JP2001114816A - Catalyst for polymerizing alpha-olefin and method for polymerizing alpha-olefin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for polymerizing an α-olefin which allows to produce a α-olefin polymer of which the stereoregularity is highly controlled and the melt tensile force is high in high yield and to provide a method of polymerization using the catalyst. SOLUTION: This catalyst for polymerizing the α-olefin is formed by combining a solid catalyst ingredient (ingredient A) obtained by bringing a solid ingredient for polymerization (A1) comprising titanium, magnesium, a halogen and an electron donor selected from the group composed of an organic acid ester, an acid halide and a diether as essential ingredients into contact with a S=O bond-containing compound (A2) and then further bringing the reactional product into contact with a silicon compound (A3) and an organoaluminum compound (ingredient B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an α-olefin polymerization catalyst and a method for polymerizing α-olefins using the same. More specifically, the present invention relates to a catalyst comprising a combination of a specific solid catalyst component and an organoaluminum compound, which has a highly controlled stereoregularity and is capable of producing a polymer having excellent melt tension. The present invention relates to a catalyst for use and a method for polymerizing an α-olefin using the same.

[0002]

2. Description of the Related Art Heretofore, in the field of magnesium-supported Ziegler-Natta type catalysts, the high stereoregularity of α-olefins has been investigated using solid catalyst components containing titanium, magnesium, halogen and an electron donor as essential components. There have been many proposals for producing polymers in high yield (for example, JP-A-57-63310 and JP-A-57-6330).
Nos. 3311, 57-63312, 58-1387
No. 05, No. 58-138706, No. 58-13871
No. 1). Among these, the solid catalyst component,
A polymerization catalyst using an organoaluminum compound and an electron donor in combination is highly practical.

However, a propylene polymer obtained using a magnesium-supported Ziegler-Natta type catalyst generally has a narrower molecular weight distribution than a propylene polymer obtained using conventional titanium trichloride. A propylene polymer having a narrow molecular weight distribution has a low melt tension, so that the fluidity at the time of melting is deteriorated and a problem is caused at the time of molding. For example, in recent years, high-speed stretching and high-speed molding have been promoted in order to increase the productivity of stretched films, but when operating with a propylene polymer having a low melt tension, neck-in and fluttering of the film occur, It is difficult to achieve this. Therefore, in order to stabilize and increase the molding speed, a propylene polymer having a higher melt tension is required.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a catalyst for producing an α-olefin with further improved melt tension.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on various catalyst components to solve the above problems, and as a result, have found that a solid catalyst component containing a specific S = O bond-containing compound and an organic By using a catalyst that combines an aluminum compound, stereoregularity is highly controlled,
The inventors have found that an α-olefin polymer having a high melt tension can be produced in a high yield, and have reached the present invention.

That is, the present invention provides an α-olefin polymerization catalyst comprising a combination of the following components (A) and (B). Component (A): a solid catalyst component obtained by contacting the following components (A1), (A2) and (A3). (A1) A solid component for polymerization containing, as essential components, titanium, magnesium, halogen, and an electron donor selected from the group consisting of organic acid esters, acid halides and diethers. (A2) S = O bond-containing compound (A3) Silicon compound Component (B): Organoaluminum compound

Further, the present invention is characterized in that the electron donor of the component (A1) is selected from the group consisting of a phthalic acid diester compound, a phthalic acid dihalide compound and a diether compound. Provide a catalyst.

[0008] Further, the present invention relates to the above-mentioned component (A2) wherein S =
The catalyst for polymerization of α-olefins, wherein the O-bond-containing compound is o-nitrobenzenesulfonyl chloride. The present invention also provides a method for polymerizing an α-olefin, which comprises contacting an α-olefin with any one of the above-mentioned α-olefin polymerization catalysts to polymerize or copolymerize the α-olefin.

[0009]

Embodiments of the present invention will be described below. The catalyst used in the present invention is a combination of a specific component (A) and a specific component (B). Here, “combined” does not mean that the components are only those listed (ie, component (A) and component (B)), and does not impair the effects of the present invention. Does not exclude coexistence of other components.

(1) Solid catalyst component (A) The catalyst component (A) of the present invention comprises a specific solid component for polymerization (component (A1)) and a compound having a specific S 特定 O bond (component (A2)). ) And a specific silicon compound (component (A3)).
Such component (A) of the present invention does not exclude the coexistence of other suitable components other than the above-mentioned essential three components.

<Component (A1)> The solid component (A1) used in the present invention is a solid component for the stereoregular polymerization of an α-olefin containing titanium, magnesium, halogen and an electron donor as essential components. is there. Here, "containing as an essential component" means that in addition to the four components listed, other purposeful elements may be contained, and each of these elements is present as a purposeful arbitrary compound. And that these elements may be present as bonded to each other.

[0012] Solid components themselves containing titanium, magnesium and halogen are known. For example, JP
No. 45688, No. 54-3894, No. 54-310
Nos. 92, 54-39483, 54-94591
Nos. 54-118484 and 54-131589
Nos. 55-75411, 55-90510, 55-90511, 55-127405, and 55
-147507, 55-155003, 56-
No. 18609, No. 56-70005, No. 56-720
No. 01, No. 56-86905, No. 56-90807
Nos. 56-155206, 57-3803, 57-34103, 57-92007, 57-
No. 121003, No. 58-5309, No. 58-531
No. 0, No. 58-5311, No. 58-8706, No. 5
8-27732, 58-32604, 58-3
No. 2605, No. 58-67703, No. 58-1172
No. 06, No. 58-127708, No. 58-18370
No. 8, No. 58-183709, No. 59-149905
And JP-A-59-149906 and JP-A-63-108008.

The magnesium compound used as a magnesium source in the present invention includes magnesium dihalide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, alkylmagnesium halide, magnesium oxide, magnesium hydroxide and magnesium hydroxide. Carboxylate and the like. Among them, Mg such as magnesium dihalide and dialkoxy magnesium
(OR ¹ ) _2-p X _p (where R ¹ is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, X represents a halogen, and p is 0 ≦ p ≦ 2.) Is preferred.

Further, as a titanium compound serving as a titanium source,
Is represented by the general formula Ti (OR^Two)_4-qX_q(Where R^TwoIs hydrocarbon
A basic group, preferably having about 1 to 10 carbon atoms;
Represents a halogen, and q is 0 ≦ q ≦ 4. )
Compounds. As a specific example, TiCl_Four,
TiBR_Four, Ti (OC_TwoH_Five) Cl_Three, Ti (OC_TwoH _Five)
_TwoCl_Two, Ti (OC_TwoH_Five)_ThreeCl, Ti (OiC_ThreeH
₇) Cl_Three, Ti (On-C_FourH₉) Cl_Three, Ti (O-
n-C_FourH₉)_TwoCl_Two, Ti (OC_TwoH_Five) BR_Three, Ti
(OC_TwoH_Five) (On-C)_FourH₉)_TwoCl, Ti (On
-C_FourH₉)_ThreeCl, Ti (OC₆H_Five) Cl_Three, Ti (O-
i-C_FourH₉)_TwoCl_Two, Ti (On-C_FiveH ₁₁) Cl_Three,
Ti (On-C₆H₁₃) Cl_Three, Ti (OC_TwoH_Five)_Four,
Ti (On-C_ThreeH₇)_Four, Ti (On-C_FourH₉)_Four,
Ti (OiC_FourH₉)_Four, Ti (On-C
₆H₁₃)_Four, Ti (On-C₈H₁₇)_Four, Ti (OCH_Two
CH (C_TwoH_Five) C_FourH₉)_FourAnd the like.

Further, a molecular compound obtained by reacting an electron donor described later with TiX ′ ₄ (where X ′ is a halogen) can be used as a titanium source. Specific examples of such molecular compounds include TiCl ₄ .CH ₃ COC _{2
H 5, TiCl 4 · CH 3} CO 2 C 2 H 5, TiCl 4 · C 6 H
₅ NO ₂ , TiCl ₄ .CH ₃ COCl, TiCl ₄ .C ₆ H
₅ COCl, TiCl ₄ .C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄
• ClCOC ₂ H ₅ , TiCl ₄ .C ₄ H ₄ O and the like.

Also, TiCl_Three(TiCl_FourWith hydrogen
Or reduced with aluminum metal, or
Including those reduced with organometallic compounds), TiB
R_Three, Ti (OC_TwoH_Five) Cl_Two, TiCl_Two, Dicyclope
Antadienyl titanium dichloride, cyclopentadi
Use of titanium compounds such as enyl titanium trichloride
Use is also possible. Among these titanium compounds, TiC
l_Four, Ti (On-C_FourH ₉)_Four, Ti (OC_TwoH_Five) Cl
_ThreeAre preferred.

Halogen is the above magnesium and
(Or) is supplied from titanium halides
Other, but common, halogen sources, such as AlCl_ThreeEtc.
Aluminum halide or SiCl_FourEtc. of silicon
Halide, PCl_Three, PCl _FiveHalogenation of phosphorus
Object, WCl₆Halides such as MoC
l _FiveKnown halo such as halides of molybdenum
It can also be supplied from a gentizing agent. Included in catalyst components
Halogen is fluorine, chlorine, bromine, iodine or
These mixtures may be used, and chlorine is particularly preferable.

Examples of the electron donor (internal donor) that can be used for producing the solid component (A1) of the present invention include oxygen-containing electron donors such as organic acid esters, acid halides, and diethers. Can be.

More specifically, (a) methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate , Methyl chloroacetate, ethyl dichloroacetate,
Methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate Organic acid monoesters such as methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, Or, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate, ethylene carbonate, norbornanedienyl-1,2-dimethylcarboxylate, and cycle C2 to C2 of an organic acid polyvalent ester such as lopropane-1,2-dicarboxylic acid-n-hexyl and diethyl 1,1-cyclobutanedicarboxylate
0 organic acid esters,

(Ii) acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, and phthaloyl isochloride; (c) methyl ether, ethyl ether, isopropyl ether; Butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-
Dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-t-butyl-2
-Methyl-1,3-dimethoxypropane, 2-t-butyl-2-isopropyl-1,3-dimethoxypropane,
2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3- Ethers having 2 to 20 carbon atoms such as diethoxypropane and 2,2-diisopropyl-1,3-diethoxypropane can be exemplified.

Two or more of these electron donors can be used. Of these, phthalic acid diester compounds, phthalic acid dihalide compounds, and diether compounds are preferred.

<Component (A2)> Component (A2) of the present invention
Is an S ＝ O bond-containing compound. Specific examples of the S ＝ O bond-containing compound used in the present invention include sulfoxide, sulfone, sulfohalide, and sulfonate. Examples of the sulfone include diphenyl sulfone, phenylmethyl sulfone, and sulfonal. Examples of the sulfo halide include benzenesulfonyl chloride, benzenesulfonyl bromide, o-nitrobenzenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, o-benzenedisulfonyl chloride, m-benzenedisulfonyl chloride,
Cyclohexanesulfonyl chloride, ethanesulfonyl chloride and the like can be mentioned. Examples of the sulfonic acid ester include ethyl benzenesulfonate, benzenesulfonic acid n
-Propyl, n-butyl benzenesulfonate, di-n-butyl m-benzenedisulfonate, di-n-butyl o-benzenedisulfonate, ethyl cyclohexanesulfonate,
Isobutyl ethanesulfonate, n-toluenesulfonate
Butyl and the like can be exemplified. Of these, particularly preferred is sulfo halide, and o-nitrobenzenesulfonyl chloride is particularly preferred.

<Component (A3)> The component (A3) used in the present invention is a silicon compound. As the silicon compound, a compound represented by the general formula R ³ _r Si (OR ⁴ ) _{4 -r} (where R ³ and R ⁴ are hydrocarbon groups having 1 or more carbon atoms, preferably about 1 to 10 carbon atoms, r is 0 ≦ r <4).

Specific examples of the silicon compound usable in the present invention
(A) (CH_Three)_ThreeCSi (CH_Three) (OCH_Three)_Two,
(CH_Three)_ThreeCSi (CH (CH_Three)_Two) (OCH_Three)_Two, (CH_Three)_ThreeC
Si (CH_Three) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (O
CH_Three)_Two, (CH_Three)_ThreeCSi (n-C_ThreeH₇) (OCH_Three)_Two, (C
H_Three)_ThreeCSi (n-C₆H₁₃) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCS
i (CH_Three) (OCH_Three)_Two, (CH_Three) (C_TwoH_Five) CHSi (C
H_Three) (OCH_Three)_Two, ((CH_Three)_TwoCHCH_Two)_TwoSi (OC
H_Three)_Two, (C_TwoH_Five) (CH_Three)_TwoCSi (CH_Three) (OCH_Three)_Two,
(C_TwoH_Five) (CH_Three)_TwoCSi (CH_Three) (OC_TwoH_Five)_Two, (CH_Three)_Three
CSi (OCH_Three)_Three, (CH _Three)_ThreeCSi (OC_TwoH_Five)_Three, (CH
_Three) (C_TwoH_Five) CHSi (OCH_Three)_Three, (CH_Three)_TwoCH (CH_Three)_Two
CSi (CH_Three) (OCH_Three)_Two, ((CH_Three)_ThreeC)_TwoSi (OC
H_Three)_Two, (C_TwoH_Five) (CH _Three)_TwoCSi (OCH_Three)_Three, (C_TwoH_Five)
(CH_Three)_TwoCSi (OC_TwoH_Five)_Three, (CH_Three)_ThreeCSi (OC (C
H_Three)_Three) (OCH_Three)_Two, ((CH_Three)_TwoCH)_TwoSi (OCH_Three)_Two,
((CH_Three)_TwoCH)_TwoSi (OC_TwoH_Five)_Two, (C_FiveH₉)_TwoSi (OC
H_Three)_Two, (C_FiveH₉)_TwoSi (OC_TwoH_Five)_Two, (C_FiveH₉) (CH_Three) S
i (OCH_Three)_Two, (C_FiveH₉) ((CH_Three)_TwoCHCH_Two) Si (OC
H_Three)_Two, (C₆H₁₁) Si (CH_Three) (OCH_Three)_Two, (C₆H₁₁)_Two
Si (OCH_Three)_Two, (C₆H₁₁) ((CH _Three)_TwoCHCH_Two) Si
(OCH_Three)_Two, ((CH_Three)_TwoCHCH_Two) ((C_TwoH_Five) (CH_Three) C
H) Si (OCH_Three)_Two, ((CH_Three)_TwoCHCH_Two) ((CH_Three)_TwoC
H) Si (OC_FiveH₁₁)_Two, HC (CH_Three)_TwoC (CH_Three)_TwoSi (C
H_Three) (OCH_Three)_Two, HC (CH_Three)_TwoC (CH_Three)_TwoSi (CH_Three)
(OC_TwoH_Five)_Two, HC (CH_Three)_TwoC (CH_Three)_TwoSi (OC
H_Three)_Three, (CH_Three)_ThreeCSi (OCH (CH_Three)_Two) (OCH_Three)_Two,
(CH_Three)_ThreeCSi (OC (CH_Three)_Three) (OCH_Three)_Two, Etc.
Alkoxysilicon compound,

(B) bis (pyrrolidino) dimethoxysilane, bis (2-methyl-pyrrolidino) dimethoxysilane, bis (3-methyl-pyrrolidino) dimethoxysilane, bis (piperidino) dimethoxysilane, bis (2-
Methyl-piperidino) dimethoxysilane, bis (3-methyl-piperidino) dimethoxysilane, bis (4-methyl-piperidino) dimethoxysilane, bis (2,2
Contains an amino group such as 6,6-tetramethyl-piperidino) dimethoxysilane, bis (2,6-dimethyl-piperidino) dimethoxysilane, bis (decahydroquinolino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane Silicon compounds,

(C) (n-C_ThreeH₇O)_TwoSi (OCH_Three)_Two,
(i-C_ThreeH₇O)_TwoSi (OCH_Three)_Two, (T−C_FourH₉O)_TwoSi
(OCH_Three)_Two, (Sec-C_FourH₉O)_TwoSi (OCH_Three)_Two, (N-
C_FourH₉O)_TwoSi (OCH_Three)_Two, (I-C_FourH₉O)_TwoSi (OC
H_Three)_Two, (N-C_ThreeH₇O) (n-C _FourH₉O) Si (OC
H_Three)_Two, (I-C_ThreeH₇O) (n-C_FourH₉O) Si (OC
H_Three)_Two, (N-C_ThreeH₇O) (t-C_FourH₉O) Si (OC
H_Three)_Two, (T−C_FourH₉O) (n-C_FourH₉O) Si (OC
H_Three)_Two, (Sec-C_FourH₉O) (i-C_FourH₉O) Si (OCH_Three)_Two
And the like.

Of these, preferred is (CH ₃ ) ₃ C
Si (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (C
H ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC
_{2 H 5) 2, (CH} 3) 3 CSi (C 2 H 5) (OCH 3) 2, (CH 3) 3
_{CSi (n-C 3 H 7} ) (OCH 3) 2, (CH 3) 3 CSi (n-
C ₆ H ₁₃ ) (OCH ₃ ) ₂ , (C ₅ H ₉ ) ₂ Si (OCH ₃ ) ₂ , (C ₅
H ₉ ) ₂ Si (OC ₂ H ₅ ) ₂ , (C ₆ H ₁₁ ) Si (CH ₃ ) (OC
H _{3) 2,} include ₂ or the like _{(C 6 H 11) 2 Si} (OCH 3).

<Other Optional Ingredients> Further, in the production of the component (A) of the present invention, as described above, optional ingredients can be included as necessary in addition to the above essential ingredients. Suitable compounds as such optional components include the following compounds.

(A) Vinyl silane compound As the vinyl silane compound, monosilane (SiH ₄ )
At least one hydrogen atom is a vinyl group (CH ₂ ＣC
H-), and some of the remaining hydrogen atoms are halogen (preferably Cl), alkyl groups (preferably hydrocarbon groups having 1 to 12 carbon atoms), aryl groups (preferably phenyl), alkoxy groups (Preferably an alkoxy group having 1 to 12 carbon atoms) and a structure substituted with others.

More specifically, CH ₂ ＣＨCH—SiH ₃ ,
_{CH 2 = CH-SiH 2 (} CH 3), CH 2 = CH-SiH
_{(CH 3) 2, CH 2} = CH-Si (C 2 H 5) 3, CH 2 =
CH—Si (CH ₃ ) ₂ (C ₂ H ₅ ), CH ₂ ＣＨCH—Si
_{(CH 3) (C 2 H} 5) 2, CH 2 = CH-Si (n-C 4 H
_{9), CH 2 = CH-} Si (C 6 H 5) 3, CH 2 = CH-S
_{i (CH 3) (C 6} H 5) 2, CH 2 = CH-Si (CH 3)
₂ (C ₆ H ₅ ), CH ₂ ＣＨCH—Si (CH ₃ ) ₂ (C ₆ H ₄ C
_{H 3), (CH 2 =} CH) (CH 3) 2 Si-O-Si (C
_{H 3) 2 (CH = CH} 2), (CH 2 = CH) 2 SiH 2,
(CH ₂ ＣＨCH) ₂ Si (CH ₃ ) ₂ , (CH ₂ ＣＨCH) ₂ S
i (C ₆ H ₅ ) _{2 and the} like.

(B) Organometallic compounds of metals of Groups I to III of the periodic table It is also possible to use organometallic compounds of metals of Groups I to III of the periodic table. Periodic Table I used in the present invention
The organometallic compounds of Group III-III metals have at least one organic group-metal bond. As the organic group in that case, a hydrocarbyl group having about 1 to 20 carbon atoms, preferably about 1 to 6 carbon atoms is representative. In an organometallic compound where at least one of the valences is filled with an organic group, the remaining valences of the metal (if any) are hydrogen, halogen, hydrocarbyloxy (hydrocarbyl is
About 1 to 20 carbon atoms, preferably about 1 to 6 carbon atoms, or the metal via an oxygen atom (specifically, -O-Al (CH ₃ )-in the case of methylalumoxane) or the like. .

Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium and tertiarybutyllithium, (b) butylethylmagnesium, dibutylmagnesium and hexylethylmagnesium. , Butylmagnesium chloride, organic magnesium compounds such as tert-butylmagnesium bromide, (c) organic zinc compounds such as diethyl zinc and dibutyl zinc, (d) trimethylaluminum, triethylaluminum, triisobutylaluminum,
There are organic aluminum compounds such as tri-n-hexylaluminum, diethylaluminum chloride, diethylaluminum hydride, diethylaluminum ethoxide, ethylaluminum sesquichloride, ethylaluminum dichloride and methylalumoxane. Of these, organoaluminum compounds are particularly preferred.

(C) Electron Donor Compound In the production of the solid component of the present invention, an electron donor compound can be optionally used, if necessary, separately from the above electron donor. Examples of such electron donor compounds include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of inorganic acids, oxygen-containing electron donors such as acid anhydrides, ammonia, amines, nitriles, and isocyanates. Such nitrogen-containing electron donors can be exemplified.

More specifically, (a) having 1 to 18 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, and isopropylbenzyl alcohol; Alcohols, (b) phenol, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol,
C6 to C2 which may have an alkyl group such as naphthol
5 phenols, (c) ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; (d) acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, etc. Aldehydes having 2 to 15 carbon atoms; (e) inorganic acid esters such as borate esters such as methyl borate and ethyl borate; and phosphate esters such as methyl phosphate and ethyl phosphate; (f) acetate amide and benzoic acid Acid amides such as acid amide and toluic acid amide; (g) amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylethylenediamine; Acetonitrile, benzonitrile,
Nitriles such as tolunitrile, (i) ethyl 2- (ethoxymethyl) -benzoate, ethyl 2- (t-butoxymethyl) -benzoate, ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxypropionate ,
Ethyl 3-ethoxy-2-s-butylpropionate, 3
Alkoxy ester compounds such as ethyl-ethoxy-2-t-butylpropionate, (j) ethyl 2-benzoylbenzoate, ethyl 2- (4′-methylbenzoyl) benzoate, 2-benzoyl-4,5-dimethyl Ketoester compounds such as ethyl benzoate can be exemplified.

The above optional components (a), (b) and (c)
Can be used alone or in combination of two or more. When these optional components are used, the effect of the present invention is further increased.

<Production of Component (A)> The component (A) is obtained by bringing the components constituting the component (A) and the optional components used as necessary into contact with each other in a stepwise or temporary manner. And / or finally by washing with an organic solvent such as a hydrocarbon solvent or a halogenated hydrocarbon solvent. Components (A1) to (A
The order of the contact in 3) is not particularly limited, but preferably, the component (A1) is brought into contact with the component (A2) first, and then the component (A3) is brought into contact with the contact product. By contacting in such an order, there is an advantage that generation of a polymer amorphous component during polymerization can be suppressed.

The contact condition of each component constituting the component (A) needs to be carried out in the absence of oxygen.
Any one can be used as long as the effects of the present invention are recognized, but the following conditions are generally preferred. The contact temperature is-
The temperature is about 50 to 200 ° C, preferably 0 to 100 ° C.
Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring / pulverizing machine, and a method of bringing into contact by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, and polysiloxanes.

The ratio of the amounts of the respective components constituting the component (A) can be arbitrary as long as the effects of the present invention are recognized, but generally, the following ranges are preferable. The amount of the titanium compound used is preferably in the range of 0.0001 to 1000, and more preferably in the range of 0.01 to 10 as a molar ratio to the amount of the magnesium compound used. When a compound for that purpose is used as a halogen source, the used amount is 0.01 to 0.01 in terms of a molar ratio with respect to the used amount of magnesium, regardless of whether the titanium compound and / or the magnesium compound contains halogen or not. 1000
And preferably in the range of 0.1 to 100. The amount of the electron donor such as an organic ester used is 0.0 mol% with respect to the amount of the magnesium compound used.
The range is preferably from 01 to 10, preferably from 0.01 to 5. The amount of the S ＝ O bond-containing compound used as the component (A2) is 0.0001 to 10 m in terms of the atomic ratio of sulfur to the titanium component constituting the component (A1) (sulfur / titanium).
ol / mol is general, preferably sulfur / titanium = 0.001 to 1 mol / mol. The amount of the silicon compound used as the component (A3) is 0.01 to 1000, preferably 0.1 to 10 as an atomic ratio of silicon to the titanium component (silicon / titanium) constituting the component (A1).
It is within the range of 0.

The amount of the vinylsilane compound used is preferably in the range of 0.001 to 1000, and more preferably in the range of 0.01 to 100 in terms of molar ratio to the titanium component constituting component (A). is there. When using aluminum and the organometallic compound, the amount used is 0.001 in molar ratio with respect to the amount of the magnesium compound used.
The range is preferably from 100 to 100, and more preferably from 0.01 to 1. When the electron donor compound is used as an optional component, the amount thereof is preferably in the range of 0.001 to 10 in a molar ratio with respect to the amount of the magnesium compound,
Preferably it is in the range of 0.01 to 5.

The component (A1) is produced, for example, by the following production method using other components as required. (A) A method in which a magnesium halide is brought into contact with an electron donor and a titanium-containing compound. (B) A method in which alumina or magnesia is treated with a phosphorus halide compound, and a magnesium halide, an electron donor, and a titanium-halogen-containing compound are brought into contact therewith. (C) A reaction product obtained by contacting a titanium halide and / or a silicon halide and an electron donor with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer-silicon compound is not affected. A method of washing with an active organic solvent.

As the polymer-silicon compound used here, those represented by the following formula are suitable.

[0042]

Embedded image

(Here, R ⁵ is a hydrocarbon group having about 1 to 10 carbon atoms, and r represents a degree of polymerization such that the viscosity of the polymer-silicon compound is about 1 to 100 centistokes.) Specifically, methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7, Preferred is 9-pentamethylcyclopentasiloxane and the like.

(D) dissolving the magnesium compound with titanium tetraalkoxide and / or an electron donor,
A method in which a titanium compound and an electron donor are brought into contact with a solid component precipitated with a halogenating agent or a titanium halide compound, or they are separately brought into contact with each other.

(E) After reacting an organomagnesium compound such as a Grignard reagent with a halogenating agent, a reducing agent and the like,
A method in which an electron donor is brought into contact with this, if necessary, and then a titanium compound and an electron donor are brought into contact with each other or separately.

(F) A method in which a halogenating agent and / or a titanium compound is contacted with an alkoxymagnesium compound in the presence or absence of an electron donor, or separately.

Among these production methods, (A)
(C), (d) and (f) are preferred. Component (A)
In the middle and / or at the end of its preparation, an inert organic solvent such as an aliphatic or aromatic hydrocarbon solvent (for example,
Hexane, heptane, toluene, cyclohexane, etc.),
Alternatively, it can be washed with a halogenated hydrocarbon solvent (for example, n-butyl chloride, 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene, etc.).

The component (A) used in the present invention may be used after a prepolymerization step comprising contacting and polymerizing a vinyl group-containing compound such as an olefin, a diene compound, or styrene. it can.
Specific examples of the olefins used in the prepolymerization include, for example, those having about 2 to 20 carbon atoms, specifically, ethylene, propylene, 1-butene, 3-methylbutene-1, 1-pentene, 1- Hexene, 4-methylpentene-1, 1-octene, 1-decene, 1-undecene,
Examples of the diene compound include 1,3-butadiene, isoprene, 1,4-hexadiene, 1,5-hexadiene, 1,3-pentadiene, 1,4-pentadiene, 2,4 -Pentadiene,
2,6-octadiene, cis-2, trans-4-
Hexadiene, trans-2, trans-4-hexadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene,
2,4-heptadiene, dicyclopentadiene, 1,3
-Cyclohexadiene, 1,4-cyclohexadiene,
Cyclopentadiene, 1,3-cycloheptadiene, 4
-Methyl-1,4-hexadiene, 5-methyl-1,4
-Hexadiene, 1,9-decadiene, 1,13-tetradecadiene, p-divinylbenzene, m-divinylbenzene, o-divinylbenzene, dicyclopentadiene and the like. Specific examples of styrenes include styrene, α-methylstyrene, allylbenzene, chlorostyrene and the like.

The reaction conditions between the titanium component in the component (A1) and the vinyl group-containing compound may be any conditions as long as the effects of the present invention are recognized, but generally the following ranges are preferable. The prepolymerization amount of the vinyl group-containing compound is in the range of 0.001 to 100 g, preferably 0.1 to 50 g, and more preferably 0.5 to 10 g per 1 g of the titanium solid component. The reaction temperature during the prepolymerization is -150 to 15
0 ° C., preferably 0-100 ° C. A polymerization temperature that is lower than the “main polymerization”, that is, the polymerization temperature when the α-olefin is polymerized, is preferable. In general, the reaction is preferably performed with stirring, and at that time, an inert solvent such as hexane or heptane may be used.

[0050] (2) Component (B): Specific examples of the organoaluminum compound component used in the organic aluminum compound present invention (component _{^{(B)), R 6 3}} -s AlX s or R ⁷
_3-t Al (OR ⁸ ) _t (where R ⁶ and R ^{7 each} have 1 carbon atom)
To 20 are a hydrocarbon group or a hydrogen atom, R ⁸ is a hydrocarbon group, X is a halogen, and s and t are 0 ≦ s <3 and 0 <t <3, respectively. ).

Specifically, (a) trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and tri-n-decylaluminum; Alkyl aluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, and ethylaluminum dichloride; (c) alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride donor; Examples thereof include alkyl aluminum alkoxides such as diethyl aluminum phenoxy donor.

These organoaluminum compounds (a) to (d) are combined with another organometallic compound, for example, R ⁹ _3-u Al (OR
¹⁰ ) _u (where R ⁹ and R ¹⁰ are the same or different and are a hydrocarbon group having 1 to 20 carbon atoms, and u is 0 <u ≦
3. )) Can also be used in combination. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum and diethylaluminum ethoxide and diethylaluminum monochloride And the like. The ratio between the organoaluminum compound component (B) and the titanium component in the solid catalyst component (A) is as follows:
Al / Ti = 1 to 1000 mol / mol is common,
Preferably, Al / Ti is used at a ratio of 10 to 500 mol / mol.

(3) α-Olefin Polymerization Method The α-olefin polymerization method of the present invention is preferably used for slurry polymerization using a hydrocarbon solvent, liquid phase solventless polymerization substantially using no solvent, or gas phase polymerization. Applied. As a polymerization solvent in the case of slurry polymerization, a hydrocarbon solvent such as pentane, hexane, heptane, and cyclohexane is used.

The polymerization method employed may be any method such as continuous polymerization, batch polymerization, or multistage polymerization. The polymerization temperature is usually about 30 to 200 ° C, preferably 50 to 150 ° C, and the polymerization pressure is atmospheric pressure to 300 kg.
/ Cm ² , preferably atmospheric pressure to 100 kg / cm ^2, at which time hydrogen can be used as a molecular weight regulator.

The α-olefin to be polymerized by the catalyst system of the present invention has a general formula R ¹¹ —CH ＝ CH ₂ (where R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms and has a branched group. May be)
It is represented by Specifically, there are α-olefins such as propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. These α-
In addition to olefin homopolymerization, copolymerization with a monomer copolymerizable with an α-olefin (eg, ethylene, other α-olefins, dienes, styrenes, etc.) can also be performed. These copolymerizable monomers can preferably be used up to 15% by weight in random copolymerization and up to 50% by weight in block copolymerization.

[0056]

The present invention will be described in more detail with reference to the following examples. The method and apparatus for measuring each physical property value in the present invention are described below.

[MFR] Apparatus: Melt indexer manufactured by Takara Co., Ltd. Measurement method: JIS-K6758.

[ME] Apparatus: Melt indexer manufactured by Takara Corp. Measurement method: 1.0 mm in diameter and 8.0 mm in length at 190 ° C.
And extruded under a load in the orifice at an extrusion speed of 0.
At 1 g / min, the polymer extruded from the orifice was quenched in methanol, and the value of (diameter of strand diameter / orifice diameter) was calculated.

<Example-1> [Production of component (A)] In a flask sufficiently purged with nitrogen,
200 ml of dehydrated and deoxygenated n-heptane were introduced, and then 0.4 mol of MgCl ₂ and Ti (On-
0.8 mol of C ₄ H ₉ ) ₄ was introduced and reacted at 95 ° C. for 2 hours. After the completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced, followed by a reaction for 3 hours. The resulting solid component was washed with n-heptane.

Next, into a flask sufficiently purged with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced,
The solid component synthesized above was converted to 0.24 mo in terms of Mg atom.
1 was introduced. Then, SiCl ₄ was added to 25 ml of n-heptane.
0.4 mol was mixed, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, n-
Washed with heptane. Next, 0.024 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, and 90
The reaction was carried out at a temperature of 1 hour. After the completion of the reaction, the resultant was washed with n-heptane. Then, TiCl ₄ 0.
The mixture was heated to 70 ° C., and 1.58 mmol of o-nitrobenzenesulfonyl chloride was introduced.
The reaction was performed at 90 ° C. for 2 hours. After the completion of the reaction, the resultant was washed with n-heptane. Its titanium content was 2.0% by weight.

Next, into a flask sufficiently purged with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced,
4 g of the solid component synthesized above was introduced, and Al (C_Two
H_Five) _Three(TEA) 1.69 g and as component (A3)
(T-C_FourH₉) Si (CH_Three) (OCH_Three))_Two0.5m
was added and contacted at 30 ° C. for 2 hours. After contact is over,
Wash thoroughly with n-heptane, mainly magnesium chloride
(A) was obtained. The titanium content of this is
It was 1.4% by weight.

[Polymerization polymerization] In a 1.5-liter stainless steel autoclave equipped with a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane, and 125 m2 of TEA as the component (B) were used.
g, and 15 mg of the component (A) produced as described above, and then 33 ml of hydrogen, were introduced, the temperature was increased and the pressure was increased, and the polymerization pressure was 5 k.
Propylene was polymerized under the conditions of g / cm ² G, a polymerization temperature of 75 ° C., and a polymerization time of 2 hours. After completion of the polymerization, the obtained polymer slurry was separated by filtration, and the polymer was dried. As a result, 204.9 g of a polymer was obtained. Therefore, the amount of polymer produced per gram of catalyst (hereinafter referred to as catalyst yield) is 13,600 (g-PP / g).
-Catalyst). The amount of the low stereoregular attack polymer dissolved in the filtrate was 0.3% by weight, and the amount of by-products was extremely small. (Hereinafter, the amount of the polymer obtained from the filtrate may be abbreviated as the attack amount.) The obtained polymer has an MFR of 2.9 (dg / mi).
n), polymer bulk density = 0.40 (g / cc), ME =
1.50.

<Examples 2 to 3> In the production of the component (A) in Example 1, the same procedure was carried out except that the addition amount of the component (A2) and the hydrogenation amount during the polymerization were changed. The polymerization was carried out in exactly the same way. Table 1 shows the results.

Comparative Example 1 The component (A) was prepared in exactly the same manner as in Example 1, except that the component (A2), o-nitrobenzenesulfonyl chloride, was not used. And the polymerization of propylene were also carried out in Example-1.
And went exactly the same. Table 1 shows the results.

Example 4 Production of Component (A) 75 mg of anhydrous MgCl ₂ , 37.5 ml of decane, and 225 mmol of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to form a homogeneous solution. In this solution, 11.3 mmol of phthalic anhydride was added.
Was added and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve. After cooling the thus obtained homogeneous solution to room temperature, 1.8 mol of TiCl ₄ kept at −20 ° C.
The whole amount was charged dropwise over 1 hour. The temperature of the obtained mixture was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 18.8 mmol of 2,2-diisopropyl-1,3-dimethoxypropane was added.
Stirring was maintained at the same temperature for a period of time. After completion of the reaction, a solid portion was collected again by hot filtration, and sufficiently washed with decane at 110 ° C. and hexane at room temperature until no free titanium compound was detected in the washing solution. Then, TiCl ₄ 0.
The mixture was heated to 70 ° C., and 1.58 mmol of o-nitrobenzenesulfonyl chloride was introduced.
The reaction was performed at 90 ° C. for 2 hours. After completion of the reaction, washing was sufficiently performed using hexane until no free titanium compound was detected in the washing solution. This had a titanium content of 2.5% by weight. Then, 0.7 ml of dicyclopentyldimethoxysilane as the component (A3) and 1.69 g of TEA as the component (A4) were contacted at 30 ° C. for 2 hours. After completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. This had a titanium content of 2.5% by weight.

[Polymerization of Propylene] In a 1.5-liter stainless steel autoclave having a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane, and 125 m2 of TEA as the component (B) were used.
g, and 15 m of the prepolymerized catalyst component produced above.
g, then 33 ml of hydrogen were introduced, the temperature was raised and the pressure increased, polymerization pressure = 5 kg / cm ² G, polymerization temperature = 75 ° C., polymerization time =
Propylene was polymerized under the conditions of 2 hours. After polymerization,
The obtained polymer slurry was separated by filtration, and the polymer was dried. The results are as shown in Table-2.

<Example-5> [Production of component (A)] In a flask sufficiently purged with nitrogen,
20 g of Mg (OC ₂ H ₅ ) ₂ and 160 ml of toluene were added to form a suspended state. After stirring at room temperature for 15 minutes,
After introducing 40 ml of Cl _{4, the} temperature was raised to 80 ° C. while stirring, 5.7 ml of di-n-butyl phthalate was introduced, and then the temperature in the system was further raised to 110 ° C. and reacted for 2 hours. . After completion of the reaction, the supernatant was removed and toluene 2
Washing was performed 3 times at 90 ° C. using 00 ml. Then TiC
l ₄ by mixing 10ml heated to 70 ° C., introducing o- nitrobenzenesulfonyl chloride 1.58 mmol, were reacted for 2 hours at 90 ° C.. After the reaction was completed, washing was sufficiently performed using toluene until no free titanium compound was detected in the washing solution. It has a titanium content of 2.8.
% By weight.

Next, 0.7 ml of dicyclopentyldimethoxysilane and 1.69 g of TEA as the component (A3) were brought into contact at 30 ° C. for 2 hours. After completion of the contact, the resultant was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. This had a titanium content of 2.5% by weight.

[Polymerization Polymerization] The polymerization of propylene was carried out under the same conditions as in Example 1. The results are shown in Table
As shown in FIG.

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

According to the present invention, it is possible to obtain an α-olefin polymer having an extremely high melt tension in a high yield. The obtained polymer is suitably used for applications such as packaging materials such as films and sheets for which high performance molding ability is required.

[Brief description of the drawings]

FIG. 1 is a flowchart illustrating a method for producing a catalyst of the present invention.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission Date] March 14, 2000 (200.3.1)
4)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

Further, as a titanium compound serving as a titanium source,
Is represented by the general formula Ti (OR^Two)_4-qX_q(Where R^TwoIs hydrocarbon
A basic group, preferably having about 1 to 10 carbon atoms;
Represents a halogen, and q is 0 ≦ q ≦ 4. )
Compounds. As a specific example, TiCl_Four,
TiBr _Four, Ti (OC_TwoH_Five) Cl_Three, Ti (OC_TwoH _Five)
_TwoCl_Two, Ti (OC_TwoH_Five)_ThreeCl, Ti (OiC_ThreeH
₇) Cl_Three, Ti (On-C_FourH₉) Cl_Three, Ti (O-
n-C_FourH₉)_TwoCl_Two, Ti (OC_TwoH_Five) Br _Three, Ti
(OC_TwoH_Five) (On-C)_FourH₉)_TwoCl, Ti (On
-C_FourH₉)_ThreeCl, Ti (OC₆H_Five) Cl_Three, Ti (O-
i-C_FourH₉)_TwoCl_Two, Ti (On-C_FiveH ₁₁) Cl_Three,
Ti (On-C₆H₁₃) Cl_Three, Ti (OC_TwoH_Five)_Four,
Ti (On-C_ThreeH₇)_Four, Ti (On-C_FourH₉)_Four,
Ti (OiC_FourH₉)_Four, Ti (On-C
₆H₁₃)_Four, Ti (On-C₈H₁₇)_Four, Ti (OCH_Two
CH (C_TwoH_Five) C_FourH₉)_FourAnd the like.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

Also, TiCl_Three(TiCl_FourWith hydrogen
Or reduced with aluminum metal, or
Including those reduced with organometallic compounds), TiB
r _Three, Ti (OC_TwoH_Five) Cl_Two, TiCl_Two, Dicyclope
Antadienyl titanium dichloride, cyclopentadi
Use of titanium compounds such as enyl titanium trichloride
Use is also possible. Among these titanium compounds, TiC
l_Four, Ti (On-C_FourH ₉)_Four, Ti (OC_TwoH_Five) Cl
_ThreeAre preferred.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction contents]

(Here, R ⁵ is a hydrocarbon group having about 1 to 10 carbon atoms, and x represents a degree of polymerization such that the viscosity of the polymer-silicon compound becomes about 1 to 100 centistokes.) Specifically, methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7, Preferred is 9-pentamethylcyclopentasiloxane and the like.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction contents]

[0050] (2) Component (B): Specific examples of the organic aluminum compound used in the organic aluminum compound present invention (component _{^{(B)), R 6 3}} -s AlX s or R ⁷
_3-t Al (OR ⁸ ) _t (where R ⁶ and R ^{7 each} have 1 carbon atom)
To 20 are a hydrocarbon group or a hydrogen atom, R ⁸ is a hydrocarbon group, X is a halogen, and s and t are 0 ≦ s <3 and 0 <t <3, respectively. ).

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction contents]

Specifically, (a) trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and tri-n-decylaluminum; diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride Lai de of which alkyl aluminum halide, (c) diethylaluminum hydride, diisobutylaluminum high dry de of which alkylaluminum hydride, (d) diethylaluminum ethoxy de, diethylaluminum phenoxy de
Do any alkyl aluminum alkoxide, and the like.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction contents]

These organoaluminum compounds (a) to (d) are combined with another organometallic compound, for example, R ⁹ _3-u Al (OR
¹⁰ ) _u (where R ⁹ and R ¹⁰ are the same or different and are a hydrocarbon group having 1 to 20 carbon atoms, and u is 0 <u ≦
3. )) Can also be used in combination. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum and diethylaluminum ethoxide and diethylaluminum monochloride And the like. The ratio of the organoaluminum compound of the component (B) and the titanium component in the solid catalyst component of the component (A) is Al
/ Ti = 1 to 1000 mol / mol is generally used, and preferably, Al / Ti is used at a ratio of 10 to 500 mol / mol.

Continued on the front page F-term (reference) 4J028 AA01A AB01A AC04A AC05A AC06A AC07A AC14A AC15A AC17A BA01A BA01B BB00A BB01B BC15B BC16B BC24B BC27B BC34A CB44A CB84A DB02A DB03A EB02 FA05 EB03 FA11 EB03 FA05 GA07 GA09 GB01 4J100 AA00Q AA02Q AA03P AA04P AA07P AA16P AA17P AB01Q AS01Q AS11Q CA01 CA04 DA09 FA09 JA58

Claims (4)

[Claims] 1. Component (A) and component (B) shown below
And α-olefin polymerization catalysts. Component (A): a solid catalyst component obtained by contacting the following component (A1), component (A2), and component (A3). (A1) A solid component for polymerization containing, as essential components, titanium, magnesium, halogen, and an electron donor selected from the group consisting of organic acid esters, acid halides and diethers. (A2) S = O bond-containing compound (A3) Silicon compound Component (B): Organoaluminum compound 2. The α-olefin polymerization system according to claim 1, wherein the electron donor of the component (A1) is selected from the group consisting of a phthalic acid diester compound, a phthalic acid dihalide compound and a diether compound. catalyst. 3. The α-olefin polymerization catalyst according to claim 1, wherein the S ＝ O bond-containing compound of the component (A2) is o-nitrobenzenesulfonyl chloride. 4. An α-olefin is brought into contact with the α-olefin polymerization catalyst according to claim 1 by contacting the α-olefin with the catalyst.
-A method for polymerizing α-olefins, comprising polymerizing or copolymerizing olefins.