JPH1180235A - Catalyst component for alpha-olefin polymerization, catalyst and alpha-olefin polymerization process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst component which can give a high yield of a high-quality α-olefin without the necessity for removing catalyst residues, a catalyst and an α-olefin polymerization process. SOLUTION: This catalyst component for α-olefin polymerization is obtained by a catalytic reaction of the following components (A1 to A5): a solid component (A1) containing titanium, magnesium, halogen atoms and an electron donor as the essential constituents; a halogenated silicon compound (A2) represented by the formula: R<1> m SiX4-m (wherein R<1> is H or a hydrocarbon group; X is halogeno; and 0<=m<4); a vinylsilane compound (A3); a silicon compound (A4) represented by the formula: R<2> R<3> 3-n Si(OR<4> )n (wherein R<2> is a saturated aliphatic hydrocarbon group; R<3> is a saturated or unsaturated aliphatic hydrocarbon group or a hydrocarbon group containing a heteroatom; R<4> is a hydrocarbon group; and 1<=n<=3); and an organoaluminum compound (A5).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a solid catalyst component for the polymerization of α-olefins, a catalyst using the same, and α-olefin polymerization.
The present invention relates to a method for polymerizing an olefin. More specifically, the present invention provides an α-olefin capable of obtaining a polymer in an extremely high yield by polymerizing an α-olefin using a catalyst obtained by combining a specific fixed catalyst component and an organoaluminum compound. The present invention relates to a catalyst component for olefin polymerization, a catalyst using the same, and a method for polymerizing an α-olefin.

[0002]

2. Description of the Related Art In recent years, many proposals have been made to produce a highly stereoregular polymer of α-olefin in high yield by using a solid component containing titanium, magnesium, halogen and an electron donor as essential components. (For example,
JP-A Nos. 57-63310, 57-63311, 57-63312, 58-138705, 58
138706 and 58-138711). Among these, a polymerization catalyst using the solid catalyst component and the organoaluminum compound component in combination is one of high practicality. However, to the inventor's knowledge, even with this catalyst system, the yield of α-olefin polymer cannot be said to be sufficient, and further improvement has been desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention has a high olefin polymerization activity, and therefore, can obtain an α-olefin polymer in a high yield. An object of the present invention is to provide a catalyst component from which an α-olefin polymer can be obtained, a catalyst, and a method for polymerizing an α-olefin.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on various catalyst components. As a result, specific silicon compounds, vinylsilane compounds and organoaluminum compounds are specified as transition metal-containing solid components. The present inventors have found that an α-olefin polymer having high stereoregularity can be provided in an extremely high yield by combining an organoaluminum compound with a solid catalyst component prepared by subjecting the compound to a contact treatment, and arrived at the present invention. That is,
The present invention provides the following solid catalyst component for α-olefin polymerization.

The following component (A1), component (A2),
A solid catalyst component for α-olefin polymerization obtained by contacting component (A3), component (A4) and component (A5). Component (A1): a solid component containing titanium, magnesium, halogen and an electron donor as essential components (however, the electron donor excludes the silicon compound of the component (A4)) Component (A2): In the following general formula: The halogen-containing silicon compound represented by the general formula R ¹ _m SiX _4-m (where R ¹ is a hydrogen atom, a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, X is a halogen, and m is 0 ≦ m.
<4) Component (A3): a vinylsilane compound (however, excluding a silicon compound having an alkoxy group) Component (A4): a silicon compound represented by the following general formula: R ² R ³ _3-n Si ( OR ⁴ ) _n (where R ² is a saturated aliphatic hydrocarbon group, R ³ is a saturated or unsaturated aliphatic hydrocarbon group or a hetero atom-containing hydrocarbon group, R ⁴ is a hydrocarbon group, and n is 1 ≦ n ≦ 3) Component (A5): Organoaluminum Compound The present invention also provides the following α-olefin polymerization catalyst.

An α-olefin polymerization catalyst comprising a combination of the above-described solid catalyst component (A) and the following component (B). Component B: organoaluminum compound component The present invention further provides a method for polymerizing or copolymerizing an α-olefin using the above-mentioned catalyst for α-olefin polymerization. Is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The process for producing an α-olefin polymer according to the present invention comprises a specific component (A) and a specific component (B).
Wherein the α-olefin is polymerized in the presence of a catalyst comprising the combination of (Olefin polymerization catalyst) The catalyst used in the present invention,
It 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 The solid catalyst component (A) of the present invention comprises a specific solid component (component (A1)), a specific silicon compound (component (A2)), and a vinylsilane compound component (component (A3)). ), A specific silicon compound (component (A4)) and an organoaluminum compound component (component (A5)). Such solid catalyst component (A) of the present invention does not exclude the coexistence of other suitable components other than the above essential five components.

Component (A1): Solid Component The solid component (A1) used in the present invention is a catalyst for the stereoregular polymerization of α-olefins containing titanium, magnesium, halogen and an electron donor as essential components. It is a solid component. Here, “containing as an essential component” means that, in addition to the three components listed, a purposeful other element 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.

[0010] The solid components themselves, including titanium, magnesium, halogen and electron donors, are known per se.
For example, JP-A-53-45688 and JP-A-54-3894.
Nos. 54-31092, 54-39483, 54-94591, 54-118484, 54
No. 131589, No. 55-75411, No. 55-9
No. 0510, No. 55-90511, No. 55-1274
No. 05, No. 55-147507, No. 55-15500
No. 3, No. 56-18609, No. 56-70005,
Nos. 56-72001, 56-86905, 56
-90807, 56-155206, 57-3
No. 4103, No. 57-92007, No. 57-1210
No. 03, No. 58-5309, No. 58-5310, No. 58-5331, No. 58-8706, No. 58-32
No. 604, No. 58-32605, No. 58-67703
No. 58-117206, No. 58-127708
Nos. 58-183708 and 58-183709
Nos. 59-149905 and 59-149906
Nos. 64-20204, 64-24806, JP-A-2-77413, 2-107610, and 3-
No. 39302, No. 3-234707, No. 4-2939
Nos. 10 and 4-296304 are used.

The magnesium compound used as a magnesium source in the present invention includes magnesium dihalide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate and the like. Is mentioned. Among them, Mg (OR ⁶ ) _2-p X _p (here, R ⁶
Is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, X represents a halogen, and p is 0 ≦ p ≦ 2. )
Is preferred.

As a titanium compound serving as a titanium source,
Is represented by the general formula Ti (OR⁷)_4-qX_q(Where R⁷Is charcoal
A hydride group, preferably one having about 1 to 10 carbon atoms
X represents a halogen, and q is 0 ≦ q ≦ 4. )so
And the compounds represented. As a specific example, TiC
l_Four, TiBr_Four, Ti (OC_TwoH_Five) Cl_Three, Ti
(OC_TwoH_Five)_TwoCl_Two, Ti (OC_TwoH_Five)_ThreeCl,
Ti (Oi-C_ThreeH₇) Cl _Three, Ti (On-C
_FourH₉) Cl_Three, Ti (On-C_FourH₉)_TwoCl_Two, T
i (OC_TwoH_Five) Br_Three, Ti (OC_TwoH_Five) (On-
C_FourH₉)_TwoCl, Ti (On-C_FourH₉)_ThreeCl, T
i (OC₆H_Five) Cl_Three, Ti (Oi-C_FourH₉)_TwoC
l_Two, Ti (OC₆H₁₁) Cl_Three, Ti (OC₆H₁₃)
Cl_Three, Ti (OC_TwoH_Five)_Four, Ti (On-C
_ThreeH₇)_Four, Ti (On-C_FourH₉)_Four, Ti (Oi-
C_FourH₉)_Four, Ti (On-C₆H₁₃)_Four, Ti (On
-C₆H₁₇)_Four, Ti (OCH_TwoCH (C_TwoH_Five) C_Four
H₉)_FourAnd the like.

Further, TiX '_Four(Where X 'is a halogen
It is. ) By reacting with an electron donor described later
The compound can also be used as a titanium source. like that
Specific examples of the molecular compound include TiCl_Four・ CH_ThreeCO
C_TwoH_Five, TiCl_Four・ CH _ThreeCO_TwoC_TwoH_Five, TiC
l_Four・ C₆H_FiveNO_Two, TiCl_Four・ CH_ThreeCOCl,
TiCl_Four・ C₆H_FiveCOCl, TiCl_Four・ C₆H_Five
CO_TwoC_TwoH_Five, TiCl_Four・ ClCOC_TwoH_Five, Ti
Cl_Four・ C_FourH_FourO and the like.

Further, TiCl ₃ (including TiCl ₄ reduced with hydrogen, reduced with aluminum metal, reduced with an organometallic compound, etc.), TiBr
_{3, Ti (OC 2 H 5} ) Cl 2, TiCl 2, the use of dicyclopentadienyl titanium dichloride, cyclopentadienyl titanium trichloride titanium compounds such as chloride are also possible. Among these titanium compounds, Ti
Cl ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₂ H ₅ ) C
l _{3 and the} like are preferable.

Halogen is selected from magnesium and / or
Or usually supplied from a halogenated compound of titanium
But other halogen sources such as AlCl_ThreeAl
Minium halides and SiCl_FourEtc silicon halo
Genide, 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.

Electron donors (internal donors) include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides. Examples include oxygen-containing electron donors, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, and sulfur-containing electron donors such as sulfonic acid esters.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol,
Octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol,
C1-C18 alcohols such as isopropylbenzyl alcohol, (b) phenol, cresol,
C6-C2 which may have an alkyl group such as xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol, and naphthol;
Phenols having 5 to 15 carbon atoms, (c) ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone;
C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde;
(E) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl cellosolve, 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, methyl toluate, ethyl toluate,
Amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-
Organic acid monoester such as 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, cyclopropane-1,2-dicarboxylic acid-n-hexyl, 1,
C2-C20 organic acid esters of organic acid polyvalent esters such as diethyl 1-cyclobutanedicarboxylate;
(F) inorganic acid esters such as silicate esters such as ethyl silicate and butyl silicate, provided that the above-mentioned general formula R ² R
³ _3-n Si (OR ⁴ ) _n Excluding silicon compounds represented by _n , those having 2 to 15 carbon atoms such as (g) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, and phthaloyl isochloride. Acid halides, (thi) methyl ether, ethyl ether,
Monoesters having 2 to 15 carbon atoms such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, or 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, -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- Diethers having 2 to 20 carbon atoms such as diethoxypropane and 2,2-diisopropyl-1,3-diethoxypropane;
Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; amines such as (nu) methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine; Nitriles such as acetonitrile, benzonitrile, tolunitrile, (ヲ) ethyl 2- (ethoxymethyl) -benzoate,
Ethyl 2- (t-butoxymethyl) -benzoate, ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxy-2-s-butylpropionate, 3-ethoxy-2- alkoxy ester compounds such as ethyl t-butyl propionate,
(W) ethyl 2-benzoylbenzoate, ethyl 2- (4'-methylbenzoyl) benzoate, 2-benzoyl-
Ketoester compounds such as ethyl 4,5-dimethylbenzoate, (f) methyl benzenesulfonate, ethyl benzenesulfonate, ethyl p-toluenesulfonate, p-
Examples thereof include sulfonic esters such as isopropyl toluenesulfonate, n-butyl p-toluenesulfonate, and s-butyl p-toluenesulfonate. Two or more of these electron donors can be used. Of these, preferred are organic acid ester compounds, acid halide compounds and ether compounds. Particularly preferred are organic acid monoester compounds having 2 to 10 carbon atoms, phthalic acid diester compounds having 2 to 20 carbon atoms, and phthalic acid. Dihalide compounds and diether compounds having 2 to 20 carbon atoms.

Component (A2) Halogen-Containing Silicon Compound The silicon compound (component (A)
2)) has the general formula R¹ _mSix_4-m(Where R¹Is water
Atom, saturated aliphatic hydrocarbon group or aromatic hydrocarbon group
X is a halogen, and m is 0 ≦ m <4.
). Component (A2) is a compound of the formula
A mixture of plural types may be used. A cable that can be used in the present invention
Specific examples of the iodine compound (component (A2)) are as follows.
is there.

SiCl_Four, CH_ThreeSiCl_Three, HSiC
l_Three, CH_ThreeSiCl_Two, CH_ThreeCHClSiCl_Three,
(C_TwoH_Five) SiCl_Three, (CH_Three)_TwoSiCl_Two, H
Si (CH_Three)_TwoCl, C_ThreeH₇SiCl_Three, CH
_Three(C_TwoH_Five) SiCl_Two, SiBr_Four, (CH_Three)_Three
SiCl, CH_Three(CH_Two)_ThreeSiCl_Three, (C
_TwoH₆) _TwoSiCl_Two, CH_Three(CH_Two)_FourSiC
l_Three, CH_Three(CH_Two)_Three(CH_Three) SiCl_Two, (C
₆H_Five) SiCl_Three, (C₆H_Five) HSiCl_Two, (C
yc-C₆H₁₁) SiCl_Three, CH_Three(CH_Two)_FiveSi
Cl_Three, C₆H_FiveCH_TwoSiCl_Three, (C₆H_Five) (C
H_Three) SiCl_Two,

[0020]

Embedded image

CH ₃ (CH ₂ ) ₆ SiCl ₃ , CH
₃ (CH ₂ ) ₆ (CH ₃ ) SiCl ₂ , (CH ₃ ) (C
H ₂ ) ₇ SiCl ₃ , CH ₃ (CH ₂ ) ₆ (CH ₃ ) S
iCl ₂ , (CH ₃ CH ₂ CH ₂ ) ₃ SiCl, CH ₃
(CH ₂ ) ₉ SiCl ₃ , CH ₃ (CH ₂ ) ₉ (C
H ₃₎ SiCl _2, mention may be made of _{(C 6 H 5) 2 SiCl} 2 and the like. Of these, preferred is S
iCl ₄ , CH ₃ SiCl ₃ , (C ₂ H ₅ ) SiCl ₃
And the like.

Component (A3) Vinyl silane compound The vinyl silane compound used in the present invention includes at least one hydrogen atom in monosilane (SiH ₄ ) replaced by a vinyl group (CH ₂ −CH—), and the remaining hydrogen atom Wherein some of them are replaced by halogen (preferably Cl), alkyl group (preferably C1 to C12 hydrocarbon group), aryl group (preferably phenyl), or group having a siloxy group. It shows. The vinylsilane compound may be a mixture of a plurality of types (however, excluding a silicon compound having a Si—O—C bond, specifically, an alkoxy group). Specifically, the expression

[0023]

Embedded image

(However, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ^12, R ^13, R ¹⁴ is each independently an alkyl group or an aryl group of C 6-8 having 1 to 6 carbon atoms, R ¹⁵ is a 2-6 saturated or carbon from 1 to 6 carbon atoms non It shows a saturated aliphatic hydrocarbon group, and n shows the integer of 1-10. )
Preferably, a compound represented by ^{_{CH 2 = CH-SiR 8 R}} 9 R 10.

More specifically, CH_Two= CH-Si
H_Three, CH_Two= CH-SiH_Two(CH_Three), CH_Two= C
H-SiH (CH_Three)_Two, CH_Two= CH-Si (C
H_Three)_Three, CH_Two= CH-SiCl_Three, CH_Two= CH-
SiCl_Two(CH_Three), CH_Two= CH-SiCl (CH
_Three)_Two, CH_Two= CH-SiH (Cl) (CH_Three), C
H_Two= CH-Si (C_TwoH_Five)_Three, CH_Two= CH-Si
Cl (C_TwoH_Five)_Two, CH_Two= CH-SiCl_Two(C_Two
H_Five), CH_Two= CH-Si (CH_Three)_Two(C
_TwoH_Five), CH_Two= CH-Si (CH_Three) (C_TwoH_Five)
_Two, CH_Two= CH-Si (n-C _FourH₉), CH_Two= C
H-Si (C₆H_Five)_Three, CH_Two= CH-Si (C
H_Three) (C₆H_Five)_Two, CH_Two= CH-Si (CH_Three)
_Two(C₆H_Five), CH_Two= CH-Si (CH_Three)_Two(C
₆H_FourCH_Three), (CH_Two= CH)_TwoSiH_Two, (CH
_Two= CH)_TwoSiCl_Two, (CH_Two= CH)_TwoSi (C
H_Three)_Two, (CH_Two= CH)_TwoSi (C₆H_Five)_Two,
(CH_Two= CH) (CH_Three)_TwoSi-O-Si (C
H_Three)_Two(CH = CH_Two), (CH_Two= CH) (C
H_Three)_TwoSi-O-Si (CH_Three)_Two-O-Si (CH
_Three)_Two(CH = CH_Two) And the like.

Component (A4) Silicon Compound The silicon compound used in the present invention has a general formula R^TwoR^Three
_3-nSi (OR^Four)_n(Where R^TwoIs an aliphatic hydrocarbon
And R is^ThreeIs a saturated or unsaturated aliphatic hydrocarbon group
Or a heteroatom-containing hydrocarbon group;^TwoSame as
There may be. R ^FourIs a hydrocarbon group, and n is 1 ≦ n ≦
3. ). Preferably, R^Two
Is a branched aliphatic hydrocarbon group or a cycloaliphatic hydrocarbon group.
Yes, R^ThreeIs a saturated hydrocarbon or heteroatom-containing carbon
A hydrogen group;^FourIs a hydrocarbon group having 1 or more carbon atoms.
Where n is 1 ≦ n ≦ 3.

The silicon compound may be a mixture of hetero compounds of the silicon compound of the present formula. Here, when R ² is a branched aliphatic hydrocarbon group, it is preferable that R ² is branched from a carbon atom adjacent to a silicon atom. In this case, the branching group is preferably an alkyl group, a cycloalkyl group, or an aryl group (for example, a phenyl group or a methyl-substituted phenyl group). More preferred R ² is a carbon atom adjacent to a silicon atom, that is, the α-position carbon atom is a secondary or tertiary carbon atom. In particular, those having a tertiary carbon atom bonded to a silicon atom are preferred. When R ² is a branched hydrocarbon group, the number of carbon atoms is usually 3 to 20, preferably 4 to 10. Also, R ²
Is a cycloaliphatic hydrocarbon group, usually has 4 to 4 carbon atoms.
20, preferably 5-10. R ³ is preferably a hydrocarbon group or a heteroatom-containing hydrocarbon group and has 1 carbon atom.
-20, preferably 1-10 hydrocarbon groups or heteroatom-containing hydrocarbon groups. R ⁴ is a hydrocarbon group having 1 or more carbon atoms, and has 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms.
0, and more preferably 1-4 aliphatic hydrocarbon groups.

Specific examples of the silicon compound usable in the present invention
Is as follows. (CH_Three)_ThreeCSi (CH_Three)
(OCH_Three)_Two, (CH_Three)_ThreeCSi (C_TwoH _Five) (O
CH_Three)_Two, (CH_Three)_ThreeCSi (n-C_ThreeH₇) (O
CH_Three)_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇) (O
CH_Three)_Two, (CH_Three)_ThreeCSi (n-C₆H₁₃) (O
CH_Three)_Two, (CH_Three)_ThreeCSi (CH_Three) (OC_TwoH
_Five)_Two, (C_TwoH_Five)_ThreeCSi (CH_Three) (OCH_Three)
_Two, (CH_Three)_Two(C_TwoH_Five) CSi (CH_Three) (OC
H_Three)_Two, (C_TwoH_Five)_Two(CH_Three) CSi (CH_Three)
(OCH_Three)_Two, (C_TwoH₆) (CH_Three)_TwoCSi (C
H_Three) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (OCH
_Three)_Three, (CH_Three)_ThreeCSi (OC_TwoH_Five)_Three, (CH
_Three)_Two(C_TwoH_Five) CSi (OCH_Three)_Three, ((C
H_Three)_ThreeC)_TwoSi (OCH_Three)_Two, (C_TwoH_Five)
_Two(CH_Three) CSi (OCH_Three)_Three, (C_TwoH_Five) (C
H_Three)_TwoCSi (OC_TwoH_Five)_Three, (CH_Three)_ThreeCSi
(OiC_ThreeH₇) (OCH_Three)_Two, (CH_Three)_ThreeC
Si (On-C_ThreeH₇) (OCH_Three)_Two, (CH_Three)
_ThreeCSi (OC_TwoH_Five) (OCH_Three)_Two, (I-C_ThreeH
₇) (CH_Three) _TwoCSi (CH_Three) (OCH_Three)_Two,
(I-C_ThreeH₇) (CH_Three)_TwoCSi (C _TwoH_Five) (O
CH_Three)_Two, (I-C_ThreeH₇) (CH_Three)_TwoCSi (n
-C_ThreeH₇) (OCH_Three)_Two, (I-C_ThreeH₇) (CH
_Three)_TwoCSi (i-C_ThreeH₇) (OCH_Three)_Two, (I-
C_ThreeH₇) (CH_Three)_TwoCSi (CH_Three) (OC
_TwoH_Five)_Two, (I-C_ThreeH₇) (CH_Three)_TwoCSi (O
CH_Three)_Three, (I-C_ThreeH₇) (CH_Three)_TwoCSi (O
C_TwoH_Five)_Three, (CH_Three)_ThreeCSi (CH_Three) (OC_Two
H_Five) (OCH_Three), (CH_Three)_ThreeCSi (CH_Three)
(OC_FourH₉) (OCH_Three), (1-CH_Three-C
_FiveH₆) Si (CH_Three) (OCH_Three)_Two, (1-CH_Three
-C_FiveH₆) Si (n-C_ThreeH₇) (OCH_Three)_Two,
(1-CH_Three-C₆H_Ten) Si (CH_Three) (OCH_Three)
_Two, (1-CH_Three-C₆H_Ten) Si (i-C_ThreeH₇)
(OCH_Three)_Two, (CH_Three)_ThreeCSi (N (C_TwoH_Five)
_Two) (OCH_Three)_Two, (CH _Three)_ThreeCSi (OSi (C
H_Three)_Three) (OCH_Three)_Two, (I-C_ThreeH₇)_TwoSi
(OCH_Three)_Two, (I-C_ThreeH₇)_TwoSi (OC
_TwoH_Five)_Two, (C_FiveH₉)_TwoSi (OCH_Three)_Two, (C
_FiveH₉)_TwoSi (OC_TwoH_Five)_Two, (C_FiveH₉) (I-
C_ThreeH₇) Si (OCH_Three)_Two, (C_FiveH₁₁)_TwoSi
(OCH_Three)_Two, (C_FiveH ₁₁) (I-C_ThreeH₇) Si
(OCH_Three)_Two, (I-C_ThreeH₇) (S-C_FourH₉) S
i (OCH_Three)_Two, (S-C_FourH₉)_TwoSi (OC
H_Three)_Two, (C_FiveH₉) (C₆H₁₁) Si (OCH_Three)
_Two, (2-CH_Three-C_FiveH₉)_TwoSi (OCH_Three) _Two,
(2-CH_Three-C_FiveH₉)_TwoSi (OC_TwoH_Five)_Two,
(3-CH_Three-C_FiveH ₉)_TwoSi (OCH_Three)_Two, (3
-CH_Three-C_FiveH₉)_TwoSi (OC_TwoH_Five)_Two,

[0029]

Embedded image

(CH_Three)_ThreeCSi (CH_Three) (OC_TwoH
_Five)_Two, (CH_Three)_ThreeCSi (CH_Three) (On-C)_Three
H₇)_Two, (CH_Three)_ThreeCSi (CH_Three) (OiC
_ThreeH₇)_Two, (CH_Three)_ThreeCSi (CH_Three) (On-
C_FourH₉)_Two, (CH_Three)_ThreeCSi (CH_Three) (O-i
-C_FourH₉)_Two, (CH_Three)_ThreeCSi (CH_Three) (O-
t-C_FourH₉)_Two, (CH_Three)_ThreeCSi (CH_Three) (O
-N-C₆H₁₃)_Two, (CH_Three)_ThreeCSi (CH_Three)
(On-C₈H₁₇)_Two, (CH_Three)_ThreeCSi (C
H_Three) (On-C)_TenH_{twenty one})_Two, (CH_Three)_ThreeCSi
(C_TwoH₆) (OC_TwoH₆)_Two, (CH_Three)_ThreeCSi
(N-C_ThreeH₇) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCS
i (i-C_ThreeH₇) (OC_TwoH_Five)_Two, (CH_Three)_ThreeC
Si (n-C_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_Three
CSi (i-C_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)
_ThreeCSi (s-C_FourH₉) (OC_TwoH_Five)_Two, (C
H_Three)_ThreeCSi (t-C_FourH₉) (OC_TwoH_Five)_Two,
(CH_Three)_ThreeCSi (n-C_FiveH₁₁) (OC
_TwoH_Five)_Two, (CH_Three)_ThreeCSi (c-C_FiveH₉) (O
C_TwoH_Five)_Two, (CH_Three) _ThreeCSi (n-C₆H₁₃)
(OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (c-C
₆H ₁₁) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (C_Two
H_Five) (On-C)_ThreeH₇) _Two, (CH_Three)_ThreeCSi
(C_TwoH_Five) (OiC_ThreeH₇)_Two, (CH_Three)_ThreeC
Si (C_TwoH_Five) (On-C)_FourH₉)_Two, (CH_Three)
_ThreeCSi (C_TwoH_Five) (OiC_FourH₉)_Two, (CH
_Three)_ThreeCSi (C_TwoH_Five) (OsC_FourH₉) _Two,
(CH_Three)_ThreeCSi (C_TwoH_Five) (OtC_FourH₉)
_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (On-C)₆H
₁₃)_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (On-C)
₈H₁₇)_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (On
-C_TenH_{twenty one}) _Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇)
(On-C_ThreeH₇)_Two, (CH_Three) _ThreeCSi (i-C
_ThreeH₇) (OiC_ThreeH₇)_Two, (CH_Three)_ThreeCSi
(I-C_ThreeH₇) (On-C)_FourH₉)_Two, (CH_Three)
_ThreeCSi (i-C_ThreeH₇) (OiC_FourH₉)_Two,
(CH_Three)_ThreeCSi (i-C_ThreeH₇) (OsC_FourH
₉)_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇) (Ot
-C_FourH₉)_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇)
(On-C₆H₁₃)_Two, (CH_Three)_ThreeCSi (i-C
_ThreeH₇) (On-C)₈H₁₇)_Two, (CH_Three)_ThreeCSi
(I-C_ThreeH₇) (On-C)_TenH_{twenty one})_Two, (CH_Three)
_ThreeCSi (On-C_ThreeH₇) (OC_TwoH_Five)_Two, (C
H_Three)_ThreeCSi (OiC_ThreeH₇) (OC
_TwoH_Five)_Two, (CH_Three) _ThreeCSi (On-C_FourH₉)
(OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (OiC_Four
H₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (O-s
-C_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi
(OtC_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_Three
CSi (On-C_FiveH₁₁) (OC_TwoH_Five)_Two, (CH
_Three)_ThreeCSi (O-C-C_FiveH₉) (OC_TwoH_Five)_Two,
(CH_Three)_ThreeCSi (On-C₆H ₁₃) (OC
_TwoH_Five)_Two, (CH_Three)_ThreeCSi (O-C-C_FiveH₁₁)
(OC_TwoH_Five)_Two, (I-C_ThreeH₇)_TwoSi (OC_TwoH
_Five)_Two, (I-C_FourH₉)_TwoSi (OC_TwoH_Five)_Two,
(S-C_FourH₉)_TwoSi (OC_TwoH_Five)_Two, (Neo-
C_FiveH₁₁)_TwoSi (OC_TwoH_Five)_Two, (C-C_FiveH₉)
_TwoSi (OC_TwoH_Five)_Two, (C-C_FiveH₉)_TwoSi (O
-N-C_ThreeH₇)_Two, (C-C_FiveH₉)_TwoSi (On
-C_FourH₉)_Two, (C-C_FiveH₉)_TwoSi (On-C
_FiveH₁₁)_Two, (C-C_FiveH ₉)_TwoSi (On-C₈H
₁₇)_Two, (C-C₆H₁₁)_TwoSi (OC_TwoH_Five)_Two,
(C-C₆H₁₁)_TwoSi (On-C_ThreeH₇)_Two, (C
-C₆H₁₁)_TwoSi (On-C_FourH₉)_Two, (C-C
₆H₁₁)_TwoSi (On-C_FiveH₁₁)_Two, (C-C₆H
₁₁)_TwoSi (On-C₈H₁₇)_Two, (C-C₆H₁₁)
_TwoSi (CH_Three) (OC_TwoH_Five)_Two, (C-C₆H₁₁)
Si (CH_Three) (On-C)_ThreeH₇)_Two, (C-C₆H
₁₁) Si (CH_Three) (On-C)_FourH₉)_Two, (C-C
₆H₁₁) Si (CH_Three) (On-C)_FiveH₁₁)_Two, (C
-C₆H₁₁) Si (CH_Three) (On-C)₈H₁₇)_Two,
(C-C₆H₁₁) Si (C_TwoH_Five) (OC_TwoH_Five)_Two,
(C-C₆H₁₁) Si (n-C_FourH₉) (OC_TwoH_Five)
_Two, (C-C₆H₁₁) Si (c-C_FiveH₉) (OC_TwoH
_Five)_Two, (C_TwoH_Five)_ThreeCSi (CH_Three) (OC
_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (CH_Three) (On
-C_ThreeH₇)_Two, (C_TwoH _Five)_ThreeCSi (CH_Three) (O
-Ic_ThreeH₇)_Two, (C_TwoH_Five)_ThreeCSi (CH _Three)
(On-C_FourH₉)_Two, (C_TwoH_Five)_ThreeCSi (CH
_Three) (OiC_FourH₉)_Two, (C_TwoH_Five)_ThreeCSi
(CH_Three) (OtC_FourH₉)_Two, (C_TwoH _Five)_ThreeC
Si (CH_Three) (On-C)₆H₁₃)_Two, (C_TwoH_Five)
_ThreeCSi (CH _Three) (On-C)₈H₁₇)_Two, (C_TwoH
_Five)_ThreeCSi (CH_Three) (On-C)_TenH_{twenty one})_Two, (C
_TwoH_Five)_ThreeCSi (C_TwoH_Five) (OC_TwoH_Five)_Two, (C
_TwoH_Five) _ThreeCSi (n-C_ThreeH₇) (OC_TwoH_Five)_Two,
(C_TwoH_Five)_ThreeCSi (i-C_ThreeH₇) (OC_TwoH_Five)
_Two, (C_TwoH_Five)_ThreeCSi (n-C_FourH₉) (OC_TwoH
_Five)_Two, (C_TwoH_Five)_ThreeCSi (i-C_FourH₉) (OC
_TwoH_Five)_Two, (C_TwoH_Five) _ThreeCSi (s-C_FourH₉)
(OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (t-C_FourH
₉) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (n-C
_FiveH₁₁) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (c
-C_FiveH₉) (OC_TwoH_Five)_Two, (C_TwoH_Five) _ThreeCSi
(N-C₆H₁₃) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeC
Si (c-C₆H₁₁) (OC_TwoH_Five)_Two, H (CH_Three)
_TwoC (CH_Three)_TwoCSi (CH_Three) (OC_TwoH_Five)_Two,
H (CH_Three)_TwoC (CH_Three)_TwoCSi (C_TwoH_Five) (O
C_TwoH_Five)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi
(N-C_ThreeH₇) (OC_TwoH_Five)_Two, H (CH_Three)_TwoC
(CH_Three)_TwoCSi (i-C_ThreeH₇) (OC
_TwoH_Five)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi (n
-C_FourH₉) (OC_TwoH_Five)_Two, H (CH_Three)_TwoC (C
H_Three)_TwoC (CH_Three) Si (On-C_ThreeH₇)_Two, H
(CH_Three)_TwoC (CH_Three)_TwoCSi (CH_Three) (O-i
-C_ThreeH₇)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi
(CH_Three) (On-C)_FourH₉)_Two, H (CH_Three)_TwoC
(CH_Three)_TwoCSi (C_TwoH_Five) (On-C)_ThreeH₇)
_Two, (CH_Three)_Two(C_TwoH _Five) CSi (CH_Three) (OC
_TwoH_Five)_Two, (CH_Three)_Two(C_TwoH_Five) CSi (C
H_Three) (On-C)_ThreeH₇)_Two, (CH_Three)_Two(C_TwoH
_Five) CSi (CH_Three) (On-C)_FourH₉)_Two, (CH
_Three)_Two(C_TwoH_Five) CSi (C_TwoH_Five) (On-C)_Four
H₉)_Two, (CH_Three)_ThreeCSi (OC_TwoH_Five)_Three, (C
H_Three)_ThreeCSi (On-C_ThreeH₇)_Three, (CH_Three)_Three
CSi (OiC_ThreeH₇)_Three, (CH_Three)_ThreeCSi
(On-C_FourH₉)_Three, (CH_Three)_ThreeCSi (O-i
-C_FourH₉) _Three, (CH_Three)_ThreeCSi (OtC_FourH
₉)_Three, (CH_Three)_ThreeCSi (On-C₆H₁₂)_Three,
(CH_Three)_ThreeCSi (On-C₈H₁₇)_Three, (C
H_Three)_ThreeCSi (On-C_TenH_{twenty one})_Three, (CH_Three)_Two
(C_TwoH_Five) CSi (OC_TwoH_Five) _Three, (CH_Three)
_Two(C_TwoH_Five) CSi (On-C)_ThreeH₇)_Three, (CH
_Three)_Two(C_TwoH_Five) CSi (OiC_ThreeH₇)_Three,
(CH_Three)_Two(C_TwoH_Five) CSi (On-C)_FourH₉)
_Three, (CH_Three)_Two(C_TwoH_Five) CSi (OiC_FourH
₉) _Three, (CH_Three)_Two(C_TwoH_Five) CSi (OtC)
_FourH₉)_Three, (CH_Three)_Two(C_TwoH_Five) CSi (On
-C₆H₁₂)_Three, (CH_Three)_Two(C_TwoH_Five) CSi (O
-N-C₈H₁₇)_Three, (CH_Three)_Two(C_TwoH_Five) CSi
(On-C_TenH_{twenty one}) _Three, (CH_Three) (C_TwoH_Five)_TwoC
Si (OC_TwoH_Five)_Three, (CH_Three) (C_TwoH_Five)_TwoCS
i (On-C_ThreeH₇)_Three, (CH_Three) (C_TwoH_Five)_Two
CSi (OiC_ThreeH₇)_Three, (CH_Three) (C
_TwoH_Five)_TwoCSi (On-C_FourH₉)_Three, (CH_Three)
(C_TwoH_Five)_TwoCSi (OiC_FourH₉)_Three, (CH
_Three) (C_TwoH_Five)_TwoCSi (OtC_FourH₉)_Three,
(CH_Three) (C_TwoH_Five)_TwoCSi (On-C₆H₁₂)
_Three, (CH_Three) (C_TwoH_Five)_TwoCSi (On-C₈H
₁₇)_Three, (CH_Three) (C_TwoH_Five)_TwoCSi (On-C
_TenH_{twenty one})_Three, H (CH_Three)_TwoC (CH_Three)_TwoCSi (O
C_TwoH_Five)_Three, H (CH_Three)_TwoC (CH_Three)_TwoCSi
(On-C_ThreeH₇)_Three, H (CH_Three)_TwoC (CH_Three)
_TwoCSi (OiC_ThreeH₇) _Three, H (CH_Three)_TwoC
(CH_Three)_TwoCSi (On-C_FourH₉)_Three, H (CH
_Three)_TwoC (CH_Three)_TwoCSi (OiC_FourH₉)_Three,
H (CH_Three)_TwoC (CH_Three)_TwoCSi (OtC_FourH
₉)_Three, H (CH_Three)_TwoC (CH_Three)_TwoCSi (On
-C₆H₁₂)_Three, H (CH_Three)_TwoC (CH_Three)_TwoCSi
(On-C₈H₁₇)_Three, H (CH_Three)_TwoC (CH_Three)
_TwoCSi (On-C_TenH_{twenty one})_Three, (CH_Three)_ThreeCSi
(CH_Three) (OC_TwoH_Five) (On-C)_ThreeH₇), (C
H_Three)_ThreeCSi (CH_Three) (OC_TwoH_Five) (On-C)
_FourH₉), (CH_Three)_ThreeCSi (CH _Three) (OC
_ThreeH₆) (On-C)₈H₁₇),

[0031]

Embedded image

And the like. Component (A5) Organoaluminum Compound The organoaluminum compound (component (A)
5)), R ¹⁶ _3-s AlX _s or R ¹⁷
_3-t Al (OR ¹⁸ ) (where R ¹⁶ and R ¹⁷ are a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, R ¹⁸ is a hydrocarbon group, X is halogen, s and t represents 0 ≦ s <3 and 0 <t <3, respectively.) Specifically, (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and tri-n-decylaluminum; Alkyl aluminum halides such as chloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride; And alkylaluminum alkoxides.

The organoaluminum compound component (component (A5)) of (a) to (d) may be a mixture of a plurality of compounds of the formula. 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.

Among these, an embodiment using a trialkylaluminum is preferred. Component (A) Production of Solid Catalyst Component for α-Olefin Polymerization Component (A) is obtained by bringing each component constituting component (A) into contact with component (A1) in a stepwise or temporary manner, and intermediate and / or Alternatively, it can be produced by finally washing with an organic solvent such as a hydrocarbon solvent or a halogenated hydrocarbon solvent. Preferably, washing is not performed in the middle of the contact between the components.

In this case, a solid product containing titanium, magnesium, halogen and an electron donor as essential components is first prepared, and a halogen-containing silicon compound, a vinylsilane compound, a silicon compound of the above general formula and an organoaluminum compound component are prepared. Can be simultaneously or sequentially contacted (a so-called four-step method). At this time,
The order of contact is arbitrary as long as the effects of the present invention are recognized, and two or more components may be mixed first and brought into contact. The combination of components at the time of mixing is arbitrary as long as the effects of the present invention can be obtained. Preferably, the contact of the organoaluminum compound component with component (A1) is after the contact of the halogen-containing silicon compound. More preferably, component (A1) is added to component (A2), component (A3), component (A
A preferred method is to make contact in the order of 4) and component (A5).

The conditions for contacting the components constituting the component (A) can be any conditions as long as the effects of the present invention are recognized, but generally the following conditions are preferred. The contact temperature is about −50 to 200 ° C., preferably 0 to 150 ° C.
It is. 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 preferred. The amount of the titanium compound to be used is preferably in the range of 0.0001 to 1000, more preferably 0.001 to 100, and still more preferably 0.01 to 1000 in terms of molar ratio with respect to the amount of the magnesium compound to be used. It is within the range of 10. When a compound for that purpose is used as a halogen source, the amount of the compound to be used may be 0.01 in a molar ratio with respect to the amount of magnesium to be used regardless of whether or not the titanium compound and / or the magnesium compound contains halogen. ~ 100
The value is preferably in the range of 0, and preferably in the range of 0.1 to 100. The amount of the silicon compound used as the component (A2) is 0.01 to 1,000, preferably 0.1 to 100, in terms of the atomic ratio of silicon to the titanium component (silicon / titanium) constituting the component (A). .

When the vinylsilane compound is used, the amount thereof is preferably in the range of 0.001 to 1000, and more preferably 0.01 to 100 in terms of molar ratio to the titanium component constituting the component (A). is there. When aluminum is used, the amount thereof is preferably in the range of 0.001 to 100, more preferably 0.01 to 1, in terms of molar ratio with respect to the amount of the magnesium compound. The amount of the electron donor used is 0.001 to 10 in a molar ratio with respect to the amount of the magnesium compound.
, And preferably in the range of 0.01 to 5. The component (A) used in the present invention is used as a component which has undergone a prepolymerization step comprising contacting and polymerizing an organoaluminum compound component and a vinyl group-containing compound such as an olefin, a diene compound, and styrene. Can also. Specific examples of 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, 1-eicosene and the like, and specific 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, tra
ns-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-
There are divinylbenzene, o-divinylbenzene, dicyclopentadiene and the like. Specific examples of styrenes include styrene, α-methylstyrene, allylbenzene,
Chlorstyrene and the like.

The reaction conditions of the titanium component and the above-mentioned 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 0.001 to 100 g, preferably 0.1 to 100 g per gram of the titanium solid component.
It is in the range of 1 to 50 grams, more preferably 0.5 to 10 grams. The reaction temperature during the prepolymerization is -150 to 1
It is 50 degreeC, Preferably it is -10-100 degreeC, More preferably, it is 0-75 degreeC. Then, “main polymerization”, that is, α
-A polymerization temperature lower than the polymerization temperature at the time of the polymerization of the olefin is preferred. In general, the reaction is preferably performed with stirring, and at that time, an inert solvent such as n-hexane or n-heptane may be present.

(2) Component (B) Organoaluminum Compound The organoaluminum compound component (component) used in the present invention
As a specific example of (B)), R¹⁶ _3-sAlX_sOr R
¹⁷ _3-tAl (OR¹⁸) (Where R¹⁶And R ¹⁷Is carbon
A hydrocarbon group of formulas 1 to 20 or a hydrogen atom,¹⁸Is
A hydrocarbon group, X is halogen, and s and t are
0 ≦ s <3 and 0 <t <3, respectively. )
There is something. Specifically, (a) trimethylaluminum
Aluminum, triethyl aluminum, triisobutyl aluminum
, Tri-n-hexylaluminum, tri-n-o
Octyl aluminum, tri-n-decyl aluminum
Which trialkyl aluminum, (b) diethyl aluminum
Monochloride, diisobutylaluminum mono
Chloride, ethyl aluminum sesquichloride,
Alkyl aluminum such as chill aluminum dichloride
Um halide, (C) diethyl aluminum hydride
And diisobutylaluminum hydride
Kill aluminum hydride, (d) diethyl aluminum
Num ethoxide, diethylaluminum phenoxide
Such as alkyl aluminum alkoxides
You.

The organoaluminum compounds (component (B)) of (a) to (d) may be a mixture of a plurality of compounds of the formula. 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 proportion of the titanium component in the organoaluminum compound component (B) and the solid catalyst 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.

[Α-Olefin Polymerization] The α-olefin polymerization of the present invention is applied to slurry polymerization using a hydrocarbon solvent, liquid-phase solventless polymerization using substantially no solvent, or gas-phase polymerization. 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 is
Any method such as continuous polymerization, batch polymerization or multi-stage polymerization may be used. The polymerization temperature is usually about 30 to 200 ° C., preferably 50 to 150 ° C. At that 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 ¹⁹ —CH ＝ CH ₂ (where R ¹⁹ is a hydrocarbon group having 1 to 20 carbon atoms and has a branched group. ). Specifically, there are α-olefins such as propylene, butene-1, pentene-1 and hexene-1,4-methylpentene-1. In addition to homopolymerization of these α-olefins, copolymerization with monomers (eg, ethylene, α-olefins, dienes, styrenes, etc.) copolymerizable with α-olefins can also be performed. These copolymerizable monomers can be used up to 15% by weight in random copolymerization and up to 50% by weight in block copolymerization.

[0044]

【Example】

Example 1 [Production of component (A)] In a flask sufficiently purged with nitrogen,
2000 ml of dehydrated and deoxygenated n-heptane are introduced, then 2.6 mol of MgCl ₂ , Ti
5.2 mol of (On-C ₄ H ₉ ) ₄ was introduced and reacted at 95 ° C. for 2 hours. After the reaction, lower the temperature to 40 ° C,
Then, 320 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.

Next, into a flask sufficiently purged with nitrogen,
4000 ml of n-heptane purified in the same manner as above was introduced, and 1.46 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 2.62 mol of SiCl ₄ was mixed with 25 ml of n-heptane, and the mixture was added at 30 ° C., 3
It was introduced into the flask in 0 minutes and reacted at 70 ° C. for 3 hours. After the completion of the reaction, the resultant was washed with n-heptane. Then n-
0.1 ml of phthalic acid chloride in 25 ml of heptane
Five moles were mixed, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After the completion of the reaction, the resultant was washed with n-heptane. Next, 11.4 mol of TiCl ₄ was introduced and reacted at 110 ° C. for 3 hours. After completion of the reaction, the solid was washed with n-heptane to obtain a solid component (A1) for producing the component (A). The titanium content of this solid component was 2.0% by weight.

Next, 200 ml of n-heptane purified in the same manner as above was introduced into a flask sufficiently purged with nitrogen, and 4 g of the solid component (A1) synthesized above was introduced, and SiCl ₄₀ was used as component (A2). 0.035 mol was introduced and reacted at 90 ° C. for 2 hours. After the reaction, (CH ₂ ＣＨCH) Si (CH ₃ ) is further added as a component (A3).
₃ 0.006 mol, as component (A4) (t-C
_{4 H 9) (CH 3)} Si (OCH 3) 2 0.003 mol of component (A5) as _{Al (C 2 H 5) 3} 0.01
Six moles were sequentially introduced and 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 1.8% by weight.

[Polymerization of propylene] 500 ml of sufficiently dehydrated and deoxygenated n-heptane and triethylaluminum as the component (B) were placed in a 1.5 liter stainless steel autoclave having a stirring and temperature control device. 100 milligrams and 15 milligrams of component (A) prepared above, followed by 300 milligrams of hydrogen
Milliliter was introduced, and the temperature was raised and the polymerization pressure was increased to 5 kg /
Propylene was polymerized under the conditions of cm ² G, polymerization temperature = 75 ° C., and polymerization time = 2 hours. After completion of the polymerization, the obtained polymer slurry was separated by filtration, and the polymer was dried. The result is 329.5 grams of polymer,
This amount is expressed as (a). The filtrate yielded 1.0 gram of polymer, this amount being designated as (b). Therefore, the yield of the polymer (a) per 1 g of the solid catalyst component (component (A)) (hereinafter, abbreviated as polymerization activity) is 21,970.
(G / g), and the ratio of the filtrate-soluble component (b) to the total polymer yield (a + b) (hereinafter abbreviated as attack rate) was 0.3 (% by weight). The obtained polymer (a) had MFR = 10.0 (g / 10 min), polymer bulk density = 0.44 (g / cc), and polymer density =
0.9078 (g / cc). Table 1 shows the polymerization results.
Shown in

[0048] Example -2 in the preparation of Ingredient preparation of (A)] Component Example -1 (A), as component _{(A4) (t-C 4} H 9) (n-C
Except that ₃ H ₇ ) Si (OCH ₃ ) ₂ was used, the polymerization was performed in exactly the same manner, and polymerization was performed in exactly the same manner. As a result, the polymerization activity was 22,630 (g / g), and the attack rate was 0.4.
(% By weight). Further, the obtained polymer (a)
Is MFR = 5.0 (g / 10 min), polymer bulk density =
0.44 (g / cc), polymer density = 0.9084
(G / cc). The polymerization results are shown in Table 1.

Example 3 [Production of component (A)]
(CH3) as component (A3)_TwoCH) _TwoSi (C
H_Three)_TwoThe procedure was exactly the same except that
Performed similarly. As a result, the polymerization activity was 22340 (g / g).
g), and the attack rate was 0.4 (% by weight).
The obtained polymer (a) had an MFR of 16.3.
(G / 10 min), polymer bulk density = 0.45 (g / c)
c), the polymer density = 0.9082 (g / cc)
Was. The polymerization results are shown in Table 1.

[0050] In preparation of component (A) of Example -4 [Production of Component (A)] in Example 1, as a component _{(A4) (C 5 H 9} ) 2 Si (OC
H ₃₎ By same method to except using _2, polymerization was also conducted in the same manner. As a result, the polymerization activity was 20110 (g / g).
g), and the attack rate was 0.5 (% by weight).
The obtained polymer (a) had an MFR of 14.3.
(G / 10 min), polymer bulk density = 0.42 (g / c)
c), the polymer density was 0.9078 (g / cc). The polymerization results are shown in Table 1.

Example 5 [Production of Component (A)] In a flask sufficiently purged with nitrogen,
100 ml of dehydrated and deoxygenated toluene was introduced, and then 10 g of Mg (OEt) ₂ was introduced to form a suspended state. Next, 20 ml of TiCl ₄ was introduced, the temperature was raised to 90 ° C., and di-n-butyl phthalate 2.5
Milliliter was introduced, the temperature was further raised to 110 ° C., and the reaction was performed for 3 hours. After the completion of the reaction, the resultant was washed with toluene. Next, 20 ml of TiCl ₄ and 100 ml of toluene were introduced and reacted at 110 ° C. for 2 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane to obtain a solid component for producing the component (A). Its titanium content was 2.6% by weight.

Next, into a flask sufficiently purged with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced, 5 g of the solid component synthesized above was introduced, 4.0 ml of SiCl ₄ was introduced as component (A2), and the temperature was raised to 90 ° C. After reacting for an hour, (CH ₂ ＣＨCH) Si (CH ₃ ) is successively used as the component (A3).
₃ 1.2 ml and (t-C _{4
H 9) (CH 3) Si} (OC 2 H 5) 2 1.2 milliliters and component (A5) as _{Al (C 2 H 5) 3} 1.
7 grams were introduced and 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). This had a titanium content of 1.8% by weight.

[Polymerization Polymerization] Propylene polymerization was carried out under exactly the same polymerization conditions as in Example 1 except that 67 ml of hydrogen was used. As a result, the polymerization activity was 16,800 (g / g), and the attack rate was 0.8.
(% By weight). Further, the obtained polymer (a)
Is MFR = 4.9 (g / 10 min), polymer density =
0.9045 (g / cc). Table 2 shows the polymerization results.
Shown in

Comparative Example-1 In the production of component (A) of Example-1, component (A2)
Except that SiCl ₄ was not used.
The polymerization was carried out in exactly the same way. As a result, the polymerization activity was 130
80 (g / g) and the attack rate is 0.6 (% by weight)
Met. Further, the obtained polymer (a) has an MFR =
21.5 (g / 10 minutes), polymer bulk density = 0.44
(G / cc), polymer density = 0.9078 (g / c)
c). The polymerization results are shown in Table 1.

Comparative Example 2 In the production of the component (A) in Example 1, the component (A3)
(CH ₂ ＣＨCH) Si (CH ₃ ) ₃ was not used, and polymerization was performed in the same manner. As a result, the polymerization activity was 8470 (g / g), and the attack rate was 0.5 (% by weight). Further, the obtained polymer (a) had an MFR of 22.3 (g / 10 minutes), a polymer bulk density of 0.45 (g / cc), and a polymer density of 0.2.
9075 (g / cc). The polymerization results are shown in Table 1.

Comparative Example-3 In the production of component (A) in Example 1, component (A2)
After the reaction, do exactly the same except for washing thoroughly,
The polymerization was carried out in exactly the same way. As a result, the polymerization activity was 147.
50 (g / g) and the attack rate is 0.5 (% by weight)
Met. Further, the obtained polymer (a) has an MFR =
21.0 (g / 10 min), polymer bulk density = 0.42
(G / cc), polymer density = 0.9076 (g / c)
c). The polymerization results are shown in Table 1.

Comparative Example-4 In the production of the component (A) of Example-5, the component (A2)
Except that SiCl ₄ was not used.
Propylene polymerization was carried out under exactly the same polymerization conditions as in Example-5. As a result, the polymerization activity was 10330 (g / g), and the attack rate was 1.2 (% by weight). Further, the obtained polymer (a) had an MFR of 8.8 (g / 10
Min), and the polymer density was 0.9045 (g / cc). The polymerization results are shown in Table-2.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

Industrial Applicability The present invention provides a solid catalyst component for α-olefin polymerization having extremely high catalytic activity and a catalyst using the same, and it is possible to obtain an α-olefin polymer in an extremely high yield. . Furthermore, since the catalyst activity is extremely high, it is possible to provide a high-quality α-olefin polymer by a non-extraction and non-demineralization process that does not require removal of a catalyst residue composed of a transition metal compound and an organometallic compound. It is.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping an understanding of the present invention.

Claims (7)

[Claims] 1. An α-olefin polymerization solid catalyst component obtained by contacting the following components (A1), (A2), (A3), (A4) and (A5). Component (A1): a solid component containing titanium, magnesium, halogen and an electron donor as essential components (however, the electron donor excludes the silicon compound of the component (A4)) Component (A2): In the following general formula: The halogen-containing silicon compound represented by the general formula R ¹ _m SiX _4-m (where R ¹ is a hydrogen atom, a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, X is a halogen, and m is 0 ≦ m.
<4) Component (A3): a vinylsilane compound (however, excluding a silicon compound having an alkoxy group) Component (A4): a silicon compound represented by the following general formula: R ² R ³ _3-n Si ( OR ⁴ ) _n (where R ² is a saturated aliphatic hydrocarbon group, R ³ is a saturated or unsaturated aliphatic hydrocarbon group or a hetero atom-containing hydrocarbon group, R ⁴ is a hydrocarbon group, and n is 1 ≦ n ≦ 3) Component (A5): Organoaluminum Compound 2. The component (A1), component (A2), component (A3), component (A4) without washing the contact intermediate.
The solid catalyst component for α-olefin polymerization according to claim 1, wherein each component is brought into contact by adding each of the components and the component (A5). 3. Component (A1), component (A2), component (A)
3. The solid catalyst component for .alpha.-olefin polymerization according to claim 1, wherein component (A4) and component (A5) are brought into contact by sequentially adding them in this order. 4. The component (A1) wherein the electron donor is at least one compound selected from the group consisting of phthalic acid diester compounds, acetic acid cellosolve ester compounds, phthalic acid dihalide compounds and diether compounds. 5. The solid catalyst component for α-olefin polymerization according to item 1. 5. The solid catalyst component for α-olefin polymerization according to claim 1, wherein the silicon compound as the component (A4) is a compound represented by the following general formula. R ⁵ R ³ _3-n Si (OR ⁴ ) _n (where R ⁵ is a carbon atom adjacent to a silicon atom, that is, an aliphatic hydrocarbon group having a tertiary carbon atom at the α-position carbon atom; ³ is a saturated or unsaturated aliphatic hydrocarbon group or a hetero atom-containing hydrocarbon group, R ⁴ is a hydrocarbon group, n
Is 1 ≦ n ≦ 3. ) 6. An α-olefin polymerization catalyst comprising a combination of the solid catalyst component for α-olefin polymerization according to claim 1 and the following component (B). Component (B): organoaluminum compound 7. A method for polymerizing an α-olefin, comprising polymerizing or copolymerizing an α-olefin using the α-olefin polymerization catalyst according to claim 6.