acid Tributyl, tetramethyl pyromellitate, tetraethyl pyromellitate, tetrabutyl pyromellitate and the like can be mentioned.

(D) Carboxylic acid halide As the carboxylic acid halide, acid halides of the above carboxylic acids can be used. Specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, Butyric acid chloride, butyric acid bromide, butyric acid iodide, 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,
Isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, naphthalic acid dichloride. Further, monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride, and butyl phthalate chloride can also be used.

(E) Alcohols 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 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.

[0026] (f) ethers ethers 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 carbons,
^Re and ^Rf 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.

(4) Halogen The halogen-containing compounds include halogenated hydrocarbons, halogen-containing alcohols, silicon halide compounds having a hydrogen-silicon bond, groups IIIa and IVa of the periodic table,
Halides of Va group elements (hereinafter referred to as metal halides) and the like can be mentioned.

(A) Halogenated hydrocarbon As the halogenated hydrocarbon, mono- and polyhalogen-substituted saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms are used. You. 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, methylchloroform, methylbromoform, methyliodoform, 1,1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,2
2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane,
Chlorinated paraffin and the like can be mentioned. Examples of the alicyclic compound include chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, and hexachlorocyclohexane. Examples of the aromatic compound include 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.

(B) Halogen-Containing Alcohol 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 included. Compounds substituted with halogen atoms 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.

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

(D) Metal halides Metal halides include B, Al, Ga, In, Tl,
Chloride of Si, Ge, Sn, Pb, As, Sb, Bi,
Fluoride, bromide and iodide, especially BC
l ₃ , BBr ₃ , BI ₃ , AlCl ₃ , AlBr ₃ , GaC
l ₃ , GaBr _3, InCl ₃ , TlCl ₃ , SiCl ₄ , S
nCl ₄ , SbCl ₅ , SbF _{5 and the} like are preferred.

(5) Metal oxide As the component (A), a metal oxide can be used as a carrier. Metal oxides are listed in Groups II to IV of the Periodic Table of the Elements.
Oxides of elements selected from the group consisting of B ₂ O ₃ , MgO, Al ₂ O ₃ , SiO ₂ , Ca
O, TiO ₂ , ZnO, ZrO ₂ , SnO _2, BaO, Th
O _{2 and the} like. Among them, B ₂ O ₃ , MgO,
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 , SiO ₂ —
Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO or the like can also be used.

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.

(6) Preparation of component (A) Magnesium compound (component 1), titanium compound (component 2), electron-donating compound (component 3), and metal oxides and halogens which can be contacted if necessary The contact with the containing compound is performed by mixing and stirring or mechanically co-milling in the presence or absence of an inert medium. 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.

In the present invention, the component (A) is preferably prepared in the case of a solid component (A) containing magnesium, titanium, halogen and an electron donating compound as essential components, as described in JP-A-63-264607. Id 58-1985
No. 03, No. 62-146904 and the like. More specifically, it is obtained by contacting (a) metallic magnesium, (b) a halogenated hydrocarbon, and (c) a compound of the general formula X _n M (OR) _mn (the same as the above-mentioned alkoxy group-containing compound). A method of contacting a magnesium-containing solid with (d) a halogen-containing alcohol and then with (e) an electron-donating compound and (f) a titanium compound (JP-A-63-163).
No. 264607), (a) contacting a magnesium dialkoxide with a (ii) silicon halide compound having a hydrogen-silicon bond, (c) contacting a titanium halide compound, and then (d) an electron donating compound (Optionally contacting with a titanium halide compound)
JP-A-146904), (a) contacting a magnesium dialkoxide with (b) a silicon halide compound having a hydrogen-silicon bond, (c) contacting with an electron donating compound, and then (d)
A method of contacting a titanium compound (JP-A-58-1985)
03 publication). Among these, the method is desirable.

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),
Preferably, 5 to 40% by weight of Mg, 1 to 2.5% by weight of Ti, 30 to 70% by weight of halogen, and 0 to 20% by weight of an electron donating compound are contained.

Further, magnesium, titanium, halogen,
A desirable method for preparing the solid component (A ') containing a metal oxide and an electron donating compound as essential components is disclosed in
No. 162607, No. 55-94909, No. 55-115405, No. 57-108107, No. 61-21109, No. 61-174204
JP-A-61-174205 and JP-A-61-174
No. 206, 62-7706 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.

In the component (A '), Mg is preferably 2
-12%, Ti 1-5%, halogen 10-35% by weight, metal oxide 30-70% by weight, and electron-donating compound 0-20% by weight.

2. Component (B) Trimethylaluminum Trimethylaluminum is used in combination with other organoaluminum compounds, for example, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride, or a mixture thereof, which is commercially available. It can be used in combination with a complex compound.

Alternatively, it is also possible to use in combination with an organic aluminum compound other than the above, for example, an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can be used. 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.

3. Component (C) Alkylalkoxysilane Compound As the alkylalkoxysilane compound, for example, a compound represented by the following general formula: R ¹ Si (OR ² ) (OCH ₃ ) ₂ (wherein R ¹ is a branched or cyclic C 3-6 group And R ² is a branched alkyl group, an alkenyl group or an alkynyl group having 3 to 6 carbon atoms).
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.

4. Boron compounds of component (D) a boron compound component (D) is a boron compound represented by the general formula BX _3. In the formula, X is bromine, iodine, an alkyl group, an alkoxy group, an aryl group or an aryloxy group, at least one of which is bromine or iodine, and X may be the same or different. Preferably, it is a compound having two or more bromines or iodine, and more preferably a compound having two or more bromines. As the alkyl group, methyl, ethyl, propyl, butyl, hexyl, octyl, etc., as the alkoxy group, methoxy, ethoxy, propoxy,
Aryl groups such as isopropoxy, butoxy, t-butoxy and the like; phenyl and the like; aryloxy groups such as
Phenoxy and the like can be mentioned. Specific compounds include tribromoboron, ethyldibromoboron, diethylbromoboron, triiodoboron, ethyldiiodoboron,
Examples thereof include diethyliodoboron, ethoxydibromoboron, phenyldibromoboron, phenoxydibromoboron, ethoxydiiodoboron, phenyldiiodoboron, and phenoxydiiodoboron.

5. The ratio of the components (A), (B), (C) and (D) The catalyst of the present invention comprises the above-mentioned components. Preferably, the amount of the component (B) is per 1 mol of titanium in the component (A). ), 70 to 600 mol, 10 to 30 mol of the component (C) and 2 to 200 mol of the component (D). More preferably, 90 to 400 mol of the component (B), 15 to 25 mol of the component (C) and 9 to 150 mol of the component (D) are mixed per 1 mol of titanium in the component (A).

6. Prepolymerization In the present invention, the component (A) may or may not be subjected to prepolymerization. In the case of performing prepolymerization, the prepolymerization is carried out in the presence of an organoaluminum (component E) and an organic silicon compound (component F) if desired. It is performed by contacting with an olefin. The organoaluminum (component E) is preferably a trialkylaluminum, particularly triethylaluminum or triisobutylaluminum. 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, diphenyldiethoxysilane Emissions, dibenzyl diethoxy silane, divinyl phenoxy silane, diallyl propoxysilane, diphenyl diallyl silane, methyl phenyl dimethoxy silane, and the like chlorophenyl diethoxy silane. Preferred organosilicon compounds (component F) include t-butoxycyclopentyldimethoxysilane, isopropoxycyclopentyldimethoxysilane or s-butoxycyclopentyldimethoxysilane.

Examples of the olefin used in 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.

7. Polymerization of α-olefin Component (A), component (B), component (C) and component (D) pre-polymerized or not pre-polymerized as described above.
Α-olefin is polymerized in the presence of a catalyst consisting of 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 has an α
-It can be used not only for homopolymerization of olefins but also for copolymerization of two or more kinds of α-olefins. Particularly preferably, it is used for propylene homopolymerization and copolymerization thereof (which may be either random copolymerization or block copolymerization).

As the reaction conditions for 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.

[0051]

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 Catalyst Solid Component (A1) In a 1-liter reaction vessel equipped with a reflux condenser, chip-shaped metal magnesium (purity 99.
8.3 g of 5%, average particle size of 1.6 mm) and 250 ml of n-hexane were added, and the mixture was stirred at 68 ° C. for 1 hour. The metal magnesium was taken out and dried at 65 ° C. under reduced pressure. Obtained.

Next, a suspension obtained by adding 140 ml of n-butyl ether and 0.5 ml of an n-butyl ether solution of n-butylmagnesium chloride (1.75 mol / l) to the metallic magnesium was maintained at 55 ° C. N-butyl chloride 3 in 50 ml of butyl ether
A solution in which 8.5 ml was dissolved was added dropwise over 50 minutes. After performing the reaction at 70 ° C. for 4 hours with stirring, the reaction solution was kept at 25 ° C. Then, HC (OC ₂ H ₅₎ To the reaction solution ₃ 5
5.7 ml was added dropwise over 1 hour. After dropping, 60
The mixture was reacted at 15 ° C. for 15 minutes, and the reactive solid was washed six times with 300 ml each of n-hexane and dried under reduced pressure at room temperature for 1 hour to obtain a magnesium-containing solid containing 19.0% and 28.9% of Mg. 31.6 g were recovered.

In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, under a nitrogen gas atmosphere,
6.3 g of magnesium-containing solid and 50 n-heptane
into a suspension and stirred at room temperature while stirring.
A mixed solution of 20 ml (0.02 mmol) of 2-trichloroethanol and 11 ml of n-heptane was dropped from the dropping funnel over 30 minutes, and further stirred at 80 ° C. for 1 hour. The obtained solid was filtered, and n-hexane at room temperature for 10
Wash 4 times with 0 ml, then add 2 ml with 100 ml each of toluene.
Washed twice to obtain a solid component.

40 ml of toluene was added to the above solid component, and titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. Under stirring, a mixed solution of 2 ml of dibutyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, followed by stirring at 120 ° C. for 2 hours. Further, titanium tetrachloride was newly added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and
Stirred at C for 2 hours. The obtained solid substance was separated by filtration at 110 ° C., and washed seven times with 100 ml of n-hexane at room temperature. Thus, 5.5 g of the component (A1) was obtained.

(2) Polymerization of propylene In a 1.5-liter stainless steel autoclave equipped with a stirrer, under a nitrogen atmosphere, 4.5 mg of the component (A1) obtained in the above (1), 1.6 mmol of trimethylaluminum , 0.04 mmol of tribromoboron, 0.08 mmol of amyloxycyclopentyldimethoxysilane and 7 ml of n-heptane, and the mixture kept for 5 minutes was added. Then, hydrogen as a molecular weight controlling agent was added to 8000
ml (normal temperature, normal pressure) and 1 liter of liquid propylene were injected, and then the temperature of the reaction system was raised to 70 ° C., and propylene was polymerized 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 196 g, the melt flow rate (MFR) was 340 g / 10 min, and the hot heptane insoluble matter (HI) was 95.5%. The MFR is
230 ° C., 216 according to ASTM D1238
Measured under the condition of a load of 0 g, HI 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.

Example 2 (1) Preparation of Catalyst Solid Component (A2) 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., 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 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:
It contained 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. Next, drying was performed at room temperature under reduced pressure for 1 hour to obtain 8.3 g of a solid component (component A2). As a result of analysis, this component A contained 3.1% by weight of Ti, and also contained Si,
It was confirmed that Mg, 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, 10.1 mg of the component (A2) obtained in the above (1) and 1.6 of trimethylaluminum were used.
Millimol, 0.04 mmol of tribromoboron, 0.08 mmol of amyloxycyclopentyldimethoxysilane and 7 ml of n-heptane were mixed, and the mixture kept for 5 minutes was added. Next, hydrogen 8000 as a molecular weight controlling agent was used.
ml (normal temperature, normal pressure) and 1 liter of liquid propylene were injected, and then the temperature of the reaction system was raised to 70 ° C., and propylene was polymerized 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 200 g, the melt flow rate (MFR) was 345 g / 10 min, and the heptane insoluble matter (HI) was 94.7%.

Examples 3 to 4 Polymerization of propylene was carried out in the same manner as in Example 1 except that the compounds shown in Table 1 were used in place of amyloxycyclopentyldimethoxysilane and tribromoboron. Was done. Table 1 shows the results.

Example 5 Propylene was polymerized in the same manner as in Example 2 except that the compounds shown in Table 1 were used instead of tribromoboron in Example 2 (2). Table 1 shows the results.

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

Comparative Example 2 Propylene was polymerized in the same manner as in Example 2 except that triethylaluminum was used in place of the trimethylaluminum compound and tribromoboron was not used in (2) of Example 2. . Table 2 shows the results.

Comparative Example 3 Propylene was polymerized in the same manner as in Example 1 except that triethylaluminum was used instead of the trimethylaluminum compound in (2) of Example 1.
Table 2 shows the results.

Comparative Example 4 Propylene was polymerized in the same manner as in Example 2 except that triethylaluminum was used instead of the trimethylaluminum compound in (2) of Example 2.
Table 2 shows the results.

Comparative Example 5 In Example 1 (2), triethylaluminum was used in place of the trimethylaluminum compound, dicyclopentyldimethoxysilane was used in place of amyloxycyclopentyldimethoxysilane, and triiodoboron was used in place of tribromoboron. Example 1 except for using
Polymerization of propylene was carried out in the same manner as described above. Table 2 shows the results
Shown in

Comparative Example 6 In Example 1 (2), triisobutylaluminum was used in place of the trimethylaluminum compound.
Propylene was polymerized in the same manner as in Example 1 except that tribromoboron was not used. Table 2 shows the results.

Comparative Example 7 Propylene polymerization was carried out in the same manner as in Example 1 except that tribromoboron was not used in (2) of Example 1. The results are shown in Table 2.

Comparative Example 8 Polymerization of propylene was carried out in the same manner as in Example 2 except that tribromoboron was not used in (2) of Example 2. Table 2 shows the results.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

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.

Claims (1)

[Claims] 1. A solid component comprising (A) magnesium, titanium, a halogen and an electron donating compound as essential components,
(B) trimethylaluminum, (C) an alkylalkoxysilane compound and (D) a general formula BX _{3 wherein} X is
Represents Br, I, an alkyl group, an alkoxy group, an aryl group or an aryloxy group. However, at least one is Br or I. Α consisting of a boron compound represented by
-An olefin polymerization catalyst.