JPH10182724A - Catalyst component for α-olefin polymerization - Google Patents

Abstract

(57) [Problem] To provide a polymerization catalyst component capable of producing highly rigid poly (α-olefin) and having high polymerization activity. SOLUTION: (A) A solid component containing Mg, Ti, a halogen, a metal oxide and an electron donating compound as essential components is (B) an organoaluminum compound, and (C) a molecular weight of 195.
The above alkylalkoxysilane compound, and (D)
An α-olefin polymerization catalyst component which is brought into contact with an olefin (E) in the presence of an alkylalkoxysilane compound having a molecular weight of less than 195. Here, components (C) and (D)
Is an alkylalkoxysilane compound having a group having a branched structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst component for α-olefin polymerization.

[0002]

2. Description of the Related Art 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. It is also known that the stereoregularity of the resulting poly (α-olefin) can be changed by changing the silane compound (Japanese Patent Application Laid-Open No. 7-109309). Furthermore, it is also known that when a combination of a silane compound having a methoxy group and a silane compound having an ethoxy group is used, a poly (α-olefin) having high stereoregularity and improved moldability can be obtained. JP-A-7-179513).

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymerization catalyst component capable of producing highly rigid poly (α-olefin) and having high polymerization activity.

[0004]

Means for Solving the Problems The inventors of the present invention have studied the polymerization catalyst of α-olefin, and as a result, have found that a specific catalyst component can be obtained by using two types of silane compounds and organic aluminum compounds having specific molecular weights. The present inventors have found that a high-rigidity poly (α-olefin) can be produced by using, as a catalyst component, one obtained by prepolymerizing an olefin below, and completed the present invention.

That is, the present invention relates to (A) magnesium,
A solid component comprising titanium, halogen, a metal oxide and an electron-donating compound as essential components comprises (B) an organoaluminum compound, (C) an alkylalkoxysilane compound having a molecular weight of 195 or more, and (D) an alkylalkoxy compound having a molecular weight of less than 195. An α-olefin polymerization catalyst component which is brought into contact with an (E) olefin in the presence of a silane compound,
At least one of the components (C) and (D) is an α-olefin polymerization catalyst component, which is an alkylalkoxysilane compound having a group having a branched structure.

Preferred embodiments of the present invention are described below. (A) The above-mentioned catalyst component wherein the component (B) is selected from trialkylaluminum. (B) any of the above wherein the group having a branched structure is selected from a branched alkyl group, a branched alkoxy group, a branched alkenyloxy group, a branched alkynyloxy group, a cycloalkyl group and a cycloalkyloxy group Or a catalyst component described in (C) The catalyst component according to the above (b), wherein the group having a branched structure is selected from a branched alkyl group, a branched alkoxy group and a cycloalkyl group. (D) The catalyst component according to any one of the above, wherein the group having a branched structure is a group having a branch at the α-position. (E) Component (C) an alkylalkoxysilane compound,
Any of the above catalyst components having a group having a branched structure. (F) Component (C) is isopropoxycyclopentyldimethoxysilane, sec-butoxycyclopentyldimethoxysilane, di-sec-butoxypropylmethoxysilane,
Any one of the above catalyst components selected from propyltriethoxysilane, tert-butoxycyclopentyldimethoxysilane, and tert-amyloxycyclopentyldimethoxysilane. (G) The catalyst component according to any of the above, wherein the component (D) is an alkylalkoxysilane compound having a cycloalkyl group. (H) The catalyst component according to any of the above, wherein the component (D) is selected from cyclopentyltrimethoxysilane, cyclohexylmethyldimethoxysilane, and cyclopentylmethyldimethoxysilane. (I) The (E) olefin is contained in an amount of 0.1 g / g of the component (A).
The catalyst component according to any one of the above, which is incorporated by 1 to 200 g. (U) The catalyst component according to any of the above,
(G) An α-olefin polymerization catalyst comprising a combination of an organometallic compound. (R) The catalyst for polymerization of α-olefins according to (N), wherein the organometallic compound (G) is an organoaluminum compound. (Iii) The α-olefin polymerization catalyst according to the above (nu) or (l), further comprising (H) an electron donating substance. (C) The α-olefin polymerization catalyst according to (A) above, wherein (H) the electron donating substance is an organosilicon compound.

[0007]

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

The magnesium compound has the general formula MgR ^a R
It is represented by ^b . Here, ^Ra and ^Rb represent the same or different hydrocarbon groups, OR 'groups (R' is a hydrocarbon group), and halogen atoms. More specifically, the hydrocarbon group of R ^a and R ^b includes an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group having 1 to 20 carbon atoms, and the OR ′ group includes R ′ having a carbon number of 1 to 20 carbon atoms. Examples of the halogen atom include 1 to 12 alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, such as 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-B
u: isobutyl, t-Bu: tertiary butyl, He:
Hexyl, Oct: Octyl, Ph: Phenyl, cyH
e: each represents cyclohexyl.

[0010] MgMe ₂ , MgEt ₂ , Mg (i-Pr)
₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgEt
Bu, MgPh ₂ , MgcyHe ₂ , Mg (OM
e) ₂ , Mg (OEt) ₂ , Mg (OBu) ₂ , Mg
(OHe) ₂ , Mg (OOct) ₂ , Mg (OP
h) ₂ , Mg (OcyHe) ₂ , EtMgCl, BuM
gCl, HeMgCl, i-BuMgCl, t-BuMgC
1, PhMgCl, PhCH ₂ MgCl, EtMgB
r, BuMgBr, PhMgBr, BuMgI, EtO
MgCl, BuOMgCl, HeOMgCl, PhOM
gCl, EtOMgBr, BuOMgBr, EtOMg
I, MgCl ₂ , MgBr 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 is an atom of M Value, 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. Alkenyl group, aryl group of phenyl (Ph), tolyl, xylyl group, and 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.

Compound when M is carbon C (OMe) ₄ , C (OE) contained in the formula C (OR) ₄
t) ₄ , C (OPr) ₄ , C (OBu) ₄ , C (Oi−
Bu) ₄ , C (OHe) ₄ , C (OOct) ₄ : Formula XC
HC (OMe) ₃ , HC (OE) contained in (OR) ₃
t) ₃ , HC (OPr) ₃ , HC (OBu) ₃ , HC
(OHe) ₃ , HC (OPh) ₃ ; MeC (OM
e) ₃ , MeC (OEt) ₃ , EtC (OMe) ₃ , E
tC (OEt) ₃ , cyHeC (OEt) ₃ , PhC
(OMe) ₃ , PhC (OEt) ₃ , CH ₂ ClC (O
Et) ₃ , MeCHBrC (OEt) ₃ , MeCHCl
C (OEt) ₃ ; ClC (OMe) ₃ , ClC (OE
t) ₃ , ClC (Oi-Bu) ₃ , BrC (OE
t) ₃ ; MeCH (OM) contained in the formula X ₂ C (OR) ₂
e) ₂ , MeCH (OEt) ₂ , CH ₂ (OMe) ₂ ,
CH ₂ (OEt) ₂ , CH ₂ ClCH (OEt) ₂ , C
HCl ₂ CH (OEt) ₂ , CCl ₃ CH (OE
t) ₂ , CH ₂ BrCH (OEt) ₂ , PhCH (OE
t) ₂ .

Compound when M is silicon Si (OMe) ₄ , Si contained in the formula Si (OR) ₄
(OEt) ₄ , Si (OBu) ₄ , Si (Oi-Bu)
₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (O
Ph) ₄ : HSi (OE) contained in the formula XSi (OR) ₃
t) ₃ , HSi (OBu) ₃ , HSi (OHe) ₃ , H
Si (OPh) ₃ ; MeSi (OMe) ₃ , MeSi
(OEt) ₃ , MeSi (OBu) ₃ , EtSi (OE
t) ₃ , PhSi (OEt) ₃ , EtSi (OP
h) ₃ ; ClSi (OMe) ₃ , ClSi (OE
t) ₃ , ClSi (OBu) ₃ , ClSi (OP
h) ₃ , BrSi (OEt) ₃ ; Formula X ₂ Si (OR) ₂
Me ₂ Si (OMe) ₂ , Me ₂ Si (OE
t) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (OE
t) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ Si
H (OEt) ₂ ; MeBuSi (OEt) ₂ : X ₃ Si
Me ₃ SiOMe, Me ₃ SiOEt contained in OR,
Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ SiOE
t, Ph ₃ SiOEt.

Compound when M is Boron B (OEt) ₃ , B (OB) contained in the formula B (OR) ₃
u) ₃ , B (OHe) ₃ , B (OPh) ₃ .

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

Compound when M is phosphorus P (OMe) ₃ , P (OE) contained in formula P (OR) ₃
t) ₃ , P (OBu) ₃ , P (OHe) ₃ , P (OP
h) 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 ^a R ^b
· P is represented by (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 an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group. Also, q is the valence of the metal M 'and p is 0.
The number of 1-10 is shown. Specific examples of the compound represented by M′R ^c _q include AlMe ₃ , AlEt ₃ , Al (i-B
u) ₃ , AlPh ₃ , ZnMe ₂ , ZnEt ₂ , ZnB
_{u 2, ZnPh 2, CaEt 2} , CaPh 2 , and the like.

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

Metal oxides are listed in the Periodic Tables of Elements II-IV.
An oxide of an element selected from the group of families of elements, To illustrate _{them, B 2 O 3, MgO,} Al 2 O 3, SiO
_{2, CaO, TiO 2, ZnO} , ZrO 2, SnO 2,
BaO, ThO _{2 and the} like can be mentioned. Among them, B ₂
O ₃ , MgO, Al ₂ O ₃ , SiO ₂ , TiO ₂ , Zr
O ₂ is preferred, and SiO ₂ is particularly preferred. Further, composite oxides containing these metal oxides, for example, SiO ₂ -M
gO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , S
_{iO 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.

Examples of the electron donating compound include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes,
Examples thereof include alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group via carbon or oxygen, phosphoamides, thioethers, thioesters, and carbonate esters. Of these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, and ethers are preferably used.

Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid, and malonic acid. Aliphatic carboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid and fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid, cyclohexanemonocarboxylic acid, cyclohexenemonocarboxylic acid, cis-1,2- Cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,2-
Alicyclic carboxylic acids such as dicarboxylic acids, benzoic acid, toluic acid, anisic acid, aromatic monocarboxylic acids such as p-tert-butylbenzoic acid, naphthoic acid, and cinnamic acid, phthalic acid, isophthalic acid, terephthalic acid And aromatic polycarboxylic acids such as naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid and melitic acid.

As the carboxylic anhydride, anhydrides of the above-mentioned carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above-mentioned carboxylic acids can be used. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, and pivalic acid. Isobutyl, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, Diisobutyl adipate, dibutyl sebacate, 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, methyl p-toluate, p
-Tertiary 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, phthalate Diallyl acid, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, pyromellitic acid Tetrabutyl and the like.

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 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, Examples include cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and 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.

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 and R ^f are alkyl, alkenyl, cycloalkyl, aryl and 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, ethylphenyl ether and the like.

The component (A) can be prepared by contacting a metal oxide (component 1), a magnesium compound (component 2), a titanium compound (component 3) and an electron donating compound (component 4) 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, group IIIa of the periodic table,
Examples include halides of Group IVa and Group Va elements (hereinafter, referred to as metal halides). As the halogenated hydrocarbon, mono- and polyhalogen-substituted saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms 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, methylchloroform, methylbromoform, methyliodoform, 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. 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.

As the halogen-containing alcohol, one or two or more hydrogen atoms other than a hydroxyl group in a mono- or polyhydric alcohol having one or more hydroxyl groups in one molecule are substituted with a halogen atom. Compounds can be used. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine atoms, and a chlorine atom is preferable.

Examples of these compounds include 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m, o, p) -chloro Benzyl 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-bromoresorcinol, (m, o, p) -fluorophenol, p-iodophenol: 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-
Propanol, 3-chloro-1- (α-chloromethyl) -1-propanol, 2,3-dibromo-1-propanol, 1,3-dibromo-2-propanol, 2,4-dibromophenol, 2,4- Dibromo-1-naphthol: 2,2,2-trichloroethanol,
1,1,1-trichloro-2-propanol, β, β, β,-trichloro-tert-butanol, 2,3,4-trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichloro Phenol, 2,4,6-tribromophenol, 2,3,5-tribromo-2-hydroxytoluene, 2,3,5-tribromo-4-hydroxytoluene, 2,2,2-trifluoroethanol,
α, α, α-trifluoro-m-cresol, 2,4,6-triiodophenol: 2,3,4,6-tetrachlorophenol,
Examples thereof include tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,3,3-tetrafluoro-1-propanol, 2,3,5,6-tetrafluorophenol, and tetrafluororesorcin.

Examples of the silicon halide compound having a hydrogen-silicon bond include HSiCl ₃ , H ₂ SiCl ₂ , H
₃ SiCl, 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 SiCl, H 2} (C 2 H 5) SiCl, H 2 (n
-C ₄ H ₉ ) SiCl, H ₂ (C ₆ H ₄ CH ₃ ) SiC
1, 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 , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF _{5 and the} like are preferable.

The contact with component 1, component 2, component 3 and component 4, and optionally a halogen-containing compound, can be carried out in the presence or absence of an inert medium.
This can be done by mixing and stirring or by mechanically co-milling. The contact can be performed under heating at 40 to 150 ° C.

As the inert medium, saturated aliphatic hydrocarbons such as hexane, heptane and octane, saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene can be used. .

Preferred methods for preparing the component (A) in the present invention are described in JP-A-58-162607, JP-A-55-94909, JP-A-55-115405, JP-A-57-108107 and JP-A-61-108107. Two
Methods disclosed in 1109, 61-174204, 61-174205, 61-174206, 62-7706 and the like can be mentioned. 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 (JP-A-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 (JP-A-55-115405 and JP-A-57-108107), 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 (JP-A-61-1)
No. 74205) Metal oxide, alkoxy-containing magnesium compound,
A method in which a halogen element or a halogen-containing compound, an electron-donating compound and a titanium compound are brought into contact (Japanese Patent Application Laid-Open No.
-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), A method in which a solid obtained by contacting a metal oxide, hydrocarbyl magnesium and a hydrocarbyloxy group-containing compound (corresponding to the alkoxy group-containing compound) is contacted with a halogen-containing alcohol, and further contacted with an electron-donating compound and a titanium compound ( JP
62-7706). Of these, methods (1) and (2) are particularly 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), Mg is preferably 2 to 2.
12% by weight, 1 to 5% by weight of Ti, 10 to 35% by weight of halogen, 30 to 70% by weight of metal oxide, 0% of electron donating compound
-20% by weight.

The catalyst component of the present invention comprises the above component (A)
It is obtained by contacting with (E) an olefin in the presence of components (B), (C) and (D).

As the component (B) organoaluminum compound, for example, the following formula:

[0042]

(R ^k ) _r Al (Y) _{3 -r} (where R ^k is each independently a group selected from an alkyl group and an aryl group, and 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, n-butylaluminum dichloride, isobutylaluminum dichloride, n-hexyl Aluminum dichloride, n-octyl aluminum dichloride and the like can be mentioned. (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 can be mentioned. (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-hexylaluminum diethoxide,
n-octyl aluminum diethoxide and the like. (vi) trialkoxyaluminum, for example, trimethoxyaluminum, triethoxyaluminum and the like. (vii) Alkyl alumoxanes such as methylalumoxane, ethylalumoxane and the like. (viii) alkylaluminum alkoxy halides such as methylaluminum methoxychloride, ethylaluminum methoxychloride, ethylaluminum ethoxychloride, ethylaluminum ethoxybromide, isobutylaluminum methoxychloride, isobutylaluminum ethoxychloride, isobutylaluminum ethoxybromide, isobutylaluminum isopropoxychloride, Isobutyl aluminum isopropoxy bromide and the like. (ix) Dialkylaluminum monophenoxide, for example, diethylaluminum phenoxide, diisobutylaluminum phenoxide and the like. (x) Trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum and the like.

The above 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. The aryl group is, for example, a phenyl group, and the aryloxy group is, for example, a phenoxy group.

Of these, trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are particularly preferable. 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.

The component (C) alkylalkoxysilane compound is an alkylalkoxysilane compound having a molecular weight of 195 or more. Such an alkylalkoxysilane compound has, for example, the following formula:

[0047]

## STR2 ## (R ¹ ) _s Si (OR ² ) _4-s (wherein R ¹ is independently selected from an alkyl group and a cycloalkyl group, and R ² is each independently an alkyl group. S is a number in the range of 1 ≦ s ≦ 3), among those having a molecular weight of 195 or more. However, it is not limited to these.

The alkyl group preferably has 1 to 6 carbon atoms, more preferably 3 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, tert-butyl,
c-butyl group, 1-methylbutyl group, tert-pentyl group and the like.

The cycloalkyl group preferably has 3 to 3 carbon atoms.
6, and examples thereof include a cyclopentyl group and a cyclohexyl group.

The alkenyl group preferably has 2 to 6 carbon atoms and includes, for example, propenyl, butenyl, 2-methyl-3-
Butenyl group, 3-methyl-2-butenyl group, 1-methyl-3-butenyl group, 1-methyl-2-butenyl group and the like.

The alkynyl group preferably has 2 to 6 carbon atoms and includes, for example, propynyl, butynyl, 2-methyl-3-
Butynyl group, 1-methyl-3-butynyl group, 1-methyl-2-butynyl group and the like.

The component (C) alkylalkoxysilane compound preferably has a group containing a branched structure. Examples of the group having a branched structure include a branched alkyl group, a branched alkoxy group, a branched alkenyloxy group, a branched alkynyloxy group, a cycloalkyl group, and a cycloalkyloxy group. Further, the group having a branched structure is preferably a group having a branch at the α-position.

Examples of the branched alkyl group include isopropyl, tert-butyl, sec-butyl, 1-methylbutyl, tert-pentyl and the like. A branched alkoxy group is an alkoxy group having these branched alkyl groups. Examples of the branched alkenyl group include, for example, 1,
Examples thereof include a 1-dimethyl-2-propenyl group, a 1-methyl-3-butenyl group, a 1-methyl-2-butenyl group, and the like. Examples of the branched alkynyl group include a 1,1-dimethyl-2-propynyl group, a 1-methyl-3-butynyl group, a 1-methyl-2-butynyl group, and the like.

Specific compounds that can be used as component (C) include, for example, t-butoxycyclopentyldimethoxysilane, isopropoxycyclopentyldimethoxysilane, sec-butoxycyclopentyldimethoxysilane,
-sec-butoxypropylmethoxysilane, tert-pentyloxycyclopentyldimethoxysilane, (2-methyl
-3-butene-2-oxy) cyclopentyldimethoxysilane, (3-methyl-2-buten-1-oxy) cyclopentyldimethoxysilane, (2-methyl-3-butyn-2-oxy)
Cyclopentyldimethoxysilane, tert-butoxycyclohexyldimethoxysilane, isopropoxycyclohexyldimethoxysilane, sec-butoxycyclohexyldimethoxysilane, tert-amyloxycyclohexyldimethoxysilane, (2-methyl-3-butene-2-oxy)
Cyclohexyldimethoxysilane, (3-methyl-2-butene-1-oxy) cyclohexyldimethoxysilane, (2-
Methyl-3-butyn-2-oxy) cyclohexyldimethoxysilane. These can be used alone or in combination of two or more.

Preferably, the component (C) alkylalkoxysilane compound is isopropoxycyclopentyldimethoxysilane, sec-butoxycyclopentyldimethoxysilane, di-sec-butoxypropylmethoxysilane, propyltriethoxysilane, tert-butoxycyclopentyldimethoxysilane, Selected from tert-amyloxycyclopentyldimethoxysilane.

As long as the molecular weight is 195 or more, in addition to the above, alkylalkoxysilanes having a lactone group and a carboxyl group, and heterocyclic rings having silicon atoms and nitrogen atoms as ring-constituting atoms, as the alkylalkoxysilane compound (C). Alkylalkoxysilanes having a formula substituent can also be preferably used.

Component (D) is an alkylalkoxysilane compound having a molecular weight of less than 195. Such compounds are:
For example:

[0058]

(R ^{1 ′} ) _t Si (OR ^{2 ′} ) _4-t (wherein, R ^{1 ′} is independently selected from an alkyl group and a cycloalkyl group, and R ^{2 ′} is each independently. Selected from an alkyl group, an alkenyl group and an alkynyl group, and t is a number in the range of 1 ≦ t ≦ 3), and those having a molecular weight of less than 195 are exemplified. However, it is not limited to these.

The alkyl group preferably has 1 to 6 carbon atoms, more preferably 3 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, tert-butyl,
c-butyl group, 1-methylbutyl group, tert-pentyl group and the like.

The cycloalkyl group preferably has 3 to 3 carbon atoms.
6, and examples thereof include a cyclopentyl group and a cyclohexyl group.

The alkenyl group preferably has 2 to 6 carbon atoms and includes, for example, propenyl, butenyl, 2-methyl-3-
Butenyl group, 3-methyl-2-butenyl group, 1-methyl-3-butenyl group, 1-methyl-2-butenyl group and the like.

The alkynyl group preferably has 2 to 6 carbon atoms and includes, for example, propynyl, butynyl, 2-methyl-3-
Butynyl group, 1-methyl-3-butynyl group, 1-methyl-2-butynyl group and the like.

Any of the above groups can be combined as long as the molecular weight is less than 195.

Specific compounds usable as component (D) include, for example, cyclopentyltrimethoxysilane,
Examples thereof include cyclohexylmethyldimethoxysilane, cyclopentylmethyldimethoxysilane, and cyclopentylethyldimethoxysilane. These can be used alone or in combination of two or more.

As long as the molecular weight is less than 195, in addition to the above, (D) alkylalkoxysilane compounds, alkylalkoxysilanes containing a lactone group and a carboxyl group, a heterocyclic ring having a silicon atom and a nitrogen atom as ring-constituting atoms. Alkylalkoxysilanes having a formula substituent can also be preferably used.

The component (D) is preferably an alkylalkoxysilane compound having a cycloalkyl group. Preferred components (D) are selected from cyclopentyltrimethoxysilane, cyclohexylmethyldimethoxysilane, cyclopentylmethyldimethoxysilane.

The catalyst component of the present invention comprises the component (A) described above.
Is contacted with an (E) olefin in the presence of components (B), (C) and (D) described above (referred to as prepolymerization).
can get. Here, it is necessary that at least one of the components (C) and (D) is an alkylalkoxysilane compound having a group having a branched structure. If this condition is not satisfied, the stereoregularity of the resulting polymer will be reduced when the main polymerization of the α-olefin is performed.
Each component is used in the following ratio. That is, the component (B) is preferably used in an amount of 1 to 2,000 mol, more preferably 20 to 500 mol, per 1 mol of titanium in the component (A). The ratio of component (C) to component (B) is
It is preferable to mix (B) 0.1 to 40 moles as aluminum atoms, and the ratio of component (D) to component (B) is as follows:
It is preferable to mix (B) 0.1 to 40 moles as aluminum atoms with respect to 1 mole of (D). In addition, at the time of prepolymerization, an electron donating substance (component F
) Can be present. Examples of such electron donating substances include compounds containing a hetero atom such as nitrogen, sulfur, oxygen, and phosphorus.

Specific examples of the electron-donating substance containing a hetero atom are shown below.

Compounds containing a nitrogen atom: 2,2,6,6-tetramethylpiperidine, 2,6-dimethylpiperidine, 2,6-diethylpiperidine, 2,6-diisopropylpiperidine, 2,6-diisobutyl-4- Methylpiperidine, 1,2,2,6,6-pentamethylpiperidine, 2,2,5,5-tetramethylpyrrolidine, 2,
5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, 2,5-
Diisopropylpyrrolidine, 1,2,2,5,5, -pentamethylpyrrolidine, 2,2,5-trimethylpyrrolidine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-diisopropylpyridine, 2 , 6-diisobutylpyridine, 1,
2,4-trimethylpiperidine, 2,5-dimethylpiperidine,
Methyl nicotinate, ethyl nicotinate, nicotinamide, benzoamide, 2-methylpyrrole, 2,5-dimethylpyrrole, imidazole, toluamide, benzonitrile, acetonitrile, aniline, paratoluidine,
Orthotoluidine, metatoluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine and the like.

Compounds containing a sulfur atom: thiophenol, thiophene, ethyl 2-thiophenecarboxylate, ethyl 3-thiophenecarboxylate, 2-methylthiophene, methylmercaptan, ethylmercaptan, isopropylmercaptan, butylmercaptan, diethylthioether, diphenylthioether , Methyl benzenesulfonate, methyl sulfite, ethyl sulfite and the like.

Compounds containing an oxygen atom: tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2-ethyltetrahydrofuran, 2,2,5,5-tetraethyltetrahydrofuran, 2,2,5,5-tetramethyltetrahydrofuran, 2 , 2,6,6-tetraethyltetrahydropyran, 2,2,6,6-tetramethyltetrahydropyran, dioxane, dimethylether, diethylether, dibutylether, diisoamylether, diphenylether, anisole, acetophenone, acetone, methylethylketone, acetylacetone, o-Tolyl-t-butyl ketone, methyl-2,6-di-t-butyl phenyl ketone, ethyl 2-furate, isoamyl 2-furate, methyl 2-furate, propyl 2-furate and the like.

Compounds containing a phosphorus atom: triphenyl phosphine, tributyl phosphine, triphenyl phosphite, tribenzyl phosphite, diethyl phosphate, diphenyl phosphate and the like.

These electron donating substances may be used alone or in combination of two or more. These electron donating substances may be added together with other components at the time of prepolymerization, or may be added in advance to each of the above components.

The olefin used for the prepolymerization (that is, the olefin contacted with the component (A)) includes, in addition to ethylene, propylene, 1-butene, 1-hexene,
Α-olefins such as 4-methyl-1-pentene. The prepolymerization is preferably carried out in an inert medium.
As the inert medium, for example, a saturated aliphatic hydrocarbon such as normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane and the like; a saturated alicyclic hydrocarbon such as cyclopentane, cyclohexane and the like;
Aromatic hydrocarbons such as benzene, toluene, xylene and the like. Preliminary polymerization is usually performed at a temperature of 100 ° C or lower, preferably -30 ° C to + 30 ° C, more preferably -20 ° C.
Performed at a temperature of ~ 20C. The polymerization system may be either a batch system or a continuous system, and may be performed in two or more stages. When the reaction is carried out in multiple stages, the polymerization conditions can of course be changed.

In the prepolymerization system, the component (B) is used in a concentration of preferably 20 to 500 mmol / l, more preferably 30 to 200 mmol / l. The components (C) and (D) are used so that the total concentration in the prepolymerized system is preferably 5 to 200 mmol / L, more preferably 10 to 100 mmol / L. In addition, the above-mentioned optional component (F)
When used, it is preferably used such that the concentration in the prepolymerized system is 5 to 200 mmol / L.

The olefin polymer is incorporated into the component (A) by the prepolymerization, and the amount of the polymer is adjusted to 0.1 to 200 g, particularly 0.5 to 50 g per 1 g of the component (A).
g is preferable.

The catalyst component of the present invention thus prepared can be diluted or washed with the above-mentioned inert medium. However, from the viewpoint of preventing catalyst deterioration, washing is particularly preferred. 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, and a temperature range of -50 ° C to + 30 ° C, particularly -20 ° C to + 5 ° C is recommended.

The catalyst component of the present invention is used for polymerization of α-olefin (main polymerization). The present invention also relates to α, which is obtained by combining the catalyst component of the present invention and (G) an organometallic compound.
-Disclose catalysts for olefin polymerization. In addition to the catalyst
Optionally, (H) an electron donating substance can be combined.

(G) The organic metal compound is an organic compound of a metal belonging to Group I to Group III of the periodic table.
g, a compound of Ca, Zn and Al. Among these, an organoaluminum compound is particularly preferable. As the organoaluminum compound, the compounds exemplified in (B) the organoaluminum compound described above can be used. Among these, trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are particularly preferable.

Examples of the organometallic compound other than the organoaluminum compound include diethylmagnesium, ethylmagnesium chloride, diethylzinc, LiAl (C ₂ H
₅ ) ₄ , LiAl (C ₇ H ₁₅ ) _{4 and the} like.

(G) The amount of the organometallic compound used is usually from 1 to 2,000 per mole of titanium in the catalyst component.
It is 0 mol, especially 20-500 mol.

(H) As the electron donating substance, preferably, an organosilicon compound can be used. Examples of such organosilicon compounds include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane, methyltrimethoxysilane, Methyl triethoxy silane, methyl tributoxy silane, methyl triphenoxy silane, ethyl triethoxy silane, ethyl triisobutoxy silane, ethyl triphenoxy silane, butyl trimethoxy silane, butyl triethoxy silane, butyl tributoxy silane, butyl triphenoxy silane , Isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, Ludihexyloxysilane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane , Diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane, chlorophenyldiethoxysilane and the like. In addition to the organosilicon compound, it is also possible to use a compound containing a hetero atom such as nitrogen, sulfur, oxygen, phosphorus and the like exemplified for the component (F).

When (H) an electron-donating substance is used in the main polymerization reaction, the amount of the electron-donating substance is preferably (H)
The amount of the organometallic compound (G) is preferably 0.1 to 40 mol, more preferably 1 to 25 mol, as Al per 1 mol of the electron donating substance.

In the presence of the above-mentioned catalyst, α-olefin is polymerized (main polymerization reaction). As the α-olefin, a linear or branched α-olefin having 2 to 10 carbon atoms is preferable, for example, ethylene, propylene, 1-butene, pentene, 4-methyl-1-pentene, hexene, heptene, octene and the like. Is mentioned. The catalyst component of the present invention,
It can be used not only for homopolymerization of α-olefins but also for copolymerization of α-olefins or copolymerization with other olefins. The catalyst component of the present invention is particularly preferably used for propylene homopolymerization and copolymerization thereof (either random copolymerization or block copolymerization). In the case of copolymerization of an olefin, the amount of the other olefin to be copolymerized with the α-olefin is usually selected from the range of up to 30% by weight, especially the range of 0.3 to 15% by weight based on the α-olefin.

As the reaction conditions in the polymerization of α-olefin, conventional conditions can be used. For example, the reaction is carried out at a temperature of -80 to + 150 ° C, preferably 0 to 120 ° C, more preferably 40 to 120 ° C and 1 to 60 atm for 0.5 to 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. Further, the polymerization may be performed in either a batch system or a continuous system. The polymerization reaction may be performed in one stage,
Further, the polymerization may be carried out in two or more stages by changing the polymerization conditions or the type of the 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.

[0087]

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. This flask was baked in a nitrogen stream at 200 ° C. for 2 hours and further at 700 ° C. for 5 hours. Silicon oxide (Davison, trade name G)
952) 5 g and 40 ml of n-heptane were charged. Further, 20 ml of a 20% -n-heptane solution of n-butylethylmagnesium (hereinafter, referred to as BEM) (manufactured by Texas Alkyls, trade name: MAGALA BEM) was added, and 90 ° C.
For 1 hour.

After the obtained suspension was cooled to 0 ° C., a solution obtained by dissolving 11.2 g of tetraethoxysilane in 20 ml of n-heptane was dropped from the dropping funnel over 30 minutes. After dropping, the temperature was raised to 50 ° C over 2 hours,
Stirring was continued for hours. 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 make a suspension, and 2,2,2-trichloroethanol 8.0 was added thereto.
g in 10 ml of n-heptane was dropped from the dropping funnel at 25 ° C. over 15 minutes. After dropping, 25 ° C
For 30 minutes. After completion of stirring, at room temperature, 60
Washing was performed twice with ml of n-heptane and three times with 60 ml of toluene. When the obtained solid (referred to as solid component I) was analyzed, SiO ₂ : 36.6%, Mg: 5.
It contained 1% and Cl: 38.5%.

The solid component I obtained above was added to n-heptane
10 ml and 40 ml of titanium tetrachloride were added, the temperature was raised to 90 ° C., and di-n-butyl phthalate was dissolved in 5 ml of n-heptane.
6 g was added over 5 minutes. Thereafter, the temperature was raised to 115 ° C., and the reaction was carried out 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. In addition, 15 ml of n-heptane and titanium tetrachloride
40 ml was added and reacted 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 to obtain 8.3 g of a solid component (component A). As a result of analysis, this component A contained 3.1% by weight of Ti,
In addition, it was confirmed that Si, Mg, Cl and di-n-butyl phthalate were contained.

(2) Prepolymerization of Component (A) In a 200 ml reactor equipped with a stirrer, 2.5 g of the solid component A obtained in the above (1) and 100 ml of n-hexane were placed under a nitrogen gas atmosphere. -5 with stirring
Cooled to ° C. Next, a solution of triethylaluminum in n-heptane (2.0 mol / l) and a solution of isopropoxycyclopentyldimethoxysilane in n-heptane (0.
2 mol / l) and a solution of cyclopentyltrimethoxysilane in n-heptane (0.2 mol / l)
It was added so that the respective concentrations in the reaction system became 100 mmol / L, 10 mmol / L and 5 mmol / L, and the mixture was stirred for 5 minutes. Then
After reducing the pressure in the system, propylene gas was continuously supplied, and propylene was polymerized for 3 hours. After the polymerization, propylene in the gas phase was purged with nitrogen gas, and 100 ml of n-
The solid phase was washed with hexane three times at room temperature. Further, the solid phase was dried under reduced pressure for 1 hour to obtain a catalyst component A '. As a result of measuring the amount of magnesium contained in the catalyst component A ', the amount of prepolymerization was 3.1 g per 1 g of the component A.

(3) Polymerization of propylene In a 1.5-liter stainless steel autoclave equipped with a stirrer, the above catalyst component (component A ') 6 was placed under a nitrogen atmosphere.
0.2 mg, 0.4 mmol triethylaluminum,
Isopropoxycyclopentyldimethoxysilane 0.0
8 mmol and 7 ml of n-heptane were mixed and kept for 5 minutes. Then, after 3000 ml of hydrogen (normal temperature, normal pressure) as a molecular weight controlling agent and 1 liter of liquid propylene were injected, 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, the polymer was taken out, and dried.

The total amount of the polymer was 208 g, the melt flow rate (MFR) was 21.2 g / 10 min, and the heptane insoluble matter (HI) was 96.8%. The MFR is
Measured under the conditions of 230 ° C. and a load of 2160 g according to ASTM D1238, HI is the remaining amount when extracted with boiling n-heptane for 6 hours using a modified Soxhlet extractor.

Further, the rigidity of the obtained polymer was evaluated as follows. That is, 0.18% by weight of 2,6-di-tert-butyl-4-methylphenol (BHT) and distearyl thiodipropionate (DSTDP) were added to the polymer.
0.08% by weight of tetrakis- {methylene- (3,5-ditert-butylhydroxyhydrocinnamate) methane (IR
GANOX1010: trade name, manufactured by Ciba Geigy Co.) was added, and 0.06% by weight of calcium stearate was added. These were dry-blended, melt-kneaded, and pelletized. Next, a test piece was injection-molded from the pellet, and the flexural modulus was measured in accordance with JIS K-7203-1982. As a result, it was 14100 kg / cm ² . These measuring methods are the same in the following.

Examples 2 to 4 In Example 1 (2), an alkylalkoxysilane compound shown in Table 1 was used in place of the combination of isopropoxycyclopentyldimethoxysilane and cyclopentyltrimethoxysilane. In (3),
Propylene was polymerized in the same manner as in Example 1 except that the silane compounds shown in Table 1 were used instead of isopropoxycyclopentyldimethoxysilane. Also,
The properties of the obtained polymer were evaluated. Table 1 shows the results.

Comparative Examples 1 to 5 In Example 1 (2), an alkylalkoxysilane compound shown in Table 1 was used in place of the combination of isopropoxycyclopentyldimethoxysilane and cyclopentyltrimethoxysilane. In (3),
Propylene was polymerized in the same manner as in Example 1 except that the silane compounds shown in Table 1 were used instead of isopropoxycyclopentyldimethoxysilane. Also,
The properties of the obtained polymer were evaluated. Table 1 shows the results.

[0098]

[Table 1]

[0099]

According to the present invention, when a polymerization reaction of an α-olefin is carried out using the catalyst component of the present invention, a highly rigid poly (α-olefin) can be obtained, and the polymerization activity is high.

[Brief description of the drawings]

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

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuya Sakata 1-3-1 Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. 1-3-1 Nishitsurugaoka, Tonen Co., Ltd. (72) Inventor Kunihiko Imanishi 1-3-1, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama

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)
Α in contact with (E) an olefin in the presence of an alkylalkoxysilane compound having a molecular weight of 195 or more and (D) an alkylalkoxysilane compound having a molecular weight of less than 195.
-An olefin polymerization catalyst component, wherein the component (C)
And at least one of (D) is an alkylalkoxysilane compound having a group containing a branched structure.