JPH11106419A - Catalyst for polymerizing alpha-olefin - Google Patents

Abstract

(57) [Problem] To have a wide molecular weight distribution with improved moldability,
A catalyst for producing a poly-α-olefin having high stereoregularity. SOLUTION: (A) a solid component containing magnesium, titanium, halogen and an electron donating compound as essential components,
(B) an organoaluminum compound, and (C) a general formula R
¹ R ² Si (OR ³ ) (OCH ₃ ) (where R ¹ and R ² are R ¹
And a branched-free alkyl group carbon number of R ² is 4 to 10 in total. R ³ represents a branched alkyl group having 3 to 6 carbon atoms. ) A catalyst for polymerization of α-olefins comprising a dialkyldialkoxysilane represented by the following formula:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for producing a homopolymer, a random polymer and an impact copolymer of poly-α-olefin, particularly polypropylene, and more particularly to a catalyst having a wide molecular weight distribution and a suitable stereoregularity. The present invention relates to a catalyst for poly-α-olefin polymerization.

[0002]

2. Description of the Related Art Polypropylene has heat resistance, chemical resistance,
It has excellent electrical properties and good rigidity, tensile strength, optical properties and workability.
It is used for sheet molding, blow molding and the like. Further, it has a light specific gravity and is widely used in the fields of containers, packaging materials and the like.

As a catalyst for producing polypropylene, a solid catalyst system containing magnesium, titanium, halogen and an electron-donating compound as essential components is widely used because of its high activity and omission of a decatalyzing step. It is widely known that in this catalyst system, it is effective to add alkylalkoxylan as one component of the catalyst to improve the stereoregularity of polypropylene. As such an alkylalkoxysilane, a dialkyldimethoxysilane or an alkyltrimethoxysilane in which the alkyl group is a linear alkyl, a branched alkyl, or an aromatic ring is generally used. There was a problem that the molecular weight distribution of polypropylene became narrow.

[0004] Polypropylene having a broad molecular weight distribution has a lower melt viscosity at higher shear rates than polypropylene having a narrow molecular weight distribution, and is less likely to be molded at higher shear rates such as injection molding, stretched films, heat-fused fibers and the like. For products, lower melt viscosity improves productivity,
Advantageously, energy costs are reduced.

As a method for solving this problem, a method has been developed in which an alkylalkoxy having a combination of a branched alkyl group and a branched alkoxy group is added (Japanese Patent Laid-Open No. 3-1190)
Nos. 04, 5-331233, 5-331
234). However, in this type of alkylalkoxysilane, the stereoregularity of polypropylene is too high, and the use of the product is sometimes limited.

Further, as a method for producing polypropylene having a wide molecular weight distribution using a catalyst system containing a solid catalyst component essentially containing magnesium, titanium, a halogen and an electron-donating compound, a multistage reactor is used for each reactor. There is also a method for producing polymers having different molecular weights. However, in this method, it is difficult to control the reaction conditions, and this method cannot be used in a production apparatus having only a single-stage reactor. Therefore, it is desired to establish a method for expanding the molecular weight distribution by improving the catalyst system. Was rare.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst for producing a poly-α-olefin having a wide molecular weight distribution with improved moldability and high stereoregularity.

[0008]

Means for Solving the Problems The present inventors have focused on alkylalkoxysilanes to be added to a catalyst system for the polymerization of α-olefins, and have conducted intensive studies on the relationship between structures of alkyl groups and alkoxy groups and molecular weight distribution. As a result, they have found that an alkylalkoxysilane having a specific structure is effective in producing a poly-α-olefin having a wide molecular weight distribution, and completed the present invention.

That is, the present invention provides (A) a solid component containing magnesium, titanium, halogen and an electron donating compound as essential components, (B) an organoaluminum compound, and (C) a general formula R ¹ R ² Si (OR ³ ) (OCH ₃ ) (wherein, R ¹ and R ² represent a total of 4 to 10 carbon atoms of R ¹ and R ² )
Is a non-branched alkyl group. R ³ has ³ carbon atoms
And represents 6 to 6 branched alkyl groups. ) Is an α-olefin polymerization catalyst comprising a dialkyldialkoxysilane represented by the following 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) The above catalyst, wherein the component (B) is a trialkylaluminum. (C) Component (C) is t-butoxymethoxymethyl-n-
Propylsilane, t-butoxydiethylmethoxysilane, t-butoxymethoxydi-n-propylsilane, t-
The above catalyst, which is a dialkyldialkoxysilane selected from butoxy-n-butylmethoxymethylsilane, s-butoxymethoxymethyl-n-propylsilane, and s-butoxydiethylmethoxysilane. (D) The catalyst as described above, wherein the α-olefin is a linear or branched α-olefin having 2 to 10 carbon atoms.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Solid component essentially containing Ti, Mg, halogen and an electron-donating compound (A) The component (A) in the catalyst of the present invention contains magnesium, titanium, halogen and an electron-donating compound as essential components, and optionally contains a metal. An oxide can be included. Component (A)
It 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.

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 also 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 groups of X and R in the general formula of the alkoxy group-containing compound include 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.

Compound when M is Boron B (OEt) ₃ , B (OBu) contained in the 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 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.

(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 carboxylic acids can be used.

(C) Carboxylic acid ester 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 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, and the like. 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.

[0030] (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 poly-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 As metal halides, 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 desirably 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, and 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.

Also, 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) Organoaluminum Compound As the component (B) organoaluminum compound, for example, a compound represented by the general formula R ⁴ _n AlX ′ _3-n (where R ⁴ is an alkyl group, X ′
Represents a halogen atom, an alkoxy group or a hydrogen atom, and n
Is an arbitrary number in the range of 1 ≦ n ≦ 3. A) having 1 to 18 carbon atoms, such as trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide, and dialkylaluminum monohydride. Particularly preferred are several to six alkylaluminum compounds or mixtures or complex compounds thereof.

Specifically, the following compounds can be mentioned. (I) Trialkylaluminum, for example, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum and the like.

(Ii) dialkylaluminum monohalides such as dimethylaluminum chloride, dimethylaluminum bromide, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, dipropylaluminum chloride,
Di (n-butyl) aluminum chloride, diisobutylaluminum chloride, di (n-hexyl) aluminum chloride, di (n-octyl) aluminum chloride and the like can be mentioned.

(Iii) monoalkylaluminum dihalides, such as methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide, propylaluminum dichloride,
Examples include n-butylaluminum dichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride, n-octylaluminum dichloride and the like.

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

(V) dialkylaluminum monoalkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dipropylaluminum ethoxide, diisopropylaluminum ethoxide,
Examples thereof include diisobutylaluminum ethoxide, di (n-butyl) aluminum ethoxide, di (n-hexyl) aluminum ethoxide, and di (n-octyl) aluminum ethoxide.

(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 aluminum, for example, trimethoxy aluminum, triethoxy aluminum and the like.

(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 ethoxycyclolide, isobutylaluminum ethoxybromide, isobutylaluminum isobromide And propoxycyclolide, isobutylaluminum isopropoxybamide and the like.

(Ix) dialkylaluminum monophenoxide such as diethylaluminum phenoxide,
Diisobutylaluminum phenoxide and the like.

Of these, trialkylaluminum is preferred, and triethylaluminum and triisobutylaluminum are particularly preferred. Also, trialkyl aluminum is other organic aluminum compounds,
For example, it can be used in combination with industrially available diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl aluminum hydride, or a mixture or complex compound thereof.

Alternatively, it is also possible to use 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. 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) Dialkyldialkoxysilane The dialkyldialkoxysilane compound of the present invention includes a compound represented by the general formula R ¹ R ² Si (OR ³ ) (OCH ₃ ) (wherein R ¹ and R ² are R ¹ and R 4 to 1 to ² carbon atoms together
0 is an unbranched alkyl group, and R ³ has 3 to 6 carbon atoms.
Is a branched alkyl group).

R ¹ and R ² are, for example, methyl, ethyl, propyl, n-butyl, n-pentyl, n-
Hexyl group and the like. Examples of R ³ include an isopropyl group, a t-butyl group, an s-butyl group, a t-amyl group, and the like.

Specific compounds include, for example, t-butoxymethoxymethyl-n-propylsilane, t-butoxydiethylmethoxysilane, t-butoxymethoxydi-n-
Propylsilane, t-butoxy-n-butylmethoxymethylsilane, s-butoxymethoxymethyl-n-propylsilane, s-butoxydiethylmethoxysilane and the like.

5. The ratio of the components (A), (B) and (C) The catalyst of the present invention comprises the above-mentioned components.
Component (B) is used in an amount of 1 to 2,000 gmol, especially 20 to 5 g
00 gmol is preferred, and component (C) comprises component (B)
0.001 to 10 mol, especially 0.01 to 10 mol
~ 1.0 mol is desirable.

6. Polymerization of α-Olefin In the polymerization reaction of α-olefin in the present invention, α-olefin is polymerized in the presence of a catalyst comprising component (A), component (B), and component (C). Examples of the α-olefin include a linear or branched α-olefin having 2 to 10 carbon atoms.
Olefins are preferred, for example ethylene, propylene,
Butylene, pentene, hexene, heptene, octene and the like. 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. 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 performed in a liquid phase, the reaction can be performed in an inert medium such as normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, or in a liquid monomer. Further, the polymerization may be performed in either a batch system or a continuous system. 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. Further, in order to adjust the molecular weight of the produced polymer, a known molecular weight controlling agent such as hydrogen can be present in the polymerization reaction system.

[0063]

The present invention will be described in more detail with reference to the following examples. In addition, the physical property in an Example followed the following method. (1) Melt flow rate (MFR): ASTM D1
238 (230 ° C., 2160 g load condition). (2) Heptane soluble matter (HI): indicates the proportion of the crystalline polymer in the polymer, and is the remaining amount when extracted with boiling n-heptane for 6 hours using an improved Soxhlet extractor. (3) Heat of fusion (ΔHm): indicates the stereoregularity of the polymer, and was measured by differential calorimetry (DSC). That is, the sample is sealed in an aluminum pan, and the heat of fusion is measured while the temperature is raised to 200 ° C. At that time, the peak between 85 ° C and 175 ° C is defined as the melting peak, and the corresponding calorie is divided by the amount of the sample. Heat (unit J / g) was calculated. (4) Molecular weight distribution (Mw / Mn): gel permeation chromatograph (GPC, 150-manufactured by Waters)
Measured in o-dichlorobenzene at 135 ° C. using c).

Example 1 (1) Preparation of Catalyst Solid Component (A) In a 1-liter reaction vessel equipped with a reflux condenser, chip-shaped metallic 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 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.
For 2 hours. Further, titanium tetrachloride was newly added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the mixture was stirred at 120 ° 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 (A) was obtained.

(2) Polymerization of propylene In a 5-liter autoclave, which had been sufficiently dried by purging with nitrogen, 40.0 mg of the component (A) obtained in the above (1) was added.
1.2 mmol of triethylaluminum, 0.24 mmol of t-butoxymethoxymethyl-n-propylsilane and 7 ml of n-heptane were mixed, and the mixture kept for 5 minutes was added. Subsequently, 0.8 as hydrogen as a molecular weight controlling agent was added.
After injecting 3 liters and 3 liters of liquid propylene,
The temperature inside the autoclave was raised to 70 ° C. to perform polymerization. After one hour, unreacted propylene and hydrogen are purged,
The polymer was taken out of the autoclave and dried. The total amount of the obtained polymer was 759 g, and the MFR was 9.8 g / 1.
0 min, HI 97.1%, ΔHm 104 J / g, Mw
/ Mn was 5.8.

Examples 2 to 6 In Example 1 (2), instead of t-butoxymethoxymethyl-n-propylsilane, t-butoxydiethylmethoxysilane, t-butoxymethoxydi-n-propylsilane, t- Propylene was polymerized in the same manner as in Example 1 except that -butoxy-n-butylmethoxymethylsilane, s-butoxymethoxymethyl-n-propylsilane and s-butoxydiethylmethoxysilane were used. Table 1 shows the results.

Example 7 (1) Preparation of catalyst solid component (B) 170 g of commercially available magnesium diethoxide was added to 12 m in diameter.
1.2 liters of stainless steel (SUS) containing 400 stainless steel (SUS 316) balls
316) The mill pot was placed under a nitrogen gas atmosphere, and the mill pot was mounted on a shaker, and shaken at an amplitude of 10 mm and a rotation speed of 1420 rpm for 2 hours to obtain a crushed product (I). A 200 ml glass reactor equipped with a reflux condenser, dropping funnel and stirrer is thoroughly purged with nitrogen gas. After 8.3 g of the crushed material (I) and 42 ml of n-heptane were put into this reactor, a mixed solution of 14.9 g of trichlorosilane and 30 ml of n-butane was dropped from the dropping funnel over 30 minutes while stirring at room temperature. In addition, 6
Stirred at 5 ° C for 4 hours. The obtained solid was separated by filtration at 65 ° C., washed by contacting 100 ml of n-heptane at room temperature twice with 100 ml of toluene at room temperature three times with stirring for 10 minutes, and then washing the toluene slurry of the reaction solid (I). Obtained.

8.5 g of the reaction solid (I) and 26 m of toluene
Then, 5 ml of TiCl ₄ was added to the toluene slurry consisting of 1 liter and the internal temperature was raised to 80 ° C. over 20 minutes. After the temperature was raised, 1.7 g of n-dibutyl phthalate and 8 ml of toluene were added.
1 was added dropwise over 15 minutes using a dropping funnel. Thereafter, the temperature was further raised to 115 ° C.
Stirred for hours. After removing the supernatant by decantation, 10 ml of toluene was used at a temperature of 90 ° C. using 100 ml of toluene.
Washing was performed twice with stirring for minutes. Next, new toluene 2
1 ml and 51 ml of TiCl ₄ were added, and the mixture was stirred at 115 ° C. for 2 hours. The obtained solid substance was filtered at 115 ° C.,
Washed 8 times with 100 ml each of n-heptane at room temperature,
A heptane slurry of component B was obtained. Component B is composed of 2.2% by weight of titanium, 18.2% by weight of magnesium, and 3.2% by weight of silicon.
It contained 8% by weight, 58.2% by weight of chlorine and 12.5% by weight of n-dibutyl phthalate.

(2) Polymerization of Propylene 30.0 mg of the component (B) obtained in the above (1) was placed in a 5-liter autoclave which had been sufficiently dried by purging with nitrogen.
1.2 mmol of triethylaluminum, 0.24 mmol of t-butoxymethoxymethyl-n-propylsilane and 7 ml of n-heptane were mixed, and the mixture kept for 5 minutes was added. Subsequently, 0.8 as hydrogen as a molecular weight controlling agent was added.
After injecting 3 liters and 3 liters of liquid propylene,
The temperature inside the autoclave was raised to 70 ° C. to perform polymerization. After one hour, unreacted propylene and hydrogen are purged,
The polymer was taken out of the autoclave and dried. The total amount of the obtained polymer was 876 g, and the MFR was 9.9 g / 1.
0 min, HI 97.2%, ΔHm 104 J / g, Mw
/ Mn was 5.9.

Example 8 Propylene polymerization was carried out in the same manner as in Example 2 except that t-butoxydiethylmethoxysilane was used instead of t-butoxymethoxymethyl-n-propylsilane in (2) of Example 2. Was done. Table 1 shows the results.

Comparative Example 1 Into a 5-liter autoclave, which had been sufficiently dried by purging with nitrogen, 30.0 mg of the component (A) obtained above, 1.2 mmol of triethylaluminum, 0.24 g of s-butoxycyclopentyldimethoxysilane were added. Mmol and 7 ml of n-heptane were mixed and the mixture was kept for 5 minutes.
Next, 6.0 liters of hydrogen as a molecular weight control agent and 3 liters of liquid propylene were injected under pressure, and then the internal temperature of the autoclave was raised to 70 ° C. to perform polymerization. After one hour, unreacted propylene and hydrogen were purged, and the polymer was taken out of the autoclave and dried. The total amount of the obtained polymer was 789 g, the MFR was 11.2 g / 10 min,
I was 98.1%, ΔHm was 113 J / g, and Mw / Mn was 5.8.

Comparative Examples 2 to 4 In Comparative Example 1, instead of s-butoxycyclopentyldimethoxysilane, t-butoxy-t-butyldimethoxysilane, methoxymethyl-i-propoxy-i-
Propylene was polymerized in the same manner as in Comparative Example 1 except that propylsilane and t-butoxycyclopentylmethoxymethylsilane were used. Table 2 shows the results.

Comparative Example 5 20.0 mg of the above-obtained component (B), 1.2 mmol of triethylaluminum, 0.24 g of s-butoxycyclopentyldimethoxysilane were placed in a 5-liter autoclave which had been sufficiently dried by purging with nitrogen. Mmol and 7 ml of n-heptane were mixed and the mixture was kept for 5 minutes.
Next, 6.0 liters of hydrogen as a molecular weight control agent and 3 liters of liquid propylene were injected under pressure, and then the internal temperature of the autoclave was raised to 70 ° C. to perform polymerization. After one hour, unreacted propylene and hydrogen were purged, and the polymer was taken out of the autoclave and dried. The total amount of the obtained polymer was 832 g, the MFR was 12.2 g / 10 min,
I was 97.6%, ΔHm was 113 J / g, and Mw / Mn was 5.8.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

When the polymerization reaction of α-olefin is carried out using the catalyst of the present invention, poly (α-olefin) having a wide molecular weight distribution and moderately high stereoregularity 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 on the front page (72) The inventor, Manabu Mogi 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. (72) The inventor Kenichiro Suzuki 1-3-1 Oka Inside Tonen Research Institute

Claims (1)

[Claims] 1. A solid component comprising (A) magnesium, titanium, a halogen and an electron donating compound as essential components,
(B) an organoaluminum compound, and (C) a general formula R
¹ R ² Si (OR ³ ) (OCH ₃ ) (where R ¹ and R ² are R ¹
And a branched-free alkyl group carbon number of R ² is 4 to 10 in total. R ³ represents a branched alkyl group having 3 to 6 carbon atoms. ) A catalyst for polymerization of α-olefins comprising a dialkyldialkoxysilane represented by the following formula: