JP4460049B2 - α-Olefin Polymerization Catalyst Component, α-Olefin Polymerization Catalyst, and Method for Producing α-Olefin Polymer Using the Same - Google Patents

Description

  The present invention relates to an α-olefin polymerization catalyst component, an α-olefin polymerization catalyst, and an α-olefin polymerization method using the same. More specifically, the present invention relates to a heavy catalyst having excellent melt tension and the like by polymerizing α-olefin using a catalyst obtained by combining an organoaluminum compound with a solid catalyst component using a specific divalent carboxylic acid diester. The present invention relates to a highly active olefin polymerization catalyst for obtaining a coalescence and an α-olefin polymerization method using the same.

Polyolefins such as polyethylene and polypropylene are one of the most widely used plastics because of their excellent physical properties, economic efficiency, ease of molding, and adaptability to environmental problems. Researches on polymerization methods and polymerization catalysts are being continued actively. Among the polymerization catalysts, Ziegler type catalysts are the main ones, and many improvements have been disclosed in the past regarding catalyst activity and stereoregularity.
In addition to transition metal halide compounds and organoaluminum components in Ziegler-based catalysts, the use of magnesium halide supports and electron donors improves stereoregularity, simplifies the post-treatment process, and the use of organosilicon compounds Significant improvements have been made, such as further regularity.

Specifically, as a basic improvement technique, a solid catalyst component containing titanium, magnesium, halogen and an electron donor is used, and an α-olefin steric compound is used in combination with an organoaluminum compound and an electron donor as necessary. Many proposals have been made to produce ordered polymers in high yield (see, for example, Patent Documents 1 and 2).
However, a propylene polymer obtained using a magnesium-supporting Ziegler-Natta catalyst generally has a narrow molecular weight distribution as compared with a propylene polymer obtained using conventional titanium trichloride. A propylene polymer having a narrow molecular weight distribution has a low melt tension, so that the fluidity at the time of melting deteriorates and causes a problem at the time of molding. Recently, high-speed stretching and high-speed molding have been promoted in order to increase the productivity of stretched films, but problems such as film neck-in and fluttering occur when operating with a propylene polymer having a low melt tension. It is difficult to increase the speed. Therefore, a propylene polymer having a higher melt tension is necessary in order to stabilize and increase the molding speed.

In order to solve such problems, many methods for widening the molecular weight distribution have been proposed. For example, although a method using two alkoxysilicon compounds having different hydrogen responsiveness has been shown (Patent Document 3), in general, the properties of one compound appear strongly depending on use conditions and mixing conditions. Optimization is considered difficult. The use of trialkoxysilicon compounds (Patent Document 4) and the use of silicon compounds having saturated polycyclic hydrocarbon groups (Patent Document 5) are also disclosed, but they are sufficiently satisfactory in physical properties such as molecular weight distribution and stereoregularity. Is not to be done. In Patent Document 6 and the like, it is proposed to use an alkoxysilicon compound having a cyclic amino group, and although the effect on the molecular weight distribution is recognized, the odor peculiar to an amino group because the compound remains in the obtained polymer. And therefore limited in its application.
Further, Patent Document 7 and the like show a method using a sulfonic acid derivative compound as a third component. However, although the rigidity of the resin processed product improved as the molecular weight distribution is increased, the catalyst yield is increased. The stereoregularity is also lowered.

Furthermore, although Patent Documents 8 and 9 exemplify a linear saturated polycarboxylic acid ester as an internal donor, an effect on the molecular weight distribution is not recognized.
Recently, Patent Documents 10 and 11 disclose a catalyst that uses succinic acid diester as a catalyst component to increase polymer yield and stereoregularity, and Patent Document 12 discloses a polymer that uses succinic acid diester as a catalyst component. Although a catalyst that improves yield and stereoregularity and further expands the molecular weight distribution is disclosed, it cannot be said that the effect on the molecular weight distribution is sufficiently satisfied.

  As described above, in the field of polyolefins, many improvements have been made and disclosed on the Ziegler catalyst, which is the most important catalyst. However, molecular weight distribution, catalytic activity, stereoregularity, physical properties of the polymer produced, etc. In many respects, a very good catalyst has not yet been obtained.

JP-A-55-90511 (Claims, upper left column on page 2) JP 58-138711 (Claims, lower right column on page 1) JP-A-6-298835 (summary) Japanese Patent Laid-Open No. 10-176008 (summary) JP 10-204115 A (summary) JP-A-11-302314 (Abstract) JP-A-9-110922 (summary) JP 58-138706 A (Claims) JP 58-138708 A (Claims) WO00 / 63261 international publication pamphlet (summary, page 31) WO01 / 57099 international publication pamphlet (summary, page 11) WO02 / 30998 international publication pamphlet (summary, page 17)

  An object of the present invention is to solve the recent important problems of Ziegler catalysts described in paragraphs 0003 to 0006. Specifically, the present invention broadens the molecular weight distribution and improves the melt tension. It is an object of the present invention to develop a catalyst that can produce an α-olefin polymer that can be produced, has high catalytic activity, and is excellent in high-speed moldability.

In order to solve the above-mentioned problems, the present inventors have been able to broaden the molecular weight distribution and improve the melt tension, and seek a catalyst having high catalytic activity through various considerations and experiments on various catalyst components. In the process, the adsorption mode of the catalyst component to the magnesium compound component, that is, the diversity of active site precursors, is considered to be involved in the broadening of the molecular weight distribution. We came to infer that it is deeply related to the electronic contribution and the three-dimensional contribution.
As a result of examining various components based on such inference, a tartaric acid diester compound or malic acid diester compound as a specific compound in the butanedioic acid diester which is a carboxylic acid ester is used as a new catalyst component. For example, it was found that the molecular weight distribution can be expanded and the catalytic activity can be increased, and the present invention was filed as a prior invention (Japanese Patent Application No. 2002-295455), and the related invention was also filed (Japanese Patent Application No. 2002-2002). 375456 and Japanese Patent Application No. 2002-376040), and the present inventors have further studied this catalyst component and studied the catalyst component in order to solve the above-mentioned problems. As a new catalyst component, specifically a so-called internal As donor (electron donor), the use, in the same manner as the invention of the prior application, it is possible to broaden the molecular weight distribution, and has also been found that can increase the catalytic activity.

This new knowledge forms the basic requirement of the present invention and constitutes an excellent catalyst invention that has not been known so far. Specifically, it includes 15 group atoms such as nitrogen and phosphorus. A compound in which a hydrocarbon substituent or the like is substituted on the main skeleton (main chain) of butanedioic acid diester through a catalyst is used as a new catalyst component, and titanium, magnesium, halogen, and the above specific butanedioic acid By using a solid catalyst component obtained by contacting with a diester, an α-olefin polymer having a wide molecular weight distribution can be obtained in a high yield.
In addition, each of the aforementioned international publication pamphlets (described in paragraph 0005) of the above-mentioned prior art discloses a catalyst component of butanedioic acid diester related to the present invention, but the molecular weight distribution is sufficiently widened by these catalysts. In the present invention, butanedioic acid diester type compounds are used, but the hydrocarbon substituents and the like are substituted with butanedioic acid diester via 15 group atoms represented by nitrogen and phosphorus. By adopting for the first time a special compound substituted on the main skeleton (main chain), it is surprising that the molecular weight distribution can be effectively expanded, resulting in a dramatic improvement in melt tension for high-speed moldability. It was.

  That is, the first invention in the present invention is an α-olefin polymerization catalyst component (component (component (1)) containing titanium, magnesium, halogen, and butanedioic acid diester represented by the following general formula [1] or [2] as essential components. A)).

（ここでＲ^１、Ｒ^２は同一又は異なってもよい炭素数１から２０の直鎖状、分岐状又は環状の炭化水素基を示し、Ｒ^３は炭素数１から２０の直鎖状、分岐状もしくは環状の炭化水素基、又は炭化水素基を有するシラヒドロカルビル基を示し、Ｒ^４、Ｒ^７及びＲ^８は、水素又はＲ^３と同一もしくは異なってもよい炭素数１から２０の直鎖状、分岐状もしくは環状の炭化水素基、又は炭化水素基を有するシラヒドロカルビル基を示し、Ｒ^５、Ｒ^６、及びＲ^９は、水素又は炭素数１から２０の直鎖状、分岐状もしくは環状の炭化水素基を示し、Ｘは１５族から選ばれる原子を示す。〔なお、本明細書の記載においては、元素の周期律表としては、原則として、ＩＵＰＡＣ−１９８９年方式を採用している。〕）
本発明は、上記の第一の発明を基本発明単位として、以下の第二〜第七の発明単位をも含むものである。

(Wherein R ¹ and R ² represent a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may be the same or different, and R ³ represents a linear or branched hydrocarbon group having 1 to 20 carbon atoms. Or a cyclic hydrocarbon group or a silahydrocarbyl group having a hydrocarbon group, wherein R ⁴ , R ⁷ and R ⁸ are hydrogen or a straight chain having 1 to 20 carbon atoms which may be the same as or different from R ³ , A branched or cyclic hydrocarbon group, or a silahydrocarbyl group having a hydrocarbon group, wherein R ⁵ , R ⁶ , and R ⁹ are hydrogen or a linear, branched or cyclic group having 1 to 20 carbon atoms Represents a hydrocarbon group, and X represents an atom selected from Group 15. [In the description of this specification, the IUPAC-1989 system is adopted in principle as the periodic table of elements. ])
The present invention includes the following second to seventh invention units based on the first invention as a basic invention unit.

Second invention: The catalyst component for α-olefin polymerization according to the first invention, comprising an organosilicon compound and / or a diether compound component and an organoaluminum compound component.
Third invention: In the first invention or the second invention, R ⁵ , R ⁶ and R ^{9 in} the general formula [1] or [2] are hydrogen, α-olefin polymerization catalyst component .
Fourth invention: In the first invention or the second invention, butanedioic acid diester is symmetric in which R ¹ and R ^2, R ³ , R ⁴ , R ⁷ and R ^8, and R ⁵ and R ⁶ are the same. A catalyst component for α-olefin polymerization, characterized by having a structure.
Fifth invention: α-olefin polymerization catalyst comprising the catalyst component for α-olefin polymerization (component (A)) of the first invention to the fourth invention and an organoaluminum compound (component (B)). .
Sixth invention: α-olefin polymerization catalyst component (component (A)), organoaluminum compound (component (B)), organosilicon compound and / or diether compound (component (C A catalyst for α-olefin polymerization, comprising a compound selected from:
7th invention: The manufacturing method of the alpha-olefin polymer characterized by superposing | polymerizing or copolymerizing alpha-olefin in presence of the catalyst for alpha-olefin polymerization of 5th invention or 6th invention.

According to the present invention, it is possible to obtain an α-olefin polymer having a high ME (rheological characteristics described in paragraph 0092) and a high melt tension in a high yield. It is suitably used for the production of packaging materials such as films and sheets and their applications, which require excellent moldability.
Such a feature is particularly advantageous at the time of molding in industrial production such as resin processing, and is excellent in high-speed stretching and high-speed moldability, and in production stability in enhancing the productivity of stretched films and the like. Is.

Hereinafter, embodiments of the present invention will be described in detail in terms of catalyst components, catalysts, and polymerization methods.
1. α-Olefin Polymerization Catalyst Component and α-Olefin Polymerization Catalyst The α-olefin polymerization catalyst component in the present invention is a contact product of titanium, magnesium, halogen and a butanedioic acid diester compound which is a special catalyst component. It is. Such a polymerization catalyst component of the present invention allows coexistence of other desired components other than the above essential components. Specifically, the first invention in the present invention is a catalyst component for stereoregular polymerization of α-olefin containing titanium, magnesium, halogen, and a specific butanedioic acid diester compound as essential components. “Contained as an essential component” as used herein means that, in addition to the listed four components, other suitable elements may be included, and each of these elements may be any suitable compound. It does not preclude that they may be present, and that these elements may be present as bonded to each other.

  Solid components containing titanium, magnesium and halogen are known. For example, JP-A-53-45688, 54-3894, 55-75411, 56-18609, 57-3803, 58-5309, 59-149905 The ones described in the Gazettes are used.

  Examples of the magnesium compound used as a magnesium source in the present invention include magnesium dihalide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, alkylmagnesium halide, allyloxymagnesium, allyloxymagnesium halide, magnesium oxide, Examples thereof include magnesium hydroxide and magnesium carboxylate. Among these, magnesium dihalide, dialkoxymagnesium, and alkoxymagnesium halide are preferable, and magnesium dihalide is more preferable. More preferably, the hydrocarbon of the alkoxy group has 1 to 10 carbon atoms, and particularly preferable is that the halogen is chlorine.

Further, the titanium compound serving as the titanium source is represented by the general formula Ti (OR) _4-p X _p (where R is a hydrocarbon group, preferably about 1 to 10 carbon atoms, X represents a halogen, p represents a number of 0 ≦ p ≦ 4). Of these, tetravalent titanium compounds are preferable, and tetravalent titanium compounds containing halogen are more preferable.
Specific examples include TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O—iC ₃ H ₇ ) Cl ₃ , Ti (O—nC ₄ H ₉ ) Cl ₃ , Ti (O—nC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OC ₂ H ₅ ) (OC ₄ H _{9) 2 Cl, Ti (O} -nC 4 H 9) 3 Cl, Ti (OC 6 H 5) Cl 3, Ti (O-iC 4 H 9) 2 Cl 2, Ti (OC 5 H 11) Cl ₃ , Ti (OC ₆ H ₁₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₄ , Ti (O—nC ₃ H ₇ ) ₄ , Ti (O—nC ₄ H ₉ ) ₄ , Ti (O—iC ₄ H) _{9) 4, Ti (O-} nC 6 H 13) 4, Ti (O-nC 8 H 17) 4, i _{[OCH 2 CH (C 2 H 5} ) C 4 H 9 ] _4, and the like.

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

Further, TiCl ₃ (including those obtained by reducing TiCl ₄ with H ₂ , reducing with Al metal, or reducing with an organometallic compound), TiBr ₃ , Ti (OC ₂ H ₅ ) Cl ₂ , TiCl ₂ It is also possible to use titanium compounds such as dicyclopentadienyl titanium dichloride.
Among these titanium compounds, TiCl ₄ , Ti (OC ₄ H ₉ ) ₄ and Ti (OC ₂ H ₅ ) Cl ₃ are more preferable, and TiCl ₄ and Ti (OC ₄ H ₉ ) ₄ are more preferable.

The halogen is usually supplied from the above-mentioned halogen compounds of magnesium and / or titanium, but other halogen sources, for example, Group 13 halides such as AlCl ₃ , BBr ₃ , and silicon such as SiCl ₄ It is also possible to supply from a known halogenating agent such as a halide of phosphorus, such as a halide of phosphorus such as PCl ₃ and PCl ₅ , a halide of tungsten such as WCl ₆ , and a halide of molybdenum such as MoCl ₅ . The halogen contained in the catalyst component is fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.

  The butanedioic acid diester which is an important catalyst component in the present invention is a butanedioic acid diester compound represented by the following general formula [1] or [2]. The compounds are used as so-called internal donors (electron donors).

（ここでＲ^１、Ｒ^２は同一又は異なってもよい炭素数１から２０の直鎖状、分岐状又は環状の炭化水素基を示し、Ｒ^３は炭素数１から２０の直鎖状、分岐状もしくは環状の炭化水素基、又は炭化水素基を有するシラヒドロカルビル基を示し、Ｒ^４、Ｒ^７及びＲ^８は、水素又はＲ^３と同一もしくは異なってもよい炭素数１から２０の直鎖状、分岐状もしくは環状の炭化水素基、又は炭化水素基を有するシラヒドロカルビル基を示し、Ｒ^５、Ｒ^６及びＲ^９は、水素又は炭素数１から２０の直鎖状、分岐状もしくは環状の炭化水素基を示し、Ｘは１５族から選ばれる原子を示す。）

(Wherein R ¹ and R ² represent a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may be the same or different, and R ³ represents a linear or branched hydrocarbon group having 1 to 20 carbon atoms. A cyclic or cyclic hydrocarbon group, or a silahydrocarbyl group having a hydrocarbon group, wherein R ⁴ , R ⁷ and R ⁸ are hydrogen or a straight chain having 1 to 20 carbon atoms which may be the same as or different from R ³ , A branched or cyclic hydrocarbon group, or a silahydrocarbyl group having a hydrocarbon group, wherein R ⁵ , R ⁶ and R ⁹ are hydrogen or a linear, branched or cyclic carbon atom having 1 to 20 carbon atoms Represents a hydrogen group, and X represents an atom selected from Group 15.)

Specifically, R ¹ and R ² are hydrocarbon groups constituting the ester moiety in the compound, and are linear, branched or cyclic hydrocarbon groups having 1 to 20 carbon atoms, and hydrocarbons The group is an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, an allylalkyl group or an alkylallyl group, preferably an electronically neutral and stable alkyl group, aryl group or cycloalkyl group. is there. More preferably, it is a C2-C10 hydrocarbon group, More preferably, it is a C2-C6 linear alkyl group or branched alkyl group. Specifically, a methyl group, an ethyl group, an i-propyl group, an n-butyl group, an i-butyl group, an n-hexyl group, an i-hexyl group and the like are preferable, and among them, an ethyl group and an n-butyl group are preferable. I-butyl group is more preferable.

R ³ is a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, or a silahydrocarbyl group having a hydrocarbon group, and the number of substituents is 1 to 3, preferably 2 to 3. The number is more preferably 3.
The hydrocarbon group substituting the hydrocarbon group or the silahydrocarbyl group is a hydrocarbon group having 1 to 20 carbon atoms, and is a linear, branched or cyclic alkyl group, aryl group, cycloalkyl group, alkenyl group, allyl group. An alkyl group or an alkylallyl group, preferably an electronically neutral and stable alkyl group, aryl group or cycloalkyl group. A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is more preferable, and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms is still more preferable.

Specifically, R ³ represents methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, n- Hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, methylsilyl, dimethylsilyl, trimethylsilyl, methylethylsilyl, diethylsilyl, triethylsilyl, methylethylpropylsilyl , Tri-n-propylsilyl group, tri-i-propylsilyl group, tri-n-butylsilyl group, tri-i-butylsilyl group, tri-n-hexylsilyl group, tri-i-hexylsilyl group, etc. , Among them, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group A til group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a trimethylsilyl group, a triethylsilyl group, and a tri-i-butylsilyl group are preferable.

R ⁴ , R ⁷ and R ⁸ are hydrogen or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which is the same as or different from R ³ , or a silahydrocarbyl group having a hydrocarbon group, The number of substituents is 1 to 3, preferably 2 to 3, more preferably 3. R ⁴ and R ³ or R ⁷ and R ⁸ may be linked to form a cyclic structure.
The hydrocarbon group substituting the hydrocarbon group or the silahydrocarbyl group is a hydrocarbon group having 1 to 20 carbon atoms, and is a linear, branched or cyclic alkyl group, aryl group, cycloalkyl group, alkenyl group, allyl group. An alkyl group or an alkylallyl group, preferably an electronically neutral and stable alkyl group, aryl group or cycloalkyl group. A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms is more preferable, and a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is still more preferable.

Specifically, R ⁴ , R ⁷ and R ⁸ are hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group. N-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, methylsilyl group, dimethylsilyl group, trimethylsilyl group, methylethylsilyl group, diethylsilyl group, triethyl Silyl group, methylethylpropylsilyl group, tri-n-propylsilyl group, tri-i-propylsilyl group, tri-n-butylsilyl group, tri-i-butylsilyl group, tri-n-hexylsilyl group, tri-i -Hexylsilyl group and the like, among them, hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group Substitutions with high steric hindrance such as til group, i-butyl group, s-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, phenyl group, trimethylsilyl group, triethylsilyl group, tri-i-butylsilyl group Groups are preferred.
As the structure in which R ³ and R ⁴ or R ⁷ and R ⁸ are linked,

等により連結されるものが例示される。このうち、５〜１０の環状構造、特に５〜８の環状構造を取る連結基が好ましい。

What is connected by etc. is illustrated. Among these, a linking group having a cyclic structure of 5 to 10, particularly a cyclic structure of 5 to 8 is preferable.

R ⁵ , R ⁶ and R ⁹ are hydrogen or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms. In the case of a hydrocarbon group, it is a linear, branched or cyclic alkyl group, aryl group, cycloalkyl group, alkenyl group, allylalkyl group or alkylallyl group, preferably electronically neutral and stable , An alkyl group, an aryl group or a cycloalkyl group. More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms.

Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-hexyl group, i-hexyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group and the like. R ⁵ and R ⁶ are particularly preferably hydrogen, a methyl group, an ethyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R ³ and R ⁵ , R ⁴ and R ⁶ may be linked to form a cyclic structure.

The combination of R ¹ to R ⁸ is arbitrary, but preferably a symmetrical structure in which R ¹ = R ² and R ³ = R ⁴ = R ⁷ = R ⁸ and R ⁵ = R ⁶ is determined from the catalyst performance. This is particularly effective in the present invention.

The atom X is an atom that connects the main skeleton of butanedioic acid diester and the substituents R ³ , R ⁴ , R ⁷ , R ⁸ and is selected from Group 15 of the Periodic Table of Elements. Specifically, the group 15 element includes nitrogen or phosphorus, and nitrogen is preferable.

Specific examples of the disubstituted butanedioic acid diester used in the present invention are shown below.
(1) Compound consisting of substituents R ³ = R ⁴ , R ⁷ = R ⁸ 2-Dimethylamino-3-diethylaminobutanedioic acid diethyl, 2-dimethylamino-3-diethylaminobutanedioic acid di-n-propyl, 2-dimethylamino-3-diethylaminobutanedioic acid di-i-propyl, 2-dimethylamino-3-diethylaminobutanedioic acid di-n-butyl, 2-dimethylamino-3-diethylaminobutanedioic acid di-i-butyl 2-dimethylamino-3-di-i-propylaminobutanedioic acid di-n-butyl, 2-dimethylamino-3-di-i-propylaminobutanedioic acid di-i-butyl, 2-dimethylamino- 3-di-i-butylaminobutanedioic acid di-i-butyl, 2-dimethylamino-3-di-t-butylaminobutanedioic acid di-n-butyl, 2-dimethyl Ruamino-3-dicyclohexylaminobutanedioic acid di-n-butyl, 2-dimethylamino-3-diphenylaminobutanedioic acid di-n-butyl, 2-bis (trimethylsilyl) amino-3-bis (triethylsilyl) Diethyl aminobutanedioate, 2-bis (trimethylsilyl) amino-3-bis (triethylsilyl) aminobutanedioic acid di-n-propyl, 2-bis (trimethylsilyl) amino-3-bis (triethylsilyl) aminobutanedioic acid di-i -Propyl, 2-bis (trimethylsilyl) amino-3-bis (triethylsilyl) aminobutanedioic acid di-n-butyl, 2-bis (trimethylsilyl) amino-3-bis (triethylsilyl) aminobutanedioic acid di-i-butyl etc., in ^{R 3} and ^{R 4} are the same and ^{R 7} and ^{R 8} are the ^same, R 3, ^{R 4} Compound fine R ^7, R ⁸ consists of different substituents can be exemplified.

(2) Compounds in which R ⁵ and R ⁶ are hydrocarbon groups Diethyl 2,3-dimethyl-2,3-bis (dimethyl) aminobutanedioate, 2,3-dimethyl-2,3-bis (dimethyl) aminobutane Di-n-propyl acid, 2,3-dimethyl-2,3-bis (dimethyl) aminobutanedioic acid di-i-propyl, 2,3-dimethyl-2,3-bis (dimethyl) aminobutanedioic acid di-n -Butyl, 2,3-dimethyl-2,3-bis (dimethyl) aminobutanedioic acid di-i-butyl, 2,3-dimethyl-2,3-bis (dimethyl) aminobutanedioic acid di-s-butyl, , 3-Dimethyl-2,3-bis (dimethyl) aminobutanedioic acid di-t-butyl, 2,3-diethyl-2,3-bis (dimethyl) aminobutanedioic acid diethyl, 2,3-diethyl-2,3 -Screw L) aminobutanedioic acid di-n-propyl, 2,3-diethyl-2,3-bis (dimethyl) aminobutanedioic acid di-i-propyl, 2,3-diethyl-2,3-bis (dimethyl) aminobutane Di-n-butyl acid, diethyl 2,3-dimethyl-2,3-bis (diethyl) aminobutanedioate, di-n-propyl 2,3-dimethyl-2,3-bis (diethyl) aminobutanedioate, , 3-Dimethyl-2,3-bis (diethyl) aminobutanedioic acid di-i-propyl 2,3-dimethyl-2,3-bis (diethyl) aminobutanedioic acid di-n-butyl, 2,3-diethyl -2,3-bis (diethyl) aminobutanedioic acid diethyl, 2,3-diethyl-2,3-bis (diethyl) aminobutanedioic acid di-n-propyl, 2,3-diethyl-2,3-bis (diethyl) ) Aminobutanedioic acid di-i-propyl, 2,3-diethyl-2,3-bis (diethyl) aminobutanedioic acid di-n-butyl, 2,3-dimethyl-2,3-bis (di-i-propyl) ) Aminobutanedioic acid di-n-butyl, 2,3-dimethyl-2,3-bis (di-n-propyl) aminobutanedioic acid di-n-butyl, 2,3-dimethyl-2,3-bis (di) -N-butyl) aminobutanedioic acid di-n-butyl, 2,3-dimethyl-2,3-bis (di-i-butyl) aminobutanedioic acid di-n-butyl, 2,3-dimethyl-2,3 -Bis (di-t-butyl) aminobutanedioic acid di-n-butyl, 2,3-dimethyl-2,3-bis (dicyclopentyl) aminobutanedioic acid di-n-butyl, 2,3-dimethyl-2, 3-bis (dicyclohexyl) aminobutanedioic acid di- n-butyl, 2,3-dimethyl-2,3-bis (diphenyl) aminobutanedioic acid di-n-butyl, 2,3-dimethyl-2,3-bis (bis (trimethyl) silyl) aminobutanedioic acid diethyl, 2,3-Dimethyl-2,3-bis (bis (trimethyl) silyl) aminobutanedioic acid di-n-propyl, 2,3-dimethyl-2,3-bis (bis (trimethyl) silyl) aminobutanedioic acid di- i-propyl, 2,3-dimethyl-2,3-bis (bis (trimethyl) silyl) aminobutanedioic acid di-n-butyl, 2,3-dimethyl-2,3-bis (bis (trimethyl) silyl) aminobutane acid di -i- butyl, 2,3-dimethyl-2,3-bis (bis (trimethyl) silyl) aminobutanoic acid di -t- butyl, ^{R 5} and ^{R 6} is a hydrocarbon group compound And the like.

(3) Compounds in which R ³ , R ⁴ , R ⁷ and R ⁸ are the same substituents 2,3-bis (dimethyl) aminobutanedioic acid diethyl, 2,3-bis (dimethyl) aminobutanedioic acid di-n-propyl 2,3-bis (dimethyl) aminobutanedioic acid di-i-propyl, 2,3-bis (dimethyl) aminobutanedioic acid di-n-butyl, 2,3-bis (dimethyl) aminobutanedioic acid di-i- Butyl, 2,3-bis (dimethyl) aminobutanedioic acid di-s-butyl, 2,3-bis (dimethyl) aminobutanedioic acid di-t-butyl, 2,3-bis (dimethyl) aminobutanedioic acid di-n -Pentyl, 2,3-bis (diethyl) aminobutanedioic acid diethyl, 2,3-bis (diethyl) aminobutanedioic acid di-n-propyl, 2,3-bis (diethyl) aminobutanedioic acid di-n-butyl 2,3-bis (diethyl) aminobutanedioic acid di-i-butyl, 2,3-bis (di-n-propyl) aminobutanedioic acid diethyl, 2,3-bis (di-n-propyl) aminobutane Di-n-propyl acid, 2,3-bis (di-n-propyl) aminobutanedioic acid di-n-butyl 2,2-bis (di-n-propyl) aminobutanedioic acid di-i-butyl, 2 , 3-bis (di-n-propyl) aminobutanedioic acid di-t-butyl, 2,3-bis (di-i-propyl) aminobutanedioic acid di-n-propyl, 2,3-bis (di-i) -Propyl) aminobutanedioic acid di-n-butyl, 2,3-bis (di-i-propyl) aminobutanedioic acid di-i-butyl, 2,3-bis (di-i-propyl) aminobutanedioic acid di- t-butyl, 2,3-bis (di-n-butyl) a Minobtan diacid di-n-butyl 2,3-bis (di-i-butyl) aminobutanedioic acid di-n-butyl 2,3-bis (di-t-butyl) aminobutanedioic acid di-n-butyl 2,3-bis (di-n-butyl) aminobutanedioic acid di-i-butyl, 2,3-bis (di-i-butyl) aminobutanedioic acid di-i-butyl, 2,3-bis (di-) -T-butyl) aminobutanedioic acid di-i-butyl 2,3-bis (dicyclopentyl) aminobutanedioic acid di-n-butyl 2,3-bis (dicyclohexyl) aminobutanedioic acid di-n-butyl, , 3-bis (diphenyl) aminobutanedioic acid di-n-butyl, 2,3-bis (bis (trimethyl) silyl) aminobutanedioic acid diethyl, 2,3-bis (bis (trimethyl) silyl) aminobutanedioic acid di- n-propyl, , 3-bis (bis (trimethyl) silyl) aminobutanedioic acid di-i-propyl, 2,3-bis (bis (trimethyl) silyl) aminobutanedioic acid di-n-butyl, 2,3-bis (bis (trimethyl) ) Silyl) aminobutanedioic acid di-i-butyl, 2,3-bis (bis (trimethyl) silyl) aminobutanedioic acid di-t-butyl, 2,3-bis (bis (trimethyl) silyl) aminobutanedioic acid di- Examples include compounds in which R ³ , R ⁴ , R ⁷ and R ⁸ are the same substituents such as n-pentyl and 2,3-bis (bis (triethyl) silyl) aminobutanedioic acid di-n-butyl.
The disubstituted butanedioic acid diester used in the present invention is preferably a compound in which R ³ , R ⁴ , R ⁷ and R ⁸ are the same substituent.

(4) Compound in which R ³ and R ⁴ (or R ⁷ and R ⁸ ) form a ring

などのＲ^３、Ｒ^４（もしくはＲ^７、Ｒ^８）が環状を形成する化合物としての二置換のブタン二酸ジエステルが例示される。

Examples thereof include disubstituted butanedioic acid diesters as compounds in which R ³ and R ⁴ (or R ⁷ and R ⁸ ) form a ring.

  Among disubstituted butanedioic acid diesters, particularly preferred are diethyl 2,3-bis (dimethyl) aminobutanedioate, di-n-butyl 2,3-bis (dimethyl) aminobutanedioate, 2,3-bis ( Dimethyl) aminobutanedioic acid di-i-butyl, 2,3-bis (diethyl) aminobutanedioic acid diethyl, 2,3-bis (diethyl) aminobutanedioic acid di-n-butyl, 2,3-bis (diethyl) aminobutane Di-i-butyl diacid, diethyl 2,3-bis (di-i-propyl) aminobutanedioate, di-n-butyl 2,3-bis (di-i-propyl) aminobutanedioate, 2,3- Bis (di-i-propyl) aminobutanedioic acid di-i-butyl, 2,3-bis (di-i-butyl) aminobutanedioic acid diethyl, 2,3-bis (di-i-butyl) aminobutane Di-n-butyl, 2,3-bis (di-i-butyl) aminobutanedioic acid di-i-butyl, 2,3-bis (di-t-butyl) aminobutanedioic acid diethyl, 2,3-bis ( Di-t-butyl) aminobutanedioic acid di-n-butyl, 2,3-bis (di-t-butyl) aminobutanedioic acid di-i-butyl, 2,3-bis (bis (trimethyl) silyl) aminobutane Diethyl acid, 2,3-bis (bis (trimethyl) silyl) aminobutanedioic acid di-n-propyl, 2,3-bis (bis (trimethyl) silyl) aminobutanedioic acid di-i-propyl, 2,3-bis (Bis (trimethyl) silyl) aminobutanedioic acid di-n-butyl, 2,3-bis (bis (trimethyl) silyl) aminobutanedioic acid di-i-butyl, 2,3-bis (bis (trimethyl) silyl) aminobut Emission acid di -t- butyl and the like.

Next, specific examples of the monosubstituted butanedioic acid diester used in the present invention will be illustrated.
2-dimethylaminobutanedioic acid diethyl, 2-dimethylaminobutanedioic acid di-n-propyl, 2-dimethylaminobutanedioic acid di-i-propyl, 2-dimethylaminobutanedioic acid di-n-butyl, 2- Di-i-butyl dimethylaminobutanedioate, diethyl 2-diethylaminobutanedioate, di-n-propyl 2-diethylaminobutanedioate, di-i-propyl 2-diethylaminobutanedioate, di-diethylaminobutanedioate -N-butyl, 2-diethylaminobutanedioic acid di-i-butyl, 2-di-n-propylaminobutanedioic acid diethyl, 2-di-n-propylaminobutanedioic acid di-n-propyl, 2-di -N-propylaminobutanedioic acid di-i-propyl, 2-di-n-propylaminobutanedioic acid di-n-butyl, 2-di-n-propylamino Di-i-butyl butanedioate, diethyl 2-di-i-propylaminobutanedioate, di-n-propyl 2-di-i-propylaminobutanedioate, 2-di-i-propylaminobutanedioic acid Di-i-propyl, 2-di-i-propylaminobutanedioic acid di-n-butyl, 2-di-i-propylaminobutanedioic acid di-i-butyl, 2-di-n-butylaminobutane Diethyl 2-di-n-butylaminobutanedioic acid di-n-propyl, 2-di-n-butylaminobutanedioic acid di-i-propyl, 2-di-n-butylaminobutanedioic acid di- n-butyl, 2-di-n-butylaminobutanedioic acid di-i-butyl, 2-di-i-butylaminobutanedioic acid diethyl, 2-di-i-butylaminobutanedioic acid di-n-propyl 2-di-i-butylaminobutanedioic acid diacid i-propyl, 2-di-i-butylaminobutanedioic acid di-n-butyl, 2-di-i-butylaminobutanedioic acid di-i-butyl, 2-di-t-butylaminobutanedioic acid diethyl 2-di-t-butylaminobutanedioic acid di-n-propyl, 2-di-t-butylaminobutanedioic acid di-i-propyl, 2-di-t-butylaminobutanedioic acid di-n- Butyl, 2-di-t-butylaminobutanedioic acid di-i-butyl, 2-bis (trimethylsilyl) aminobutanedioic acid diethyl, 2-bis (trimethylsilyl) aminobutanedioic acid di-n-propyl, 2-bis (trimethylsilyl) ) Aminobutanedioic acid di-i-propyl, 2-bis (trimethylsilyl) aminobutanedioic acid di-n-butyl, 2-bis (trimethylsilyl) aminobutanedioic acid di-i-butyl, 2-bi Sus (triethylsilyl) aminobutanedioic acid diethyl, 2-bis (triethylsilyl) aminobutanedioic acid di-n-propyl, 2-bis (triethylsilyl) aminobutanedioic acid di-i-propyl, 2-bis (triethylsilyl) aminobutane Examples include compounds in which R ⁹ is a hydrogen substituent in the general formula [2], such as di-n-butyl diacid and di-i-butyl 2-bis (triethylsilyl) aminobutanedioate.

In addition, 2-dimethylamino-3-methylbutanedioic acid diethyl, 2-dimethylamino-3-ethylbutanedioic acid di-n-propyl, 2-dimethylamino-3-n-propylbutanedioic acid di-i-propyl, 2-dimethylamino-3-tert-butylbutanedioic acid di-n-butyl, 2-dimethylamino-3-cyclohexylbutanedioic acid di-i-butyl, 2-diethylamino-3-methylbutanedioic acid diethyl, 2-diethylamino- 3-ethylbutanedioic acid di-n-propyl, 2-diethylamino-3-n-propylbutanedioic acid di-i-propyl, 2-diethylamino-3-tert-butylbutanedioic acid di-n-butyl, 2-diethylamino- R ⁹ is a linear, branched or cyclic hydrocarbon substituent in the general formula [2], such as 3-cyclohexylbutanedioic acid di-i-butyl And the like.

  Particularly preferred among these monosubstituted butanedioic acid diesters are 2-diethylaminobutanedioic acid diethyl, 2-diethylaminobutanedioic acid di-n-butyl, 2-diethylaminobutanedioic acid di-i-butyl, 2- Di-i-propylaminobutanedioic acid diethyl, 2-di-i-propylaminobutanedioic acid di-n-butyl, 2-di-i-propylaminobutanedioic acid di-i-butyl, 2-di-i -Diethyl butylaminobutanedioate, di-n-butyl 2-di-i-butylaminobutanedioate, di-i-butyl 2-di-i-butylaminobutanedioate, 2-di-t-butylamino Diethyl butanedioate, di-n-butyl 2-di-t-butylaminobutanedioate, diethyl 2-bis (trimethylsilyl) aminobutanedioate, 2-bis (trimethylsilyl) amino Di-n-butyl butanedioate, di-i-butyl 2-bis (trimethylsilyl) aminobutanedioate, diethyl 2-bis (triethylsilyl) aminobutanedioate, di-n-bis (triethylsilyl) aminobutanedioate And butyl, 2-bis (triethylsilyl) aminobutanedioic acid di-i-butyl and the like.

2. Manufacturing method (obtainment method) of butanedioic acid diester
Butanedioic acid diester used in the preparation of the polymerization catalyst component according to the present invention, the substitution reaction _{^{2R 1 X + R 2 NH 2}} → R 2 1 -N-R 2 + 2HX by amino groups and suitable halogenated hydrocarbons
Can be synthesized. That is, in the case of alkyl substitution from diaminobutanedioic acid diester, the target compound is obtained by reacting 1,2-diaminosuccinic acid ester (α, β-diaminosuccinic acid ester) with a halogenated hydrocarbon as a starting material. Get

    There are several methods for synthesizing the precursor aminobutanedioic acid diester. Among them, the most common method is to allow a large excess of aqueous ammonia to act on a halogenated dicarboxylic acid (available from a commercial product). Aminated by

続いてエステル化を経て前駆体を得る合成法がある。概略スキームは上記の通りである。モノアミノ体も同様に合成できる。

Subsequently, there is a synthesis method for obtaining a precursor through esterification. The general scheme is as described above. Monoamino compounds can be synthesized in the same manner.

In addition to the aminobutanedioic acid diester synthesis method,
(B) A method of synthesizing an amino acid by the Streker method, in which ammonia and hydrogen cyanide are allowed to act on the aldehyde, followed by esterification. (B) An amino acid is synthesized by the Bucherer method in which an aldehyde is reacted with alkali cyanide and ammonium carbonate. Method of esterification (c) There is a method of synthesizing an amino acid via a Schmidt reaction in which hydrazoic acid is allowed to act on acetocarboxylic acid ester, followed by esterification, etc. In view of safety in view and reaction, the synthesis method in which an amino acid is synthesized from the halogenated carboxylic acid listed above and then esterified is most preferable.
In addition, the butanedioic acid diesters obtained by these synthesis methods do not proceed sufficiently, and COOH groups may remain in the butanedioic acid partially. An ester that leaves an unreacted substance may be present.

Reaction example: Synthesis of di-n-butyl 2,3-bis (dimethylamino) butanedioate
1 L (about 15 mol) of concentrated aqueous ammonia was added to a 2,000 ml flask and cooled to 4 ° C. or lower. Under stirring conditions, 200 mmol of 1,2-dibromosuccinic acid (Aldrich), which had been cooled to 4 ° C. in advance, was added dropwise to the solution and allowed to react at room temperature for at least 4 days. The reaction solution was heated and concentrated to about 100 ml, filtered once, and then concentrated again to 70 ml. After returning this solution to room temperature, 500 ml of methanol was added and allowed to stand overnight in a refrigerator. The resultant was washed successively with methanol and ether, and the resulting crude product was dissolved in 200 ml of water and recrystallized to obtain 2,3-diaminobutanedioic acid. (Yield 60%)
Subsequently, 50 ml of n-butanol was added to a 500 ml flask thoroughly purged with nitrogen, cooled to −10 ° C., and 15 ml of thionyl chloride was added under stirring conditions. 50 mmol of 2,3-diaminobutanedioic acid synthesized above was added to this solution, and the reaction was carried out at room temperature for 2 days. After concentration by evaporation, 100 ml of n-butanol was added and evaporation was repeated twice. The crude product was subjected to column chromatography to obtain the desired di-n-butyl 2,3-diaminobutanedioate. (Yield 80%)
Furthermore, after adding 100 ml of acetonitrile, 80 mmol of potassium carbonate, and 35 mmol of 2,3-diaminobutanedioic acid di-n-butyl synthesized above to a 500 ml flask sufficiently substituted with nitrogen, 180 mmol of methyl iodide was added to 20 ml of acetonitrile at 0 ° C. The reaction product was heated and reacted at 70 ° C. for 8 hours. After the reaction, the solid product was removed by filtration, and then the crude product obtained by evaporation was subjected to column chromatography. As a result, di-n-butyl 2,3-bis (dimethylamino) butanedioate was obtained. (Yield 45%)

The butanedioic acid diester used for the preparation of the polymerization catalyst component according to the present invention has a structure having a bulky substituent with a group 15 atom interposed between two carboxylic acid ester groups, and the number of substituents is at least One or more is preferable, and two is more preferable.
In addition, butanedioic acid diester may have up to four optical isomers that are enantiomeric or diastereomeric, but the compound is a racemic mixture or a racemic mixture in which a meso form or an enantiomer form is mixed. It may be a body.

Here, the difference in the catalytic action between the conventionally known catalyst component such as a dicarboxylic acid ester used as an internal donor (electron donor) and the substituted dicarboxylic acid diester used in the present invention, or the like. Considering the difference in effect due to the above, dicarboxylic acid esters known in the art include phthalic acid esters and the like, and in general, such an internal donor has two ester sites on the surface of magnesium chloride used as a carrier. It is considered that it becomes an active site precursor by adsorbing through two carbonyls and forming a state in which it acts gently in the vicinity of the titanium atom at the stage of the catalyst preparation process.
On the other hand, the dicarboxylic acid diester used in the present invention has one or more nitrogen atoms as the group 15 atom X in addition to two carbonyl oxygens in one molecule.
Although the reason why the effects shown in the present invention are exhibited has not been sufficiently analyzed, the compound has a variety of adsorption to magnesium chloride, and as a result, various active site precursors are formed. Inferred. That is, the adsorptive power of the internal donor on magnesium chloride is an interaction between both substances, and its magnitude is defined by the electronic state of the nitrogen atom of atom X. The dicarboxylic acid diester used in the present invention is characterized by the introduction of a substituent having a group X atom X, which is presumed to perturb the electronic state of the carbonyl oxygen responsible for adsorption. .
Further, since rotation (degree of freedom) around the C2 and C3 carbons is allowed, the contribution of the perturbation changes depending on the crystal environment of magnesium chloride, and the electronic state changes accordingly. This internal rotation involves the bulk of the substituent bonded to the group 15 atom, but the steric repulsive force (Coulomb force) of the two substituents is particularly important for the disubstituted dicarboxylic acid diester. Become.

  As described above, the adsorption (interaction) of electron donors differs depending on each environment, depending on the introduction of group 15 atoms (electronic effect) and the selection of substituents bonded to the site (steric effect). Thus, the difference is reflected in the interaction with the active site precursor. That is, the active point means that the catalyst function is improved, meaning that the active point is more diversified.

  From an industrial point of view, in order to provide a variety of active site precursors, it has been necessary to prepare a catalyst by sequentially or collectively introducing internal donors having different molecular structures. In the invention, by using the above concept, the diversity of active sites can be achieved with only one molecule, so that the preparation process can be greatly simplified compared to the case of using a plurality of internal donors. It can be realized, and further, it is expected to achieve a significant reduction in raw material costs in manufacturing costs.

3. Other optional components Furthermore, in the production of the polymerization catalyst component of the present invention, as described above, in the solid catalyst component, optional components can be used as necessary in addition to the above essential components. Examples of suitable optional components include the following compounds.

(I) Periodic Table (Short Period Type) Organometallic Compound of Group I to III Metal It is also possible to use an organometallic compound of Group I to Group III metal of the Periodic Table. The organometallic compounds of Group I to Group III metals used in the present invention have at least one organic group-metal bond. The organic group in that case is typically a hydrocarbyl group having about 1 to 20 carbon atoms, preferably about 1 to 6 carbon atoms. The remaining valence (if any) of the metal in the organometallic compound in which at least one of the valences is filled with an organic group is the hydrogen atom, halogen atom, hydrocarbyloxy group (the hydrocarbyl group has 1 carbon atom) About 20 to about 20 and preferably about 1 to 6), or the metal via an oxygen atom (specifically, —O—Al (CH ₃ ) — in the case of methylalumoxane) and the like.

Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium and t-butyllithium, (b) butylethylmagnesium, dibutylmagnesium, hexylethylmagnesium, butylmagnesium. Organomagnesium compounds such as chloride and t-butylmagnesium bromide, (c) organozinc compounds such as diethylzinc and dibutylzinc, (d) trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum chloride, Organic aluminum such as diethylaluminum hydride, diethylaluminum ethoxide, ethylaluminum sesquichloride, ethylaluminum dichloride, methylalumoxane There is a compound.
Among these, an organoaluminum compound is particularly preferable.

(B) Electron Donor Compound Further, when producing the above solid catalyst component, an electron donating compound different from butanedioic acid diester may be used in combination as an internal donor. Such electron donor compounds are oxygen-containing electrons such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides. Examples include donors, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, sulfur-containing electron donors such as sulfonate esters, and the like.

  More specifically, (i) alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropylbenzyl alcohol, ) Phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol, naphthol, (c) acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, C3-C15 ketones such as benzophenone, (d) acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolu Aldehydes having 2 to 15 carbon atoms such as aldehyde, naphthaldehyde, (e) methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl cellosolve, ethyl propionate, methyl butyrate, Ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate , Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyl Organic acid monoesters such as tyrolactone, α-valerolactone, coumarin, and phthalide, or diethyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl malonate, dibutyl malonate, diethyl succinate, dibutyl maleate, 1,2 -Carbon of organic acid polyvalent ester such as diethyl cyclohexanecarboxylate, norbornanedienyl-1,2-dimethylcarboxylate, cyclopropane-1,2-dicarboxylate di-n-hexyl, diethyl 1,1-cyclobutanedicarboxylate 2 to 20 organic acid esters, (f) silicate esters such as ethyl silicate and butyl silicate, inorganic acid esters such as ethylene carbonate, (to) acetyl chloride, benzoyl chloride, toluic acid chloride, anise Acid chloride, phthaloyl chloride, isochlorochloride C2-C15 acid halides such as rhoyl, (thi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, 2,2-dimethyl-1,3-dimethoxypropane, 2 , 2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl- 1,3-dimethoxypropane, 2-t-butyl-2-methyl-1,3-dimethoxypropane, 2-t-butyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1, 3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxyprop 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2,2-diisopropyl-1,3-diethoxypropane and the like having 2 to 20 carbon atoms Ethers, acid amides such as (li) acetamide, benzoic acid amide, toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine Amines such as (l) acetonitrile, benzonitrile, tolunitrile, (wo) 2- (ethoxymethyl) -ethyl benzoate, 2- (t-butoxymethyl) -ethyl benzoate, 3-ethoxy- Ethyl 2-phenylpropionate, ethyl 3-ethoxypropionate, 3-ethoxy-2 alkoxy ester compounds such as ethyl s-butylpropionate and ethyl 3-ethoxy-2-t-butylpropionate, (wa) ethyl 2-benzoylbenzoate, ethyl 2- (4'-methylbenzoyl) benzoate, 2 -Ketoester compounds such as ethyl benzoyl-4,5-dimethylbenzoate, (f) methyl benzenesulfonate, ethyl benzenesulfonate, ethyl p-toluenesulfonate, isopropyl p-toluenesulfonate, p-toluenesulfonic acid- Examples thereof include sulfonic acid esters such as n-butyl and p-toluenesulfonic acid-s-butyl.

One or more kinds of these electron donor compounds can be used. Of these, organic acid ester compounds, acid halide compounds and ether compounds are preferred, and phthalic acid diester compounds, acetic acid cellosolve ester compounds, phthalic acid dihalide compounds and diether compounds are particularly preferred.
The said arbitrary component can be used 1 type or in combination of 2 or more types. When these optional components are used, the effect of the present invention becomes greater.

In the present invention, it is particularly preferable to use an organosilicon compound and / or diether compound component in combination with an organoaluminum compound component as other components of the α-olefin polymerization catalyst component.
As an external donor of component (C), these compounds described in detail in paragraphs 0073 to 0074 and paragraphs 0076 to 0088 can be used as other components of the catalyst component for α-olefin polymerization.

4). Production of catalyst component for polymerization The contact conditions of the components constituting the catalyst component for polymerization need to be carried out in the absence of oxygen, but may be arbitrary as long as the effect of the present invention is recognized. Specifically, the following conditions are preferable.
The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C. Examples of the contact method include a mechanical method using a rotating ball mill, a vibration mill, a jet mill, a medium stirring pulverizer, and the like, and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes, and the like.

The amount ratio of each component used to constitute the polymerization catalyst component can be arbitrary as long as the effect of the present invention is recognized, but is generally preferably within the following range.
The amount of the titanium compound used is preferably in the range of 0.0001 to 1,000, preferably in the range of 0.01 to 10, in terms of molar ratio with respect to the amount of magnesium compound used.
When a compound therefor is used as the halogen source, the amount used is 0.01 in terms of molar ratio to the amount of magnesium used, regardless of whether the titanium compound and / or magnesium compound contains halogen. The range is preferably in the range of ˜1,000, preferably in the range of 0.1 to 100.
The use amount of an electron donor such as an organic ester is preferably in the range of 0.001 to 10 and preferably in the range of 0.01 to 5 as a molar ratio with respect to the use amount of the magnesium compound.
The amount of butanedioic acid diester used may be in the range of 0.001 to 1,000, more preferably in the range of 0.01 to 100, as a molar ratio to the titanium component constituting the polymerization catalyst component.
The amount of aluminum and organometallic compound used is preferably in the range of 0.001 to 100, preferably in the range of 0.01 to 1, in terms of molar ratio to the amount of magnesium compound used. .

The polymerization catalyst component is produced, for example, by the following production method using other components as necessary.
(A) A method of contacting magnesium halide with butanedioic acid diester and a titanium-containing compound.
(B) A method in which alumina or magnesia is treated with a halogenated phosphorus compound, and magnesium halide, butanedioic acid diester, or titanium halogen-containing compound is brought into contact therewith.
(C) A reaction product obtained by bringing a halogen component of titanium and / or a halogen compound of silicon and a butanedioic acid diester into contact with a solid component obtained by contacting a magnesium halide with titanium tetraalkoxide and a specific polymer silicon compound. A method of washing with an inert organic solvent.

  In addition, as a polymer silicon compound used here, what is shown by a following formula is suitable.

（ここで、Ｒは炭素数１〜１０程度の炭化水素基であり、ｑはこのポリマーケイ素化合物の粘度が１〜１００センチストークス程度となるような重合度を示す。）
具体的には、メチルハイドロジェンポリシロキサン、エチルハイドロジェンポリシロキサン、フェニルハイドロジェンポリシロキサン、シクロヘキシルハイドロジェンポリシロキサン、１，３，５，７−テトラメチルシクロテトラシロキサン、１，３，５，７，９−ペンタメチルシクロペンタシロキサン等が好ましい。

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

(D) The magnesium compound is dissolved in titanium tetraalkoxide and / or butanedioic acid diester, and the titanium compound and butanedioic acid diester are brought into contact with the solid component precipitated with the halogenating agent or titanium halogen compound, or each Method to contact separately.
(E) After allowing an organomagnesium compound such as a Grignard reagent to act with a halogenating agent or a reducing agent, contact butanedioic acid diester with this, if necessary, and then contact a titanium compound and butanedioic acid diester. Or contacting each separately.
(F) A method of contacting an alkoxymagnesium compound with a halogenating agent and / or a titanium compound in the presence or absence of butanedioic acid diester, or contacting them separately.

  Among these production methods, (a), (c), (d) and (f) are preferable. The polymerization catalyst component may be used in the middle and / or at the end of its production as an inert organic solvent, such as an aliphatic or aromatic hydrocarbon solvent (eg hexane, heptane, toluene, cyclohexane etc.) or a halogenated hydrocarbon solvent (eg , N-butyl chloride, 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene, etc.).

The polymerization catalyst component used in the present invention can be treated in advance with an organoaluminum compound (component (B)) described later and an optional organosilicon compound or diether compound (component (C)).
The amount of the organoaluminum compound used as the component (B) is generally 0.1 to 100 mol / mol in terms of the atomic ratio of aluminum to the titanium compound constituting the component (A) (aluminum / titanium), preferably 1 to It is in the range of 50 mol / mol.
The amount of the compound selected from the silicon compound or diether compound or a plurality of combinations thereof used as the component (C) is 0.001 in terms of mol ratio with respect to the content of the titanium compound in the component (A). Within the range of -100 is good, Preferably it is in the range of 0.01-20.
In the treatment with the component (B) and the component (C), a vinylsilane compound can be used as an optional component simultaneously or in advance. As the vinyl silane compound, at least one hydrogen atom in monosilane (SiH ₄ ) is replaced with a vinyl group (CH ₂ ═CH—), and some of the remaining hydrogen atoms are halogen (preferably Cl), alkyl It shows a structure substituted with a group (preferably a hydrocarbon group having 1 to 12 carbon atoms), an aryl group (preferably a phenol group), an alkoxy group (preferably an alkoxy group having 1 to 12 carbon atoms), or the like. is there.

More _{specifically, CH 2 = CH-SiH 3} , CH 2 = CH-SiH 2 (CH 3), CH 2 = CH-SiH (CH 3) 2, CH 2 = CH-Si (CH 3) 3, _{CH 2 = CH-SiCl 3,} CH 2 = CH-SiCl 2 (CH 3), CH 2 = CH-SiCl (CH 3) 2, CH 2 = CH-SiH (Cl) (CH 3), CH 2 = CH _{-Si (C 2 H 5) 3} , CH 2 = CH-SiCl (C 2 H 5) 2, CH 2 = CH-SiCl 2 (C 2 H 5), CH 2 = CH-Si (CH 3) 2 ( _{C 2 H 5), CH 2} = CH-Si (CH 3) (C 2 H 5) 2, CH 2 = CH-Si (n-C 4 H 9) 3, CH 2 = CH-Si (C 6 H _{5) 3, CH 2 = CH} -Si (CH 3) (C 6 H 5) 2, _{CH 2 = CH-Si (CH} 3) 2 (C 6 H 5), CH 2 = CH-Si (CH 3) 2 (C 6 H 4 CH 3), CH 2 = CH (CH 3) 2 Si-O _{-Si (CH 3) 2 CH =} CH 2, (CH 2 = CH) 2 -SiH 2, (CH 2 = CH) 2 -SiCl 2, (CH 2 = CH) 2 -Si (CH 3) 2, ( _{CH 2 = CH) 2 -Si (} C 6 H 5) can be exemplified _2.

  The polymerization catalyst component used in the present invention can also be used after undergoing a prepolymerization step comprising polymerizing by contacting a vinyl group-containing compound such as an α-olefin, styrenes, diene compound and the like. Specific examples of the α-olefin used in the prepolymerization include those having about 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexane, and 4-methyl. There are pentene-1, 1-octene, 1-decene, 1-undecene, 1-eicosene, and the like. Specific examples of styrenes include styrene, α-methylstyrene, allylbenzene, chlorostyrene, and diene compounds. Specific examples include 1,2-butadiene, 1,3-butadiene, isoprene, 1,4-hexadiene, 1,5-hexadiene, 1,3-pentadiene, 1,4-pentadiene, 2,3-pentadiene, 2 , 6-octadiene, 2,4-hexadiene, 1,2-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-hepta Diene, 2,4-heptadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, cyclopentadiene, 1,3-cycloheptadiene, 4-methyl-1,4-hexadiene, 5-methyl There are -1,4-hexadiene, 1,9-decadiene, 1,13-tetradecadiene, para-divinylbenzene, meta-divinylbenzene, ortho-divinylbenzene and the like. Among these, preferred are ethylene, propylene, 1-butene, 1-pentene, 1-hexane, 4-methylpentene-1, 1-octene, styrenes, divinylbenzenes, 1,5-hexadiene, and the like. .

The reaction conditions for the titanium component and the above-mentioned vinyl group-containing compound can be arbitrary as long as the effect of the present invention is recognized, but generally the following range is preferable.
The prepolymerization amount of the vinyl group-containing compound is in the range of 0.01 to 100 grams, preferably 0.1 to 50 grams, and more preferably 0.5 to 20 grams per gram of the titanium solid component. The reaction temperature during the prepolymerization is -50 ° C to 150 ° C, preferably 0 ° C to 100 ° C. A polymerization temperature lower than the polymerization temperature at the time of “main polymerization”, that is, polymerization of olefin, is preferred.
The reaction is generally preferably carried out with stirring, in which case, for example, an aliphatic or aromatic hydrocarbon solvent (eg, hexane, heptane, toluene, cyclohexane, etc.) or a halogenated hydrocarbon solvent (eg, n-chloride). An inert solvent such as butyl, 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene or the like is preferably present. Among these, aliphatic hydrocarbons such as hexane and heptane, and aromatic hydrocarbons such as toluene are particularly preferable.

5). Organoaluminum Compound The α-olefin polymerization catalyst of the present invention is a combination of the aforementioned α-olefin polymerization catalyst component and an organoaluminum compound. Here, “combination” does not mean that the components are composed only of the listed ones, and other components are allowed to coexist within a range that does not impair the effects of the present invention. The
The organoaluminum compound used in the present invention, the general formula _{^R 1} 3-r AlX r or ^{_{R 2 3-s Al (OR}} 3) s ( wherein, ^{R 1} and ^{R 2} having 1 to 20 carbon atoms carbide A hydrogen group or a hydrogen atom, R ³ is a hydrocarbon group, X is a halogen, and r and s are numbers of 0 ≦ r <3 and 0 <s <3, respectively.

Specific examples thereof include the following.
(A) Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum (b) diethylaluminum monochloride, diisobutylaluminum monochloride Alkyl aluminum halides such as ethylaluminum sesquichloride, ethylaluminum dichloride (c) diethylaluminum hydride, alkylaluminum hydrides such as diisobutylaluminum hydride (d) alkylaluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum phenoxide, etc. (D) The organoaluminum compound includes two or more May be used. In this case, it is preferable to use the trialkylaluminum or halogen-containing aluminum compound (a) to (c) above in combination with the alkylaluminum alkoxide (d). For example, combined use of triethylaluminum and diethylaluminum ethoxide, combined use of diethylaluminum monochloride and diethylaluminum ethoxide, combined use of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum, diethylaluminum ethoxide and diethylaluminum monochloride And the combination use with. The ratio of the organoaluminum compound and the titanium component in the solid catalyst component of the polymerization catalyst component is generally Al / Ti = 1 to 1,000 mol / mol, preferably Al / Ti = 10 to 500 mol. A range of / mol is preferred.

6). Optional Component In the present invention, when an α-olefin polymer is produced using this polymerization catalyst component, an electron donating compound (external donor) is optionally added as a third component in addition to the solid catalyst component and organoaluminum. May be used. External donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, diethers, polyethers, acid amides, acid anhydrides. An oxygen electron donor, a nitrogen-containing electron donor such as ammonia, an amine, a nitrile, and an isocyanate, a sulfur-containing electron donor such as a sulfonate ester, and an organosilicon compound can be used as necessary. Two or more kinds of these external donors can be used.

Among these, (a) an organosilicon compound and (b) a diether compound are particularly preferable.
(A) As an organosilicon compound, general formula R < ¹ > R < ² > ³ _- mSi (OR < ³ >) _m
(Where R ¹ is a branched aliphatic hydrocarbon group, alicyclic hydrocarbon group, or heteroatom-containing hydrocarbon group, R ² is the same or different hydrocarbon group as R ^1, and R ³ is plural. Represents a hydrocarbon group which may be the same or different, and m represents a number of 1 ≦ m ≦ 3. The silicon compound may be a mixture of a plurality of compounds of the formula.

Here, when R ¹ is a branched aliphatic hydrocarbon group, those branched from a carbon atom or a hetero atom adjacent to the silicon atom are preferable. In this case, when the atom adjacent to the silicon atom is carbon, the branched group is preferably an alkyl group, a cycloalkyl group or an aryl group (for example, a phenyl group or a methyl-substituted phenyl group), and the adjacent atom is heterogeneous. When it is an atom, it is preferably an alkyl group or a polycyclic structure having 5 or more carbon atoms that includes a heteroatom and forms a skeleton. More preferable R ¹ is a carbon atom adjacent to the silicon atom, that is, the α-position carbon atom is a secondary or tertiary carbon atom. In particular, those having a tertiary carbon atom bonded to a silicon atom are preferred. When R ¹ is a branched aliphatic hydrocarbon group, the carbon number is usually 3 to 20, preferably 4 to 10. The number of carbon atoms in the case ^{R 1} is an alicyclic hydrocarbon group is usually 5 to 20, preferably 5 to 10.

R ² is represented by a branched or linear saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which is the same as or different from R ¹ . R ³ is represented by an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

The silicon compound that can be optionally used in the present invention is preferably an alkylalkoxysilicon compound or a silicon compound containing an amino group.
The alkyl group of the alkylalkoxysilicon compound is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-hexyl group, A linear or branched alkyl group having 1 to 10 carbon atoms such as i-hexyl group is preferable, and an alicyclic hydrocarbon group having 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. Among them, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclopentyl group, and cyclohexyl group are more preferable.

Specific examples of the alkylalkoxysilicon compounds that can be used in the present invention include (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (C ₂ H ₅ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (n—C ₃ H ₇ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (n—C ₆ H ₁₃ ) (OCH ₃ ) ₂ , (C ₂ H ₅ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) (C _{2 H 5) CHSi (CH 3} ) (OCH 3) 2, ((CH 3) 2 CHCH 2) 2 Si (OCH 3) 2, (C 2 H 5) (CH 3) 2 CSi (CH 3) (OCH _{3) 2, (C 2 H} 5) (CH 3) 2 CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (OCH ₃ ) ₃ , (CH ₃ ) ₃ CSi (OC ₂ H ₅ ) ₃ , (C ₂ H ₅ ) ₃ CSi (OC _{2 H 5) 3, (CH 3} ) (C 2 H 5) CHSi (OCH 3) 3, (CH 3) 2 CH (CH 3) 2 CSi (CH 3) (OCH 3) 2, ((CH 3) 3 C) ₂ Si (OCH ₃ ) ₂ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (OCH ₃ ) ₃ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (OC ₂ H ₅ ) ₃ , (CH _{3) 3 CSi (O-tC} 4 H 9) (OCH 3) 2, (i-C 3 H 7) 2 Si (OCH 3) 2, (i-C 3 H 7) 2 Si (OC 2 H 5) _{2, (i-C 4 H} 9) 2 Si (OCH 3) 2, (C 5 H 9) 2 S _{(OCH 3) 2, (C} 5 H 9) 2 Si (OC 2 H 5) 2, (C 5 H 9) (CH 3) Si (OCH 3) 2, (C 5 H 9) (i-C 4 H ₉ ) Si (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) ₂ Si (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) (i- _{C 4 H 9) Si (OCH} 3) 2, (i-C 4 H 9) (s-C 4 H 9) Si (OCH 3) 2, (i-C 4 H 9) (i-C 3 H 7 ) Si (OC ₅ H ₁₁ ) ₂ , HC (CH ₃ ) ₂ C (CH ₃ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , HC (CH ₃ ) ₂ C (CH ₃ ) ₂ Si (CH ₃ ) _{(OC 2 H 5) 2,} HC (CH 3) 2 C (CH 3) 2 Si (OCH 3) 3, HC (CH 3) 2 C _{CH 3) 2 Si (OC 2} H 5) 3 and the like, in which preferable alkyl alkoxy silicon _{compounds, (CH 3) 3 CSi (} CH 3) (OCH 3) 2, (CH 3) 3 CSi (CH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (C ₂ H ₅ ) (OCH ₃ ) ₂ , (CH _{3) 3 CSi (n-C} 3 H 7) (OCH 3) 2, (CH 3) 3 CSi (n-C 6 H 13) (OCH 3) 2, (C 5 H 9) 2 Si (OCH 3) ₂ , (C ₅ H ₉ ) ₂ Si (OC ₂ H ₅ ) ₂ , (C ₆ H ₁₁ ) Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) ₂ Si (OCH ₃ ) ₂ .

  When the silicon compound containing an amino group is a heteroatom, the silicon compound containing an amino group preferably forms a skeleton containing an alkyl group or a heteroatom. The pyrrolidine skeleton, piperidine skeleton, pyridine skeleton, indole It is preferably a polycyclic structure having 5 to 10 carbon atoms such as a skeleton or an isoquinoline skeleton, and more preferably a pyrrolidine skeleton, a piperidine skeleton or an isoquinoline skeleton.

Specific examples of the silicon compound containing an amino group that can be used in the present invention include bis (pyrrolidino) dimethoxysilane, bis (2-methyl-pyrrolidino) dimethoxysilane, bis (3-methyl-pyrrolidino) dimethoxysilane, and bis (piperidino) dimethoxy. Silane, bis (2-methyl-piperidino) dimethoxysilane, bis (3-methyl-piperidino) dimethoxysilane, bis (4-methyl-piperidino) dimethoxysilane, bis (2,2,6,6-tetramethyl-piperidino) Examples include dimethoxysilane, bis (2,6-dimethyl-piperidino) dimethoxysilane, bis (decahydroquinolino) dimethoxysilane, and bis (perhydroisoquinolino) dimethoxysilane. Among them, bis (pyrrolidino) dimethoxysilane, Bis (decahydroquinolino) di Tokishishiran, bis silicon compounds containing (perhydroisoquinolino) amino group such as dimethoxysilane is preferable.
The amount of the organic silicon compound of the optional component (A) is 0.01 to 10, preferably 0.05 to 1, in terms of the atomic ratio of silicon to aluminum compound (silicon / aluminum).

(B) Diether compound In the present invention, in a compound having two or more ether bonds (diether compound) present via a plurality of atoms used as necessary, the atoms present between these ether bonds are carbon, One or more selected from the group consisting of silicon, oxygen, sulfur, phosphorus, and boron, and the number of atoms is two or more. Among these, a relatively bulky substituent at an atom between ether bonds, specifically an alkyl group having 2 or more carbon atoms, preferably 3 or more and having a linear, branched or cyclic structure, an aryl group, a cyclo A substituent such as an alkyl group, an alkenyl group, an allylalkyl group, or an alkylallyl group, more preferably an i-propyl group, i-butyl group, s-butyl group having 3 to 6 carbon atoms and a branched or cyclic structure, Those having substituents such as t-butyl group, cyclopentyl, cyclohexyl group and the like are desirable.
Specifically, these bulky substituents include i-pentyl group, neopentyl group, t-pentyl group, i-hexyl group, cyclopropyl group, cyclobutyl group, cyclooctyl group, etc. Of these, i-propyl, i-butyl, s-butyl, t-butyl, cyclopentyl, and cyclohexyl are preferred.

Further, the two alkoxy groups in the diether compound have a linear or branched alkyl group having 1 to 20 carbon atoms directly bonded to the same or different oxygen atom, preferably a straight chain having 1 to 10 carbon atoms. It has a chain or branched alkyl group.
A compound in which a plurality of atoms, preferably 3 to 20, more preferably 3 to 10, and particularly preferably 3 to 7 carbon atoms are contained in atoms present between two or more ether bonds is preferable. Of these, 1,3-diethers such as 1,3-dimethoxypropane are particularly preferable.

  Specific examples of the 1,3-diethers include 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, and 2-butyl. -1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1,3 -Dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-dimethoxypropane 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-dimethoxypropane, -(2-fluorophenyl) -1,3-dimethoxypropane, 2- (1-decahydronaphthyl) -1,3-dimethoxypropane, 2- (pt-butylphenyl) -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3- Dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2- Benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl 1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1, 3-dimethoxypropane, 2,2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2 -Bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2, 2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1 -Methylbutyl) -2-s-butyl-1,3-dimethoxypropane, 2,2-di-s-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2- s-Butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-benzyl-2- -Butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl- 1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1 , 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane.

  Examples of diether compounds other than 1,3-diethers include 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, and 2,2-dibenzyl-1 , 4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,2-bis (p-methylphenyl) -1,4 -Dimethoxybutane, 2,3-bis (p-chlorophenyl) -1,4-dimethoxybutane, 2,3-bis (2,3-difluorophenyl) -1,4-dimethoxybutane, 2,4-diphenyl-1 , 5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl 1,5-dimethoxy-pentane, and 2,4-diisoamyl-1,5-dimethoxy pentane.

  These can be used in combination of two or more. Of these, 1,3-diethers are preferred, and in particular, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1 , 3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1, 3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane and 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane are preferred.

The diether compound (b) is usually used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, more preferably 1 to 10 mol, per mol of titanium atom. In the present invention, (b) organosilicon compound and (b) diether compound as described above can also be used in combination as an external donor.
The said arbitrary component can be used 1 type or in combination of 2 or more types. When these optional components are used, the effect of the present invention becomes greater.

7). α-Olefin Polymerization The α-olefin polymerization of the present invention is applied to slurry polymerization using a hydrocarbon solvent, liquid phase solvent-free polymerization or gas phase polymerization using substantially no solvent. 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.

The α-olefin polymerized in the catalyst system of the present invention has the general formula R—CH═CH ₂ (where R is a hydrocarbon group having 1 to 20 carbon atoms, and may have a branching group). It is represented by Specific examples include 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
The measuring method and apparatus for each physical property value in the present invention are shown below.

(1) Melt flow rate (MFR: unit g / 10 min)
In accordance with JIS K-6758, measurement was performed using a melt indexer manufactured by Takara.
(2) ME
Apparatus: Melt indexer measurement method manufactured by Takara Co., Ltd .: Molten polymer was extruded at 190 ° C. while applying a load through an orifice diameter of 1.0 mm and a length of 8.0 mm. When the extrusion speed was 0.1 g / min, the orifice The polymer extruded from was put into methanol and quenched, and the value of the diameter diameter / orifice diameter was calculated. (Note that ME is a physical property value representing a ballast effect and a swell ratio, and is a rheological characteristic from a different viewpoint from MT. As with MT, it has a great influence on molding processability.)
(3) Melt tension (MT)
The melt tension (MT: g) was measured under the following conditions.
Apparatus: Capillograph test temperature manufactured by Toyo Seiki Seisakusho: 190 ° C
Orifice: 2.095mmφ × 8.1mm
Extrusion speed: 10 mm / min.
Take-off speed: 4 mm / min.

Example-1
[Catalyst preparation]
200 ml of dehydrated and deoxygenated n-heptane was introduced into a sufficiently nitrogen-substituted flask, and then 0.4 mol of MgCl ₂ and 0.8 mol of Ti (On-C ₄ H ₉ ) ₄ were introduced. For 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.
Next, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms. Subsequently, 0.4 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, washing with n-heptane was performed.
Next, 25 ml of n-heptane was mixed with 0.024 mol of 2,3-bis (dimethylamino) butanedioic acid dinormal butyl as a butanedioic acid diester, introduced into the flask at 70 ° C. for 60 minutes, and at 90 ° C. for 1 hour. Reacted. After completion of the reaction, it was thoroughly washed with n-heptane, and then 20 ml of TiCl ₄ was introduced and reacted at 80 ° C. for 4 hours. After completion of the reaction, it was sufficiently washed with n-heptane to obtain a solid component of the polymerization catalyst component. The titanium content of this product was 3.4% by weight.

[Polypropylene polymerization]
In a 1.5 liter stainless steel autoclave with stirring and temperature control device, 500 ml of fully dehydrated and deoxygenated n-heptane, 125 mg of triethylaluminum (TEA) as an organoaluminum compound and the above-mentioned polymerization 15 mg of the catalyst component, 20 mg of (t-C ₄ H ₉ ) (CH ₃ ) Si (OCH ₃ ) ₂ and then 130 ml of hydrogen were introduced, the temperature was raised and the pressure was increased, polymerization pressure = 0.5 MPa, polymerization temperature Propylene was polymerized under the conditions of = 75 ° C. and polymerization time = 2 hours. After the polymerization was completed, the obtained polymer slurry was separated by filtration, and the polymer was dried.
As a result, 174.1 g of polymer was obtained. Therefore, the amount of polymer produced per 1 g of catalyst (hereinafter referred to as catalyst yield) is 11,600 (g-PP / g-catalyst). The polymer obtained by filtration and drying was MFR = 15.1 (g / 10 min), and the ME value was 1.45.

Examples-2 to 3
In the production of the polymerization catalyst component of Example-1, the procedure was exactly the same except that the amount of butanedioic acid diester charged and the amount of hydrogenation during polymerization were changed, and the polymerization of propylene was also carried out in the same manner. The results are shown in Table 1.

Comparative Example-1
In the production of the polymerization catalyst component of Example-1, the polymerization catalyst component was produced in the same manner except that di-n-butyl phthalate was used in an equimolar amount instead of butanedioic acid diester, and polymerization of propylene was performed. Was carried out in exactly the same manner as in Example-1. The results are shown in Table 1.

Comparative Example-2
In the production of the polymerization catalyst component of Example-1, the polymerization catalyst component was produced in exactly the same manner except that equimolar amounts of butanedioic acid dinormal butyl were used instead of the butanedioic acid diester defined in the present invention. The polymerization of propylene was also carried out in the same manner as in Example 1 except that the amount of hydrogen was changed to 80 ml. The results are shown in Table 1.

Examples-4-8
The production of the polymerization catalyst component of Example-1 was carried out in exactly the same manner except that equimolar amounts of the compounds listed in Table 1 were used as the butanedioic acid diester, and the polymerization of propylene was carried out in the same manner. The results are shown in Table 1.

Example-9
[Catalyst preparation]
200 ml of dehydrated and deoxygenated n-heptane was introduced into a sufficiently nitrogen-substituted flask, and then 0.4 mol of MgCl ₂ and 0.8 mol of Ti (On-C ₄ H ₉ ) ₄ were introduced. For 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.
Next, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms. Subsequently, 0.4 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, washing with n-heptane was performed.
Subsequently, 0.024 mol of 2,3-bis (dimethylamino) butanedioic acid dinormal butyl which is a butanedioic acid diester was mixed with 25 ml of n-heptane and introduced into the flask at 70 ° C. for 60 minutes. For 1 hour. After completion of the reaction, it was thoroughly washed with n-heptane. 20 ml of TiCl ₄ was introduced and reacted at 80 ° C. for 4 hours. After completion of the reaction, it was sufficiently washed with n-heptane to obtain a solid component for producing a polymerization catalyst component. The titanium content of this product was 4.1% by weight.
Next, 80 ml of fully purified n-heptane was introduced into a flask sufficiently purged with nitrogen, 4 g of the solid component obtained above was introduced, and (t-C ₄ H ₉ ) Si (CH ₃ ) was introduced as component (C). 0.5 ml of (OCH ₃ ) _{2 and} 1.69 g of Al (C ₂ H ₅ ) ₃ (TEA) as component (B) were contacted at 30 ° C. for 2 hours. After completion of the contact, the catalyst component was thoroughly washed with n-heptane to obtain a catalyst component mainly composed of magnesium chloride. The titanium content of this product was 3.3% by weight.

[Polypropylene polymerization]
In a 1.5 liter stainless steel autoclave with a stirring and temperature control device, 500 ml of fully dehydrated and deoxygenated n-heptane, 125 mg of triethylaluminum (TEA) as an organoaluminum compound, and the polymerization produced above 15 mg of the catalyst component and then 130 ml of hydrogen were introduced, the temperature was raised and the pressure was raised, and propylene was polymerized under the conditions of a polymerization pressure of 0.5 MPa, a polymerization temperature of 75 ° C., and a polymerization time of 2 hours. After the polymerization was completed, the obtained polymer slurry was separated by filtration, and the polymer was dried.
As a result, 189.5 g of polymer was obtained. Therefore, the amount of polymer produced per gram of catalyst is 12,600 (g-PP / g-catalyst). The polymer obtained by drying after filtration had MFR = 14.1 (g / 10 min) and an ME value of 1.44.

Example-10
In the production of the polymerization catalyst component of Example-1, the polymerization catalyst component was produced in exactly the same manner except that equimolar amount of 2,3-bis (dimethylamino) butanedioic acid diethyl was used as the butanedioic acid diester. .

[Preparation of prepolymerization catalyst]
After 100 ml of fully dehydrated and deoxygenated n-heptane and 0.83 g of TEA were introduced into a stainless steel autoclave having an internal volume of 1.5 liter, 2 g of the solid component obtained above was introduced. The introduction of propylene was started at 20 ° C., and the introduction of propylene was stopped after 30 minutes. Thereafter, the solid component was taken out in a nitrogen atmosphere and then sufficiently washed with n-heptane to obtain a prepolymerized catalyst component for polymerization. The prepolymerization amount of propylene was 1.09 g per 1 g of the solid component.

[Polypropylene polymerization]
Into an induction stirring type 3 liter autoclave, 600 mg of triisobutylaluminum was charged under a nitrogen stream at room temperature. Further, 70 mg of t-butylmethyldimethoxysilane and 3,000 ml of hydrogen were added as external donors, and 750 g of liquid propylene was charged. The temperature was raised to 70 ° C. while stirring, and when the temperature reached 70 ° C., 10 mg of the prepolymerized polymerization catalyst component obtained above was added to initiate polymerization. After polymerization at 70 ° C. for 1 hour, excess propylene was purged to terminate the polymerization.
As a result, 302.3 g of polymer was obtained. Therefore, the amount of polymer produced per 1 g of catalyst is 30,200 (g-PP / g-catalyst). The polymer obtained by drying had MFR = 16.5 (g / 10 min) and ME value of 1.45. The results are shown in Table 2.

Example-11
In the production of the polymerization catalyst component of Example-10, the same procedure was carried out except that the butanedioic acid diester compound, the charged amount and the hydrogenation amount during polymerization were changed as shown in Table 2, and the polymerization of propylene was also carried out in the same manner. . The results are shown in Table 2.

Comparative Example-3
The production of the polymerization catalyst component of Example-10 was carried out in the same manner except that the butanedioic acid diester compound was not used, and the polymerization of propylene was carried out in the same manner. The results are shown in Table 2.

Comparative Example-4
In the production of the polymerization catalyst component of Example-10, the same procedure was carried out except that 2,2-diisopropyl-1,3-dimethoxypropane was used in the amount shown in Table 2 instead of butanedioic acid diester. The polymerization of propylene was carried out in the same manner. The results are shown in Table 2.

Example-12
[Catalyst preparation]
Into a flask thoroughly purged with nitrogen, 20 g of Mg (OC ₂ H ₅ ) ₂ and 160 ml of toluene were added to form a suspended state. After stirring for 15 minutes at room temperature, 40 ml of TiCl ₄ was introduced, and then the temperature was raised to 80 ° C. while stirring. After introducing 0.06 mol of diethyl 2,3-bis (dimethylamino) butanedioate, The temperature was raised to 110 ° C. and reacted for 2 hours. After completion of the reaction, the supernatant was removed and washed 3 times at 90 ° C. with 200 ml of toluene. Next, 10 ml of TiCl ₄ was mixed, heated to 70 ° C., and reacted at 90 ° C. for 2 hours. After completion of the reaction, the product was sufficiently washed with toluene until no free titanium compound was detected in the washing solution. The titanium content of this product was 4.1% by weight.

[Preparation of prepolymerization catalyst]
300 ml of sufficiently dehydrated and deoxygenated n-heptane and 2.5 g of TEA were introduced into a 1.5 liter stainless steel autoclave, and then 6 g of the solid component obtained above was introduced. The introduction of propylene was started at 20 ° C., and the introduction of propylene was stopped after 30 minutes. Thereafter, the solid component was taken out in a nitrogen atmosphere and then sufficiently washed with n-heptane to obtain a prepolymerized catalyst component for polymerization. The prepolymerization amount of propylene was 1.42 g per 1 g of the solid component.

[Polypropylene polymerization]
Into an induction stirring type 3 liter autoclave, 600 mg of triisobutylaluminum was charged under a nitrogen stream at room temperature. Further, 85 mg of t-butylmethyldiethoxysilane and 1,000 ml of hydrogen were added as optional components (external donor), and 750 g of liquid propylene was charged. The temperature was raised to 70 ° C. while stirring, and when the temperature reached 70 ° C., 10 mg of the prepolymerized polymerization catalyst component obtained above was added to initiate polymerization. After polymerization at 70 ° C. for 1 hour, excess propylene was purged to terminate the polymerization.
As a result, 310.6 g of polymer was obtained. Accordingly, the amount of polymer produced per 1 g of catalyst is 31,000 (g-PP / g-catalyst). The polymer obtained by drying had MFR = 13.1 (g / 10 min) and an ME value of 1.45.
The results are shown in Table 3.

Examples-13-15
In the propylene polymerization described in Example-12, the compounds and addition amounts shown in Table 3 were used as external donors instead of t-butylmethyldiethoxysilane, and the hydrogenation amount during polymerization was changed exactly. went. The results are shown in Table 3.

[Consideration of results of Examples and Comparative Examples]
By contrasting each of the above Examples and Comparative Examples, it can be understood that the catalyst yield is excellent and the properties of ME and melt tension are extremely excellent in the present invention.
Specifically, in Examples 1 to 11 and Examples 12 to 15 which further used an external donor, excellent numerical results were shown in both catalyst yield and ME and MT (melt tension). Even if it becomes considerably high (Examples 2, 11, 13, etc.), the ME value is high.
In Comparative Examples 1 and 2 in which the specific butanedioic acid diester of the present invention is not used, the catalyst yield is slightly lower than in Examples 1 to 8, and the ME value and melt tension (MT) are considerably inferior. Similarly, in Comparative Examples 3 and 4 in which the specific butanedioic acid diester of the present invention is not used, the catalyst yield is the same as in Examples 9 and 10, but the ME value and melt tension (MT) are equivalent. Inferior.

It is a flowchart for assisting the understanding of the technical contents of the present invention related to the Ziegler catalyst.

Claims (7)

A catalyst component for α-olefin polymerization containing titanium, magnesium, halogen, and butanedioic acid diester represented by the following general formula [1] or [2] as essential components.

(Wherein R ¹ and R ² represent a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may be the same or different, and R ³ represents a linear or branched hydrocarbon group having 1 to 20 carbon atoms. A cyclic or cyclic hydrocarbon group, or a silahydrocarbyl group having a hydrocarbon group, wherein R ⁴ , R ⁷ and R ⁸ are hydrogen or a straight chain having 1 to 20 carbon atoms which may be the same as or different from R ³ , A branched or cyclic hydrocarbon group, or a silahydrocarbyl group having a hydrocarbon group, wherein R ⁵ , R ⁶ and R ⁹ are hydrogen or a linear, branched or cyclic carbon atom having 1 to 20 carbon atoms Represents a hydrogen group, and X represents an atom selected from Group 15.) The catalyst component for α-olefin polymerization according to claim 1, comprising an organosilicon compound and / or a diether compound component and an organoaluminum compound component. The catalyst component for α-olefin polymerization according to claim 1 or 2, wherein R ⁵ , R ⁶ and R ^{9 in the} general formula [1] or [2] are hydrogen. The butanedioic acid diester has a symmetrical structure in which R ¹ and R ² and R ³ , R ⁴ , R ⁷ and R ^8, and each of R ⁵ and R ⁶ are the same. Item 3. An α-olefin polymerization catalyst component according to Item 2. An α-olefin polymerization catalyst comprising the catalyst component for α-olefin polymerization according to any one of claims 1 to 4 (component (A)) and an organoaluminum compound (component (B)). The compound chosen from the catalyst component (component (A)) and organoaluminum compound (component (B)) for alpha-olefin polymerization in any one of Claims 1-4, and an organosilicon compound and / or a diether compound The (alpha) -olefin polymerization catalyst characterized by including (component (C)). A method for producing an α-olefin polymer, wherein the α-olefin is polymerized or copolymerized in the presence of the α-olefin polymerization catalyst according to claim 5.

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