JP2001151816A - Propylene polymer and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing for propylene polymer excellent in molding properties, having a high CXS (content of xylene soluble part) without increasing stickiness. SOLUTION: This method manufactures a propylene polymer satisfying following properties of (1)-(6). (1) MFR of 0.1-1,000 (g/10 min) measured at 230 deg.C under 2.16 kg load. (2) CXS (xylene soluble part at 25 deg.C) of 0.5-10.0 wt.% (3) BHS (content of boiling hexane soluble part) of <=1.5 wt.% in the case of MFR=0.1-10 (g/10 min) and <=2.5 wt.% in the case of MFR>=10 (g/10 min). (4) main endothermic peak (Tm) of 153-165 deg.C measured by differential scanning calorimetry(DSC). (5) the MFR measured at 230 deg.C under 2.16 kg load and the ME measured at 190 deg.C, using an orifice of 1.0 mm satisfy the general formula ME>-0.26XlogMFR+1.55. (6) a titanium residue content included in the polymer <=2.0 wt.ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a propylene-based polymer. More specifically, the present invention relates to a propylene-based polymer having low stickiness and excellent heat resistance and moldability.

[0002]

2. Description of the Related Art Conventionally, a propylene polymer obtained using a magnesium-supported Ziegler-Natta catalyst generally has a narrower molecular weight distribution than a propylene polymer obtained using a conventional titanium trichloride catalyst. It is known. Therefore, the fluidity of the propylene-based polymer at the time of melting is poor, and there remains a problem in moldability.

[0003] Therefore, in the prior art, means for broadening the molecular weight distribution by a specific polymerization method has been often adopted. For example, there is a method in which two or more polymerization tanks are used, a plurality of propylene-based polymers having different molecular weights are produced, and these are mixed to obtain a propylene-based polymer having a wide molecular weight distribution.

However, in order to obtain a propylene-based polymer having a target molecular weight distribution by this method, it is often necessary to reduce the capacity of each polymerization tank, which leads to an increase in production cost. There were many. Therefore, a technique for obtaining a propylene-based polymer having a desired molecular weight distribution in a single polymerization tank has been desired.

In some prior arts, there has been proposed a magnesium-supported Ziegler-Natta catalyst for obtaining a propylene-based polymer having a wide molecular weight distribution without using a plurality of polymerization tanks. For example, Japanese Patent Application Laid-Open No. 3-770
No. 3, JP-A-2-170803, JP-A-4-1360
No. 06 and JP-A-4-239008, a propylene-based polymer having a wide molecular weight distribution using a magnesium-supporting Ziegler-Natta catalyst component, using two or more types of electron donors added at the time of polymerization. The manufacturing method is described. However, as far as the present inventor knows, these seem to have a problem in activity and the like, and there is a situation where further improvement is desired.

[0006] Japanese Patent Application Laid-Open No. 10-7727,
JP-A-168127 describes that a wide molecular weight distribution can be obtained by combining a magnesium-supported Ziegler-Natta catalyst component with a special electron-donating compound. However, in these techniques, the amount of xylene solubles at 23 ° C. (CXS)
Is described as 5% by weight.

On the other hand, in recent years, in the field of film molding and the like, the speed of molding has been increasing. Under such circumstances, a propylene-based polymer having a high CXS content exceeding 5% by weight is required.

By the way, generally, when CXS is increased with a magnesium-supporting Ziegler-Natta catalyst component, stickiness generally increases gradually. Even if the CXS increases, the stickiness also increases at the same time, which leads to deterioration in moldability and quality. Therefore, there is a need for a technique for increasing CXS without increasing stickiness.

Further, as described above, it is well known that a wide molecular weight distribution can generally be obtained by using a titanium trichloride-based catalyst. However, titanium trichloride-based catalysts have lower activity than magnesium-supported Ziegler-Natta catalysts, and therefore generally require removal of catalyst residues from the polymer.

In addition, it is not impossible to construct a process that does not remove catalyst residues by using a titanium trichloride catalyst under conditions of a high monomer concentration, as in so-called propylene bulk polymerization. The catalyst residue in the polymer is larger than when a magnesium-supported Ziegler-Natta catalyst is used, and has problems such as deterioration of the weather resistance of the product and generation of voids when the film is formed. are doing.

[0011]

The problem to be solved by the present invention is to overcome the above-mentioned problems and to provide a propylene-based polymer having excellent moldability and high CXS content without increasing stickiness. Is to provide.

[0012]

Means for Solving the Problems The present inventors have developed a propylene-based polymer having specific physical properties,
The present inventors have found that the above-mentioned problems can be solved, and have reached the present invention. That is, the present invention provides a propylene-based polymer having the following properties (1) to (6). (1) MFR measured at 230 ° C. under a load of 2.16 kg is 0.1 to 1000 (g / 10 min). (2) The xylene soluble content (CXS) at 25 ° C is 0.5 to 1
0.0 (% by weight). (3) Boiling n-hexane soluble matter (BHS)
= Less than 1.5 (% by weight) when 0.1 to 10 (g / 10 min), and less than 2.5 (% by weight) when MFR> 10 (g / 10 min). (4) The main endothermic peak temperature (Tm) measured by a differential scanning calorimeter (DSC) is 153 to 165 (° C.). (5) MFR measured at 230 ° C. under a load of 2.16 kg
(G / 10 min), 190 ° C., orifice diameter 1.0
The ME measured in (mm) satisfies the following general formula: ME> −0.26 × logMFR + 1.55. (6) Titanium residue contained in the polymer is 2.0 (weight p
pm). Further, the following component (A),
Provided is a method for producing a propylene-based polymer, characterized in that a propylene-based polymer is obtained by propylene-based bulk polymerization substantially containing propylene substantially in the presence of a catalyst obtained by combining (B) and (C). Things.

(A) titanium, magnesium, halogen,
A solid component containing an electron-donating compound as essential components, the general formula ^{(R 1) (R 2)} 3 - m Si (OR 3) m ( wherein, R ¹ is branched chain aliphatic hydrocarbon group or a cyclic an aliphatic hydrocarbon group, R ² is R ¹ the same or different hydrocarbon group or a hetero atom-containing hydrocarbon group, R ³
Is a hydrocarbon group having 2 or more carbon atoms, and m is 1 ≦ m ≦
A solid catalyst component obtained by contacting the solid catalyst component. (B) an organoaluminum compound. (C) the general formula ^{(R 6) (R 7)} 3 - n Si (OR 8) n ( wherein, R ⁶ is a branched chain aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group, R ⁷ is is identical to R ⁶ or a different hydrocarbon group or a hetero atom-containing hydrocarbon group, R ⁸
Is a hydrocarbon group having 1 to 12 carbon atoms, and n is
An organic silicon compound represented by the following formula: 1 ≦ n ≦ 3).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION (i) Propylene Polymer The propylene polymer of the present invention is a propylene homopolymer having specific physical properties or a propylene-based α-olefin having 2 or 4 to 12 carbon atoms. It is a copolymer with olefin.

Among them, a propylene homopolymer or a copolymer of propylene and ethylene is preferred. Particularly, a propylene homopolymer or an ethylene content of 5% by weight is preferred.
The following propylene / ethylene copolymers are preferred.

The propylene-based polymer of the present invention comprises 230
MFR measured under a load of 2.16 kg at 0.1 ° C.
000 (g / 10 min), preferably 0.1 to 50
0 (g / 10 min), and more preferably 0.
It is 3 to 200 (g / 10 min).

CXS (xylene soluble at 25 ° C.)
Is 0.5 to 10.0 (% by weight). CXS is 1
If the content exceeds 0.0% by weight, the rigidity of the molded article is significantly reduced, which is not preferable. Conversely, if CXS is less than 0.5% by weight, the film formability tends to be particularly poor, which is not preferable.

BHS (boiling n-hexane soluble matter)
Is when the MFR is 0.1 to 10 (g / 10 min).
5 (% by weight) and MFR> 10 (g / 10 mi
In the case of n), it is less than 2.5 (% by weight). If the BHS is higher than these specifications, not only the stickiness of the molded article becomes remarkable, which is not preferable, but also the particle fluidity is deteriorated in the polymerization process, which often causes a production trouble.

ME is one of the measures of the non-Newtonian property of a resin. Generally, the larger the value, the better the resin has good moldability. In the present invention, ME is represented by the general formula: ME> −0.26 × logMF
It is necessary to satisfy R + 1.55, and by satisfying the general formula, the moldability can be improved more than the propylene-based polymer obtained using a conventionally known magnesium-supported Ziegler-Natta catalyst. It becomes an excellent propylene-based polymer.

In the propylene polymer of the present invention, the main endothermic peak temperature of the melting curve obtained by a differential scanning calorimeter (DSC) is 153 to 165 (° C.). When the peak temperature exceeds 165 ° C., the crystallinity is too high and the moldability often deteriorates. If the peak temperature is lower than 153 ° C., the heat resistance is significantly reduced, and a quality problem occurs. In addition, a preferable peak temperature is 157 to 164.
(° C.), and more preferably 158 to 163.
(° C.).

In the propylene polymer of the present invention, the amount of titanium residue in the polymer is less than 2.0 (ppm by weight). If the titanium residue exceeds 2.0 ppm by weight, it is necessary to use a large amount of the additive in order to secure the weather resistance of the molded product, which is not preferable. The titanium residue in the polymer is a titanium residue derived from the catalyst used for the polymerization, and when an additive containing titanium such as titania is intentionally added, the titanium derived from the additive is used as the titanium residue. It goes without saying that it is not included in the titanium residue specified in the invention.

(Ii) Production The production of the propylene-based polymer of the present invention is optional as long as the propylene-based polymer specified by the present invention can be obtained. it can.

As a catalyst that can be used in the production of the present invention, a propylene polymerization catalyst generally comprising the following components can be mentioned. Here, “combined” does not mean that the components are only those exemplified, and does not exclude the purposeful coexistence of the fourth component.

(A) titanium, magnesium, halogen,
A solid component containing an electron-donating compound as essential components, the general formula ^{(R 1) (R 2)} 3 - m Si (OR 3) m ( wherein, R ¹ is branched chain aliphatic hydrocarbon group or a cyclic an aliphatic hydrocarbon group, R ² is R ¹ the same or different hydrocarbon group or a hetero atom-containing hydrocarbon group, R ³
Is a hydrocarbon group having 2 or more carbon atoms, and m is 1 ≦ m ≦
A solid catalyst component obtained by contacting the solid catalyst component. (B) an organoaluminum compound. (C) The general formula (R ⁴ ) _{4 - n} Si (OR ⁵ ) _n (where R ⁴
Is a hydrocarbon group, R ⁵ is a hydrocarbon group having 12 or less carbon atoms, and n is an organic silicon compound represented by 1 ≦ n ≦ 3, or a general formula (R ⁶ ) (R ⁷⁾ _{3 -
n} Si (OR ⁸ ) _n (where R ⁶ is a branched aliphatic hydrocarbon group or a cycloaliphatic hydrocarbon group, and R ⁷ is the same or different hydrocarbon group or heteroatom-containing hydrocarbon as R ⁶⁾ R ⁸ is a hydrocarbon group having 1 to 12 carbon atoms, and n represents a number satisfying 1 ≦ n ≦ 3).

(Iii) Solid catalyst component (A) The solid catalyst component (A) of the present invention is a contact product of a specific solid component and a specific silicon compound. Such solid catalyst component (A) of the present invention does not exclude the coexistence of other components that are suitable.

The solid component used in the present invention is titanium,
It is a solid component for stereoregular polymerization of propylene containing magnesium and halogen as essential components. Here, "contained as an essential component" means, in addition to titanium, magnesium, and halogen, does not exclude the coexistence of a suitable other element. It indicates that the compound may be present as any purposeful compound, and may also be present as being bonded to each other.

(Iv) Solid component The solid component itself containing titanium, magnesium and halogen is known. For example, JP-A-53-4
5688, JP-A-54-3894, JP-A-54-3
No. 1092, JP-A-54-39483, JP-A-54-394.
No. 94591, JP-A-54-118484, JP-A-5-118
4-131589, JP-A-55-75411, JP-A-55-90510, JP-A-55-90511, JP-A-55-127405, and JP-A-55-147507.
JP-A-55-155003, JP-A-56-186
09, JP-A-56-70005, JP-A-56-72
001, JP-A-56-86905, JP-A-56-9
0807, JP-A-56-155206, JP-A-57
-3803, JP-A-57-34103, JP-A-57-34103
-92007, JP-A-57-112003, JP-A-58-5309, JP-A-58-5310, and JP-A-5-5310.
8-5311, JP-A-58-8706, JP-A-58-8706
-27732, JP-A-58-32604, JP-A-5-32
8-32605, JP-A-58-67703, JP-A-58-117206, JP-A-58-127708,
JP-A-58-183708, JP-A-58-18070
9, JP-A-59-149905, JP-A-59-14
9906, JP-A-63-108008, JP-A-3-108
No. 72503, JP-A-7-258328, JP-A-8-
269125, JP-A-10-168142, JP-A-11-21309 and the like can be used.

Examples of the magnesium compound serving as a magnesium source used in the present invention include magnesium dihalide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, and magnesium carboxylate. be able to.

Of these, magnesium dihalide, dialkoxymagnesium, or a compound represented by the general formula: Mg
^{_{(OR 9) 2 - p X}} p ( where, R ⁹ is a hydrocarbon group, preferably of the order of 1 to 12 carbon atoms, X is a halogen, p is a number comprised 0 ≦ p ≦ 2 Is preferable.

Further, as the titanium compound serving as a titanium source, the general formula ^{_{Ti (OR 10) 4 - q}} X q (R 10 is a hydrocarbon group, preferably of the order of 1 to 10 carbon atoms, X
Represents a halogen, and q is 0 ≦ q ≦ 4).

As specific examples, TiCl ₄ , TiBr ₄ ,
Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , T
_{i (OC 2 H 5) 3} Cl, Ti (O-i-C 3 H 7) Cl 3,
_{Ti (O-n-C 4} H 9) Cl 3, Ti (O-n-C
_{4 H 9) 2 Cl 2,} Ti (OC 2 H 5) Br 3, Ti (OC 2 H
_{5) (O-n-C} 4 H 9) 2 Cl, Ti (O-n-C 4 H 9)
₃ Cl, Ti (OC ₆ H ₅ ) Cl ₃ , Ti (OiC
_{4 H 9) 2 Cl 2,} Ti (O-n-C 5 H 11) Cl 3, Ti
_{(O-n-C 6 H} 13) Cl 3, Ti (OC 2 H 5) 4, Ti
(On-C ₃ H ₇ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti
_{(O-i-C 4 H} 9) 4, Ti (O-n-C 6 H 13) 4, T
_{i (O-n-C 8} H 17) 4, Ti (OCH 2 CH (C
_{2 H 5) C 4 H 9} ) 4 , and the like.

Further, TiX_Four(Where X is halogen
), A molecular compound reacted with an electron donor described below
Can also be used as a titanium source. Such a molecule
Specific examples of the compound include TiCl_Four・ CH_ThreeCOC
_TwoH_Five, TiCl_Four・ CH_ThreeCO_TwoC_TwoH_Five, TiCl_Four・ C₆
H_FiveNO_Two, TiCl_Four・ CH_ThreeCOCl, TiCl_Four・ C₆
H_FiveCOCl, TiCl_Four・ C₆H_FiveCO_TwoC_TwoH_Five, TiC
l_Four・ C₆H_Five(CO_TwoC_TwoH_Five) _Two, TiCl_Four・ ClCOC
_TwoH_Five, TiCl_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, TiCl
_{4, Ti (O-n-} C 4 H 9) 4, Ti (O-n-C 4 H 9)
Cl ₃ and Ti (OC ₂ H ₅ ) Cl ₃ are preferred.

The halogen is usually supplied from the above-mentioned halides of magnesium and / or titanium, but may be other halogen sources, for example, aluminum halides such as AlCl ₃ or silicon such as SiCl ₄ . Halide, phosphorus halide such as PCl ₃ , PCl ₅ , tungsten halide such as WCl ₆ , MoC
It may be supplied from known halogenating agents such as halides of molybdenum l ₅ etc.. The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred.

In the production of the solid component used in the present invention, Al (OC ₂ H ₅ ) ₃ , Al
_{(O-i-C 3 H} 7) 3, Al (OCH 3) 2 aluminum compounds such as Cl, and _{B (OCH 3) 3, B} (OC
_{2 H 5) 3, B (} OC 6 H 5) use of other components of the boron compounds such as ₃ are possible, no problem is that they remain in the solid component as a component of aluminum and boron and the like.

Further, when producing this solid component,
It can also be prepared using an electron donor as an internal donor. Electron donors (internal donors) that can be used in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides,
Examples thereof include oxygen-containing electron donors such as acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, (a) methanol, ethanol, propanol, butanol, pentanol,
C1-C18 alcohols such as hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropylbenzyl alcohol, (b) phenol, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol, C6 to C25 phenols which may have an alkyl group such as naphthol, (c) acetone,
C3 to C15 ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; (d) C2 to C1 such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde;
5 aldehydes, (e) 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, cyclo Ethyl hexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, methyl toluate, ethyl toluate, Amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone, α-valerolactone,
Organic acid monoesters such as coumarin and phthalide, or diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate, ethylene carbonate, norbornanedi Enil-1,
2-dimethylcarboxylate, cyclopropane-1,
C2-C20 organic acid esters of organic acid polyvalent esters such as 2-dicarboxylic acid-n-hexyl and diethyl 1,1-cyclobutanedicarboxylate, (f) ethyl silicate, butyl silicate, phenyltriethoxy Inorganic acid esters such as silicate esters such as silane, provided that
The aforementioned general formula ^{(R 1) (R 2)} 3 - m Si (OR 3) a silicon compound represented by _m is excluded, (g) acetyl chloride, benzoyl chloride, chloride toluic acid, anisic acid chloride, phthaloyl chloride, C2 to C15 acid halides such as phthaloyl isochloride; C2 to C20 ethers such as (thi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; ) Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, (nu) methylamine,
Ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine,
Amines such as picoline and tetramethylethylenediamine; nitriles such as (ル) acetonitrile, benzonitrile and tolunitrile; (ヲ) 2- (ethoxymethyl)
-Ethyl benzoate, ethyl 2- (t-butoxymethyl) -benzoate, ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxy-2-s-butylpropionate, 3 Alkoxy esters such as ethyl-ethoxy-2-t-butylpropionate, (v) ethyl 2-benzoylbenzoate, ethyl 2- (4'-methylbenzoyl) benzoate,
Examples thereof include ketoester compounds such as ethyl 2-benzoyl-4,5-dimethylbenzoate. Two or more of these electron donors can be used.

Among these, preferred are organic acid ester compounds and acid halide compounds, and particularly preferred are phthalic acid diester compounds, cellosolve acetate compounds and phthalic dihalide compounds.

[0039] (v) in the silicon compound present invention for use in contact with the solid component, the silicon compound used in contact with a solid component described above has the general formula ^{(R 1) (R 2)} 3 - m Si
(OR ³ ) _m (where R ¹ is a branched aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group, and R ² is the same or different hydrocarbon group or hetero atom-containing hydrocarbon as R ¹ ) R ³ is a hydrocarbon group having 2 or more carbon atoms, and m represents a number satisfying 1 ≦ m ≦ 3).

The silicon compound may be a mixture of plural kinds of the silicon compounds represented by the above general formula. Here, when R ¹ is a branched aliphatic hydrocarbon group, it is preferable that R ¹ 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 ¹ 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, a tertiary carbon atom bonded to a silicon atom is preferable. When R ¹ is a branched hydrocarbon group, the number of carbon atoms is usually 3-20, preferably 4-1.
0. When R ¹ is a cyclic aliphatic hydrocarbon group, the number of carbon atoms is usually 4 to 20, preferably 5 to 10.

R ² is preferably a hydrocarbon group or a hetero atom-containing hydrocarbon group which is the same as or different from R ^1, and is a hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms or a hetero atom-containing hydrocarbon group. .

R ³ is a hydrocarbon group having 2 or more carbon atoms,
It is an aliphatic hydrocarbon group having 2 to 20, preferably 2 to 10, and more preferably 2 to 4 carbon atoms.

Specific examples of such silicon compounds are as follows. In the following formula, n represents normal,
i represents iso, s represents secondary, t represents tertiary, and c represents cyclo.

(CH_Three)_ThreeCSi (CH_Three) (OC
_TwoH_Five)_Two, (CH_Three)_ThreeCSi (CH_Three) (On-C)
_ThreeH₇)_Two, (CH_Three)_ThreeCSi (CH_Three) (OiC
_ThreeH₇)_Two, (CH_Three) _ThreeCSi (CH_Three) (On-C)
_FourH₉)_Two, (CH_Three)_ThreeCSi (CH_Three) (OiC
_FourH₉)_Two, (CH_Three)_ThreeCSi (CH_Three) (OtC
_FourH₉)_Two, (CH_Three)_ThreeCSi (CH_Three) (On-C)₆H
₁₃)_Two, (CH_Three)_ThreeCSi (CH_Three) (On-C)
₈H₁₇)_Two, (CH_Three)_ThreeCSi (CH_Three) (On-C)_Ten
H_{twenty one})_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (OC_TwoH_Five)_Two,
(CH_Three)_ThreeCSi (n-C_ThreeH₇) (OC_TwoH_Five)_Two, (C
H_Three)_ThreeCSi (i-C_ThreeH₇) (OC_TwoH_Five)_Two, (CH_Three)
_ThreeCSi (n-C_FourH ₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCS
i (i-C_FourH₉) (OC_TwoH_Five)_Two, (CH_Three) _ThreeCSi
(S-C_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (t
-C_FourH₉) (OC _TwoH_Five)_Two, (CH_Three)_ThreeCSi (n-C_Five
H₁₁) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (c-C
_FiveH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (n-C
₆H₁₃) (OC_TwoH_Five) _Two, (CH_Three)_ThreeCSi (c-C₆H
₁₁) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (C_TwoH _Five) (O
-N-C_ThreeH₇)_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (O-
i-C_ThreeH₇)_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (On
-C_FourH₉)_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (Oi-
C_FourH₉)_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (OsC_Four
H₉)_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)_Ten
H_{twenty one})_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇) (On-
C_ThreeH₇)_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇) (O-i
-C_ThreeH₇)_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇) (O-
n-C_FourH₉)_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇) (O
-Ic_FourH₉)_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇)
(OsC_FourH₉)_Two, (CH_Three)_ThreeCSi (i-C
_ThreeH₇) (OtC_FourH₉)_Two, (CH _Three)_ThreeCSi (i-
C_ThreeH₇) (On-C)₆H₁₃)_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)_ThreeC
Si (On-C_ThreeH₇) (OC_TwoH_Five)_Two, (CH_Three)_ThreeC
Si (OiC_ThreeH₇) (OC_TwoH_Five)_Two, (CH_Three)_ThreeC
Si (On-C_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeC
Si (OiC_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeC
Si (O-s-C_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeC
Si (OtC_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeC
Si (On-C_FiveH₁₁) (OC_TwoH_Five)_Two, (CH_Three)_ThreeC
Si (O-C-C_FiveH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeC
Si (On-C₆H₁₃) (OC_TwoH_Five)_Two, (CH_Three)_ThreeC
Si (O-C-C₆H₁₁) (OC_TwoH_Five)_Two, (I-C
_ThreeH₇)_TwoSi (OC_TwoH_Five)_Two, (I-C_FourH₉)_TwoSi (O
C_TwoH_Five)_Two, (S-C_FourH₉)_TwoSi (OC_TwoH_Five)_Two, (N
eo-C_FiveH₁₁)_TwoSi (OC_TwoH_Five)_Two, (C-C_FiveH₉)_Two
Si (OC_TwoH_Five)_Two, (C-C_FiveH₉)_TwoSi (On-C
_ThreeH₇)_Two, (C-C_FiveH₉)_TwoSi (On-C_FourH₉)_Two,
(C-C_FiveH₉)_TwoSi (On-C_FiveH₁₁)_Two, (C-C_Five
H₉)_TwoSi (On-C₈H₁₇)_Two, (C-C₆H₁₁)_TwoS
i (OC_TwoH_Five)_Two, (C-C₆H₁₁)_TwoSi (On-C_Three
H₇)_Two, (C-C₆H₁₁)_TwoSi (On-C_FourH₉)_Two,
(C-C₆H₁₁)_TwoSi (On-C_FiveH₁₁)_Two, (C-C
₆H₁₁)_TwoSi (On-C₈H₁₇)_Two, (C-C₆H₁₁)
Si (CH_Three) (OC_TwoH_Five)_Two, (C-C₆H₁₁) Si
(CH_Three) (On-C)_ThreeH₇)_Two, (C-C₆H_{1 1}) Si
(CH_Three) (On-C)_FourH₉)_Two, (C-C₆H₁₁) 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) (Oi-
C_ThreeH₇)_Two, (C_TwoH_Five)_ThreeCSi (CH_Three) (On-C)_Four
H₉)_Two, (C_TwoH_Five)_ThreeCSi (CH_Three) (OiC
_FourH₉)_Two, (C_TwoH_Five)_ThreeCSi (CH_Three) (OtC_FourH
₉)_Two, (C_TwoH_Five)_ThreeCSi (CH_Three) (On-C)
₆H₁₃)_Two, (C_TwoH_Five)_ThreeCSi (CH_Three) (On-C)₈
H₁₇)_Two, (C_TwoH_Five)_ThreeCSi (CH_Three) (On-C)_Ten
H_{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_FourH₉) (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)_ThreeCSi (c-C₆H₁₁) (OC_TwoH_Five)
_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi (CH_Three) (OC_Two
H_Five)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi (C_TwoH_Five)
(OC_TwoH_Five)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi (n
-C_ThreeH₇) (OC_TwoH_Five)_Two, H (CH_Three)_TwoC (CH_Three)_Two
CSi (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 (CH_Three)_TwoC (CH_Three) Si (On-C_Three
H₇)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi (CH_Three)
(OiC_ThreeH₇)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCS
i (CH_Three) (On-C)_FourH₉)_Two, H (CH_Three)_TwoC (C
H_Three)_TwoCSi (C_TwoH_Five) (On-C)_ThreeH₇)_Two, (C
H_Three)_Two(C_TwoH_Five) CSi (CH_Three) (OC_TwoH_Five)_Two, (C
H_Three) _Two(C_TwoH_Five) CSi (CH_Three) (On-C)
_ThreeH₇)_Two, (CH_Three)_Two(C_TwoH_Five) CSi (CH_Three) (O-
n-C_FourH₉)_Two, (CH_Three)_Two(C_TwoH_Five) CSi (C
_TwoH_Five) (On-C)_FourH₉)_Two, (CH_Three)_ThreeCSi (OC_Two
H_Five)_Three, (CH_Three)_ThreeCSi (On-C_ThreeH₇)_Three, (C
H_Three)_ThreeCSi (OiC_ThreeH₇)_Three, (CH_Three)_ThreeCSi
(On-C_FourH₉)_Three, (CH_Three)_ThreeCSi (OiC_Four
H₉)_Three, (CH_Three)_ThreeCSi (OtC_FourH₉)_Three, (C
H_Three)_ThreeCSi (On-C₆H₁₂)_Three, (CH_Three)_ThreeCSi
(On-C₈H₁₇)_Three, (CH_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)_ThreeH
₇)_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_FourH₉)_Three,
(CH_Three)_Two(C_TwoH_Five) CSi (OtC)_FourH₉)_Three,
(CH_Three)_Two(C_TwoH_Five) CSi (On-C)₆H₁₂)_Three,
(CH_Three)_Two(C_TwoH_Five) CSi (On-C)₈H₁₇)_Three,
(CH_Three)_Two(C_TwoH_Five) CSi (On-C)_TenH_{twenty one})_Three,
(CH_Three) (C_TwoH_Five)_TwoCSi (OC_TwoH_Five)_Three, (CH_Three)
(C_TwoH_Five)_TwoCSi (On-C_ThreeH₇)_Three, (CH_Three)
(C_TwoH_Five)_TwoCSi (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-C₆H₁₃)_Three, (CH_Three)
(C_TwoH_Five)_TwoCSi (On-C₈H₁₇)_Three, (CH_Three)
(C_TwoH_Five)_TwoCSi (On-C_TenH_{twenty one})_Three, H (C
H_Three)_TwoC (CH_Three)_TwoCSi (OC_TwoH_Five)_Three, H (CH_Three)
_TwoC (CH_Three)_TwoCSi (On-C_ThreeH₇)_Three, H (C
H_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 (Ot-
C_FourH₉)_Three, H (CH_Three)_TwoC (CH_Three)_TwoCSi (On
-C₆H₁₂)_Three, H (CH_Three)_TwoC (CH_Three)_TwoCSi (O-
n-C₈H₁₇)_Three, H (CH_Three)_TwoC (CH_Three)_TwoCSi (O
-N-C_TenH_{twenty one})_Three, (CH_Three)_ThreeCSi (CH_Three) (OC
_TwoH_Five) (On-C)_ThreeH₇), (CH_Three)_ThreeCSi (C
H_Three) (OC_TwoH_Five) (On-C)_FourH₉), (CH_Three)_ThreeC
Si (CH_Three) (OC_TwoH_Five) (On-C)₈H₁₇), Si
(OC_TwoH_Five)_Three,

[0046]

Embedded image

[0047]

Embedded image And the like.

(Vi) Optional Components Used for Contact with Solid Components Further, in the production of the solid catalyst component (A) of the present invention, optional components may be included as necessary in addition to the above essential components. This is as described above. 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 groups). , An alkoxy group (preferably an alkoxy group having 1 to 12 carbon atoms), and the like.

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 (CH 3) 3, CH 2 = C
H—SiCl ₃ , CH ₂ ＣＨCH—SiCl ₂ (CH ₃ ), C
_{H 2 = CH-SiCl (CH} 3) 2, CH 2 = CH-SiH
_{(Cl) (CH 3),} CH 2 = CH-Si (C 2 H 5) 3,
_{CH 2 = CH-SiCl (C} 2 H 5) 2, CH 2 = CH-S
iCl ₂ (C ₂ H ₅ ), CH ₂ ＣＨCH—Si (CH ₃ ) ₂ (C
_{2 H 5), CH 2 =} CH-Si (CH 3) (C 2 H 5) 2, C
_{H 2 = CH-Si (n} -C 4 H 9), CH 2 = CH-Si
(C ₆ H ₅ ) ₃ , CH ₂ ＣＨCH—Si (CH ₃ ) (C
_{6 H 5) 2, CH 2} = CH-Si (CH 3) 2 (C 6 H 5), C
H ₂ ＣＨCH (CH ₃ ) ₂ (C ₆ H ₄ CH ₃ ), (CH ₂ ＣC
_{H) (CH 3) 2 Si} -O-Si (CH 3) 2 (CH = CH
₂ ), (CH ₂ ＣＨCH) ₂ SiH ₂ , (CH ₂ ＣＨCH) ₂ Si
Cl ₂ , (CH ₂ ＣＨCH) ₂ Si (CH ₃ ) ₂ , (CH ₂ ＣC
H) ₂ Si (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 organic metal compounds of metals of Groups I to III of the periodic table as optional components. The organometallic compounds of Group I to Group III metals used in the present invention 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. The remaining valence (if any) of the metal of the organometallic compound in which at least one of the valences is filled with an organic group is a hydrogen atom, a halogen atom, a hydrocarbyloxy group (the hydrocarbyl group has 1 to 1 carbon atoms). About 20, preferably 1
6) or the metal via an oxygen atom (specifically, -O-Al (C
H ₃ )-) Others are satisfied.

Specific examples of such organometallic compounds include (a) methyllithium, n-butyllithium,
An organolithium compound such as tert-butyllithium, (b)
Organic magnesium compounds such as butylethylmagnesium, dibutylmagnesium, hexylethylmagnesium, butylmagnesium chloride, tertiarybutylmagnesium bromide, etc. (c) Organic zinc compounds such as diethylzinc, dibutylzinc, etc., (d) trimethylaluminum, triethylaluminum, triisobutyl Aluminum, tri-n-hexylaluminum, diethylaluminum chloride,
There are organoaluminum compounds such as diethylaluminum hydride, diethylaluminum ethoxide, ethylaluminum sesquichloride, ethylaluminum dichloride and methylalumoxane. Of these, organoaluminum compounds are particularly preferred.

The optional components (a) vinylsilane compound and (ii) organometallic compound 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.

(Vii) Production of solid catalyst component (A) The solid catalyst component (A) is prepared by stepwise or temporarily mixing the components constituting the solid catalyst component (A) or, if necessary, the above-mentioned optional components. In contact with each other, in the middle and / or
Alternatively, it can be produced by finally washing with an organic solvent such as a hydrocarbon solvent or a halogenated hydrocarbon solvent.

In this case, a solid product containing titanium, magnesium and halogen as essential components is first produced, and the solid product is brought into contact with a silicon compound of the above general formula (a two-step method). In the process of producing a solid product containing magnesium, magnesium and halogen as essential components, it is possible to produce the component (A) at once by using the silicon compound already present (in other words, a one-step method). The preferred scheme is the former.

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 the following conditions are generally preferred. The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° 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 solid catalyst 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 to be used is preferably in the range of 0.0001 to 1000, more preferably 0.01 to 10, in terms of molar ratio with respect to the amount of the magnesium compound to be used. When a compound for that purpose is used as a halogen source, the amount of the compound may be used regardless of whether or not the titanium compound and / or the magnesium compound contains halogen.
0.0 in molar ratio to the amount of magnesium used
It is preferably in the range of 1 to 1000, preferably 0.1 to 10
It is within the range of 0.

[0057] In preparing the solid catalyst component (A), the general formula of contacting the solid component ^{(R 1) (R 2)} 3 - m Si (O
The amount of the silicon compound represented by R ³ ) _m is 0.01 to 1000, preferably 0.1 to 100 in terms of the atomic ratio of silicon to the titanium component (silicon / titanium) constituting the solid catalyst component (A). Is within the range.

When the vinylsilane compound is used, its amount is preferably in the range of 0.001 to 1000 in terms of molar ratio to the titanium component constituting the solid catalyst component (A).
Preferably it is in the range of 0.01-100. When the aluminum and boron compounds are used, the amount thereof is preferably in the range of 0.001 to 100 in terms of a molar ratio with respect to the amount of the magnesium compound, and is preferably 0.1 to 100.
It is in the range of 01-1. When the electron donor is used, its use amount is preferably in the range of 0.001 to 10, more preferably 0.01 to 5, in terms of molar ratio with respect to the use amount of the magnesium compound.

[0059] The solid catalyst component (A), the solid component and the general formula ^{(R 1) (R 2)} 3 - m Si (OR 3) a silicon compound represented by _m (hereinafter, (A) to (F )
(Hereinafter simply referred to as a silicon compound), and using other components such as an electron donor, if necessary, for example, by the following production method. (A) A method in which a magnesium halide is brought into contact with an electron donor, a titanium-containing compound, and a silicon compound as required. (B) A method in which alumina or magnesia is treated with a phosphorus halide compound, and is contacted with a magnesium halide, an electron donor, a silicon compound, and a titanium halide-containing compound. (C) washing a reaction product obtained by contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound with an inert organic solvent; Then, a method of contacting with a silicon compound.

The polymer silicon compound has a general formula:-(Si (H) (R ¹¹ ) O) _r- (where R ¹¹ is a hydrocarbon group having about 1 to 10 carbon atoms;
Shows 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
7,9-pentamethylcyclopentasiloxane is preferred. (D) dissolving a magnesium compound with a titanium tetraalkoxide and / or an electron donor to form a solid component precipitated with a halogenating agent or a titanium halogen compound;
A method in which a silicon compound and a titanium compound are brought into contact with each other or 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, contacting it with an electron donor as necessary, and then contacting a silicon compound and, if necessary, a titanium compound. Or contacting each separately. (F) A method of contacting an alkoxymagnesium compound with a halogenating agent and / or a titanium compound or a silicon compound in the presence or absence of an electron donor or separately.

Among these production methods, (A)
(C), (d) and (f) are preferred. In general formula ^{(R 1) (R 2)} 3 - in contacting step with _m Si (OR ³⁾ _m and a solid component, either coexist sulfonate compound, or, before or after the contacting step, sulfonic acid Esters may be added.

The solid catalyst component (A) may be used during and / or at the end of its preparation in an inert organic solvent, such as an aliphatic or aromatic hydrocarbon solvent (for example hexane, heptane,
Washing with toluene, cyclohexane, etc.) or a halogenated hydrocarbon solvent (eg, n-butyl chloride, 1,2-dichloroethylene, carbon tetrachloride chlorobenzene, etc.) is possible.

The solid catalyst component (A) used in the present invention comprises:
It can also be used as one that has undergone a prepolymerization step of contacting and polymerizing a vinyl group-containing compound such as an olefin, a diene compound, or styrene.
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. These can also be used as a mixture.

The reaction conditions between 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 amount of the pre-polymerized 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
The temperature is 50 ° C, preferably 0 to 100 ° C. Further, a polymerization temperature lower than the polymerization temperature at the time of “main polymerization”, that is, the polymerization of α-olefin is preferable. In general, the reaction is preferably carried out with stirring, in which case n-hexane, n-hexane,
An inert solvent such as heptane can also be present.

(Viii) Organoaluminum compound
(B) Component of organoaluminum compound (B) used in the present invention
As an example, R¹² _{Three - s}AlX_sOr R¹³ _{Three - t}Al (O
R¹⁴)_t(Where R¹²And R¹³Has 1 to 20 carbon atoms
A hydrocarbon group or a hydrogen atom;¹⁴Is a hydrocarbon radical
X is halogen, and s and t are each 0 ≦
s <3, 0 <t <3).
is there.

Specifically, (a) trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, (b) diethylaluminum monochloride, diisobutylaluminum monochloride , Alkyl aluminum halides such as ethyl aluminum sesquichloride, ethyl aluminum dichloride,
(C) Alkyl aluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; and (d) alkylaluminum alkoxides such as diethylaluminum ethoxide and diethylaluminum phenoxide.

A plurality of these organoaluminum compounds (a) to (d) can 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. In addition, an alumoxane such as methylalumoxane, ethylalumoxane, isobutylalumoxane, etc. can be used in combination with the organoaluminum compounds (a) to (d).

[0068] (ix) an organic silicon compound (C) silicon compound (C) used in the present invention is, (R ^{₄₎ 4} _{- n}
Si (OR ⁵ ) _n (where R ⁴ is a hydrocarbon group, and R ⁵
Is a hydrocarbon group having 1 to 12 carbon atoms, and n is
1 ≦ n ≦ 3) is an organosilicon compound represented by the general formula: Here, R ⁴ is a hydrocarbon group having 1 to 30, preferably 1 to 20 carbon atoms. R ⁵ has 1 to 1 carbon atoms
12, preferably 1 to 10 hydrocarbon groups.

Specific examples of the silicon compound that can be used in the present invention are as follows. In the following formula, n represents normal, i represents iso, s represents secondary, t represents tertiary, and c represents cyclo.

Si (OCH_Three)_Four, Si (OC_TwoH_Five)_Four,
Si (On-C_ThreeH₇)_Four, Si (OiC_ThreeH₇)_Four,
Si (On-C_FourH₉)_Four, Si (OiC_FourH₉)_Four,
Si (O-s-C_FourH₉)_Four, Si (OtC_FourH₉)_Four,
Si (On-C₆H₁₃)_Four, CH_ThreeSi (OCH_Three)_Three,
CH_ThreeSi (OC_TwoH_Five)_Three, C_TwoH_FiveSi (OCH_Three)_Three, C
_TwoH_FiveSi (OC_TwoH_Five)_Three, CH_Two= CH-Si (OC
H_Three)_Three, CH_Two= CH-Si (OC_TwoH_Five)_Three, N-C_ThreeH₇
Si (OCH_Three)_Three, N-C_ThreeH₇Si (OC_TwoH_Five)_Three, I
-C_ThreeH₇Si (OCH_Three)_Three, I-C_ThreeH₇Si (OC
_TwoH_Five)_Three, N-C_FourH₉Si (OCH_Three)_Three, N-C_FourH₉S
i (OC_TwoH_Five)_Three, N-C₈H₁₇Si (OCH_Three)_Three, N-
C₈H₁₇Si (OC_TwoH_Five)_Three, C₆H_FiveSi (OCH_Three)_Three,
C₆H_FiveSi (OC _TwoH_Five)_Three, (CH_Three)_TwoSi (OCH_Three)
_Two, (CH_Three)_TwoSi (OC_TwoH_Five)_Two, (CH _Three)_TwoSi (O
-N-C_ThreeH₇)_Two, (CH_Three)_TwoSi (OiC
_ThreeH₇)_Two, (CH_Three)_TwoSi (On-C_FourH₉)_Two, (CH
_Three)_TwoSi (OiC_FourH₉)_Two, (CH_Three) _TwoSi (O-
s-C_FourH₉)_Two, (CH_Three)_TwoSi (OtC_FourH₉)_Two,
(C_TwoH_Five)_TwoSi (OCH_Three)_Two, (C_TwoH_Five)_TwoSi (OC
_TwoH_Five)_Two, (CH_Two= CH)_TwoSi (OCH_Three)_Two, (CH_Two
= CH)_TwoSi (OC_TwoH_Five)_Two, (N-C_ThreeH₇)_TwoSi
(OCH _Three)_Two, (N-C_ThreeH₇)_TwoSi (OC_TwoH_Five)_Two,
(I-C_ThreeH₇)_TwoSi (OCH_Three)_Two, (I-C_ThreeH₇)_TwoS
i (OC_TwoH_Five)_Two, (C₆H_Five)_TwoSi (OCH_Three)_Two, (C
₆H _Five)_TwoSi (OC_TwoH_Five)_Two, (CH_Three)_ThreeSi (OC
H_Three), (CH_Three)_ThreeSi (OC_TwoH_Five), (CH_Three)_ThreeSi
(On-C_ThreeH₇), (CH_Three)_ThreeSi (OiC
_ThreeH₇), (CH_Three)_ThreeSi (On-C_FourH₉), (C
H_Three)_ThreeSi (OiC_FourH₉), (CH_Three)_ThreeSi (O-
s-C_FourH₉), (CH_Three)_ThreeSi (OtC_FourH₉),
(C _TwoH_Five)_ThreeSi (OCH_Three), (C_TwoH_Five)_ThreeSi (OC_Two
H_Five), (C_TwoH_Five)_ThreeSi (On-C_ThreeH₇), (C
_TwoH_Five)_ThreeSi (OiC_ThreeH₇), (C_TwoH_Five)_ThreeSi (O
-N-C_FourH₉), (C_TwoH_Five)_ThreeSi (OiC
_FourH₉), (C_TwoH_Five)_ThreeSi (O-s-C_FourH₉), (C_TwoH
_Five)_ThreeSi (OtC_FourH₉), (C₆H_Five)_ThreeSi (OC
H_Three), (C₆H_Five)_ThreeSi (OC_TwoH_Five), (CH_Three)_ThreeCS
i (CH_Three) (OCH_Three)_Two, (CH_Three)_ThreeCSi (CH_Three)
(OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (CH_Three) (On-
C_ThreeH₇)_Two, (CH_Three)_ThreeCSi (CH_Three) (OiC_Three
H₇)_Two, (CH_Three)_ThreeCSi (CH_Three) (On-C)
_FourH₉)_Two, (CH_Three)_ThreeCSi (CH_Three) (OiC
_FourH₉)_Two, (CH_Three)_ThreeCSi (CH_Three) (OtC
_FourH₉)_Two, (CH_Three)_ThreeCSi (CH_Three) (On-C)₆H
₁₃)_Two, (CH_Three)_ThreeCSi (CH_Three) (On-C)
₈H₁₇)_Two, (CH_Three)_ThreeCSi (CH_Three) (On-C)_Ten
H_{twenty one})_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (OCH_Three)_Two,
(CH_Three)_ThreeCSi (C_TwoH_Five) (OC_TwoH_Five)_Two, (CH_Three)
_ThreeCSi (n-C_ThreeH₇) (OCH_Three)_Two, (CH_Three)_ThreeCS
i (n-C_ThreeH₇) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi
(I-C_ThreeH₇) (OCH_Three)_Two, (CH_Three)_ThreeCSi (i-
C_ThreeH₇) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (n-C_FourH
₉) (OCH_Three) _Two, (CH_Three)_ThreeCSi (n-C_FourH₉)
(OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (i-C _FourH₉) (O
CH_Three)_Two, (CH_Three)_ThreeCSi (i-C_FourH₉) (OC
_TwoH_Five)_Two, (CH_Three)_ThreeCSi (s-C_FourH₉) (OCH_Three)
_Two, (CH_Three)_ThreeCSi (s-C_FourH₉) (OC_TwoH_Five)_Two,
(CH_Three)_ThreeCSi (t-C_FourH₉) (OCH_Three)_Two, (CH
_Three)_ThreeCSi (t-C_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_Three
CSi (n-C_FiveH₁₁) (OCH_Three)_Two, (CH_Three)_ThreeCS
i (n-C_FiveH₁₁) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi
(C-C _FiveH₉) (OCH_Three)_Two, (CH_Three)_ThreeCSi (c-
C_FiveH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (n-C₆H
₁₃) (OCH_Three)_Two, (CH_Three)_ThreeCSi (n-C₆H₁₃)
(OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (c-C₆H₁₁) (O
CH_Three)_Two, (CH_Three)_ThreeCSi (c-C₆H₁₁) (OC_TwoH
_Five)_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (On-C)_ThreeH₇)
_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (OiC_ThreeH₇)_Two,
(CH_Three)_ThreeCSi (C_TwoH_Five) (On-C)_FourH₉)_Two,
(CH_Three)_ThreeCSi (C_TwoH_Five) (OiC_FourH ₉)_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)₆H₁₃)_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) (Oi-
C_ThreeH₇)_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇) (On
-C_FourH₉)_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇) (O-
i-C_FourH₉)_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇) (O
-S-C_FourH₉)_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₇)
(OtC_FourH₉)_Two, (CH_Three)_ThreeCSi (i-C
_ThreeH₇) (On-C)₆H₁₃)_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
(OCH_Three) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (On
-C_ThreeH₇) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (O-i
-C_ThreeH₇) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (On
-C_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (O-i
-C_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (O-s
-C_FourH₉) (OC_TwoH_Five)_Two, (CH _Three)_ThreeCSi (Ot
-C_FourH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (On
-C_FiveH₁₁) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (O-c
-C_FiveH₉) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (On
-C₆H₁₃) (OC_TwoH_Five)_Two, (CH_Three)_ThreeCSi (O-c
-C₆H₁₁) (OC_TwoH_Five)_Two, (I-C_ThreeH₇)_TwoSi (O
CH_Three)_Two, (I-C_ThreeH₇)_TwoSi (OC_TwoH_Five)_Two, (I-
C_FourH₉)_TwoSi (OCH_Three)_Two, (I-C_FourH₉)_TwoSi (O
C_TwoH_Five)_Two, (S-C_FourH₉)_TwoSi (OCH_Three)_Two, (S-
C_FourH₉)_TwoSi (OC_TwoH_Five)_Two, (Neo-C_FiveH₁₁)_TwoS
i (OCH_Three)_Two, (Neo-C_FiveH₁₁)_TwoSi (OC
_TwoH_Five)_Two, (C-C_FiveH₉)_TwoSi (OCH_Three)_Two, (C-C
_FiveH₉)_TwoSi (OC_TwoH_Five)_Two, (C-C_FiveH₉)_TwoSi (O
-N-C_ThreeH₇)_Two, (C-C_FiveH₉)_TwoSi (On-C_Four
H₉)_Two, (C-C_FiveH₉)_TwoSi (On-C_FiveH₁₁)_Two,
(C-C _FiveH₉)_TwoSi (On-C₈H₁₇)_Two, (C-C₆
H₁₁)_TwoSi (OCH_Three)_Two, (C-C₆H₁₁)_TwoSi (O
C_TwoH_Five)_Two, (C-C₆H₁₁)_TwoSi (On-C
_ThreeH₇)_Two, (C-C₆H₁₁)_TwoSi (On-C_FourH₉)_Two,
(C-C₆H₁₁)_TwoSi (On-C_FiveH₁₁)_Two, (C-C
₆H₁₁)_TwoSi (On-C₈H₁₇)_Two, (C-C₆H₁₁)
Si (CH_Three) (OCH_Three)_Two, (C-C₆H₁₁) Si (C
H_Three) (OC_TwoH_Five)_Two, (C-C₆H₁₁) Si (CH_Three)
(On-C_ThreeH₇)_Two, (C-C₆H₁₁) Si (CH_Three)
(On-C_FourH₉)_Two, (C-C₆H₁₁) Si (CH_Three)
(On-C_FiveH₁₁)_Two, (C-C₆H₁₁) Si (CH_Three)
(On-C₈H₁₇)_Two, (C-C₆H₁₁) Si (C
_TwoH_Five) (OCH_Three)_Two, (C-C₆H₁₁) Si (C_TwoH_Five)
(OC_TwoH_Five)_Two, (C-C₆H₁₁) Si (n-C_FourH₉)
(OCH_Three)_Two, (C-C₆H₁₁) Si (n-C_FourH₉)
(OC_TwoH_Five)_Two, (C-C₆H₁₁) Si (c-C_FiveH₉)
(OCH_Three)_Two, (C-C₆H₁₁) Si (c-C_FiveH₉)
(OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (CH_Three) (OC
H_Three)_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) (OiC_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)_ThreeCSi (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) (OCH_Three)_Two, (C
_TwoH_Five)_ThreeCSi (C_TwoH_Five) (OC_TwoH_Five)_Two, (C_TwoH_Five)_Three
CSi (n-C_ThreeH₇) (OCH_Three)_Two, (C_TwoH_Five) _ThreeCS
i (n-C_ThreeH₇) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi
(I-C_ThreeH₇) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (i
-C_ThreeH₇) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (n-C
_FourH₉) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (n-C
_FourH₉) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (i-C
_FourH₉) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (i-C
_FourH₉) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (s-C
_FourH₉) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (s-C
_FourH₉) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (t-C
_FourH ₉) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (t-C
_FourH₉) (OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (n-C_FiveH
₁₁) (OCH_Three)_Two, (C_TwoH_Five)_ThreeCSi (n-C_FiveH₁₁)
(OC_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (c-C_FiveH₉) (O
CH_Three)_Two, (C_TwoH_Five)_ThreeCSi (c-C_FiveH₉) (OC_TwoH
_Five)_Two, (C_TwoH_Five)_ThreeCSi (n-C₆H₁₃) (OC
H_Three)_Two, (C_TwoH_Five)_ThreeCSi (n-C₆H₁₃) (OC
_TwoH_Five)_Two, (C_TwoH_Five)_ThreeCSi (c-C₆H₁₁) (OC
H_Three)_Two, (C_TwoH_Five)_ThreeCSi (c-C₆H₁₁) (OC
_TwoH_Five)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi (CH_Three)
(OCH_Three)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi (CH
_Three) (OC_TwoH_Five)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi
(C_TwoH_Five) (OCH_Three)_Two, H (CH_Three)_TwoC (CH_Three)_TwoC
Si (C_TwoH_Five) (OC_TwoH_Five)_Two, H (CH_Three)_TwoC (C
H_Three)_TwoCSi (n-C_ThreeH₇) (OCH_Three)_Two, H (C
H_Three)_TwoC (CH_Three)_TwoCSi (n-C_ThreeH₇) (OC_TwoH_Five)
_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi (i-C_ThreeH₇)
(OCH_Three)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi (i-
C_ThreeH₇) (OC_TwoH_Five)_Two, H (CH_Three)_TwoC (CH_Three)_TwoC
Si (n-C_FourH₉) (OCH_Three)_Two, H (CH_Three)_TwoC (C
H_Three)_TwoCSi (n-C_FourH₉) (OC_TwoH_Five)_Two, H (C
H_Three)_TwoC (CH_Three)_TwoC (CH_Three) Si (On-C
_ThreeH₇)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCSi (CH_Three)
(OiC_ThreeH₇)_Two, H (CH_Three)_TwoC (CH_Three)_TwoCS
i (CH_Three) (On-C)_FourH₉)_Two, H (CH_Three)_TwoC (C
H_Three)_TwoCSi (C_TwoH_Five) (On-C)_ThreeH₇)_Two, (C
H_Three)_Two(C_TwoH_Five) CSi (CH_Three) (OCH_Three) _Two, (C
H_Three)_Two(C_TwoH_Five) CSi (CH_Three) (OC_TwoH_Five)_Two, (C
H_Three)_Two(C_TwoH_Five) CSi (CH_Three) (On-C)
_ThreeH₇)_Two, (CH_Three)_Two(C_TwoH_Five) CSi (CH_Three) (O-
n-C_FourH₉)_Two, (CH_Three)_Two(C_TwoH_Five) CSi (C
_TwoH_Five) (On-C)_FourH₉)_Two, (CH_Three)_ThreeCSi (OC
H_Three)_Three, (CH_Three)_ThreeCSi (OC_TwoH_Five)_Three, (CH_Three)_Three
CSi (On-C_ThreeH₇)_Three, (CH_Three)_ThreeCSi (O-
i-C_ThreeH₇)_Three, (CH_Three)_ThreeCSi (On-C
_FourH₉)_Three, (CH_Three)_ThreeCSi (OiC_FourH₉)_Three, (C
H_Three)_ThreeCSi (OtC_FourH₉)_Three, (CH_Three)_ThreeCSi
(On-C₆H₁₂)_Three, (CH_Three)_ThreeCSi (On-C
₈H₁₇)_Three, (CH_Three)_ThreeCSi (On-C_{1 0}H_{twenty one})_Three,
(CH_Three)_Two(C_TwoH_Five) CSi (OCH_Three)_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) C
Si (OiC_FourH₉)_Three, (CH_Three)_Two(C_TwoH_Five) CS
i (OtC_FourH₉)_Three, (CH_Three)_Two(C_TwoH_Five) CSi
(On-C₆H₁₂)_Three, (CH_Three)_Two(C_TwoH_Five) CSi
(On-C₈H₁₇)_Three, (CH_Three)_Two(C_TwoH_Five) CSi
(On-C_TenH_{twenty one})_Three, (CH_Three) (C_TwoH_Five)_TwoCSi
(OCH_Three)_Three, (CH_Three) (C_TwoH_Five)_TwoCSi (OC
_TwoH_Five)_Three, (CH_Three) (C_TwoH_Five)_TwoCSi (On-C_ThreeH
₇)_Three, (CH_Three) (C_TwoH_Five)_TwoCSi (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-C₆H₁₃)_Three,
(CH_Three) (C_TwoH_Five)_TwoCSi (On-C₈H₁₇)_Three,
(CH_Three) (C_TwoH_Five)_TwoCSi (On-C_TenH_{twenty one})_Three,
H (CH_Three)_TwoC (CH_Three)_TwoCSi (OCH_Three)_Three, H (C
H_Three)_TwoC (CH_Three)_TwoCSi (OC_TwoH_Five)_Three, H (CH_Three)
_TwoC (CH_Three)_TwoCSi (On-C_ThreeH₇)_Three, H (C
H_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 (Ot-
C_FourH₉)_Three, H (CH_Three)_TwoC (CH_Three)_TwoCSi (On
-C₆H₁₂)_Three, H (CH_Three)_TwoC (CH_Three)_TwoCSi (O-
n-C₈H₁₇)_Three, H (CH_Three)_TwoC (CH_Three)_TwoCSi (O
-N-C_TenH_{twenty one})_Three, (CH_Three)_ThreeCSi (CH_Three) (OC
H_Three) (On-C)_ThreeH₇), (CH_Three)_ThreeCSi (CH_Three)
(OC_TwoH_Five) (On-C)_ThreeH₇), (CH_Three)_ThreeCSi
(CH_Three) (OC_TwoH_Five) (On-C)_FourH₉), (CH_Three)
_ThreeCSi (CH_Three) (OC_TwoH_Five) (On-C)₈H₁₇),
Si (OCH_Three)_Three,

[0071]

Embedded image

[0072]

Embedded image And the like. These can be used as a mixture.

[0073] Further, component (C) ^{is, (R 6) (R 7} ) 3 - n
Si (OR ⁸ ) _n (where R ⁶ is a branched aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group, and R ⁷ is the same or different hydrocarbon group or hetero atom-containing hydrocarbon as R ⁶ ) R ⁸ is a hydrocarbon group having 1 to 12 carbon atoms, and n represents a number satisfying 1 ≦ n ≦ 3). Among the organosilicon compounds listed above, those satisfying the above requirements can be appropriately selected and used. These may be used as a mixture.

In the propylene polymerization of the present invention, the amounts of the components (A), (B) and (C) can be arbitrary as long as the effects of the present invention are recognized. Is preferably within the range. Component (B) is used in an amount of 0.1 to 1 with respect to propylene supplied to the reactor.
0000 (mol. Ppm), preferably 1 to 1000
(Mol. Ppm), more preferably 10 to 300.
(Mol. Ppm). In addition, component (C)
The amount of used is, based on propylene supplied to the reactor,
The range is 0.0000001 to 100 (mol. Ppm), preferably 0.000001 to 50 (mol. Ppm), and particularly preferably 0.00001 to 20 (mol. Pm).

(X) Polymerization of Propylene The polymerization method for producing the propylene-based polymer of the present invention may be any method as long as the target propylene-based polymer of the present invention can be obtained. For example, slurry polymerization using a hydrocarbon solvent, bulk polymerization using substantially no solvent, solution polymerization, gas phase polymerization, and the like can be mentioned. Among these, bulk polymerization is most preferred, in which high activity is obtained and high CXS is obtained relatively easily.

The polymerization is carried out by supplying an olefin, hydrogen, a transition metal catalyst component, an organoaluminum compound and, if necessary, an electron-donating compound to a polymerization tank. The polymerization can take any form such as continuous polymerization, batch polymerization, semi-batch polymerization and the like.

As the polymerization tank, any conventionally known polymerization tank can be used. That is, a tank-type polymerization tank, a loop-type polymerization tank, or the like can be used. The polymerization tanks may be used alone, or in series or in parallel.
Further, a polymerization tank and a classifier may be used in combination.

The olefin supplied to the polymerization tank is mainly propylene, but ethylene, 1-butene, 1-pentene, hexene, octene or the like may be used as a comonomer. Moreover, you may use these mixtures. In addition, an inert hydrocarbon compound such as methane, ethane, or propane may be contained in propylene or the comonomer. The olefin is generally used after being purified by dehydration using a molecular sieve or the like before being supplied to the polymerization tank.

In order to control the molecular weight of the olefin polymer, hydrogen may be used as an auxiliary. Hydrogen is usually subjected to purification such as dehydration and deoxygenation before being supplied to the polymerization tank. The supply amount of hydrogen is not particularly limited, and it is sufficient to supply an amount of hydrogen necessary to obtain a desired molecular weight according to the properties of the catalyst to be used. It is preferable to control the amount of supplied hydrogen by using both the actually measured value of the hydrogen supply rate by the flow meter and the actually measured value of the hydrogen concentration in the polymerization tank by the process gas chromatography.

In the present invention, the polymerization temperature, polymerization pressure, average residence time and the like are not particularly limited. These can be arbitrarily set depending on the capacity of the process, the performance of the catalyst, economic reasons, and the like. Generally, the polymerization temperature is about 20 to 200 ° C., preferably about 50 to 150 ° C., and the polymerization pressure is atmospheric pressure to about 300 kg / cm ² G, preferably atmospheric pressure to about 100 kg / cm ² G,
The average residence time is often about 0.1 to 10 hours, preferably about 0.2 to 6 hours.

[0081]

The following examples illustrate the invention more specifically.
This is for clarification. The present invention deviates from its gist.
Unless otherwise, this is not a limitation. What
In the following examples, Me, Et, Bu, and Ph are
Methyl, ethyl, n-butyl, phenyl, respectively
Represents a group. Further, m. r. Represents a molar ratio. Ma
DEP, TOL, TEA, TBEDMS, CMDM
S is diethyl phthalate, toluene,
Chill aluminum, t-BuEtSi (OMe) _Two,
Represents clohexylmethyldimethoxysilane. t-B
u represents a tertiary butyl group.

[MFR] MFR was measured according to JIS-K6758 using a melt indexer manufactured by Takara.

[CXS] CXS was measured by the following method. About 1 g of a polypropylene powder sample was precisely weighed in an eggplant-shaped flask, and 200 ml of xylene was added thereto, and the mixture was heated to boiling and completely dissolved. Thereafter, this was quenched in a water bath at 25 ° C., and the precipitated solid portion was filtered.
0 ml was evaporated to dryness in a platinum dish, further dried under reduced pressure, and weighed. CXS was calculated as the amount of xylene solubles in a polypropylene powder sample.

[BHS] BHS was measured by the following method. After about 2 g of a polypropylene powder sample was precisely weighed and transferred into a thimble, the thimble was set in an improved Soxhlet extractor. Extraction was performed for 3 hours while refluxing normal hexane. After completion of the extraction, the thimble was taken out of the extractor, and normal hexane was completely removed with a drier. Then, the amount of sample remaining in the thimble was precisely weighed. BH
S was calculated as a boiling normal hexane soluble content in a polypropylene powder sample.

[DSC] The main endothermic peak temperature was PERK.
It was determined by the following method using DSC-2 manufactured by IN-ELMER. A sample (about 5 mg) was melted at 200 ° C. for 3 minutes, and then cooled to 30 ° C. at a rate of 10 ° C./min.
The temperature was raised to 200 ° C. at 10 ° C./min to obtain a melting curve, and the main endothermic peak temperature (Tm) was determined.

[ME] ME was measured by the following method using a melt indexer manufactured by Takara. A polypropylene sample was prepared at 190 ° C. at an inner diameter of 1.0 mm and a length of 8.0.
When the extrusion speed was 0.1 g / min, the strand extruded from the orifice was quenched in ethanol when the extrusion speed was 0.1 g / min, and the ratio between the thickness of the solidified strand and the orifice diameter was defined as ME. .

[Titanium Residue] Titanium residue was measured by the following method. About 2 g of a polypropylene powder sample was pressed using a mold at a temperature of 190 ° C. and a pressure of 50 kg / cm ² G to prepare a pressed piece having a thickness of 1.5 (mm). In the press, the preheating time is 30 seconds,
The pressing time was 30 seconds. Fluorescent X
The sample was analyzed using an X-ray spectrometer, and titanium residues in the sample were quantified. Note that calibration of the X-ray fluorescence spectrometer was performed using a titanium standard sample prepared separately.

(Example 1) (1) Production of solid component [0101] A 10 component equipped with a stirring blade, a thermometer, a jacket, and a cooling coil was prepared.
In a 0 liter reactor, Mg (OEt)_Two： 30mol
And then Ti (OBu)_FourIs charged with Mg
(OEt)_TwoTi (OB)
u)_Four/Mg=0.60 (mr)
I do. Further, 19.2 kg of toluene was charged and stirred.
While the temperature was rising. After reacting at 139 ° C. for 3 hours, 13
The temperature is lowered to 0 ° C. and MeSi (OPh)_ThreeSolution of toluene
With Mg (OEt) previously charged_TwoTo the magnesium inside
On the other hand, MeSi (OPh)_Three/Mg=0.67 (m.
r. ). The torque used here
The amount of ene was 7.8 kg. 130 ° C after completion of addition
At room temperature for 2 hours, and then cooled to room temperature.
t) _FourWas added. Si (OEt)_FourThe amount of
Mg (OEt)_TwoS for magnesium in
i (OEt)_Four/Mg=0.056 (mr)
I did it.

Next, toluene was added to the obtained reaction mixture so that the magnesium concentration became 0.58 (mol / L · TOL). Further, diethyl phthalate was added to magnesium in Mg (OEt) ₂ previously charged so that DEP / Mg = 0.10 (mr). The resulting mixture was cooled to −10 ° C. with continued stirring, and TiCl ₄ was added dropwise over 2 hours to obtain a homogeneous solution. It should be noted that TiCl ₄ is used as compared to magnesium in Mg (OEt) ₂ previously charged,
Cl _{4 /} Mg was set to 4.0 (mr). After completion of TiCl ₄ addition, 0.5 ° C./m with stirring
The temperature was raised to 15 ° C. in, and kept at the same temperature for 1 hour. Next, the temperature was raised again to 50 ° C. at a rate of 0.5 ° C./min, and maintained at the same temperature for 1 hour. 118 ° C at 1 ° C / min
, And the treatment was performed at the same temperature for 1 hour.

After completion of the treatment, the stirring was stopped, the supernatant was removed, and the slurry was washed with toluene to a residual liquid ratio of 1/73 to obtain a slurry.

Next, toluene and TiCl ₄ were added to the obtained slurry at room temperature. Note that TiCl ₄
Indicates that TiCl ₄ / Mg (OEt) ₂ = 5.0 (m.p.) with respect to magnesium in Mg (OEt) ₂ previously charged.
r. ). Toluene is TiCl
_{4 The} concentration was adjusted to 2.0 (mol / L · TOL). The temperature of this slurry was increased while stirring, and
The reaction was performed at a temperature of 1 ° C. for 1 hour. After completion of the reaction, stop stirring,
After removing the supernatant, the residual liquid ratio was 1/15 with toluene.
The solid component was washed to be 0 to obtain a solid component slurry.

(2) Production of solid catalyst component (A) Of the solid components obtained in Example 1 (1), 400 g
Was transferred to another reactor having a stirring blade, a thermometer, and a cooling jacket, and diluted with normal hexane to a solid component concentration of 5.0 (g / l). While stirring the resulting slurry at 15 ° C., trimethylvinylsilane, TEA and TBMDES were added. Here, TBMDES indicates t-butylmethyldiethoxysilane, and t-butyl indicates a tertiary butyl group. In addition, TEA, trimethylvinylsilane, TBMD
The amount of ES added was 3.1 (mmol) and 0.2 (m) with respect to 1 g of the solid component in the solid catalyst component (A), respectively.
l), 0.2 (ml).

After the addition, stirring was continued for 15 minutes.
The temperature was maintained at 30 ° C. for 1 hour, and the temperature was further raised to 30 ° C., followed by stirring at the same temperature for 2 hours. Next, the temperature was again lowered to 15 ° C., and while maintaining the same temperature, 1.2 kg of propylene gas was fed into the gas phase of the reactor at a constant speed over 72 minutes to perform prepolymerization. After the feed was completed, the stirring was stopped to remove the supernatant, and then the solid was washed with normal hexane to obtain a slurry of the solid catalyst component (A). The residual liquid ratio was 1 /
It was set to 12. The obtained solid catalyst component (A) had 2.8 g of a propylene polymer per 1 g of the solid catalyst component (A).

(3) Polymerization of propylene Triethylaluminum: 2.7 m in an induction-stirring autoclave (capacity: 2 liters) at room temperature under a nitrogen stream.
mol and TBEDMS: 0.001 mmol. Then, after charging 750 g of liquid propylene,
Hydrogen was converted to a gaseous hydrogen concentration of 75 mol
1%. The temperature was raised to 75 ° C. with stirring, and when the temperature reached 75 ° C., 10.7 mg of the solid catalyst component (A) obtained in Example 1 (2) was used as the solid component amount contained in (A). The polymerization was started by the addition. After polymerization at 75 ° C. for 1 hour, excess propylene was purged to terminate the polymerization. The obtained propylene polymer is 463
g. When the obtained propylene polymer was analyzed, it was found that MFR = 1.6 (g / 10 min) and CXS
= 5.1 (% by weight), BHS = 0.5 (% by weight), Tm
= 160.1 (° C), ME = 1.574, Ti residue =
0.49 (ppm by weight).

[0095] (Example 2) (1) As shown in the polymerization Figure 2 propylene, stirred gas-phase polymerization tank 8 of the stirrer with liquid phase polymerization vessel 1,0.5M ³ having an inner volume of 0.4 m ³ Between, sedimentation hydraulic classifier 4, concentrator 3 (liquid cyclone),
And a classification system comprising a countercurrent pump 13 and
By a process incorporating a degassing system consisting of a double tube heat exchanger 5 and a fluidized flash tank 6, propylene
Continuous production of a homopolymer was performed.

Liquid propylene, hydrogen, TEA, and TBEDMS were continuously fed to the liquid phase polymerization tank 1. The feed amounts of liquefied propylene, TEA, and TBEDMS were 170 g / hr and 27.7 g / h, respectively.
r, 2.92 mg / hr, and hydrogen has a total pressure of 32.20 mg / hr.
Feeding was performed so as to be 5 kgf / cm ² G. Further, the solid catalyst component (A) obtained in Example 1 (2) was
0.41 g / hr as a solid component contained in (A)
It was fed so that. Further, the polymerization tank 1 was cooled such that the polymerization temperature became 75 ° C.

The slurry polymerized in this polymerization tank was fed to the hydraulic classifier 4 using the slurry pump 2 at a volume flow rate of about 12 m ³ / hr. From the lower part of the hydraulic classifier 4,
A slurry containing a relatively large amount of large-diameter particles was extracted, and the remaining slurry was supplied to the concentrator 3 from above the hydraulic classifier 4. From the upper part of the concentrator 3, a supernatant liquid containing almost no solid particles was taken out, and supplied to the lower part of the hydraulic classifier using the pump 13 as a countercurrent.

On the other hand, the slurry containing a relatively large amount of small-diameter particles extracted from the lower part of the concentrator 3 was circulated to the liquid-phase polymerization tank 1. The extraction rate of the slurry extracted from the lower part of the hydraulic classifier 4 was adjusted to be about 25 kg / hr as the polypropylene particles contained in the slurry. The average residence time of the polypropylene particles in the liquid phase polymerization tank 1 and the circulation line was 1.2 hours.

The slurry extracted from the lower part of the hydraulic classifier 4 was fed to the fluidized flash tank 6 via the double tube heat exchanger 5. In the fluidizing flash tank 6, the temperature in the tank was maintained at 70 ° C. while feeding heated propylene gas from below. The solid polypropylene particles obtained here were sent to the gas phase polymerization tank 8.

In order to enhance the mixing effect, CO was fed into the gas phase polymerization tank 8 provided with an auxiliary stirring blade to deactivate the catalyst. Then, the polypropylene polymer is
It was withdrawn from the lower part of the gas phase polymerization tank 8, sent to a fluidized drier 17 through a screw feeder 16, and dried at a temperature of 90 ° C. for an average residence time of 0.5 hours. Note that nitrogen was used for drying. The dried polypropylene polymer particles were sent to the hopper 18. Finally, a propylene homopolymer was taken out of the hopper as a product.

When the obtained propylene polymer was analyzed, MFR = 2.9 (g / 10 min) and CXS = 7.
0 (% by weight), BHS = 1.3 (% by weight), Tm = 16
0.3 (° C.), ME = 1.503, Ti residue = 0.31
(Ppm by weight).

Comparative Example 1 (1) Production of Solid Catalyst Component (A) Solid catalyst component (A) was prepared in the same manner as in Example 1 (2) except that TBEDMS was used instead of TBMDES.
Was manufactured. The obtained solid catalyst component (A) had 2.7 g of the propylene polymer per 1 g of the solid catalyst component (A).

(2) Polymerization of Propylene Propylene was polymerized in the same manner as in Example 1 (3) except that the solid catalyst component (A) obtained in Comparative Example 1 (1) was used. . The resulting propylene polymer is
It was 452 g. When the obtained propylene polymer was analyzed, MFR = 0.2 (g / 10 min),
CXS = 0.8 (% by weight), BHS = 0.8 (% by weight), Tm = 164.8 (° C.), ME = 1.520, T
i residue = 0.50 (weight ppm).

Comparative Example 2 (1) Polymerization of Propylene Propylene was produced in the same manner as in Example 2 (1) except that the solid catalyst component (A) obtained in Comparative Example 1 (1) was used. Was polymerized. When the obtained propylene polymer was analyzed, MFR = 0.4 (g / 10 min), C
XS = 0.9 (% by weight), BHS = 1.0 (% by weight),
Tm = 164.7 (° C), ME = 1.511, and Ti residue = 0.32 (ppm by weight).

Example 3 (1) Production of Component (A) 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then 0.4 mol of MgCl ₂ and Ti (OBu) 0.8 mol of 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 methylhydropolysiloxane (20
48 ml (Centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.

Then, the flask was 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. Then, as a silicon compound, t
1.6 ml of BuMeSi (OEt) ₂ was introduced, and 35
Contact for 2 hours at ° C. After the contact is completed, the component (A) is mainly washed with n-heptane and thoroughly washed with magnesium chloride.
I got The titanium content was 2.3 (% by weight).

(2) Polymerization of Propylene The solid catalyst component (A) produced in Example 3 (1) was used, and CMDMS was used instead of TBEDMS.
Polymerization of propylene was carried out in the same manner as in Example 1 (3) except that 01 mmol was used.

The amount of the obtained propylene polymer was 382 g. When the obtained propylene polymer was analyzed, MFR = 1.5 (g / 10 min) and CXS =
5.9 (% by weight), BHS = 0.5 (% by weight), Tm =
160.0 (° C.), ME = 1.570, Ti residue = 0.
64 (ppm by weight).

Example 4 (1) Polymerization of Propylene The solid catalyst component (A) was prepared in the same manner as in Example 3 (1) except that 0.01 mmol of TBMDES was used instead of TBEDMS. Propylene was polymerized in the same manner as in Example 1 (3). The amount of the obtained propylene polymer was 350 g. When the obtained propylene polymer was analyzed, MFR = 2.2 (g / 10
min), CXS = 3.8 (% by weight), BHS = 0.7
(% By weight), Tm = 160.1 (° C.), ME = 1.53
0, Ti residue = 0.70 (weight ppm).

[Brief description of the drawings]

FIG. 1 is a flowchart for assisting understanding of a catalyst suitable for producing a propylene-based polymer of the present invention.

FIG. 2 is a process flow diagram illustrating one embodiment of the invention.

[Explanation of symbols]

 1, liquid phase polymerization tank 2, slurry pump 3, concentration tank 4, liquid classifier 5, double tube heat exchanger 6, fluidized flash tank 7, gas blower 8, gas phase polymerization tank 9, circulation gas cooler 10 , Gas blower 11, heat exchanger 12, cyclone 13, pump 14, cyclone 15, hopper 16, screw feeder 17, fluid dryer 18, hopper 19, powder sampling line

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasuhiro Kashiwagi 3-10-10 Shiodori, Kurashiki-shi, Okayama Japan Polychem Corporation Process Development Center F-term (reference) 4J028 AA01A AB01A AC04A AC05A AC06A AC07A BA01A BA02B BB00A BB01B BC04A BC05A BC15B BC16B BC17B BC19B BC24B BC25B BC27B BC34A BC34B CA15A CA22A CA25A CB23A CB25A CB27A CB43A CB44A CB45A CB52A CB53A CB58A CB63A CB64A CB66A CB68A CB92A EA01 EB02 EB04 EB05 EB07 EB08 EB09 GA07 GA19 GA21 4J100 AA02Q AA03P AA04Q AA07Q AA16Q AA19Q CA01 CA04 DA22 DA40 DA42 FA18

Claims (4)

[Claims] 1. A propylene-based polymer which satisfies the following properties (1) to (6). (1) MFR measured at 230 ° C. under a load of 2.16 kg is 0.1 to 1000 (g / 10 min). (2) The xylene soluble content (CXS) at 25 ° C is 0.5 to 1
0.0 (% by weight). (3) Boiling n-hexane soluble matter (BHS)
= Less than 1.5 (% by weight) when 0.1 to 10 (g / 10 min), and less than 2.5 (% by weight) when MFR> 10 (g / 10 min). (4) The main endothermic peak temperature (Tm) measured by a differential scanning calorimeter (DSC) is 153 to 165 (° C.). (5) MFR measured at 230 ° C. under a load of 2.16 kg
(G / 10 min), 190 ° C., orifice diameter 1.0
The ME measured in (mm) satisfies the general formula: ME> −0.26 × logMFR + 1.55. (6) Titanium residue contained in the polymer is 2.0 (weight p
pm). 2. The propylene polymer according to claim 1, which is produced by propylene bulk polymerization using propylene itself as a medium. 3. A propylene bulk polymerization essentially comprising propylene in the presence of a catalyst comprising the following components (A), (B) and (C): Item 4. The propylene-based polymer according to item 1. (A) A solid component containing titanium, magnesium, halogen, and an electron donating compound as essential components has a general formula (R
^{_{1) (R 2) 3 -}} m Si (OR 3) m ( wherein, R ¹ is branched chain aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group,
R ² is a hydrocarbon group or a hetero atom-containing hydrocarbon group which is the same as or different from R ¹ , R ³ is a hydrocarbon group having 2 or more carbon atoms, and m represents a number satisfying 1 ≦ m ≦ 3 ) Is contacted with a solid catalyst component. (B) an organoaluminum compound. (C) The general formula (R ⁴ ) _{4 - n} Si (OR ⁵ ) _n (where R ⁴
Is a hydrocarbon group, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, and n represents a number satisfying 1 ≦ n ≦ 3). 4. A propylene-based polymer is obtained by bulk polymerization of propylene containing substantially propylene in the presence of a catalyst comprising the following components (A), (B) and (C). A method for producing a propylene polymer. (A) A solid component containing titanium, magnesium, halogen, and an electron donating compound as essential components has a general formula (R
^{_{1) (R 2) 3 -}} m Si (OR 3) m ( wherein, R ¹ is branched chain aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group,
R ² is a hydrocarbon group or a hetero atom-containing hydrocarbon group which is the same as or different from R ¹ , R ³ is a hydrocarbon group having 2 or more carbon atoms, and m represents a number satisfying 1 ≦ m ≦ 3 ) Is contacted with a solid catalyst component. (B) an organoaluminum compound. (C) the general formula ^{(R 6) (R 7)} 3 - n Si (OR 8) n ( wherein, R ⁶ is a branched chain aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group, R ⁷ is is identical to R ⁶ or a different hydrocarbon group or a hetero atom-containing hydrocarbon group, R ⁸
Is a hydrocarbon group having 1 to 12 carbon atoms, and n is
An organic silicon compound represented by the following formula: 1 ≦ n ≦ 3).