JP4975295B2 - α-Olefin Polymerization Catalyst and Method for Producing α-Olefin Polymer - Google Patents

Description

  The present invention relates to an α-olefin polymerization catalyst and a method for producing an α-olefin polymer. Specifically, by using a specific vinylsilane compound as a catalyst component, the stereoregularity is high and the particle properties are good. The present invention relates to an α-olefin polymerization catalyst that can efficiently produce an α-olefin polymer and has extremely high catalytic activity, and a polymerization method of an α-olefin polymer using the same.

Α-Olefin polymer represented by polypropylene is excellent in various physical properties such as rigidity and heat resistance, is rich in molding processability, can be manufactured at a relatively low cost, and has less derivation of environmental problems. Therefore, it is used for a wide range of applications as a basic industrial resin material, and its demand is increasing.
Thus, α-olefin polymers such as polypropylene having excellent performance and advantages from various viewpoints have been manufactured industrially mainly by Ziegler-Natta catalysts from the past, but heavy materials having more excellent physical properties. In order to produce the polymer more advantageously industrially, in the Ziegler-Natta catalyst, the polymerization activity is increased, the stereoregularity of the polymer is improved, the molecular weight distribution is widened, the molding processability is improved, and the polymerization process is improved. Various improvements continue to be made, such as increasing efficiency.

  In the Ziegler-Natta catalyst, which is basically a combination of a transition metal compound and an organometallic compound and can be polymerized even at a low pressure and can produce a polymer having high stereoregularity, titanium is used as the catalyst carrier. And a catalyst using a solid catalyst component containing halogen as an essential component has been developed, and the catalyst activity has been enhanced by using various carriers, and then a catalyst having enhanced catalyst activity and stereoregularity using an electron donor. After that, for example, various organosilicon compounds are newly adopted as catalyst components to improve the catalytic activity and stereoregularity, and to improve the molecular weight distribution. The achievement of improving moldability and crystallinity by employing an external donor component is also mentioned.

Furthermore, in Ziegler-Natta catalysts, many proposals have been made to improve various functions of the catalyst by adding an organosilicon compound to the catalyst component. As a typical example, halogenation using silicon halide is proposed. A method of increasing the catalytic activity and polymer particle size by contacting a contact solution of magnesium and tetraalkoxytitanium with a precipitating agent (see Patent Document 1), adoption of an organosilicon compound having a branched hydrocarbon group Discloses a polymerization method for obtaining a highly stereoregular polymer (see Patent Document 2), a catalyst component (see Patent Document 3) that uses a vinylsilane compound as a component to enhance both catalytic activity and stereoregularity, and the like. .
Recently, research on polymerization catalysts containing vinylsilane compounds as a component has been continued, and prepolymerization treatment is performed in a state where an organosilicon compound, a divinylsilane compound, and an organoaluminum compound coexist in a solvent, thereby improving the dispersibility of the catalyst particles. A polymerization catalyst (see Patent Document 4) that eliminates operation troubles in the polymerization process is also proposed.

As outlined above, Ziegler-Natta catalysts have various polymerization processes such as improved catalyst properties such as catalyst activity and polymer properties such as stereoregularity or improved particle properties of the resulting polymer. Improvements and results from the viewpoint have been accumulated, but α-olefin polymers represented by polypropylene are very excellent resin materials from various physical properties and attributes, and are used as basic industrial materials. Since it is particularly important and widely used, there is a constant demand for further improvements in various physical properties and various performances by enhancing catalytic activity, improving stereoregularity, or improving polymer particle properties.
However, as far as the present inventors know, a Ziegler-Natta catalyst that exhibits sufficient performance in all of the catalyst performance such as catalytic activity, stereoregularity, polymer particle properties and molding processability has not yet been realized. Further improvement of various physical properties and various performances of α-olefins such as polypropylene by developing a novel polymerization catalyst is a current situation that is strongly desired by various industries such as the automobile industry, electrical products and packaging materials.

Japanese Patent Laid-Open No. 61-285203 (Claims and upper right column on page 1) JP-A-62-17066 (claims and upper left column on page 2) Japanese Patent Laid-Open No. 3-234707 (claims 1 and page 2, upper right column) JP 2003-292523 A (summary)

  Against the background of the current state of technology in α-olefin polymers such as polypropylene with Ziegler-Natta catalyst as outlined in paragraphs 0002-0005, the present invention is based on industry demands in the main fields of application of α-olefins. In order to further improve various physical properties and performances of α-olefin polymers at high locations, Ziegler that shows sufficient performance in all catalytic performances such as catalytic activity, stereoregularity, polymer particle properties and molding processability An object of the present invention is to develop a Natta catalyst and to realize a method for producing an α-olefin polymer having various physical properties and performances further improved by using such a polymerization catalyst. .

  In order to solve the problems of the present invention, in view of the improvement of the catalyst technology in the Ziegler-Natta catalyst outlined in the background art, the present inventors have developed the catalytic activity, stereoregularity or polymerization in the Ziegler-Natta catalyst. In order to improve catalyst performance such as particle properties and molding processability, it is considered that the use of vinylsilane compounds as catalyst components, which have been researched and developed recently, is suitable. From various viewpoints such as the effect of catalyst and chemical structure on the catalyst function and polymer, and the relationship between the three-dimensional structure and electronic state of the compound and the catalytic action, etc. The demonstration by.

  By the way, the present applicant has previously found that when a vinylsilane compound is used as a polymerization catalyst for α-olefin such as propylene, a highly stereoregular and highly active catalyst can be obtained. A patent application was filed as an invention (Patent Document 3 described above), and a prepolymerization treatment was performed in a state where an organosilicon compound, a divinylsilane compound, and an organoaluminum compound coexisted in a solvent, thereby increasing the dispersibility of the catalyst particles and a polymerization step. Since the patent application has also been filed as a prior invention for the polymerization catalyst that eliminates the operation trouble of the above (Patent Document 4 mentioned above), the present inventors have considered the polymerization for the solution of the above-mentioned problems based on these inventions. Each of the two coordinations, coordinated to titanium and coordinated to the surface of the magnesium halide support, considered to be the active center of the reaction. It was deeper consideration from the point of view of control to.

  As a result, it is recognized that if a vinylsilane compound having a specific chemical structure is selected, a catalyst component that exhibits high performance in terms of catalyst performance such as stereoregularity, particle properties, and catalytic activity can be obtained. It came to create.

（ここで、Ｒは炭化水素基、水素原子又はハロゲンを表し、Ｘは孤立電子対を有する遊離基を表し、１≦ｉ≦３、０≦ｊ≦２、１≦ｋ≦３、ｉ＋ｊ + ｋ＝４である。）
固体触媒成分としては、チタン、マグネシウム、ハロゲンを固体成分として含有し、また、有機ケイ素化合物をも併用する。そして、固体触媒成分は有機アルミニウム化合物と組み合わされて重合触媒を形成する。 In the present invention, as a vinyl silane compound as a solid catalyst component in a Ziegler-Natta catalyst for polymerizing α-olefin, a substituent having a lone pair is bonded to a phenyl group bonded to a silicon atom. The main characteristic is to employ a specific vinylsilane compound represented by the following formula.

(Wherein R represents a hydrocarbon group, hydrogen atom or halogen, X represents a free radical having a lone pair, 1 ≦ i ≦ 3, 0 ≦ j ≦ 2, 1 ≦ k ≦ 3, i + j + k. = 4)
As the solid catalyst component, titanium, magnesium and halogen are contained as solid components, and an organosilicon compound is also used in combination. The solid catalyst component is combined with the organoaluminum compound to form a polymerization catalyst.

  In the polymerization catalyst of the present invention, by being formed from each of the above components, in particular, by selecting and employing a vinylsilane compound having a specific chemical structure, stereoregularity, particle properties, catalytic activity A polymerization catalyst exhibiting high performance in the catalyst performance such as is obtained, which has been demonstrated by contrasting each of Examples and Comparative Examples described later.

  The polymerization catalyst of the present invention may further use, as an additional requirement, an organosilicon compound, a compound having at least two ether bonds and an electron donor compound as a catalyst component. An organoaluminum compound, a compound having at least two ether bonds, and an electron donor compound can also be contained.

  For the vinylsilane compound having a specific chemical structure of the solid catalyst component, which is a basic requirement in the present invention, each patent document described in paragraph 0006 in the background art described above and other prior art patent documents are scrutinized. However, only a vinylsilane compound in which X is a hydrogen atom or a methyl group in the chemical structural formula described in paragraph 0011 can be found, and the vinylsilane compound having a specific chemical structure of the present invention was first employed as a solid catalyst component. Is.

  In the above, the background of the creation of the present invention, the specific configuration of the invention, the main features, the comparison with the prior art, etc. have been generally described. The invention consists of the following unit groups of the invention. The first invention is a basic invention, and the other inventions add additional requirements to the basic invention or make it an embodiment.

（ここで、Ｒは炭化水素基、水素原子又はハロゲンを表し、Ｘは孤立電子対を有する遊離基を表し、１≦ｉ≦３、０≦ｊ≦２、１≦ｋ≦３、ｉ＋ｊ + ｋ＝４である。）
（ＩＩＩ）有機ケイ素化合物（Ｃ）
〔ｉｉ〕有機アルミニウム化合物（Ｄ）
第二発明：更に、下記の成分〔ｉｉｉ〕〜〔ｖ〕の一つ以上を用いることを特徴とする、第一発明におけるα−オレフィン重合用触媒。
〔ｉｉｉ〕有機ケイ素化合物（Ｃ’）
〔ｉｖ〕少なくとも二つのエーテル結合を有す化合物（Ｅ）
〔ｖ〕電子供与体化合物（Ｆ）
第三発明：更に、成分（Ｉ）が電子供与体化合物（Ｆ’）を用い、成分〔ｉ〕が有機アルミニウム化合物（Ｄ’）及び／又は少なくとも二つのエーテル結合を有す化合物（Ｅ’）を用いることを特徴とする、第一発明又は第二発明におけるα−オレフィン重合用触媒。
第四発明：ビニルシラン化合物（Ｂ）が、下記式で表される化合物であることを特徴とする、第一発明〜第三発明のいずれかにおけるα−オレフィン重合用触媒。

（ここで、Ｒは炭化水素基、水素原子又はハロゲンを表し、Ｘは孤立電子対を有する遊離基を表し、１≦ｉ≦３、０≦ｊ≦２、１≦ｋ≦３、ｉ＋ｊ + ｋ＝４である。）
第五発明：ビニルシラン化合物（Ｂ）が、下記式で表される化合物であることを特徴とする、第一発明〜第三発明のいずれかにおけるα−オレフィン重合用触媒。

（ここで、Ｒは炭化水素基、水素原子又はハロゲンを表し、Ｙは孤立電子対を有する官能基を表す。Ｒ’は炭化水素基、水素原子又はハロゲンを表し、Ｒ’が炭化水素基である場合は任意に孤立電子対を有する官能基で置換されていてもよい。１≦ｉ≦３、０≦ｊ≦２、１≦ｋ≦３、０≦ｚ≦３、ｉ＋ｊ + ｋ＝４である。）
第六発明：ビニルシラン化合物（Ｂ）中のＸ又はＹにおける孤立電子対が、ヘテロ原子に由来するものであることを特徴とする、第一発明〜第五発明のいずれかにおけるα−オレフィン重合用触媒。
第七発明：ビニルシラン化合物（Ｂ）中のＸ又はＹにおける孤立電子対が、ハロゲン原子に由来するものであることを特徴とする、第一発明〜第五発明のいずれかにおけるα−オレフィン重合用触媒。
第八発明：第一発明〜第七発明のいずれかにおけるα−オレフィン重合用触媒を用いてα−オレフィンを重合又は共重合することを特徴とする、α−オレフィン重合体又は共重合体の製造方法。 First invention: α-olefin polymerization catalyst comprising the following components [i] and [ii].
[I] Solid catalyst component (I) obtained by contacting the following components (I) to (III): Solid component (A) containing titanium, magnesium and halogen as essential components
(II) Vinylsilane compound (B) represented by the following formula

(Wherein R represents a hydrocarbon group, hydrogen atom or halogen, X represents a free radical having a lone pair, 1 ≦ i ≦ 3, 0 ≦ j ≦ 2, 1 ≦ k ≦ 3, i + j + k. = 4)
(III) Organosilicon compound (C)
[Ii] Organoaluminum compound (D)
Second invention: The α-olefin polymerization catalyst according to the first invention, wherein one or more of the following components [iii] to [v] are further used.
[Iii] Organosilicon compound (C ′)
[Iv] Compound (E) having at least two ether bonds
[V] Electron donor compound (F)
Third invention: Furthermore, component (I) uses an electron donor compound (F ′), and component [i] is an organoaluminum compound (D ′) and / or a compound (E ′) having at least two ether bonds. The α-olefin polymerization catalyst in the first invention or the second invention, characterized in that is used.
Fourth invention: The α-olefin polymerization catalyst according to any one of the first to third inventions, wherein the vinylsilane compound (B) is a compound represented by the following formula.

(Wherein R represents a hydrocarbon group, hydrogen atom or halogen, X represents a free radical having a lone pair, 1 ≦ i ≦ 3, 0 ≦ j ≦ 2, 1 ≦ k ≦ 3, i + j + k. = 4)
Fifth invention: The α-olefin polymerization catalyst according to any one of the first invention to the third invention, wherein the vinylsilane compound (B) is a compound represented by the following formula.

(Wherein R represents a hydrocarbon group, a hydrogen atom or a halogen, Y represents a functional group having a lone pair of electrons. R ′ represents a hydrocarbon group, a hydrogen atom or a halogen, and R ′ represents a hydrocarbon group. In some cases, it may be optionally substituted with a functional group having a lone pair of electrons: 1 ≦ i ≦ 3, 0 ≦ j ≦ 2, 1 ≦ k ≦ 3, 0 ≦ z ≦ 3, i + j + k = 4 is there.)
6th invention: For alpha-olefin polymerization in any one of 1st invention-5th invention characterized by the lone electron pair in X or Y in a vinylsilane compound (B) originating in a hetero atom. catalyst.
Seventh Invention: For α-olefin polymerization according to any one of the first to fifth inventions, wherein the lone pair of electrons in X or Y in the vinylsilane compound (B) is derived from a halogen atom. catalyst.
Eighth Invention: Production of an α-olefin polymer or copolymer, characterized in that an α-olefin is polymerized or copolymerized using the α-olefin polymerization catalyst according to any one of the first invention to the seventh invention. Method.

  The α-olefin polymerization catalyst of the present invention has high catalytic activity and can contribute to reducing the cost of producing an α-olefin polymer, and also has good particle properties. It is possible to increase the productivity of manufacturing plants, and the α-olefin polymer produced has high stereoregularity and excellent physical properties such as rigidity and heat resistance. It can be suitably used for applications such as automobile parts, home appliance parts, and packaging materials that are required to be highly functional.

  In the above, the outline relating to the present invention and the skeleton of the structure of the invention have been outlined, so in the following, in order to explain the invention group in the present invention in detail, embodiments of the invention for mainly each component in the polymerization catalyst will be described. Describe specifically.

（ここで、Ｒは炭化水素基、水素原子又はハロゲンを表し、Ｘは孤立電子対を有する遊離基を表し、１≦ｉ≦３、０≦ｊ≦２、１≦ｋ≦３、ｉ＋ｊ + ｋ＝４である。）
（ＩＩＩ）有機ケイ素化合物（Ｃ）
〔ｉｉ〕有機アルミニウム化合物（Ｄ） 1. Basic Structure of α-Olefin Polymerization Catalyst The basic structure of the polymerization catalyst in the present invention is an α-olefin polymerization catalyst comprising the following components [i] and [ii]. Here, “consisting of” does not mean that the components are only listed (that is, component [i] and component [ii]), and naturally follows the purpose of the present invention. It includes the coexistence of other components.
[I] Solid catalyst component (I) obtained by contacting the following components (I) to (III): Solid component (A) containing titanium, magnesium and halogen as essential components
(II) Vinylsilane compound (B) represented by the following formula

(Wherein R represents a hydrocarbon group, hydrogen atom or halogen, X represents a free radical having a lone pair, 1 ≦ i ≦ 3, 0 ≦ j ≦ 2, 1 ≦ k ≦ 3, i + j + k. = 4)
(III) Organosilicon compound (C)
[Ii] Organoaluminum compound (D)

2. Component [i] (solid catalyst component)
(1) Solid component (A)
The solid component (A) used in the present invention is (I) a solid component of an α-olefin polymerization catalyst containing titanium, magnesium and halogen as essential components. Any material can be used as long as it contains these as essential components.
Here, “containing as an essential component” means that in addition to the listed three components, other elements in accordance with the object of the present invention may be included, and each element is in accordance with the object of the present invention. It may be present as an arbitrary compound, and each element may be present as a bond to each other.
In addition, although each exemplary compound in the following is listing only a representative compound and describing the specification simply, it cannot be overemphasized that the structure of this invention is not restrict | limited to these description.

(1-1) Component materials i) Titanium source Any titanium compound can be used as the titanium source. Representative examples include compounds disclosed in JP-A-3-234707. Regarding the valence of titanium, a titanium compound having any valence of tetravalent, trivalent, divalent, and zero valent can be used, preferably tetravalent and trivalent titanium compounds, more preferably tetravalent. It is desirable to use the titanium compound.
Specific examples of tetravalent titanium compounds include titanium halide compounds typified by titanium tetrachloride, alkoxy titanium compounds typified by tetrabutoxy titanium, and Ti-O-Ti bonds typified by tetrabutoxy titanium dimer. And the like, and the like, and the like, and the like, there can be mentioned organotitanium compounds represented by dicyclopentadienyltitanium dichloride. Of these, titanium tetrachloride and tetrabutoxy titanium are particularly preferred.
Specific examples of the trivalent titanium compound include titanium halide compounds represented by titanium trichloride. As titanium trichloride, a compound produced by any known method such as a hydrogen reduction type, a metal aluminum reduction type, a metal titanium reduction type, or an organoaluminum reduction type can be used.
The above titanium compounds can be used not only alone but also in combination with a plurality of compounds. Further, a mixture of the above titanium compounds or a compound whose average composition formula is a mixed formula thereof (for example, a compound such as Ti (OBu) _m Cl _4-m ; 0 <m <4), or a phthalate ester Complexes with other compounds such as Ph (CO ₂ Bu) ₂ .TiCl ₄ and the like can also be used.

B) Magnesium source Any magnesium compound can be used as the magnesium source. Representative examples include compounds disclosed in JP-A-3-234707.
Generally, magnesium halide compounds typified by magnesium chloride, alkoxymagnesium compounds typified by diethoxymagnesium, oxymagnesium compounds typified by metal magnesium or magnesium oxide, typified by magnesium hydroxide Hydroxymagnesium compounds, Grignard compounds typified by butylmagnesium chloride, organometallic magnesium compounds typified by butyloctylmagnesium, magnesium salts of inorganic and organic acids typified by magnesium carbonate and magnesium stearate, In addition, a compound in which a mixture thereof or an average composition formula thereof is a mixed formula thereof (for example, a compound such as Mg (OEt) _m Cl _2-m ; 0 <m <2) can be used.
Of these, magnesium chloride, diethoxymagnesium, metallic magnesium and butylmagnesium chloride are preferred.

C) Halogen source As the halogen, fluorine, chlorine, bromine, iodine, and a mixture thereof can be used. Of these, chlorine is preferred.
The halogen is generally supplied from the above titanium compound and / or magnesium compound, but can also be supplied from other compounds. Typical examples include silicon halide compounds typified by silicon tetrachloride, aluminum halide compounds typified by aluminum chloride, halogenated organic compounds typified by 1,2-dichloroethane and benzyl chloride, Halogenated borane compounds represented by trichloroborane, phosphorus halide compounds represented by phosphorus pentachloride, tungsten halide compounds represented by tungsten hexachloride, molybdenum halide compounds represented by molybdenum pentachloride And so on. These compounds can be used not only alone but also in combination. Of these, silicon tetrachloride is preferred.

D) Optional component The solid component (A) may contain an electron donor as an optional component. Typical examples of the electron donor compound (F ′) include compounds disclosed in JP-A No. 2004-124090. In general, organic acids and inorganic acids and their derivatives (esters, acid anhydrides, acid halides, amides) compounds, ether compounds, ketone compounds, aldehyde compounds, alcohol compounds, amine compounds, etc. It is desirable to use it.

Examples of the organic acid compound that can be used as an electron donor include aromatic polycarboxylic acid compounds represented by phthalic acid, aromatic carboxylic acid compounds represented by benzoic acid, and 2-n-butyl-malonic acid. Malonic acid or 2-n-butyl-succinic acid having one or two substituents at the 2-position as in Example 1 of JP-A-2003-119216 (Examples of JP-T-2003-522231) As in 1), aliphatic polycarboxylic acid compounds represented by succinic acid having one or two substituents at the 2-position or one or more substituents at the 2-position and 3-position, respectively, represented by propionic acid Examples thereof include aliphatic carboxylic acid compounds, aromatic and aliphatic sulfonic acid compounds represented by benzenesulfonic acid and methanesulfonic acid, and the like. These carboxylic acid compounds and sulfonic acid compounds may have an arbitrary number of unsaturated bonds at arbitrary positions in the molecule like maleic acid, regardless of whether they are aromatic or aliphatic.
Aliphatic and aromatic alcohols can be used as the alcohol that is a constituent of the ester. Among these alcohols, alcohols composed of aliphatic free radicals having 1 to 20 carbon atoms such as ethyl group, butyl group, isobutyl group, heptyl group, octyl group and dodecyl group are preferable. More preferably, an alcohol composed of an aliphatic radical having 2 to 12 carbon atoms is desirable. In addition, an alcohol having an alicyclic free group such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group can also be used. Fluorine, chlorine, bromine, and iodine can be used as the halogen that is a constituent element of the acid halide. Of these, chlorine is preferred. In the case of polyhalides of polyvalent organic acids, the plurality of halogens may be the same or different. Aliphatic and aromatic amines can be used as the amine that is a constituent of the amide. Among these amines, preferred examples include ammonia, aliphatic amines typified by ethylamine and dibutylamine, and amines having aromatic free radicals typified by aniline and benzylamine in the molecule.

Examples of ether compounds that can be used as electron donors include aliphatic ether compounds typified by dibutyl ether, aromatic ether compounds typified by diphenyl ether, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane Aliphatic polyhydric ether compounds represented by 1,3-dimethoxypropane having one or two substituents at the 2-position, such as 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, Examples thereof include polyvalent ether compounds having an aromatic free radical represented by 9-bis (methoxymethyl) fluorene in the molecule. Preferred examples of the polyvalent ether compounds may be selected from the examples of the compound (E) having at least two ether bonds described in the present specification.
Examples of the ketone compound that can be used as an electron donor include aliphatic ketone compounds typified by methyl ethyl ketone, aromatic ketone compounds typified by acetophenone, 2,2,4,6,6-pentamethyl-3,5. Examples thereof include polyvalent ketone compounds represented by heptanedione (Example 1 of JP-A-7-233209).
Examples of the aldehyde compound that can be used as the electron donor include aliphatic aldehyde compounds typified by propionaldehyde, aromatic aldehyde compounds typified by benzaldehyde, and the like.
Examples of alcohol compounds that can be used as electron donors include aliphatic alcohol compounds represented by butanol and 2-ethylhexanol, phenol derivative compounds represented by phenol and cresol, glycerin and 1,1′-bi- Examples thereof include aliphatic or aromatic polyhydric alcohol compounds represented by 2-naphthol.
Examples of amine compounds that can be used as electron donors include aliphatic amine compounds represented by diethylamine, nitrogen-containing alicyclic compounds represented by 2,2,6,6-tetramethyl-piperidine, and aniline. Aromatic amine compounds represented, nitrogen atom-containing aromatic compounds represented by pyridine, 1,3-bis (dimethylamino) -2,2-dimethylpropane (Example 1 of JP-A-6-263816) And the like, and the like.

As a compound that can be used as an electron donor, a compound containing a plurality of the above functional groups in the same molecule can also be used. Examples of such compounds include acetic acid- (2-ethoxyethyl) (Example 1 of JP-A-60-130607) and ethyl 3-ethoxy-2-tert-butylpropionate (JP-A-6-271613). Ester compounds having an alkoxy group in the molecule represented by Example 1) of the publication, ketoester compounds represented by 2-benzoyl-ethyl benzoate (Example 1 of JP-A-3-43407), ( 1-t-butyl-2-methoxyethyl) methylketone (Ketoether compounds represented by Example 1 of JP-A-10-245412), N, N-dimethyl-2,2-dimethyl-3-methoxypropylamine (Aminoether compounds typified by (Example 1 of JP-A-2003-261614)), halogenoe typified by epoxy chloropropane And the like ether compounds (Example of JP 2004-523599).
These electron donors can be used alone or in combination with a plurality of compounds. Of these, preferred are diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, phthalic acid ester compounds typified by diheptyl phthalate, phthalic acid halide compounds typified by phthaloyl dichloride, 2-n- Malonic acid ester compounds having one or two substituents at the 2-position, such as butyl-diethyl malonate (Example 1 of JP-A-2003-119216), 2-n-butyl-diethyl succinate (special Succinic acid ester compounds having one or two substituents at the 2-position or one or more substituents at the 2-position and 3-position, as in Example 1) of Table 2003-522231, 2-isopropyl- One in the 2-position such as 2-isobutyl-1,3-dimethoxypropane and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane Or aliphatic polyvalent ether compounds represented by 1,3-dimethoxypropane having two substituents (Examples of JP-A-3-294302), represented by 9,9-bis (methoxymethyl) fluorene And polyvalent ether compounds having an aromatic free radical in the molecule (Examples of JP-A-8-333413).

  Examples of the inorganic acid compound that can be used as the electron donor include carbonic acid, phosphoric acid, silicic acid, sulfuric acid, and nitric acid. As derivatives of these inorganic acids, it is desirable to use esters. Specific examples include tetraethoxysilane (ethyl silicate), tetrabutoxysilane (butyl silicate), and tributyl phosphate.

(1-2) Preparation method of solid component (A) Although the contact conditions of each component to be used for preparing the solid component (A) in the present invention need not be oxygen, Arbitrary conditions can be used in the range which does not impair an effect. In general, the following conditions are preferred.
The contact temperature is about −50 to 200 ° C., preferably 0 to 150 ° C. Examples of the contact method include a mechanical method using a rotating ball mill, a vibration mill, and the like, and a method of contacting by stirring in the presence of an inert solvent.
In the preparation of the solid component (A), washing with an inert solvent may be performed in the middle and / or finally. Examples of preferable solvent species include aliphatic hydrocarbon compounds such as heptane, aromatic hydrocarbon compounds such as toluene, and halogen-containing hydrocarbon compounds such as 1,2-dichloroethylene and chlorobenzene.

(1-3) Component Amount Ratio The amount ratio of each component constituting the solid component (A) in the present invention can be any as long as the effects of the present invention are not impaired. Is preferably within the following range.
The amount of titanium compound used is a molar ratio (number of moles of titanium compound / number of moles of magnesium compound) with respect to the amount of magnesium compound used, and is preferably in the range of 0.0001 to 1,000. In particular, the range of 0.01 to 10 is desirable.
In the case of using a halogen source compound in addition to the magnesium compound and the titanium compound, the amount of the magnesium compound used depends on whether the magnesium compound and the titanium compound each contain a halogen or not. The molar ratio with respect to the amount used (number of moles of the halogen source compound / number of moles of the magnesium compound) is preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100. The inside is desirable.
When using an electron donor as an optional component in preparing the solid component (A), the amount used is a molar ratio (number of moles of electron donor / number of moles of magnesium compound) to the amount of magnesium compound used. , Preferably in the range of 0.001 to 10, particularly preferably in the range of 0.01 to 5.

(1-4) Specific example of preparation method As a preparation method of the solid component (A) in this invention, arbitrary methods can be used. Specifically, the following method can be exemplified. In addition, this invention is not restrict | limited at all by the following illustration.
B) Co-grinding method This is a method of supporting a titanium compound on a magnesium compound by co-grinding a magnesium compound containing halogen represented by magnesium chloride with the titanium compound. If necessary, co-pulverization may be performed simultaneously with an optional component such as an electron donor or in a separate step. As the mechanical pulverization method, an arbitrary pulverizer such as a rotating ball mill or a vibration mill can be used. Not only a dry pulverization method without using a solvent but also a wet pulverization method in which co-pulverization is performed in the presence of an inert solvent can be used.

B) Heat treatment method This is a method in which a magnesium compound containing a halogen typified by magnesium chloride and a titanium compound are stirred in an inert solvent to carry out a contact treatment, and the titanium compound is supported on the magnesium compound. When a liquid compound such as titanium tetrachloride is used as the titanium compound, the contact treatment can be performed without an inert solvent. If necessary, optional components such as an electron donor and a silicon halide compound may be contacted simultaneously or in a separate step. The contact temperature is not particularly limited, but it is often preferable to perform the contact treatment at a relatively high temperature of about 90 ° C to 130 ° C.

C) Dissolving precipitation method A magnesium compound containing halogen represented by magnesium chloride is dissolved by contacting with an electron donor, and the resulting solution is contacted with a precipitating agent to cause a precipitation reaction to form particles. Is the method. Examples of electron donors used for dissolution include alcohol compounds, epoxy compounds, phosphate ester compounds, silicon compounds having an alkoxy group, titanium compounds having an alkoxy group, ether compounds, and the like. . Examples of the precipitating agent include titanium halide compounds, silicon halide compounds, hydrogen chloride, halogen-containing hydrocarbon compounds, siloxane compounds having Si-H bonds (including polysiloxane compounds), aluminum compounds Etc. can be illustrated. As a method for contacting the dissolving solution with the precipitating agent, the precipitating agent may be added to the dissolving solution, or the dissolving solution may be added to the precipitating agent. When the titanium compound is not used in either the dissolution or precipitation process, the titanium compound is supported on the magnesium compound by further bringing the particles formed by the precipitation reaction into contact with the titanium compound. Further, if necessary, the particles thus formed may be contacted with an optional component such as a titanium halide compound or a silicon halide compound, or may be contacted with an electron donor. In this case, the electron donor may be different from that used for dissolution, or may be the same. There is no restriction | limiting in particular about the contact order of these arbitrary components, You may make it contact as an independent process, and can also contact together in the case of melt | dissolution, precipitation, and contact with titanium compounds. An inert solvent may be present in any step of dissolution, precipitation, and contact with an optional component.

D) Granulation method As with the dissolution precipitation method, a magnesium compound containing halogen such as magnesium chloride is dissolved by contact with an electron donor, and the resulting solution is granulated mainly by a physical method. Is the method. The example of the electron donor used for dissolution is the same as that of the dissolution precipitation method. Examples of granulation techniques include a method in which a high-temperature solution is dropped into a low-temperature inert solvent, a method in which the solution is sprayed from a nozzle toward a high-temperature gas phase, and a method in which the solution is directed to a low-temperature gas phase. And a method of cooling the solution by ejecting it from a nozzle. The titanium compound is supported on the magnesium compound by bringing the particles formed by granulation into contact with the titanium compound. Furthermore, you may make it contact with arbitrary components, such as a halogenated silicon compound and an electron donor, as needed. In this case, the electron donor may be different from that used for dissolution, or may be the same. There is no restriction | limiting in particular about the contact order of these arbitrary components, You may make it contact as an independent process, and can also contact together in the case of melt | dissolution or contact with a titanium compound. Further, an inert solvent may be present in any of the steps of dissolution, contact with titanium compounds, and contact with optional components.

E) Method of halogenating Mg compound This is a method of halogenating a magnesium compound containing no halogen by bringing a halogenating agent into contact therewith. Examples of magnesium compounds containing no halogen include dialkoxy magnesium compounds, magnesium oxide, magnesium carbonate, magnesium salts of fatty acids, and the like. When dialkoxymagnesium compounds are used, those prepared in the system by reaction of magnesium metal and alcohol can also be used. When this preparation method is used, it is common to form particles by granulation or the like at the stage of a magnesium compound containing no halogen which is a starting material. Examples of the halogenating agent include titanium halide compounds, halogenated silicon compounds, and halogenated phosphorus compounds. When a halogenated titanium compound is not used as the halogenating agent, the halogen-containing magnesium compound formed by halogenation is further brought into contact with the titanium compound, whereby the titanium compound is supported on the magnesium compound. Further, if necessary, the particles thus formed may be contacted with an optional component such as a titanium halide compound or a silicon halide compound, or may be contacted with an electron donor. The order of contacting these optional components is not particularly limited, and may be contacted as an independent process, or may be contacted together when halogenated magnesium compound is not halogenated or contacted with titanium compounds. . Further, an inert solvent may be present in any step of halogenation, contact with titanium compounds, and contact with optional components.

F) Precipitation method from an organic magnesium compound This is a method in which a precipitation agent is brought into contact with a solution of an organic magnesium compound such as a Grignard reagent typified by butyl magnesium chloride or a dialkyl magnesium compound. Examples of the precipitating agent include titanium compounds, silicon compounds, hydrogen chloride and the like. When a titanium compound is not used as the precipitating agent, the titanium compound is supported on the magnesium compound by further bringing the particles formed by the precipitation reaction into contact with the titanium compound. Further, if necessary, the particles thus formed may be contacted with an optional component such as a titanium halide compound or a silicon halide compound, or may be contacted with an electron donor. There is no restriction | limiting in particular about the contact order of these arbitrary components, You may make it contact as an independent process, and can also contact together in the case of precipitation and contact with titanium compounds. Further, an inert solvent may be present in any of the steps of precipitation, contact with titanium compounds, and contact with an optional component.

G) Impregnation method This is a method in which a solution of an organic magnesium compound or a solution in which a magnesium compound is dissolved with an electron donor is impregnated into an inorganic compound carrier or an organic compound carrier. Examples of the organomagnesium compounds are the same as those of the precipitation method from the organomagnesium compounds. The magnesium compound used for dissolving the magnesium compound may or may not contain halogen, and examples of the electron donor are the same as those of the dissolution precipitation method. Examples of the inorganic compound carrier include silica, alumina, and magnesia. Examples of the organic compound carrier include polyethylene, polypropylene, and polystyrene. The carrier particles after the impregnation treatment are fixed by depositing a magnesium compound by a chemical treatment with a precipitation agent or a physical treatment such as drying. Examples of the precipitating agent are the same as those of the dissolution precipitation method. When a titanium compound is not used as a precipitating agent, the titanium compound is supported on the magnesium compound by further contacting the particles thus formed with the titanium compound. Further, if necessary, the formed particles may be brought into contact with an optional component such as a titanium halide compound or a halogenated silicon compound, or may be brought into contact with an electron donor. There is no restriction | limiting in particular about the contact order of these arbitrary components, You may contact as an independent process, and can also contact together in the case of impregnation, precipitation, and contact with titanium compounds. Further, an inert solvent may be present in any step of impregnation, precipitation, contact with titanium compounds, and contact with optional components.

H) Combined method The methods described in the above a) to g) can also be used in combination. Examples of combinations include a method in which magnesium chloride is co-ground with an electron donor and then heat-treated with a titanium halide compound, and the magnesium chloride compound is co-ground with an electron donor and then dissolved using another electron donor. Further, a method of precipitating with a precipitant, a method of dissolving a dialkoxymagnesium compound with an electron donor and bringing it into contact with a halogenated titanium compound, and simultaneously halogenating the magnesium compound, a dialkoxymagnesium compound By contacting with carbon dioxide, the carbonate ester magnesium compounds are generated and dissolved at the same time. The formed solution is impregnated into silica, and then contacted with hydrogen chloride to halogenate the magnesium compound and simultaneously precipitate and fix it. Contact with titanium halide compounds It can be exemplified a method of carrying a titanium compound by.

（ここで、Ｒは炭化水素基、水素原子又はハロゲンを表し、Ｘは孤立電子対を有する遊離基を表し、１≦ｉ≦３、０≦ｊ≦２、１≦ｋ≦３、ｉ＋ｊ + ｋ＝４である。） (2) Vinylsilane compound (B)
(2-1) Basic structure As the vinylsilane compound (B) used in the solid catalyst component of the present invention, it is important to use vinylsilane compounds having a specific structure. In the vinylsilane compounds, at least one hydrogen atom of monosilane (SiH ₄ ) is substituted with a vinyl group, at least one is substituted with an aromatic radical having a specific structure, and a part or all of the remaining hydrogen atoms are other radicals. Is a compound having a structure substituted by the following general formula.

(Wherein R represents a hydrocarbon group, hydrogen atom or halogen, X represents a free radical having a lone pair, 1 ≦ i ≦ 3, 0 ≦ j ≦ 2, 1 ≦ k ≦ 3, i + j + k. = 4)

は、特定の構造を有する芳香族遊離基を表す。Ｘは芳香環の任意の位置に結合していてよいが、好ましくはパラ位又はオルト位に結合している。とりわけ、Ｘがパラ位に結合していることが望ましく、この場合には芳香族遊離基は次の様に表される。

式中、Ｘは孤立電子対を有する遊離基を表す。 In the formula, i represents the number of vinyl groups and takes a value of 1 or more and 3 or less. More preferably, the value of i is 1 or 2. R represents a hydrocarbon group, a hydrogen atom or a halogen. When R is a hydrocarbon group, it is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 12 carbon atoms. When R is halogen, it is selected from fluorine, chlorine, bromine and iodine. Of these, chlorine is preferred. Specific examples of preferable R include an alkyl group typified by a methyl group and a butyl group, a cycloalkyl group typified by a cyclohexyl group, an aryl group typified by a phenyl group, a hydrogen atom, and chlorine. Particularly preferable examples of R include a methyl group, an ethyl group, a hydrogen atom, and chlorine. j represents the number of R and takes a value of 0 or more and 2 or less. More preferably, the value of j is 1 or more and 2 or less. When j is 2, a plurality of R may be the same as or different from each other. Where

Represents an aromatic radical having a specific structure. X may be bonded to any position of the aromatic ring, but is preferably bonded to the para position or the ortho position. In particular, it is desirable that X is bonded to the para position. In this case, the aromatic radical is represented as follows.

In the formula, X represents a free radical having a lone pair.

(2-2) About lone pair The origin of the lone pair is preferably a heteroatom or a halogen atom. When the lone pair contained in X is derived from a heteroatom, the heteroatom is preferably selected from oxygen, nitrogen, sulfur and phosphorus, more preferably oxygen or nitrogen, particularly preferably oxygen. is there. Any functional group containing a hetero atom can be selected. Examples of preferred functional groups include hydroxy groups, hydrosulfide groups, hydropolysulfide groups, ether groups (including oxygen-containing aromatic ring structures such as furan), sulfide groups (including sulfur-containing aromatic ring structures such as thiophene), polysulfides Group, carbonyl group (carboxylic acid group, ketone group, aldehyde group, ester group, acid halide group, acid anhydride, amide group, imide group, carbamate group, etc.) and part or all of oxygen atoms in the functional group Functional groups substituted with sulfur, sulfoxide groups, sulfone groups, sulfur organic oxygen acids (sulfonic acid, sulfinic acid or sulfenic acid) and their derivatives (sulfonamides, etc.), amino groups (sulfur-containing aromatics such as imidazole and pyridine) Ring structure), imino group, cyanide group, isocyanide group, cyanate group, isocyanate Groups, thiocyanate groups, isothiocyanate groups, hydroxylamino groups, oxime groups, amine oxide groups, nitro groups, nitroso groups, diazo groups, hydrazino groups, phosphine groups, phosphine oxide groups, phosphorus organic oxygen acids (such as phosphinic acids) and Those derivatives (phosphoamide etc.) etc. can be mentioned. The number of carbons contained in X is not particularly limited, but is preferably a free radical having 1 to 20 carbons. Particularly preferably, X is an ether having 1 to 20 carbon atoms.
When the lone pair contained in X is derived from halogen, the halogen is preferably selected from fluorine, chlorine, bromine and iodine. Of these, chlorine or bromine is preferred. Examples of functional groups include halogens, halogenoalkyl groups, halogenoaryl groups, halogenoallyl groups, and the like. Particularly preferred is halogen.

ここで、Ｙは孤立電子対を有する官能基を表す。Ｒ’は炭化水素基、水素原子又はハロゲンを表し、Ｒ’が炭化水素基である場合は任意に孤立電子対を有する官能基で置換されていてもよい。ｚはＲ’の数を表し、０以上３以下の値を取る。−Ｙ−Ｒ’zでＸに相当するので、好ましいＲ’の例については上記のＸに関する記載に従う。 The position of the lone electron pair in the free radical X is not particularly limited, but particularly preferably the lone electron pair exists at a position adjacent to the aromatic ring. In this case, aromatic free radicals are represented as shown below.

Here, Y represents a functional group having a lone electron pair. R ′ represents a hydrocarbon group, a hydrogen atom or a halogen, and when R ′ is a hydrocarbon group, it may be optionally substituted with a functional group having a lone pair of electrons. z represents the number of R ′ and takes a value of 0 or more and 3 or less. Since —Y—R′z corresponds to X, preferred examples of R ′ follow the above description regarding X.

(2-3) Specific Example of Compound Specific examples of the vinylsilane compound (B) used in the present invention are shown below. Examples of the compound in which X in the vinylsilane compound (B) has an ether group include the following compounds.
(P-methoxyphenyl) dimethylvinylsilane, bis (p-methoxyphenyl) methylvinylsilane, (p-methoxyphenyl) methyldivinylsilane, bis (p-methoxyphenyl) divinylsilane, (p-methoxyphenyl) trivinylsilane, tris ( p-methoxyphenyl) vinylsilane, (p-ethoxyphenyl) dimethylvinylsilane, bis (p-ethoxyphenyl) methylvinylsilane, (p-ethoxyphenyl) methyldivinylsilane, bis (p-ethoxyphenyl) divinylsilane, (pn) -Propoxyphenyl) dimethylvinylsilane, (p-i-propoxyphenyl) dimethylvinylsilane, (pn-butoxyphenyl) dimethylvinylsilane, (ps-butoxyphenyl) dimethylvinylsilane, (pi Butoxyphenyl) dimethylvinylsilane, (pt-butoxyphenyl) dimethylvinylsilane, [p- (n-octyloxy) phenyl] dimethylvinylsilane, [p- (n-dodecyloxy) phenyl] dimethylvinylsilane, (p-phenoxyphenyl) ) Dimethylvinylsilane, (p-anisylphenyl) dimethylvinylsilane, [(p-tolyloxy) phenyl] dimethylvinylsilane, (p-methoxyphenyl) diethylvinylsilane, (p-methoxyphenyl) di-n-butylvinylsilane, (p- Methoxyphenyl) di-n-octylvinylsilane, (p-methoxymethylphenyl) dimethylvinylsilane, (p-methoxyethylphenyl) dimethylvinylsilane, (p-methoxymethoxymethylphenyl) dimethylvinyl Silane, (o-methoxyphenyl) dimethyl vinyl silane, (2,4-dimethoxyphenyl) dimethylvinylsilane, and the like (2,4,6-trimethoxyphenyl) dimethylvinylsilane.

Examples of the compound in which X in the vinylsilane compound (B) has a carbonyl group include the following compounds.
(P-acetylphenyl) dimethylvinylsilane, (p-acetylacetylphenyl) dimethylvinylsilane, (p-acetonylphenyl) dimethylvinylsilane, (p-benzoylphenyl) dimethylvinylsilane, p- (dimethylvinylsilyl) benzaldehyde, p- ( Dimethylvinylsilyl) methyl benzoate, p- (dimethylvinylsilyl) phenyl acetate, [p- (acetyloxycarbonyl) phenyl] dimethylvinylsilane, p- (dimethylvinylsilyl) benzoic acid-N, N-dimethylamide, N- Methyl-p- (dimethylvinylsilyl) -acetanilide, p- (dimethylvinylsilyl) benzoic acid chloride, and the like.

Examples of the compound in which X in the vinylsilane compound (B) has a halogen include the following compounds.
(P-bromophenyl) dimethylvinylsilane, (p-bromophenyl) methyldivinylsilane, bis (p-bromophenyl) methylvinylsilane, bis (p-bromophenyl) divinylsilane, (p-chlorophenyl) dimethylvinylsilane, (p- Chlorophenyl) methyldivinylsilane, bis (p-chlorophenyl) methylvinylsilane, bis (p-chlorophenyl) divinylsilane, (p-fluorophenyl) dimethylvinylsilane, (p-iodophenyl) dimethylvinylsilane, (p-bromophenyl) diethylvinylsilane , (P-bromophenyl) di-n-butylvinylsilane, (p-bromophenyl) di-n-octylvinylsilane, (o-bromophenyl) dimethylvinylsilane, (2,4-dibromophenyl) dimethyl Vinylsilane, (2,4,6-tribromophenyl) dimethylvinylsilane, (α-bromo-p-tolyl) dimethylvinylsilane, (α, α-dibromo-p-tolyl) dimethylvinylsilane, (α, α, α-tribromo) -P-tolyl) dimethylvinylsilane, (α-chloro-p-tolyl) dimethylvinylsilane, p- (2-bromoethyl) phenyldimethylvinylsilane, p- (3-bromo-n-propyl) phenyldimethylvinylsilane, p-[( p-bromophenyl) phenyl] dimethylvinylsilane and the like.

Other specific examples of the vinylsilane compound (B) include the following compounds.
(N, N-dimethyl-p-anilyl) dimethylvinylsilane, p- (dimethylvinylsilyl) phenylmethylsulfide, p- (dimethylvinylsilyl) phenylmethylsulfoxide, p- (dimethylvinylsilyl) phenylmethylsulfone, p -(Dimethylvinylsilyl) phenyldimethylphosphine, 2-bromo-4-methoxyphenyldimethylvinylsilane, 3-bromo-4-methoxyphenyldimethylvinylsilane, 2,6-dibromo-4-methoxyphenyldimethylvinylsilane, 3,5-dibromo -4-methoxyphenyldimethylvinylsilane, 4-bromo-2-methoxyphenyldimethylvinylsilane, 4-bromo-3-methoxyphenyldimethylvinylsilane, p- (p-bromophenoxy) phenyldimethylvinylsila , 2-bromo-4-(N, N-dimethylamino) phenyl dimethyl vinyl silane, 3-bromo-4-(N, N-dimethylamino) phenyl dimethylvinylsilane.

Among these examples, preferred examples of the vinylsilane compound (B) include (p-methoxyphenyl) dimethylvinylsilane, bis (p-methoxyphenyl) methylvinylsilane, (p-methoxyphenyl) methyldivinylsilane, bis (p- Methoxyphenyl) divinylsilane, (p-ethoxyphenyl) dimethylvinylsilane, bis (p-ethoxyphenyl) methylvinylsilane, (p-ethoxyphenyl) methyldivinylsilane, bis (p-ethoxyphenyl) divinylsilane, (pn- (Propoxyphenyl) dimethylvinylsilane, (pi-propoxyphenyl) dimethylvinylsilane, (pn-butoxyphenyl) dimethylvinylsilane, (ps-butoxyphenyl) dimethylvinylsilane, (pi-butoxyphenyl) di Tilvinylsilane, (pt-butoxyphenyl) dimethylvinylsilane, (p-phenoxyphenyl) dimethylvinylsilane, (p-anisylphenyl) dimethylvinylsilane, (p-methoxyphenyl) di-n-butylvinylsilane, (p-methoxy) Methylphenyl) dimethylvinylsilane, (p-methoxyethylphenyl) dimethylvinylsilane, (p-methoxymethoxymethylphenyl) dimethylvinylsilane, (2,4-dimethoxyphenyl) dimethylvinylsilane, (p-bromophenyl) dimethylvinylsilane, (p- Bromophenyl) methyldivinylsilane, bis (p-bromophenyl) methylvinylsilane, bis (p-bromophenyl) divinylsilane, (p-chlorophenyl) dimethylvinylsilane, (p-chlorophenyl) Nyl) methyldivinylsilane, bis (p-chlorophenyl) methylvinylsilane, bis (p-chlorophenyl) divinylsilane, (p-bromophenyl) diethylvinylsilane, (p-bromophenyl) di-n-butylvinylsilane, (2,4 -Dibromophenyl) dimethylvinylsilane, (2,4,6-tribromophenyl) dimethylvinylsilane, (N, N-dimethyl-p-anilyl) dimethylvinylsilane, p- (dimethylvinylsilyl) phenylmethylsulfide, 2-bromo- 4-methoxyphenyldimethylvinylsilane, 3-bromo-4-methoxyphenyldimethylvinylsilane, 4-bromo-2-methoxyphenyldimethylvinylsilane, 4-bromo-3-methoxyphenyldimethylvinylsilane, 3-bromo-4- (N, N Mention may be made of (dimethylamino) phenyldimethylvinylsilane.
Particularly preferably, (p-methoxyphenyl) dimethylvinylsilane, bis (p-methoxyphenyl) methylvinylsilane, (p-methoxyphenyl) methyldivinylsilane, bis (p-methoxyphenyl) divinylsilane, (p-phenoxyphenyl) dimethyl Vinylsilane, (p-anisylphenyl) dimethylvinylsilane, (p-bromophenyl) dimethylvinylsilane, (p-bromophenyl) methyldivinylsilane, bis (p-bromophenyl) methylvinylsilane, bis (p-bromophenyl) divinylsilane And (2,4-dibromophenyl) dimethylvinylsilane, (N, N-dimethyl-p-anilyl) dimethylvinylsilane, and p- (dimethylvinylsilyl) phenylmethylsulfide. Most preferred are (p-methoxyphenyl) dimethylvinylsilane and (p-bromophenyl) dimethylvinylsilane.

(2-4) Action of vinylsilane compound The action of improving the performance of the polymerization catalyst when the vinylsilane compound having a specific structure of the present invention is employed will be considered.
A general vinylsilane compound has a larger steric hindrance than an α-olefin monomer and cannot be polymerized by a Ziegler-Natta catalyst. However, since an organic silyl group having a very high electron donating property exists, carbon- Since the charge density of the carbon double bond is very high, coordination to the titanium atom, which is the active center, is considered to be very fast. Therefore, it is expected that the extraction of the titanium compound into the solvent can be suppressed. Among the vinylsilane compounds having a lone electron pair, if a functional group having a lone electron pair is present at a position adjacent to the aromatic ring, it is considered that the effect of improving the catalytic activity by such titanium stabilization is further improved. That is, when a vinylsilane compound having an aromatic ring to which a free radical having a lone pair is bonded is used, it can be considered that a higher improvement effect can be expected when the lone pair exists at a position adjacent to the aromatic ring.

(3) Organosilicon compound (C)
As the organosilicon compound used in the solid catalyst component of the present invention, compounds disclosed in JP-A No. 2004-124090 can be used. In general, it is desirable to use a compound represented by the following formula.
R ¹ R ² _a Si (OR ³ ) _b
(Here, R ¹ represents a hydrocarbon group or a hetero atom-containing hydrocarbon group. R ² represents an arbitrary radical selected from hydrogen, halogen, a hydrocarbon group, and a hetero atom-containing hydrocarbon group. R ³ represents Represents a hydrocarbon group, 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, a + b = 3)
The hydrocarbon group that can be used as R ¹ is generally one having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the hydrocarbon group for R ¹ include a linear aliphatic hydrocarbon group typified by an n-propyl group, a branched aliphatic hydrocarbon typified by an i-propyl group and a t-butyl group. Groups, alicyclic hydrocarbon groups represented by cyclopentyl group and cyclohexyl group, aromatic hydrocarbon groups represented by phenyl group, and the like. More preferably, R ¹ is a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group, among others, i-propyl group, i-butyl group, t-butyl group, texyl group, cyclopentyl group, cyclohexyl group and the like. It is desirable to use When R ¹ is a heteroatom-containing hydrocarbon group, the heteroatom is preferably selected from nitrogen, oxygen, sulfur, phosphorus, and silicon, and particularly preferably nitrogen or oxygen. The skeleton structure of the hetero atom-containing hydrocarbon group of R ^1, it is desirable to select from the example of R ¹ is a hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable. R ² represents hydrogen, a halogen, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. Examples of halogen that can be used as R ² include fluorine, chlorine, bromine, and iodine. When R ² is a hydrocarbon group, it generally has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ² include a branched aliphatic hydrocarbon group represented by a methyl group or an ethyl group, a branch represented by an i-propyl group or a t-butyl group. And an aliphatic hydrocarbon group typified by a cycloaliphatic hydrocarbon group, a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. Among them, it is desirable to use a methyl group, an ethyl group, a propyl group, an i-propyl group, an i-butyl group, an s-butyl group, a t-butyl group, a texyl group, a cyclopentyl group, a cyclohexyl group, or the like. When R ² is a heteroatom-containing hydrocarbon group, it is desirable to select from the examples in the case where R ¹ is a heteroatom-containing hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable. When the value of a is 2, two R ² may be the same or different. Regardless of the value of a, R ² may be the same as or different from R ¹ . The hydrocarbon group that can be used as R ³ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Specific examples include a linear aliphatic hydrocarbon group typified by a methyl group or an ethyl group, a branched aliphatic hydrocarbon group typified by an i-propyl group or a t-butyl group, and the like. it can. Of these, a methyl group and an ethyl group are most preferable. When the value of b is 2 or more, a plurality of R ³ may be the same or different.

などを挙げることができる。これらの有機ケイ素化合物類は単独で用いるだけでなく、複数の化合物を併用することもできる。 Preferred examples of the organosilicon compound used in the present invention include t-Bu (Me) Si (OMe) ₂ , t-Bu (Me) Si (OEt) ₂ , t-Bu (Et) Si (OMe) ₂ , t _{-Bu (n-Pr) Si (} OMe) 2, c-Hex (Me) Si (OMe) 2, c-Hex (Et) Si (OMe) 2, c-Pen 2 Si (OMe) 2, c-Pr ₂ Si (OMe) ₂ , c-Bu ₂ Si (OMe) ₂ , i-Pr (i-Bu) Si (OMe) ₂ , n-Pr (Me) Si (OMe) ₂ , TexylSi (OMe) ₃ , t -BuSi (OEt) ₃ , (Et ₂ N) ₂ Si (OMe) ₂ , (Et ₂ N) Si (OEt) ₃ ,

And so on. These organosilicon compounds can be used alone or in combination with a plurality of compounds.

(4) Optional component (4-1) Organoaluminum compound (D ′)
The solid catalyst component used in the present invention is obtained by bringing the solid component (A), the vinylsilane compound (B) and the organosilicon compound (C) into contact with each other. An aluminum compound (D ′) may be contacted as an optional component.
As the organoaluminum compound that can be used in the present invention, compounds disclosed in JP-A No. 2004-124090 can be used. In general, it is desirable to use a compound represented by the following formula.
R ⁴ _c AlX _d (OR ⁵ ) _e
(Here, R ⁴ represents a hydrocarbon group. X represents a halogen or hydrogen. R ⁵ represents a hydrocarbon group or a bridging group by Al. C ≧ 1, 0 ≦ d ≦ 2, 0 ≦ e ≦ 2) , C + d + e = 3.)
R ⁴ is a hydrocarbon group, preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms. Specific examples of R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group. Among these, a methyl group, an ethyl group, and an isobutyl group are preferable. X is halogen or hydrogen. Examples of halogen that can be used as X include fluorine, chlorine, bromine, iodine, and the like. Of these, chlorine is preferred. R ⁵ is a hydrocarbon group or a bridging group by Al. When R ⁵ is a hydrocarbon group, R ⁵ can be selected from the same group as exemplified for the hydrocarbon group of R ⁴ . In addition, alumoxane compounds typified by methylalumoxane can be used as the organoaluminum compound.

  Examples of compounds that can be used as the organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum ethoxide, and methylalumoxane. . Of these, triethylaluminum and triisobutylaluminum are preferable. As the organoaluminum compound, not only a single compound but also a plurality of compounds can be used in combination.

(4-2) Compound (E ′) having at least two ether bonds
The solid catalyst component used in the present invention may be contacted with a compound (E ′) having at least two ether bonds as an optional component as long as the effects of the invention are not impaired. As the compound having at least two ether bonds that can be used in the present invention, compounds disclosed in JP-A-3-294302 and JP-A-8-333413 can be used. In general, it is desirable to use a compound represented by the following formula.
R ⁸ O−C (R ⁷ ) ₂ −C (R ⁶ ) ₂ −C (R ⁷ ) ₂ −OR ⁸
(Here, R ⁶ and R ⁷ represent any free radical selected from hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. R ⁸ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group.)
The hydrocarbon group that can be used as R ⁶ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples include linear aliphatic hydrocarbon groups typified by n-propyl groups, branched aliphatic hydrocarbon groups typified by i-propyl groups and t-butyl groups, cyclopentyl groups, and cyclohexyl groups. And an alicyclic hydrocarbon group represented by (1) and an aromatic hydrocarbon group represented by a phenyl group. More preferably, it is desirable to use a branched aliphatic hydrocarbon group or alicyclic hydrocarbon group as R ⁶ , and in particular, i-propyl group, i-butyl group, i-pentyl group, cyclopentyl group, cyclohexyl group, etc. It is desirable to use Two R ⁶ may combine to form one or more rings. In this case, a cyclopolyene structure containing 2 or 3 unsaturated bonds in the ring structure can be taken. It may also be condensed with other cyclic structures. Regardless of whether monocyclic, polycyclic, or condensed, one or more hydrocarbon groups may be present as substituents on the ring. Substituents on the ring are generally those having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples include linear aliphatic hydrocarbon groups typified by n-propyl groups, branched aliphatic hydrocarbon groups typified by i-propyl groups and t-butyl groups, cyclopentyl groups, and cyclohexyl groups. And an alicyclic hydrocarbon group represented by (1) and an aromatic hydrocarbon group represented by a phenyl group. R ⁷ represents an arbitrary radical selected from hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. Specifically, it can be selected from the examples of R ⁶ . Preferably it is hydrogen. R ⁸ represents a hydrocarbon group or a hetero atom-containing hydrocarbon group. Specifically, it can be selected from the examples when R ⁶ is a hydrocarbon group. Preferably, it is a hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkyl group. Most preferred is a methyl group.
When R ^{6 to} R ⁸ are hetero atom-containing hydrocarbon groups, the hetero atom is preferably selected from nitrogen, oxygen, sulfur, phosphorus, and silicon. Regardless of whether R ^{6 to} R ⁸ are hydrocarbon groups or heteroatom-containing hydrocarbon groups, they may optionally contain halogen. When R ^{6 to} R ⁸ contain a hetero atom and / or halogen, the skeleton structure is preferably selected from the examples in the case of a hydrocarbon group. Moreover, the substituents of R ^{6 to} R ⁸ may be the same as or different from each other.

Preferred examples of the compound having at least two ether bonds that can be used in the present invention include 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2 -Diisobutyl-1,3-diethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1, 3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-t-butyl-1,3-dimethoxypropane, 2-methyl-2-phenyl- 1,3-dimethoxypropane, 9,9-bis (methoxymethyl) fluorene, 9, -Bis (methoxymethyl) -1,8-dichlorofluorene, 9,9-bis (methoxymethyl) -2,7-dicyclopentylfluorene, 9,9-bis (methoxymethyl) -1,2,3,4 Tetrahydrofluorene, 1,1-bis (1′-butoxyethyl) cyclopentadiene, 1,1-bis (α-methoxybenzyl) indene, 1,1-bis (phenoxymethyl) -3,6-dicyclohexylindene, 1, Examples thereof include 1-bis (methoxymethyl) benzonaphthene and 7,7-bis (methoxymethyl) -2,5-nobornadinene. Among them, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl -1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, and 9,9-bis (methoxymethyl) fluorene are preferred.
These compounds having at least two ether bonds can be used not only alone but also in combination with a plurality of compounds. Further, it may be the same as or different from the polyvalent ether compound used as the electron donor (F ′) which is an optional component in the solid component (A).

(5) Preparation method of solid catalyst component (5-1) Contact method The solid catalyst component used in the present invention is obtained by contacting the solid component (A), the vinylsilane compound (B) and the organosilicon compound (C). . At this time, other optional components such as the organoaluminum compound (D ′) and the compound (E ′) having at least two ether bonds may be brought into contact with each other by any method as long as the effects of the present invention are not impaired. . As the contact condition of each constituent component of the solid catalyst component, it is necessary that oxygen does not exist, but any condition can be used as long as the effect of the present invention is not impaired. In general, the following conditions are preferred.
The contact temperature is about −50 to 200 ° C., preferably −10 to 100 ° C., more preferably 0 to 70 ° C., and particularly preferably 10 ° C. to 60 ° C. Examples of the contact method include a mechanical method using a rotating ball mill and a vibration mill, and a method of contacting by stirring in the presence of an inert diluent. Preferably, it is desirable to use a method of contacting with stirring in the presence of an inert diluent.

(5-2) Component Amount Ratio The amount ratio of each component constituting the solid catalyst component in the present invention may be any as long as it does not impair the effects of the present invention. The following range is preferable. The amount of the vinylsilane compound (B) used is a molar ratio to the titanium component constituting the solid component (A) (number of moles of vinylsilane compound (B) / number of moles of titanium atoms), preferably 0.001 to 1,000. And particularly preferably within the range of 0.01 to 100.
The amount of the organosilicon compound (C) used is a molar ratio with respect to the titanium component constituting the solid component (A) (number of moles of organosilicon compound (C) having an alkoxy group / number of moles of titanium atoms), preferably It is in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100.
The amount used in the case of using an organoaluminum compound as an optional component is the atomic ratio of aluminum to the titanium component constituting the solid component (A) (number of moles of aluminum atoms / number of moles of titanium atoms), preferably from 0.1. It is within the range of 100, and particularly preferably within the range of 1 to 50. When a compound having at least two ether bonds is used as an optional component, the amount used is a molar ratio to the titanium component constituting the solid component (A) (number of moles of compound having at least two ether bonds / number of moles of titanium atoms). ), Preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100.

(5-3) Contacting Procedure Regarding the contacting procedure of the solid component (A), the vinylsilane compound (B) and the organosilicon compound (C), any procedure can be used. As a specific example,
Procedure [1]: Method of contacting the organosilane compound (C) after contacting the vinylsilane compound (B) with the solid component (A) Procedure [2]: Organosilicon compound (C) with the solid component (A) Method of contacting vinylsilane compound (B) after contacting Procedure [3]: A method of contacting all compounds simultaneously can be exemplified. Among these, the procedure [1] and the procedure [3] are preferable. Also, the vinyl silane compound (B) and the organosilicon compound (C) can be brought into contact with the solid component (A) any number of times. At this time, both the vinylsilane compound (B) and the organosilicon compound (C) may be the same or different from each other. When an organoaluminum compound is further used as an optional component, it can be contacted in any order as described above. Among these,
Procedure [4]: Method of contacting the vinylsilane compound (B) with the solid component (A), then contacting the organosilicon compound (C), and further contacting the organoaluminum compound (D ′) Procedure [5]: Solid Method in which the vinylsilane compound (B) and the organosilicon compound (C) are contacted with the component (A), and then the organoaluminum compound (D ′) is contacted. Procedure [6]: A method in which all the compounds are simultaneously contacted is preferable. . The organoaluminum compound can be contacted a plurality of times as described above. At this time, the organoaluminum compounds used a plurality of times may be the same or different. Even when the compound (E ′) having at least two ether bonds and / or other compounds are used as optional components, they can be contacted in any order as described above.
In the preparation of the solid catalyst component (A-1), washing with an inert solvent may be performed in the middle and / or finally. Examples of preferable solvent species include aliphatic hydrocarbon compounds such as heptane, aromatic hydrocarbon compounds such as toluene, and halogen-containing hydrocarbon compounds such as 1,2-dichloroethylene and chlorobenzene.

3. Organoaluminum compound (D)
In the polymerization catalyst of the present invention, it is essential to use a solid catalyst component and an organoaluminum compound (D) as catalyst components. As the organoaluminum compound (D) that can be used in the present invention, compounds disclosed in JP-A No. 2004-124090 can be used. Preferably, it can be selected from the same group as exemplified in the organoaluminum compound (D ′) which is an optional component in preparing the solid catalyst component. At this time, the organoaluminum compound (D ′) used as an optional component in preparing the solid catalyst component and the organoaluminum compound (D) used as an essential component of the catalyst may be the same or different. As the organoaluminum compound (D), not only a single compound but also a plurality of compounds can be used in combination.
The amount of the organoaluminum compound (D) used is a molar ratio to the titanium component constituting the solid catalyst component (number of moles of organoaluminum compound (D) / number of moles of titanium atoms), preferably in the range of 1 to 5,000. And particularly preferably within the range of 10 to 500.

4). Other optional components in the catalyst In the polymerization catalyst of the present invention, it is essential to use the solid catalyst component and the organoaluminum compound (D) as the catalyst component. However, the organosilicon compound ( Any component such as C ′) and the compound (E) having at least two ether bonds can be used.
(1) Organosilicon compound (C ′)
As the organosilicon compound (C ′) used as an optional component in the polymerization catalyst of the present invention, compounds disclosed in JP-A No. 2004-124090 can be used. Preferably, it can be selected from the same group as exemplified in the organosilicon compound (C) used in the solid catalyst component. At this time, the organosilicon compound (C) used as an essential component in preparing the solid catalyst component and the organosilicon compound (C ′) used as an optional component of the catalyst may be the same or different. As the organosilicon compound (C ′), not only a single compound but also a plurality of compounds can be used in combination.

(2) Compound (E) having at least two ether bonds
As the compound (E) having at least two ether bonds that can be used as an optional component in the polymerization catalyst of the present invention, the compounds disclosed in JP-A-3-294302 and JP-A-8-333413 are used. Can do. Preferably, it can be selected from the same group as exemplified in the compound (E ′) having at least two ether bonds used in the solid catalyst component. At this time, the compound (E ′) having at least two ether bonds used as an optional component in preparing the solid catalyst component and the compound (E) having at least two ether bonds used as an optional component of the catalyst are the same. May be different. As the compound having at least two ether bonds, not only a single compound but also a plurality of compounds can be used in combination.

(3) Other optional components As long as the effects of the present invention are not impaired, components other than the organosilicon compound (C ′) and the compound (E) having at least two ether bonds can be used as optional components of the catalyst. . For example, a compound similar to the previous electron donor (F ′) is used as the electron donor (F), or as disclosed in JP-A-2004-124090, C (═O) N By using the compound (G) having a bond, it is possible to suppress the formation of an amorphous component such as a cold xylene-soluble component (CXS). In this case, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 1-ethyl-2-pyrrolidinone and the like can be mentioned as preferred examples. As the compound (G) having a C (═O) N bond in the molecule, not only a single compound but also a plurality of compounds can be used in combination. An organometallic compound having a metal atom other than aluminum, such as diethyl zinc, can also be used.

(4) Component Amount Ratio of Arbitrary Component The amount of the optional component used in the catalyst of the present invention may be arbitrary as long as the effects of the present invention are not impaired, but generally it is preferably within the following range. The amount used in the case of using the organosilicon compound (C ′) is a molar ratio to the titanium component constituting the solid catalyst component (the number of moles of the organosilicon compound (C ′) / the number of moles of titanium atoms), preferably 0.00. It is in the range of 01 to 50,000, particularly preferably in the range of 0.5 to 500.
When the compound (E) having at least two ether bonds is used, the amount used is a molar ratio to the titanium component constituting the solid catalyst component (the number of moles of the compound (E) having at least two ether bonds / mol of titanium atoms). Number), preferably in the range of 0.01 to 50,000, particularly preferably in the range of 0.5 to 500.
When the compound (G) having a C (= O) N bond in the molecule is used, the amount used is a molar ratio to the titanium component constituting the solid catalyst component (compound having a C (= O) N bond in the molecule ( The number of moles of G) / the number of moles of titanium atoms) is preferably in the range of 0.001 to 5,000, particularly preferably in the range of 0.05 to 500.

5. Prepolymerization The solid catalyst component in the present invention may be prepolymerized before being used in the main polymerization. As the monomer in the prepolymerization, compounds disclosed in JP-A No. 2004-124090 can be used. Specific examples of the compound include olefins typified by ethylene, propylene, 1-butene, 3-methylbutene-1, 4-methylpentene-1, styrene, α-methylstyrene, allylbenzene, chlorostyrene, and the like. And 1,3-butadiene, isoprene, 1,3-pentadiene, 1,5-hexadiene, 2,6-octadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,9-decadiene And diene compounds represented by divinylbenzene and the like. Among these, ethylene, propylene, 3-methylbutene-1, 4-methylpentene-1, styrene, divinylbenzenes and the like are preferable.
In the case of using a prepolymerized solid catalyst component, the prepolymerization can be performed by an arbitrary procedure in the preparation procedure of the solid catalyst component. For example, after prepolymerizing the solid component (A), the vinylsilane compound (B) and the organosilicon compound (C) can be contacted. Moreover, after making a solid component (A), a vinylsilane compound (B), and an organosilicon compound (C) contact, prepolymerization can also be performed. Furthermore, when the solid component (A), the vinylsilane compound (B) and the organosilicon compound (C) are brought into contact with each other, preliminary polymerization may be performed simultaneously.
Arbitrary conditions can be used for the reaction conditions of a solid catalyst component or a solid component (A), and said monomer in the range which does not impair the effect of this invention. In general, the following range is preferable. The amount of prepolymerization is in the range of 0.001 to 100 g, preferably 0.1 to 50 g, more preferably 0.5 to 10 g, based on the solid catalyst component or solid component (A) per gram. Is desirable. As a method for supplying the monomer, any method can be used such as a method for maintaining the monomer in the reaction tank at a constant speed, a constant pressure state or a constant concentration, a combination thereof, or a stepwise change. The reaction temperature during the prepolymerization is -150 to 150 ° C, preferably 0 to 100 ° C. And it is desirable to make the reaction temperature at the time of preliminary polymerization lower than the polymerization temperature at the time of main polymerization. The prepolymerization time is preferably in the range of 5 minutes to 24 hours. In general, the reaction is preferably carried out with stirring, and an inert solvent such as hexane or heptane can also be present.
The prepolymerization may be performed a plurality of times, and the monomers used at this time may be the same or different. Moreover, it can wash | clean with inert solvents, such as hexane and heptane, after preliminary polymerization. After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst, but may be dried if necessary.
Further, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can coexist during or after the contact of the above components.

6). Polymerization of α-olefin (1) Polymerization conditions α-olefin polymerization using the novel polymerization catalyst of the present invention is slurry polymerization using a hydrocarbon solvent, liquid phase solventless polymerization using substantially no solvent, or gas phase. Applied to polymerization and so on. As a polymerization solvent in the case of slurry polymerization, hydrocarbon solvents such as pentane, hexane, heptane and cyclohexane are used. The polymerization method employed may be any method such as continuous polymerization, batch polymerization or multistage polymerization. The polymerization temperature is usually about 30 to 200 ° C., preferably 50 to 150 ° C. At that time, hydrogen can be used as a molecular weight regulator.

(2) α-Olefin The α-olefin polymerized by the catalyst of the present invention has the general formula R—CH═CH ₂ (wherein R is a hydrocarbon group having 1 to 20 carbon atoms and has a branched group. It may also be represented by). Specifically, α-olefins such as propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1.
In addition to homopolymerization of these α-olefins, copolymerization with monomers (for example, 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.

(3) α-Olefin Polymer The index (characteristic value) of the α-olefin polymer polymerized according to the present invention is not particularly limited, and can be appropriately adjusted according to various applications. In general, the MFR of the α-olefin polymer is preferably in the range of 0.01 to 10,000 g / 10 minutes, particularly preferably in the range of 0.1 to 1,000 g / 10 minutes. .
The amount of cold xylene solubles (CXS), which is an amorphous component, generally varies in preferred range depending on the application. For applications where high rigidity is preferred, such as injection molding applications, the amount of CXS is preferably in the range of 0.01 to 3.0% by weight, particularly preferably 0.05 to 1.5% by weight. And particularly preferably within the range of 0.1 to 1.0% by weight. Here, the value of CXS is a value measured by the method defined in the following examples.
Further, the polymer particles obtained by the present invention exhibit excellent particle properties. In general, the particle properties of polymer particles are evaluated by polymer bulk density, particle size distribution, particle appearance, and the like. In particular, the polymer particles obtained according to the invention have a polymer bulk density in the range of 0.35 to 0.55 g / ml, preferably in the range of 0.40 to 0.50 g / ml.

  In order to describe the present invention more specifically, preferred examples and comparative examples corresponding thereto are described below. The contrast between each example and each comparative example demonstrates the rationality and significance of the requirements of the configuration of the present invention, and further demonstrates the superiority of the present invention over the prior art.

The measurement methods of various physical properties, the production methods of α-olefin polymers, the evaluation methods thereof and the like in the following Examples and Comparative Examples are as follows.
[Measurement method of physical properties]
1) MFR
Apparatus: Melt indexer manufactured by Takara Co., Ltd. Measuring method: Based on JIS-K6921, evaluation was performed under the conditions of 230 ° C. and 21.18 N.
2) Polymer bulk density The bulk density of the powder sample was measured using an apparatus according to ASTM D1895-69.
3) CXS
The sample (about 5 g) was completely dissolved once in 140 ° C. p-xylene (300 ml). Thereafter, the mixture was cooled to 23 ° C., and a polymer was precipitated at 23 ° C. for 12 hours. After the precipitated polymer was filtered off, p-xylene was evaporated from the filtrate. The polymer remaining after evaporation of p-xylene was dried under reduced pressure at 100 ° C. for 2 hours. The polymer after drying was weighed, and the value of CXS was obtained as the weight% with respect to the sample.
4) Density Using the extruded strand obtained at the time of MFR measurement, the density gradient tube method was used according to JIS-K7112 D method.

[Preparation of vinylsilane compound (B)]
As the vinylsilane compound (B) employed in the examples, a commercially available product (manufactured by Shin-Etsu Chemical Co., Ltd.) was used. (In addition, these vinylsilane compounds can generally be obtained by the reaction of trichlorovinylsilane and a Grignard reagent.)

[Example 1]
(Preparation of solid component (A))
A 10 L autoclave equipped with a stirrer was sufficiently replaced with nitrogen, and 2 L of purified toluene was introduced. To this, 200 g of Mg (OEt) ₂ and 1 L of TiCl ₄ were added at room temperature. The temperature was raised to 90 ° C. and 50 ml of di-n-butyl phthalate was introduced. Thereafter, the temperature was raised to 110 ° C. to carry out a reaction for 3 hours. The reaction product was thoroughly washed with purified toluene. Subsequently, the refined toluene was introduce | transduced and the whole liquid quantity was adjusted to 2L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was performed for 2 hours. The reaction product was thoroughly washed with purified toluene. Subsequently, the refined toluene was introduce | transduced and the whole liquid quantity was adjusted to 2L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was performed for 2 hours. The reaction product was thoroughly washed with purified toluene. Furthermore, the solid component (A) was obtained by substituting the solvent for n-heptane using the refined n-heptane, and vacuum-drying. As a result of analysis, the Ti content of the solid component (A) was 2.8 wt%.

(Preparation of solid catalyst component)
A glass flask having a capacity of 500 ml equipped with a stirrer was sufficiently replaced with nitrogen, and 4 g of the solid component (A) was introduced. Thereafter, purified n-heptane was introduced to adjust the concentration of the solid component (A) to 20 g / L. Here, 1.0 ml of (p-methoxyphenyl) dimethylvinylsilane is used as the vinylsilane compound (B), 1.0 ml of t-Bu (Me) Si (OMe) ₂ is used as the organosilicon compound (C), and n of Et ₃ Al - heptane diluent 1.5g was added as _Et 3 Al, were 2hr reaction at 30 ° C.. The reaction product was thoroughly washed with purified n-heptane.
Next, purified n-heptane was introduced into the slurry, and the concentration of the solid component (A) was adjusted to 20 g / L. After cooling the slurry to 15 ° C., the n- heptane dilution of _Et 3 Al 0.5 g was added as _Et 3 Al, were fed slowly propylene 9g. After the supply of propylene was completed, the reaction was further continued for 10 minutes. Next, the gas phase was sufficiently replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. Thereafter, vacuum drying was performed to obtain a solid catalyst component. This solid catalyst component contained 2.0 g of polypropylene per 1 g of the solid component. As a result of analysis, the portion of the solid catalyst component excluding polypropylene contained 1.9 wt% Ti and 3.6 wt% t-Bu (Me) Si (OMe) ₂ .

(Propylene polymerization)
A stainless steel autoclave having an internal volume of 3.0 L having a stirring and temperature control device was sufficiently heated and dried, and then cooled to room temperature. After thoroughly purging the autoclave with propylene, an organic aluminum compound (D) as _Et 3 Al of n- heptane diluent was 550mg added as _Et 3 Al. Next, 8,000 ml of hydrogen and 1,000 g of propylene were sequentially introduced into the autoclave. After adjusting the internal temperature of the autoclave to 70 ° C., 7 mg (excluding the prepolymerized polymer) of the solid catalyst component prepared above was injected to initiate polymerization. After 1 hour, 10 ml of ethanol was injected to terminate the polymerization. When the polymer was dried and weighed, 58,800 g of polymer was obtained per gram of the solid catalyst component excluding the prepolymerized polymer (hereinafter referred to as “catalytic activity 58,800 g / g-catalyst”). . The analysis results of the obtained polymer are shown in Table 1.

[Example 2]
The same procedure as in Example 1 was conducted except that (p-bromophenyl) dimethylvinylsilane was used instead of (p-methoxyphenyl) dimethylvinylsilane as the vinylsilane compound (B). The results are shown in Table 1.

[Comparative Example 1]
The same procedure as in Example 1 was performed except that vinyltrimethylsilane was used instead of (p-methoxyphenyl) dimethylvinylsilane as the vinylsilane compound (B). The results are shown in Table 1.
[Comparative Example 2]
As a vinyl silane compound (B), it carried out like Example 1 except having used p-tolyl dimethyl vinyl silane instead of (p-methoxyphenyl) dimethyl vinyl silane. The results are shown in Table 1.

[Example 3]
(Preparation of solid component (A))
A 10 L autoclave equipped with a stirrer was sufficiently replaced with nitrogen, and 2 L of purified n-heptane was introduced. Further, 250 g of MgCl ₂ and 1.8 L of Ti (On-Bu) ₄ were added, and a reaction was performed at 95 ° C. for 2 hours. The reaction product was cooled to 40 ° C. and 500 ml of methyl hydrogen polysiloxane (20 centistokes) was added. After 5 hours of reaction at 40 ° C., the precipitated solid product was thoroughly washed with purified n-heptane.
Subsequently, purified n-heptane was introduced to adjust the concentration of the solid product to 200 g / L. Here, 300 ml of SiCl ₄ was added and a reaction was carried out at 90 ° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced so that the concentration of the reaction product was 100 g / L. A liquid prepared by mixing 30 ml of phthalic acid dichloride with 270 ml of purified n-heptane was prepared in advance, and the mixed liquid was added to an autoclave and reacted at 90 ° C. for 1 hr. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced so that the concentration of the reaction product was 200 g / L. To this, 1 L of TiCl ₄ was added and a reaction was carried out at 95 ° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane to obtain a slurry of the solid component (A). A portion of this slurry was sampled and dried. As a result of analysis, the Ti content of the solid component (A) was 2.5 wt%.

(Preparation of solid catalyst component)
A 500 ml glass flask equipped with a stirrer was sufficiently replaced with nitrogen, and 4 g of the solid component (A) slurry was introduced as a solid component (A). Thereafter, purified n-heptane was introduced to adjust the concentration of the solid component (A) to 20 g / L. Here, 1.5 ml of (p-methoxyphenyl) dimethylvinylsilane as the vinylsilane compound (B), 1.5 ml of (c-Pen) ₂ Si (OMe) ₂ as the organosilicon compound (C), n of Et ₃ Al - heptane diluent 1.5g was added as _Et 3 Al, were 2hr reaction at 30 ° C.. The reaction product was thoroughly washed with purified n-heptane.
Next, purified n-heptane was introduced into the slurry, and the concentration of the solid component (A) was adjusted to 20 g / L. After cooling the slurry to 15 ° C., the n- heptane dilution of _Et 3 Al 0.5 g was added as _Et 3 Al, were fed slowly propylene 9g. After the supply of propylene was completed, the reaction was further continued for 10 minutes. Next, the gas phase was sufficiently replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. Thereafter, vacuum drying was performed to obtain a solid catalyst component. This solid catalyst component contained 2.0 g of polypropylene per 1 g of the solid component. As a result of analysis, the portion of the solid catalyst component excluding polypropylene contained 1.7 wt% Ti and 5.5 wt% (c-Pen) ₂ Si (OMe) ₂ .

(Propylene polymerization)
A stainless steel autoclave having an internal volume of 3.0 L having a stirring and temperature control device was sufficiently heated and dried, and then cooled to room temperature. After sufficiently substituting the inside of the autoclave with propylene, 550 mg of Et ₃ Al as an organoaluminum compound (D) as an Et ₃ Al diluted solution as Et ₃ Al and (i-Pr) ₂ Si as an optional organosilicon compound 85 mg of (OMe) ₂ was added. Next, 5,000 ml of hydrogen and 1,000 g of propylene were sequentially introduced into the autoclave. After adjusting the internal temperature of the autoclave to 75 ° C., 7 mg (excluding the prepolymerized polymer) of the solid catalyst component prepared above was injected to initiate polymerization. After 1 hour, 10 ml of ethanol was injected to terminate the polymerization. The polymer was dried and weighed. The results are shown in Table 2.

[Comparative Example 3]
The same procedure as in Example 3 was performed except that p-tolyldimethylvinylsilane was used in place of (p-methoxyphenyl) dimethylvinylsilane as the vinylsilane compound. The results are shown in Table 1.

[Consideration of results of Examples and Comparative Examples]
By contrasting the above Examples 1 to 3 and Comparative Examples 1 to 3 of the prior art, the present invention is superior to the comparative example in terms of catalyst activity, polymer bulk density, cold xylene solubles (CXS), etc. It is clear that the results are obtained.
Specifically, in comparison with Comparative Examples 1 and 2, Examples 1 and 2 have high catalytic activity and polymer bulk density, good CXS, and the same density.
Compared with Comparative Example 3, Example 3 also has high catalytic activity and polymer bulk density, good CXS, and the density is equivalent.
Therefore, in the polymerization catalyst of the present invention, the activity of the catalyst is high and the stereoregularity and particle properties of the polymer are good, and the rationality and significance of the requirements of the composition of the present invention and the superiority over the prior art are proved. Has been.

It is a flowchart figure which shows the structural component of the polymerization catalyst of this invention.

Claims (8)

An α-olefin polymerization catalyst comprising the following components [i] and [ii], wherein the vinylsilane compound (B) is a vinylsilane compound (B) represented by the following formula: Catalyst .
[I] Solid catalyst component (I) obtained by contacting the following components (I) to (III): Solid component (A) containing titanium, magnesium and halogen as essential components
(II) Vinylsilane compound (B)

(Wherein R represents a hydrocarbon group, hydrogen atom or halogen, X represents a free radical having a lone pair, 1 ≦ i ≦ 3, 0 ≦ j ≦ 2, 1 ≦ k ≦ 3, i + j + k. = 4)
(III) Organosilicon compound (C)
[Ii] Organoaluminum compound (D) The α-olefin polymerization catalyst according to claim 1, wherein one or more of the following components [iii] to [v] are used.
[Iii] Organosilicon compound (C ′)
[Iv] Compound (E) having at least two ether bonds
[V] Electron donor compound (F) Further, component (I) uses an electron donor compound (F ′), and component [i] uses an organoaluminum compound (D ′) and / or a compound (E ′) having at least two ether bonds. The α-olefin polymerization catalyst according to claim 1, wherein the catalyst is for α-olefin polymerization. The catalyst for α-olefin polymerization according to any one of claims 1 to 3, wherein the vinylsilane compound (B) is a compound represented by the following formula.

(Wherein R represents a hydrocarbon group, hydrogen atom or halogen, X represents a free radical having a lone pair, 1 ≦ i ≦ 3, 0 ≦ j ≦ 2, 1 ≦ k ≦ 3, i + j + k. = 4) The catalyst for α-olefin polymerization according to any one of claims 1 to 3, wherein the vinylsilane compound (B) is a compound represented by the following formula.

(Wherein R represents a hydrocarbon group, a hydrogen atom or a halogen, Y represents a functional group having a lone pair of electrons. R ′ represents a hydrocarbon group, a hydrogen atom or a halogen, and R ′ represents a hydrocarbon group. In some cases, it may be optionally substituted with a functional group having a lone pair of electrons: 1 ≦ i ≦ 3, 0 ≦ j ≦ 2, 1 ≦ k ≦ 3, 0 ≦ z ≦ 3, i + j + k = 4 is there.) The α-olefin polymerization catalyst according to any one of claims 1 to 5, wherein the lone electron pair in X or Y in the vinylsilane compound (B) is derived from a hetero atom. . The catalyst for α-olefin polymerization according to any one of claims 1 to 5, wherein the lone pair of electrons in X or Y in the vinylsilane compound (B) is derived from a halogen atom. . A method for producing an α-olefin polymer or copolymer, wherein the α-olefin is polymerized or copolymerized using the α-olefin polymerization catalyst according to any one of claims 1 to 7. .

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