JP5393098B2 - Novel transition metal compound, olefin polymerization catalyst using the same, and α-olefin polymerization or copolymerization method - Google Patents

Description

  The present invention relates to a novel transition metal compound, a catalyst for olefin polymerization using the same, and a polymerization or copolymerization method of α-olefin, and more particularly, a balance between ethylene or an α-olefin having 4 to 20 carbon atoms and propylene. Novel transition metal compound capable of forming a metallocene-based catalyst that produces an α-olefin copolymer having a high molecular weight while having excellent reactivity, an olefin polymerization catalyst using the same, and polymerization of α-olefin Or, it relates to a copolymerization method.

Polypropylene resin materials have many excellent performances in terms of moldability and various physical properties, as well as economic efficiency and adaptability to environmental problems, and are therefore widely used and used as industrial materials. .
Further, due to its importance in the industrial field, further improvements in performance are constantly demanded in many ways. For example, in order to improve flexibility and impact resistance, propylene homopolymer and ethylene-propylene rubber are used. A method of adding so-called elastomer, and a method of producing a so-called block copolymer by multi-stage polymerization in which propylene and ethylene or α-olefin are subsequently copolymerized after homopolymerization of propylene are carried out.

Such a polypropylene resin material is industrially produced mainly by a Ziegler catalyst and a metallocene catalyst, but still contains many problems to be solved.
For example, a propylene block copolymer obtained by polymerizing in the presence of a Ziegler catalyst always contains low molecular weight components (oligomer components, etc.) due to the nature of the catalyst. In addition to causing smoke generation and off-flavors, various problems such as bad effects such as odor and deterioration of blocking properties due to stickiness are derived after processing.

  On the other hand, it has been well known that a high isotactic polypropylene can be obtained by polymerizing propylene using a metallocene-based catalyst different from the conventional Ziegler-based catalyst. It is also disclosed that a so-called block copolymer is produced (see, for example, Patent Document 1), and further, a propylene-ethylene block copolymer having good rigidity and impact resistance is produced (for example, patents). References 2 and 3).

  Metallocene catalysts generally have higher polymerization activity than Ziegler catalysts, and can produce polymers having a narrow molecular weight distribution and uniformity of copolymer composition distribution, but the synthesis is complicated. There are still many problems that need to be improved, such as the problem of economics due to the use of metallocene compounds and MAO, and the need to further increase and improve the polymerization activity, the molecular weight and stereoregularity of the polymer.

For metallocene catalysts, various improvements have been made from various viewpoints. For example, in order to improve the rigidity of a propylene-ethylene block copolymer, a transition metal that gives a polypropylene having a high melting point. Although compounds have been disclosed (see, for example, Patent Documents 4 and 5), when copolymerization of propylene and ethylene or α-olefin is carried out using a catalyst comprising these transition metal compounds, ethylene or α-olefin It is problematic that the reactivity of is relatively low compared to the reactivity of propylene. In other words, in order to obtain a copolymer having the desired ethylene or α-olefin content, it is necessary to polymerize by supplying a gas having a monomer ratio greatly different from the content in the copolymer. In extreme cases, a copolymer having a desired content may not be produced.
For such problems, for example, it has been proposed that the reactivity of propylene and the reactivity of ethylene or α-olefin are changed by changing the transition metal compound used (for example, Patent Documents 6 and 7). , See Non-Patent Document 1), a transition metal compound satisfying both reactivity in a well-balanced manner has not been known so far, particularly when copolymerization of propylene and ethylene or α-olefin is performed in the gas phase A transition metal compound that satisfies the above-described reactivity in a well-balanced manner has not yet been known.
For example, in order to exhibit high impact resistance in a propylene-ethylene block copolymer, it is necessary to exhibit a lower glass transition temperature. To satisfy this, propylene and ethylene or α-olefin are required. It is preferable that the respective contents in the copolymer satisfy a specific range (for example, see Non-Patent Document 2). Therefore, in terms of the performance of the catalyst in production, it is necessary that the reactivity of propylene and the reactivity of ethylene or α-olefin are balanced and within a certain range.

Furthermore, when a transition metal compound known so far is used, when copolymerization of propylene and ethylene or α-olefin is carried out in the gas phase, there is a problem that the molecular weight of the resulting copolymer is lowered. .
Under such circumstances, in order to exhibit high impact resistance in the propylene-ethylene block copolymer, it is necessary that the copolymer has a molecular weight of a certain value or higher. There is also a need for transition metal compounds and catalysts that can produce.

JP-A-4-337308 Japanese Patent Laid-Open No. 11-228648 JP-A-11-240929 Japanese Patent Laid-Open No. 11-240909 Japanese Patent Laid-Open No. 2000-95791 WO 2004-87775 JP 2007-308486 A

Journal of the American Chemical Society 2001, 123, 9555. Polymer 2001, 42, 9611

  In view of the above-mentioned problems of the prior art, an object of the present invention is to provide an α-olefin copolymer having a high molecular weight while having a balanced reactivity between ethylene or an α-olefin having 4 to 20 carbon atoms and propylene. It is an object of the present invention to provide a novel transition metal compound capable of forming a metallocene catalyst that forms a coalescence, a catalyst for olefin polymerization using the same, and a method for polymerizing or copolymerizing α-olefin.

  As a result of various studies to solve such problems, the present inventors have found that the ligand structure of the transition metal compound as the metallocene compound in the metallocene-based polymerization catalyst has symmetry and catalytic activity due to its basic skeleton. The balance of the reactivity of ethylene or α-olefin with propylene and the molecular weight, taking into account the empirical rules from the viewpoint of the mechanism of polymer formation at the point and the effect of the steric effect of the substituent on the coordination monomer and the growing polymer In search of an improvement method, a multifaceted consideration and an experimental search were conducted. In the process, when a transition metal compound having a specific three-dimensional structure was formed, ethylene or α having 4 to 20 carbon atoms was formed. -It has been found that a catalytic function that exhibits a balanced reactivity between olefin and propylene, which leads to a high molecular weight, is manifested. Thus, the present invention has been completed.

  That is, according to the first invention of the present invention, a transition metal compound represented by the following general formula (I) is provided.

（式中、Ｒ^１は、炭素数１から４のアルキル基、Ｒ^２は、メチル基、Ｒ^３は、炭素数３から１０の２級又は３級のアルキル基、Ｒ^４及びＲ^５は、それぞれ独立して、水素原子、炭化水素基、ケイ素含有炭化水素基又はハロゲン化炭化水素基、Ｒ^６は、炭素数６以上の、炭化水素基、ハロゲン化炭化水素基又はケイ素含有炭化水素基、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立して、水素原子、炭化水素基、ケイ素含有炭化水素基又はハロゲン化炭化水素基である。
また、Ｑは、置換基を有してもよいシリレン基或いは置換基を有してもよいゲルミレン基であり、Ｘ及びＹは、それぞれ独立して、Ｍとσ結合を形成する配位子であり、Ｍは、周期律表第４族の遷移金属である。）

(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is a methyl group, R ³ is a secondary or tertiary alkyl group having 3 to 10 carbon atoms, and R ⁴ and R ⁵ are Each independently a hydrogen atom, hydrocarbon group, silicon-containing hydrocarbon group or halogenated hydrocarbon group, R ⁶ is a hydrocarbon group, halogenated hydrocarbon group or silicon-containing hydrocarbon group having 6 or more carbon atoms, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group.
Q is a silylene group which may have a substituent or a germylene group which may have a substituent, and X and Y are each independently a ligand which forms a σ bond with M. And M is a transition metal of Group 4 of the Periodic Table. )

Moreover, according to 2nd invention of this invention, the catalyst component for olefin polymerization characterized by including the transition metal compound which concerns on 1st invention is provided.

Moreover, according to the 3rd invention of this invention, the catalyst for olefin polymerization characterized by including following component (A) and (B) and component (C) arbitrarily is provided.
Component (A): transition metal compound according to the first invention Component (B): an organoaluminum oxy compound, an ionic compound or Lewis capable of reacting with component (A) to convert component (A) into a cation Compound selected from acids Component (C): Fine particle carrier

Moreover, according to the 4th invention of this invention, the catalyst for olefin polymerization characterized by including the following component (A) and (D) and component (E) arbitrarily is provided.
Component (A): Transition metal compound according to the first invention Component (D): Compound selected from ion-exchange layered compound or inorganic silicate Component (E): Organoaluminum compound

Furthermore, according to the fifth invention of the present invention, the polymerization or copolymerization of an α-olefin characterized by polymerizing or copolymerizing an α-olefin in the presence of the olefin polymerization catalyst according to the third or fourth invention. A copolymerization method is provided.

By the way, the metallocene metal complex which constitutes the basic constitution of the present invention is a novel transition metal compound, which is characterized by the electronic and steric structure of its ligand. A catalytic function that exhibits a balanced reactivity between 20 α-olefins and propylene, which in turn leads to a high molecular weight, is manifested.
The metallocene complex is composed of a novel transition metal compound having a structure represented by the above general formula (I), and is used as a catalyst component of an olefin polymerization catalyst in the present invention, and is combined with a promoter or the like. To form an α-olefin polymerization catalyst.

By using the transition metal compound of the present invention as a catalyst component for olefin polymerization, the balance between ethylene or an α-olefin having 4 to 20 carbon atoms and propylene can be achieved as demonstrated by the comparison of Examples and Comparative Examples described later. It is possible to realize a metallocene catalyst for α-olefin polymerization that gives a copolymer having high reactivity and high molecular weight.
The reason is not necessarily clear, but the transition metal compound represented by the chemical formula (I) in the present invention is a substituent having an appropriate steric effect at the R ² position at the 4-position of the cyclopentadienyl ring moiety. And a three-dimensionally unique structure in which bulky substituents are respectively arranged at the position of R ³ , and it is assumed that these characteristics bring about the specificity of the present invention. Can do.

  The transition metal compound of the present invention is a novel compound that can be used as a metallocene complex and used as a catalyst component of an olefin polymerization catalyst or as an α-olefin polymerization catalyst in combination with a co-catalyst. it can. In particular, when the α-olefin polymerization catalyst of the present invention is used when copolymerizing propylene and ethylene or an α-olefin having 4 to 20 carbon atoms, propylene and the copolymerization monomer exhibit balanced reactivity. As a result, it is possible to perform the polymerization by rationally supplying a gas having a monomer ratio that does not substantially differ from the content in the copolymer, and at the same time, a catalytic function that brings about a high molecular weight is manifested.

  The novel transition metal compound of the present invention is a compound represented by the above general formula (I), which is employed as a metallocene complex, as a catalyst component of an olefin polymerization catalyst, or in combination with a cocatalyst or the like. It can be used as a catalyst for α-olefin polymerization.

  Hereinafter, the transition metal compound of the present invention, the metallocene catalyst containing it, the polymerization method, the resulting propylene / ethylene-α-olefin block copolymer, and the like will be described in detail.

1. Transition metal compound used for olefin polymerization catalyst component (1) Structure of transition metal compound The transition metal compound forming the metallocene complex in the metallocene catalyst of the present invention is a novel transition metal compound represented by the following general formula (I). is there.

（式中、Ｒ^１は、炭素数１から４のアルキル基、Ｒ^２は、水素原子又は炭素数１から６のアルキル基、Ｒ^３は、炭素数３から１０の２級又は３級のアルキル基、Ｒ^４及びＲ^５は、それぞれ独立して、水素原子、炭化水素基、ケイ素含有炭化水素基又はハロゲン化炭化水素基、Ｒ^６は、炭素数６以上の、炭化水素基、ハロゲン化炭化水素基又はケイ素含有炭化水素基、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立して、水素原子、炭化水素基、ケイ素含有炭化水素基又はハロゲン化炭化水素基である。
また、Ｑは、置換基を有してもよいシリレン基或いは置換基を有してもよいゲルミレン基であり、Ｘ及びＹは、それぞれ独立して、Ｍとσ結合を形成する配位子であり、Ｍは、周期律表第４族の遷移金属である。）
なお、本願の明細書においては、周期律表は長周期型のものを使用している。

Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³ is a secondary or tertiary alkyl group having 3 to 10 carbon atoms. The groups R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group, and R ⁶ is a hydrocarbon group or halogenated carbon group having 6 or more carbon atoms. The hydrogen group or the silicon-containing hydrocarbon group, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group.
Q is a silylene group which may have a substituent or a germylene group which may have a substituent, and X and Y are each independently a ligand which forms a σ bond with M. And M is a transition metal of Group 4 of the Periodic Table. )
In the specification of the present application, the long periodic table is used as the periodic table.

(2) Features of transition metal compounds The features of the transition metal compounds of the present invention as complex ligands are fundamental in chemical structure and specific in steric arrangement as substituents. In the 4-position of the cyclopentadienyl ring moiety, a substituent having an appropriate steric effect at the position of R ^{2 in} the above general formula (I) and a bulky substitution at the position of R ³ It has a unique and novel structure in which each group is arranged.
Furthermore, the transition metal compound of the present invention naturally has a 2 It includes two isomers (a; commonly referred to as anti isomers) and (b; commonly referred to as syn isomers).
However, in order to produce a high molecular weight α-olefin polymer, from the viewpoint of regulating the growth direction of the polymer chain and the coordination direction of the monomer, the above compound (a), that is, M, It is preferable to use a compound in which two ligands facing each other across a plane including X and Y are not in a relationship between an entity and a mirror image with respect to the plane.

The reason (mechanism) for the transition metal compound of the present invention to exhibit a unique catalytic function in olefin polymerization has not been fully elucidated so far, but the present inventors consider as follows. Yes.
In transition metal compounds having C ₂ symmetry (symmetry having a two-fold rotation axis) as typically shown in the above-mentioned Patent Document 4, the steric and electronic environment of two coordination fields is Are the same. In this case, the reactivity ratio between propylene and a monomer to be copolymerized such as ethylene or an α-olefin having 4 to 20 carbon atoms is determined in a coordination field environment determined by the ligand structure of the transition metal compound. The
On the other hand, in the transition metal compound having no C ₂ symmetry, as shown in the chemical formula (I) in the present invention, steric and electronic environment of the coordination field with two from its low symmetry is not identical. In this case, the reactivity ratio of the monomer to be copolymerized with propylene is different in each coordination field. In such a coordination field environment, for example, the reaction of propylene is relatively large in one coordination field (extremely only propylene can selectively react), and in the other coordination field, It is presumed that the reactivity of the monomer to be polymerized is relatively large (in the extreme, only the copolymerization monomer can selectively react). It is considered that the reactivity ratio of γ varies greatly.

Further, it is well known to those skilled in the art that the molecular weight of the obtained copolymer is determined by the balance between the polymerization reaction and the termination reaction, but the cyclopentadienyl derivative represented by the general formula (I) In the transition metal compound consisting of a hydroazurenyl derivative and a hydroazurenyl derivative, the steric effect of the substituents substituted on each affects the polymerization termination reaction due to elimination of the polymer chain. It is considered that the degree of the effect varies greatly depending on the bulkiness.
If the steric effect due to the substituent at this part is small, the polymer chain can be freely arranged, and the hydrogen atom at the β-position can be easily extracted, resulting in a decrease in molecular weight. Conversely, this steric effect is large. If the coordination field is narrowed too much, it is assumed that the methyl group at the β-position of the polymer chain is extracted, resulting in a decrease in molecular weight.

In the present invention, by placing a substituent having an appropriate steric size at the position of R ² and a bulky substituent at the position of R ³ , the environment of one coordination field is compared to the other. The reactivity ratio between propylene and the comonomer is more balanced, and an appropriate spatial distance is maintained between the arranged substituent and the growing polymer, so that the hydrogen at the β position It is presumed that both the extraction of atoms and methyl groups is suppressed. As a result, it is considered that the ethylene or α-olefin content and molecular weight of the obtained copolymer can be improved at the same time.

  By the way, in order to show the grounds that the transition metal compound of the present invention is a novel compound, each patent document and non-patent document described in the background art, as well as other patent documents, are examined in detail. No. 226712 discloses some transition metal compounds similar to the present invention as exemplary compounds, but is merely an exemplary description of the enumeration, and the description of such compounds actually synthesized and confirmed is I can't find anything. Further, in Japanese Patent Application Laid-Open No. 2003-292700, Japanese Patent Application Laid-Open No. 2004-2310, Japanese Patent Application Laid-Open No. 2004-155739, Japanese Patent Application Laid-Open No. 2007-308486, etc. It is merely an illustrative description, and the novel transition metal compound of the present invention is not found. Moreover, such a compound is actually synthesized, and the reactivity between propylene and ethylene or an α-olefin having 4 to 20 carbon atoms is further increased. There is no description that confirms that the molecular weight has particularly excellent properties.

(3) Details of Transition Metal Compound In general formula (I), R ¹ is an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl and t-butyl groups. Among them, R ¹ is preferably a methyl, ethyl, or n-propyl group, and more preferably a methyl group.

R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl and cyclohexyl groups. Can be mentioned. Among them, R ² is preferably a substituent other than a hydrogen atom, and more preferably a methyl group.

R ³ is a secondary or tertiary alkyl group having 3 to 10 carbon atoms. Specific examples of the alkyl group include i-propyl, cyclopropyl, s-butyl, t-butyl, cyclohexyl group and the like. Among these, R ³ is preferably an i-propyl or t-butyl group, and more preferably a t-butyl group.

R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group.
Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, In addition to alkyl groups such as cyclohexyl, alkenyl groups such as vinyl, propenyl, and cyclohexenyl, phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, t-butylphenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl, anthryl And aryl groups such as
Specific examples of the silicon-containing hydrocarbon group preferably include trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl, and alkylsilylalkyl groups such as bis (trimethylsilyl) methyl.
In the halogenated hydrocarbon group, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated hydrocarbon group is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group.
Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2,1 , 1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 2-, 3-, 4-substituted fluorophenyl, 2-, 3-, 4-substituted Chlorophenyl, 2-, 3-, 4-substituted bromophenyl, 2,4-, 2,5-, 2,6-3,5-substituted difluorophenyl, 2,4-, 2,5 -, 2,6-, 3,5-substituted dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophene Le, pentafluorophenyl and pentachlorophenyl and the like.
Among them, R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl and butyl, and R ⁵ is preferably a hydrogen atom.

R ⁶ is a sterically bulky hydrocarbon group, halogenated hydrocarbon group or silicon-containing hydrocarbon group having 6 or more carbon atoms, and R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently , A hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group.
Specific examples of the sterically bulky hydrocarbon group having 6 or more carbon atoms include phenyl group, tolyl group, dimethylphenyl group, mesityl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, i-propylphenyl group, Di-propylphenyl group, tri-i-propylphenyl group, n-butylphenyl group, di-n-butylphenyl group, tri-n-butylphenyl group, t-butylphenyl group, di-t-butylphenyl group, tri-t- Examples thereof include aryl groups such as butylphenyl group, biphenylyl group, p-terphenyl group, m-terphenyl group, naphthyl group, anthryl group, and phenanthryl group.
In the sterically bulky halogenated hydrocarbon substituent having 6 or more carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated hydrocarbon substituent is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group. Specifically, fluorodimethylphenyl group, (fluoromethyl) methylphenyl group, ethylfluorophenyl group, diethylfluorophenyl group, triethylfluorophenyl group, fluoro i-propylphenyl group, fluorodi i-propylphenyl group, (fluoro i -Propyl) i-propylphenyl group, fluorotri-i-propylphenyl group, n-butylfluorophenyl group, di-n-butylfluorophenyl group, (fluorobutyl) butylphenyl group, tri-n-butylfluorophenyl group, t- Butylfluorophenyl group, di-t-butylfluorophenyl group, tri-t-butylfluorophenyl group, fluorobiphenylyl group, fluoro p-terphenyl group, fluoro m-terphenyl group, fluoronaphthyl group, fluoroanthryl group, fluoro And phenanthryl groups.
Specific examples of the sterically bulky silicon hydrocarbon substituent having 6 or more carbon atoms include silyl groups such as trimethylsilylphenyl, triethylsilylphenyl, isopropyldimethylsilylphenyl, t-butyldimethylsilylphenyl, and phenyldimethylsilylphenyl. And substituted aryl groups.

R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are not particularly bulky groups and represent a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing hydrocarbon group.
Specific examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, i-propyl and n-butyl, and alkenyl groups such as vinyl, propenyl, and cyclohexenyl.
The halogenated hydrocarbon group is a compound in which a halogen atom is substituted at an arbitrary position of the above hydrocarbon group. Halogen is preferably fluorine, chlorine or bromine, among which fluorine or chlorine is preferred.
Specific examples of the halogenated hydrocarbon include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl and the like.
Specific examples of silicon-containing hydrocarbon groups include trialkylsilyl groups such as trimethylsilyl, triethylsilyl and t-butyldimethylsilyl, trialkylsilylmethyl groups such as trimethylsilylmethyl and triethylsilylmethyl, dimethylphenylsilylmethyl, dimethyltolylsilyl Examples thereof include di (alkyl) (aryl) silylmethyl groups such as methyl. Among these, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are particularly preferably hydrogen atoms.

In general formula (I), Q is a bridging group that connects two cyclopentadienyl rings. Q represents a silylene group which may have a substituent or a germylene group which may have a substituent.
Specific examples of Q include methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene and other alkylsilylene groups, methyl (phenyl) silylene, methyl (Alkyl) (aryl) silylene groups such as (tolyl) silylene, arylsilylene groups such as diphenylsilylene, and silacyclobutenyl, silacyclopropyl, silacyclohexyl, and silafluorenyl groups in which the substituent on silicon has a cyclic structure Groups. Moreover, the substituent which replaced the silicon atom of the said substituent with the germanium atom is mentioned similarly.

  M represents a transition metal of Group 4 of the periodic table, and is preferably zirconium or hafnium.

(4) Synthesis of Transition Metal Compound The transition metal compound of the present invention can be synthesized by any method with respect to the substituents or bonding modes.
A typical synthesis route is as shown in the following reaction formula. For example, when R ¹ , R ² and R ³ are included as substituents of the cyclopentadienyl moiety, and R ⁴ and R ⁶ are included as substituents of the hydroazurenyl moiety, they can be synthesized as follows.

Ｒ^１基を有するシクロペンタジエン（１）とＲ^３基を有するアルデヒド（２）との脱水縮合反応により、置換フルベン（３）が得られる。（３）をＲ^２基を有するリチウム試剤を用いてアルキル化した後、ジクロロジメチルシランとの反応を行うと、クロロシリル化されたシクロペンタジエニル誘導体（４）が得られる。この際、ケイ素原子が置換する位置は、シクロペンタジエニル誘導体上に配置する置換基の立体的に一番空いている位置に決定される。一方、Ｒ^４基を有するアズレン（５）に対して、Ｒ^６基を有するリチウム試剤を反応させると、アズレニル部分の４位にＲ^６基が付加した（６）が得られる。これをそのまま（４）と反応させると、架橋配位子（７）が得られ、引き続き公知の方法で、脱プロトン化した後、四塩化ジルコニウムなどとの反応で、目的とする遷移金属化合物（８）を合成することができる。
なお、かかる合成経路に基づけば、本発明の他の遷移金属化合物も容易に合成できることは明らかである。

Substituted fulvene (3) is obtained by a dehydration condensation reaction between cyclopentadiene (1) having R ¹ group and aldehyde (2) having R ³ group. When (3) is alkylated with a lithium reagent having an R ² group and then reacted with dichlorodimethylsilane, a chlorosilylated cyclopentadienyl derivative (4) is obtained. At this time, the position where the silicon atom is substituted is determined as the most sterically free position of the substituent arranged on the cyclopentadienyl derivative. On the other hand, when a lithium reagent having an R ⁶ group is reacted with azulene (5) having an R ⁴ group, an R ⁶ group is added to the 4-position of the azulenyl moiety (6). When this is reacted with (4) as it is, a bridging ligand (7) is obtained. Subsequently, after deprotonation by a known method, reaction with zirconium tetrachloride or the like makes the desired transition metal compound ( 8) can be synthesized.
It is obvious that other transition metal compounds of the present invention can be easily synthesized based on such a synthesis route.

(5) Specific examples of transition metal compounds Preferred specific examples of the transition metal compounds of the present invention are shown below. Hafnium dichloride is selected as a representative example, and examples of the names are given in the compounds of the structural formulas shown below.
The compound of this structural formula is called dichloro [dimethylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium. .

ところで、本発明は、新規な遷移金属化合物を主要な構成としているので、基本的には多数の遷移金属化合物の例示が必要であるが、明細書を簡潔簡明な記載とするために、遷移金属化合物の例示は煩雑な記載を避けて主要な代表例にとどめている。したがって、以下に列挙する遷移金属化合物以外の遷移金属化合物も、本願の特許請求の範囲において記載される範囲内において全て包含される。例えば、以下の具体例において、ハフニウムの代わりにチタニウム或いはジルコニウム、また、ジクロライドの代わりに他のＸ，Ｙである化合物も例示されているに等しいといえる。なお、以下の例示においては、類似性の高い化合物を段落毎にまとめている。

By the way, since the present invention mainly comprises a novel transition metal compound, it is basically necessary to exemplify a large number of transition metal compounds. However, in order to make the specification concise and concise, the transition metal compound is required. The illustration of the compound avoids a complicated description, and has left it as the main representative example. Accordingly, transition metal compounds other than the transition metal compounds listed below are also included in the scope described in the claims of the present application. For example, in the following specific examples, it can be said that titanium or zirconium instead of hafnium, and other X and Y compounds instead of dichloride are exemplified. In the following examples, compounds with high similarity are summarized for each paragraph.

(1) Dichloro [dimethylsilylene {2-methyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (2) dichloro [dimethylsilylene {2- Methyl-4- (cyclopropylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (3) dichloro [dimethylsilylene {3- (2-methylbutyl) -5-methylcyclopenta Dienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (4) dichloro [dimethylsilylene {2-methyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl- 4-phenyl-4H-azurenyl)] hafnium (5) dichloro [dimethylsilylene {2-methyl-4- ( Black hexyl methyl) cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

(6) Dichloro [dimethylsilylene {2-methyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (7) dichloro [dimethylsilylene { 3- (1-Cyclopropylethyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (8) dichloro [dimethylsilylene {3- (1,2-dimethylbutyl) ) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (9) dichloro [dimethylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclo Pentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (10) dichloro [dimethylsilyl Emissions {3- (1-cyclohexyl-ethyl) -5-methyl-cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

(11) Dichloro [dimethylsilylene {2-methyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (12) dichloro [dimethylsilylene { 2-methyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (13) dichloro [dimethylsilylene {3- (1-ethyl-2- Methylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (14) dichloro [dimethylsilylene {2-methyl-4- (1-t-butylpropyl) cyclopenta Dienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (15) dichloro [dimethyl Rushiriren {2-methyl-4- (1-cyclohexyl-propyl) cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

(16) Dichloro [dimethylsilylene {3- (1-i-propylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (17) dichloro [dimethylsilylene { 3- (1-cyclopropylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (18) dichloro [dimethylsilylene {3- (1-s-butylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azul)] hafnium (19) dichloro [dimethylsilylene {3- (1-t-butylbutyl) -5-methylcyclopentadienyl} (2-Methyl-4-phenyl-4H-azuler)] hafnium (20) dichloro [dimethylsilylene {3- 1-cyclohexyl-butyl) -5-methyl-cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

(21) Dichloro [dimethylsilylene {2-ethyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (22) dichloro [dimethylsilylene {2- Ethyl-4- (cyclopropylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (23) dichloro [dimethylsilylene {3- (2-methylbutyl) -5-ethylcyclopenta Dienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (24) dichloro [dimethylsilylene {2-ethyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl- 4-phenyl-4H-azulenyl)] hafnium (25) dichloro [dimethylsilylene {2-ethy 4- (cyclohexylmethyl) cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

(26) Dichloro [dimethylsilylene {2-ethyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (27) dichloro [dimethylsilylene { 2-ethyl-4- (1-cyclopropylethyl) -methyl) -cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (28) dichloro [dimethylsilylene {3- (1, 2-Dimethylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (29) dichloro [dimethylsilylene {2-ethyl-4- (1,2,2- Trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (30) di Lolo [dimethylsilylene {2-ethyl-4- (1-cyclohexyl-ethyl) cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

(31) Dichloro [dimethylsilylene {2-ethyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (32) dichloro [dimethylsilylene { 2-ethyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (33) dichloro [dimethylsilylene {3- (1-ethyl-2- Methylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (34) dichloro [dimethylsilylene {2-ethyl-4- (1-t-butylpropyl) cyclopenta Dienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (35) dichloro [dimethyl Rushiriren {2-ethyl-4- (1-cyclohexyl-propyl) cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

(36) Dichloro [dimethylsilylene {3- (1-i-propylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (37) dichloro [dimethylsilylene { 3- (1-cyclopropylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (38) dichloro [dimethylsilylene {3- (1-s-butylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (39) dichloro [dimethylsilylene {3- (1-t-butylbutyl) -5-ethylcyclopentadienyl} (2-Methyl-4-phenyl-4H-azurenyl)] hafnium (40) dichloro [dimethylsilylene { - (1-cyclohexyl-butyl) -5-ethyl-cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

(41) Dichloro [dimethylsilylene {2-n-propyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (42) dichloro [dimethylsilylene { 3- (Cyclopropylmethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (43) dichloro [dimethylsilylene {3- (2-methylbutyl) -5 -N-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (44) dichloro [dimethylsilylene {2-n-propyl-4- (2,2-dimethylpropyl) cyclopenta Dienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (45) dichloro [di Chirushiriren {3- (cyclohexylmethyl) -5-n-propyl-cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

(46) Dichloro [dimethylsilylene {2-n-propyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (47) dichloro [dimethyl Silylene {3- (1-cyclopropylethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (48) dichloro [dimethylsilylene {3- (1, 2-dimethylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (49) dichloro [dimethylsilylene {2-n-propyl-4- (1, 2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafniu (50) dichloro [dimethylsilylene {3- (1-cyclohexylethyl) -5-n-propyl-cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

(51) Dichloro [dimethylsilylene {2-n-propyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (52) dichloro [dimethyl Silylene {2-n-propyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (53) dichloro [dimethylsilylene {3- (1- Ethyl-2-methylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (54) dichloro [dimethylsilylene {2-n-propyl-4- (1) -T-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafniu (55) dichloro [dimethylsilylene {2-n-propyl-4- (1-cyclohexyl-propyl) cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

(56) Dichloro [dimethylsilylene {3- (1-i-propylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (57) dichloro [dimethyl Silylene {3- (1-cyclopropylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (58) dichloro [dimethylsilylene {3- (1- s-butylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (59) dichloro [dimethylsilylene {3- (1-t-butylbutyl) -5 n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (60) B [dimethylsilylene {3- (1-cyclohexyl-butyl) -5-n-propyl-cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

(61) Dichloro [methylphenylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (62) dichloro [ Diphenylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (63) dichloro [silafluorenyl {2-methyl- 4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium

(64) Dichloro [dimethylgermylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (65) dichloro [ Methylphenylgermylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (66) dichloro [diphenylgermylene { 2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (67) dichloro [silagermylenyl {2-methyl-4- ( 1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl) Hafnium

(68) Dichloro [dimethylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-ethyl-4-phenyl-4H-azurenyl)] hafnium (69) dichloro [dimethyl Silylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (4-phenyl-2-i-propyl-4H-azurenyl)] hafnium

(70) Dichloro [dimethylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} {2-methyl-4- (4-t-butylphenyl) -4H-azurenyl}] Hafnium (71) dichloro [dimethylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} {2-methyl-4- (4-methoxyphenyl) -4H-azurenyl}] hafnium (72) Dichloro [dimethylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] hafnium (73 ) Dichloro [dimethylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} {2-methyl 4- (2-naphthyl) -4H- azulenyl}] hafnium

  As described above, in the above series of compounds, one or both of the two chlorine atoms corresponding to the X and Y portions of the general formula (I) are fluorine atom, bromine atom, iodine atom, methyl group, phenyl group. Further, compounds substituted for benzyl group, dimethylamino group, diethylamino group and the like can also be exemplified. Further, it is equivalent to a compound in which the central metal M of the compound exemplified above is replaced with titanium or zirconium instead of hafnium.

By the way, in general, in the technical field of olefin polymerization catalysts, it is known that the catalytic action is greatly influenced by the metal species of the transition metal compound as the catalyst component, and only the metal species of certain transition metal catalysts are used. There is no theoretical guarantee that other different catalysts have equivalent catalysis. However, it has been confirmed through experiments that when Group 4 zirconium, titanium, and hafnium are used as the metallocene catalyst component, it has been confirmed by experiments and is well known to those skilled in the art. No. 60-130604, JP-A-4-100808).
Therefore, it can be said that the above examples of the metallocene compounds in the specification of the present application are reasonable and are not merely enumerated.

2. Olefin Polymerization Catalyst The transition metal compound of the present invention forms an olefin polymerization catalyst component, which can be used as an olefin polymerization catalyst, including, for example, the olefin polymerization catalyst component as component (A), It is preferably used as a catalyst for olefin polymerization described in 1.

(1) Olefin polymerization catalyst (i)
The olefin polymerization catalyst (i) is a catalyst comprising a component (A) and a component (B). “Consisting of” is not intended to exclude the case of containing other components in addition to these components, and may be a system further including, for example, a carrier (C) or an organoaluminum compound.

Specific examples of the component (B) include the following (B-1) to (B-3).
(B-1) Aluminum oxy compound (B-2) An ionic compound or Lewis acid capable of reacting with component (A) to convert component (A) into a cation (B-3) solid acid

  (B-1) In aluminum oxy compounds, it is well known that aluminum oxy compounds can activate metallocene complexes. Specific examples of such compounds include the following general formulas (II) to (IV). And the compounds represented.

上記の各一般式中において、Ｒ^ａは、水素原子又は炭化水素基、好ましくは炭素数１〜１０、特に好ましくは炭素数１〜６の炭化水素基を示す。また、複数のＲ^ａは、それぞれ同一でも異なっていてもよい。また、ｐは０〜４０、好ましくは２〜３０の整数を示す。一般式のうち、一番目及び二番目の式で表される化合物は、アルミノキサンとも称される化合物であって、これらの中では、メチルアルミノキサン又はメチルイソブチルアルミノキサンが好ましい。上記のアルミノキサンは、各群内および各群間で複数種併用することも可能である。そして、上記のアルミノキサンは、公知の様々な条件下に調製することができる。
一般式の三番目で表される化合物は、一種類のトリアルキルアルミニウム又は二種類以上のトリアルキルアルミニウムと、一般式Ｒ^ｂＢ（ＯＨ）_２で表されるアルキルボロン酸との１０：１〜１：１（モル比）の反応により得ることができる。一般式中、Ｒ^ｂは、炭素数１〜１０、好ましくは炭素数１〜６の炭化水素基を示す。

In each of the above general formulas, R ^a represents a hydrogen atom or a hydrocarbon group, preferably ^a C 1-10 hydrocarbon group, particularly preferably ^a C 1-6 hydrocarbon group. Moreover, several ^Ra may be same or different, respectively. P represents an integer of 0 to 40, preferably 2 to 30. Among the general formulas, the compounds represented by the first and second formulas are compounds also referred to as aluminoxanes. Among these, methylaluminoxane or methylisobutylaluminoxane is preferable. The above aluminoxanes can be used in combination within a group and between groups. And said aluminoxane can be prepared on well-known various conditions.
The compound represented by the third general formula is 10: 1 to 1 type trialkylaluminum or two or more types of trialkylaluminum and alkylboronic acid represented by the general formula R ^b B (OH) ₂ . It can be obtained by a 1: 1 (molar ratio) reaction. In the general formula, R ^b represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

The compound (B-2) is an ionic compound or a Lewis acid capable of reacting with the component (A) to convert the component (A) into a cation. Examples of such an ionic compound include carbonium. Examples thereof include complexes of cations such as cations and ammonium cations with organic boron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron, and tris (pentafluorophenyl) boron.
Examples of the Lewis acid as described above include various organic boron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halide compounds such as aluminum chloride and magnesium chloride are exemplified.
In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with a component (A) and can convert a component (A) into a cation. Examples of the metallocene catalyst using the non-coordinating boron compound described above are disclosed in JP-A-3-234709 and JP-A-5-247128.

  Examples of the solid acid (B-3) include alumina, silica-alumina, and silica-magnesia.

In the olefin polymerization catalyst (i) of the present invention, the carrier (C) as an optional component is composed of an inorganic or organic compound, and is usually a fine particle carrier having a particle diameter of 5 μm to 5 mm, preferably 10 μm to 2 mm. is there.
Examples of the inorganic carrier include oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , ZnO, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO. ₂ , composite oxides such as SiO ₂ —Cr ₂ O ₃ and SiO ₂ —Al ₂ O ₃ —MgO.
Examples of the organic carrier include (co) polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturation such as styrene and divinylbenzene. Examples thereof include porous polymer fine particle carriers made of hydrocarbon (co) polymers and the like.
The specific surface area of these particles is usually 20~1,000m ² / g, preferably 50~700m ² / g, pore volume is usually 0.1 cm ³ / g or more, preferably 0.3 cm ³ / g or more, more preferably 0.8 cm ³ / g or more.
The olefin polymerization catalyst (i) of the present invention includes, as an optional component other than the fine particle carrier, for example, an active hydrogen-containing compound such as H ₂ O, methanol, ethanol and butanol, an electron donating compound such as ether, ester and amine, Alkoxy-containing compounds such as phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane, and diphenyldimethoxysilane can be included.
Other optional components include tri-lower aluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum, halogen-containing alkylaluminum such as diethylaluminum chloride, diisobutylaluminum chloride and methylaluminum sesquichloride, and diethylaluminum hydride. Alkyl-containing alkylaluminums such as alkylaluminum hydride, diethylaluminum ethoxide, dimethylaluminum butoxide, and aryloxy-containing alkylaluminums such as diethylaluminum phenoxide.

  In the olefin polymerization catalyst (i) of the present invention, an ionic compound or Lewis acid capable of reacting with an aluminum oxy compound, component (A) to convert component (A) into a cation is used as component (B). In addition to being used alone, these three components can be used in appropriate combination. In addition, one or more of the above lower alkyl aluminum, halogen-containing alkyl aluminum, alkyl aluminum hydride, alkoxy-containing alkyl aluminum, and aryloxy-containing alkyl aluminum are optional components, but an aluminum oxy compound, an ionic compound, or It is preferable to contain it in the olefin polymerization catalyst (i) in combination with a Lewis acid.

The catalyst for olefin polymerization (i) of the present invention can be prepared by bringing the components (A) and (B) into contact with each other in the presence or absence of the monomer to be polymerized inside and outside the polymerization tank. . That is, the components (A) and (B) and the component (C) may be separately introduced into the polymerization tank as necessary, or the components (A) and (B) are introduced into the polymerization tank after contacting them in advance. May be. Further, the component (C) may be impregnated with the mixture of the components (A) and (B) and then introduced into the polymerization tank.
The above-mentioned contact of each component may be performed in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene in an inert gas such as nitrogen. The contact temperature is preferably in the range of −20 ° C. to the boiling point of the solvent, particularly in the range of room temperature to the boiling point of the solvent. The catalyst thus prepared may be used without washing after preparation, or may be used after washing. Furthermore, you may use it combining a component newly as needed after preparation.

(2) Olefin polymerization catalyst (ii)
The olefin polymerization catalyst (ii) is a catalyst comprising the component (A) and the component (D) and, if necessary, the component (E) used. The meaning of “consisting of” is the same intention as described in the olefin polymerization catalyst (i).

Component (D) is selected from the group consisting of ion-exchangeable layered compounds or inorganic silicates, and component (E) is an organoaluminum compound.
Of the component (D), the ion-exchange layered compound occupies most of the clay mineral, and is preferably an ion-exchange layered silicate.
An ion-exchange layered silicate (hereinafter, sometimes simply referred to as “silicate”) has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other and have a binding force. Refers to a silicate compound in which the ions to be exchanged are exchangeable. Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates. You may go out. Various known silicates can be used. Specifically, the following layered silicates described in “Clay Mineralogy” by Asakura Shoten (1995) by Haruo Shiramizu are given as typical examples.

2: 1 type minerals Smectite family such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, etc .; vermiculite family such as vermiculite; mica family such as mica, illite, sericite, sea green stone; Pyrophyllite such as phyllite and talc-talc group; chlorite group such as magnesium chlorite.
2: 1 Ribbon-type minerals such as sepiolite and palygorskite.

The silicate used as a raw material in the present invention may be a layered silicate in which the above mixed layer is formed. In the present invention, the main component silicate is preferably a silicate having a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. As the silicate used in the present invention, those obtained as natural products or industrial raw materials can be used as they are without any particular treatment, but chemical treatment is preferred. Specific examples include acid treatment, alkali treatment, salt treatment, organic matter treatment, and the like. These processes may be used in combination with each other. In the present invention, these treatment conditions are not particularly limited, and known conditions can be used.
Moreover, since these ion-exchange layered silicates usually contain adsorbed water and interlayer water, it is preferable to use them after removing the water by heating and dehydrating under an inert gas flow.

In the olefin polymerization catalyst (ii) of the present invention, an example of the organoaluminum compound as the optional component (E) is represented by the following general formula.
AlR _a X _3-a
In the general formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents hydrogen, halogen, an alkoxy group, or a siloxy group, and a represents a number greater than 0 and 3 or less. Specific examples of the organoaluminum compound represented by the general formula include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, halogen or alkoxy such as diethylaluminum monochloride, diethylaluminum monomethoxide An alkyl aluminum is mentioned. Of these, trialkylaluminum is preferred.
In the olefin polymerization catalyst (ii) of the present invention, an aluminoxane such as methylaluminoxane can be used as the component (E) in addition to the organoaluminum compound represented by the above general formula. Moreover, said organoaluminum compound and aluminoxane can also be used together.

The olefin polymerization catalyst (ii) of the present invention can be prepared by the same method as in the case of the olefin polymerization catalyst (i). At this time, the contact method of the component (A) and the component (D) with the optional component (E) is not particularly limited, but the following method can be exemplified.
(1) Method of contacting component (A) and component (D) (2) Method of adding optional component (E) after contacting component (A) and component (D) (3) Component (A) Method of adding component (D) after contacting optional component (E) (4) Method of adding component (A) after contacting component (D) and optional component (E) (5) Each component ( A), (D), and (E) are contacted simultaneously.
This contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin. During or after the contact of each of the above components, a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may coexist or contact.
Moreover, you may perform contact of said each component in inert hydrocarbon solvents, such as pentane, hexane, heptane, toluene, and xylene, in inert gas, such as nitrogen. The contact is preferably performed at a temperature between −20 ° C. and the boiling point of the solvent, particularly at a temperature between room temperature and the boiling point of the solvent.

(3) Use amount of catalyst component and others The use amount of component (A) and component (B) or component (D) is used in an optimum ratio among the respective combinations.
When component (B) is an aluminum oxy compound, the molar ratio of Al / transition metal is usually from 10 to 100,000, more preferably from 100 to 20,000, particularly from 100 to 10,000. On the other hand, when an ionic compound or Lewis acid is used as the component (B), the molar ratio of the transition metal to the transition metal is 0.1 to 1,000, preferably 0.5 to 100, more preferably 1 to 50. It is.
When a solid acid is used as component (B) or an ion-exchange layered compound is used as component (D), the transition metal complex is in the range of 0.001 to 10 mmol, preferably 0.001 to 1 mmol, per 1 g of component. It is.
These use ratios are examples of normal ratios, and the present invention is limited by the range of use ratios described above as long as the catalyst meets the purpose of the invention. It is natural that it must not be.

  Before using a catalyst for polyolefin production comprising a transition metal complex and a co-catalyst as a catalyst for olefin polymerization (main polymerization), it is supported on a carrier, if necessary, and then ethylene, propylene, 1-butene, 1-hexene. , 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and other olefins may be preliminarily polymerized in a small amount. A known method can be used as the prepolymerization method.

3. Olefin polymerization (1) Olefin used for polymerization The olefin that can be polymerized by the olefin polymerization catalyst of the present invention is basically an α-olefin, and propylene, 1-butene, 3-methylbutene-1, 3-methylpentene- 1,4-methylpentene-1 and the like are used, and conjugated dienes such as vinylcycloalkane and butadiene, non-conjugated dienes such as 1,5-hexadiene, styrene, and derivatives thereof are also exemplified. In particular, propylene is preferably used.
Further, the polymerization can be suitably applied to random copolymerization and block copolymerization in addition to homopolymerization. Examples of the comonomer in the copolymerization include ethylene or an α-olefin having 4 to 20 carbon atoms. Specific examples include 1-butene, 1-pentene, 1-hexene, 1-octene and the like.

(2) Polymerization reaction The polymerization reaction is carried out in the presence of an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene, cyclohexane, or a solvent such as a liquefied α-olefin, or a substantially solvent or monomer liquid. A method in which gas phase polymerization is performed in the absence of a phase is preferable. The gas phase polymerization can be performed using a reaction apparatus such as a fluidized bed, a stirred bed, and a stirred fluidized bed equipped with a stirred mixer.
The conditions such as the polymerization temperature and the polymerization pressure are not particularly limited, but the polymerization temperature is generally −50 to 350 ° C., preferably 0 to 300 ° C., and the polymerization pressure is usually normal pressure to about 2,000 kgf / cm. ² , preferably normal pressure to 1,500 kgf / cm ² , more preferably normal pressure to 1,300 kgf / cm ² . Further, hydrogen may be present as a molecular weight regulator in the polymerization system.

4). Analysis of characteristic values of polymerized polymer Content of copolymer component (rubber-like component, hereinafter referred to as “CP”) in the propylene-based block copolymer obtained using the catalyst of the present invention, CP The α-olefin polymerization ratio is determined by the following method.
In addition, although the following examples are when ethylene is used as the α-olefin in the CP, α-olefins other than ethylene are obtained using a method according to the following example.

(1) Analytical device to be used (i) Cross fractionation device CFC T-100 manufactured by Dia Instruments
(Ii) Fourier transform infrared absorption spectrum analysis FT-IR, Perkin Elmer 1760X
A fixed wavelength infrared spectrophotometer attached as a CFC detector is removed and an FT-IR is connected instead, and this FT-IR is used as a detector. The transfer line from the outlet of the solution eluted from the CFC to the FT-IR is 1 m long, and the temperature is maintained at 140 ° C. throughout the measurement. The flow cell attached to the FT-IR has an optical path length of 1 mm and an optical path width of 5 mmφ, and is maintained at 140 ° C. throughout the measurement.
(Iii) Gel permeation chromatography (GPC)
Three GPC columns (AD806MS manufactured by Showa Denko KK) are connected in series to the subsequent stage of the CFC.

(2) CFC measurement conditions (i) Solvent: orthodichlorobenzene (ODCB)
(Ii) Sample concentration: 4 mg / mL
(Iii) Injection volume: 0.4 mL
(Iv) Crystallization: The temperature is lowered from 140 ° C. to 40 ° C. over about 40 minutes.
(V) Fractionation method: Fractionation temperature at the time of temperature-raising elution fractionation is 40, 100, 140 ° C., and fractionation is performed in all three fractions. In addition, the elution ratio (unit:% by weight) of the component eluting at 40 ° C. or lower (fraction 1), the component eluting at 40 to 100 ° C. (fraction 2), and the component eluting at 100 to 140 ° C. (fraction 3), respectively It is defined as W40, W100, and W140. W40 + W100 + W140 = 100. Moreover, each fractionated fraction is automatically transported to the FT-IR analyzer as it is.
(Vi) Solvent flow rate during elution: 1 mL / min

(3) Measurement conditions of FT-IR After elution of the sample solution from the GPC at the latter stage of the CFC starts, FT-IR measurement is performed under the following conditions, and GPC-IR data is collected for each of the above-described fractions 1 to 3. .
(I) Detector: MCT
(Ii) Resolution: 8 cm ⁻¹
(Iii) Measurement interval: 0.2 minutes (12 seconds)
(Iv) Number of integrations per measurement: 15 times

(4) Post-treatment and analysis of measurement results The elution amount and molecular weight distribution of the components eluted at each temperature are obtained using the absorbance at 2945 cm ⁻¹ obtained by FT-IR as a chromatogram. The elution amount is normalized so that the total elution amount of each elution component is 100%. Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.
Standard polystyrenes used are the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is created by injecting 0.4 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. Conversion to molecular weight uses a general calibration curve with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical values are used for the viscosity equation ([η] = K × M ^α ) used at that time.
(I) Calibration curve using standard polystyrene K = 0.000138, α = 0.70
(Ii) Sample measurement of propylene-based block copolymer K = 0.000103, α = 0.78
Ethylene content distribution of each eluted component (ethylene content distribution along the molecular weight axis), using the ratio between the absorbance of the absorbance and 2927cm ^-1 of 2956Cm ^-1 obtained by GPC-IR, polyethylene and polypropylene, and ¹³ Converted to ethylene polymerization rate (mol%) using a calibration curve prepared in advance using ethylene-propylene-rubber (EPR) and mixtures thereof whose ethylene content is known by C-NMR measurement, etc. And ask.

(5) CP content The CP content of the propylene-based block copolymer in the present invention is defined by the following formula (I), and is determined by the following procedure.
CP content (% by weight) = W40 × A40 / B40 + W100 × A100 / B100 (I)
In the formula (I), W40 and W100 are the elution ratios (unit:% by weight) in each of the above-mentioned fractions, and A40 and A100 are the average ethylene content of actual measurement in each fraction corresponding to W40 and W100. (Unit: wt%), and B40 and B100 are the ethylene content (unit: wt%) of CP contained in each fraction. A method for obtaining A40, A100, B40, and B100 will be described later.

The meaning of the formula (I) is as follows. That is, the first term on the right side of the formula (I) is a term for calculating the amount of CP contained in fraction 1 (portion soluble at 40 ° C.). When fraction 1 contains only CP and no PP, W40 contributes to the CP content derived from fraction 1 as a whole, but fraction 1 contains a small amount of PP in addition to the components derived from CP. Since components derived from the components (extremely low molecular weight components and atactic polypropylene) are also included, it is necessary to correct the portion. Therefore, by multiplying W40 by A40 / B40, the amount derived from the CP component in fraction 1 is calculated. For example, when the average ethylene content (A40) of fraction 1 is 30% by weight and the ethylene content (B40) of CP contained in fraction 1 is 40% by weight, 30/40 = 3/4 of fraction 1 (Ie, 75% by weight) is derived from CP, and 1/4 is derived from PP. Thus, the operation of multiplying A40 / B40 in the first term on the right side means that the contribution of CP is calculated from the weight% (W40) of fraction 1.
The same applies to the second term on the right side, and for each fraction, the CP content is calculated by adding and calculating the contribution of CP.

The average ethylene content A40 fraction 1 to 3, A100, A140 is an ethylene content of weight ratio and each data point for each data point in the chromatogram absorbance 2945cm ^-1 (absorbance 2956Cm ^-1 and 2927cm ^{- (} Obtained from the ratio to the absorbance of ¹ ).

The ethylene content corresponding to the peak position in the differential molecular weight distribution curve of fraction 1 is defined as B40 (unit is% by weight). With respect to fraction 2, it is considered that the rubber part is completely eluted at 40 ° C. and cannot be defined with the same definition. Therefore, in the present invention, it is defined as B100 = 100. B40 and B100 are ethylene contents of CP contained in each fraction, but it is practically impossible to obtain this value analytically. This is because there is no means for completely separating and separating PP and CP mixed in the fraction. As a result of examination using various model samples, it was found that B40 can explain the effect of improving the material properties well by using the ethylene content corresponding to the peak position of the differential molecular weight distribution curve of fraction 1. It was. Further, B100 has crystallinity derived from ethylene chain, and the amount of CP contained in these fractions is relatively small compared to the amount of CP contained in fraction 1; The approximation is closer to the actual situation, and there is almost no error in calculation. Therefore, the analysis is performed with B100 = 100. Therefore, the CP content can be determined according to the following formula (II).
CP content (% by weight) = W40 × A40 / B40 + W100 × A100 / 100 (II)
That is, W40 × A40 / B40, which is the first term on the right side of the formula (II), indicates the CP content (% by weight) having no crystallinity, and W100 × A100 / 100, which is the second term, is a CP having crystallinity. Content (% by weight) is indicated.

The ethylene content in the copolymer component is determined by the following formula (III) using the content of the copolymer component determined by the formula (II).
Ethylene content (% by weight) in copolymer component = (W40 × A40 + W100 × A100 + W140 × A140) / [copolymer component content (% by weight)] (III)

  The significance of setting the three types of fractionation temperatures is as follows. In the CFC analysis of the present invention, only polymers having no crystallinity from 40 ° C. (for example, most of CP, or extremely low molecular weight components and atactic components among propylene polymer components (PP)) are separated. It has the meaning that it is a necessary and sufficient temperature condition. 100 ° C. means only components that are insoluble at 40 ° C. but become soluble at 100 ° C. (eg, components having crystallinity due to the chain of ethylene and / or propylene and PP having low crystallinity in CP) The temperature is necessary and sufficient to elute. 140 ° C. is a component that is insoluble at 100 ° C. but becomes soluble at 140 ° C. (for example, a component having particularly high crystallinity in PP and a component having extremely high molecular weight and extremely high ethylene crystallinity in CP ) Only, and the temperature is necessary and sufficient to recover the entire amount of the propylene-based block copolymer used for the analysis. It should be noted that W140 does not contain any CP component, or even if it is present, it is extremely small and can be substantially ignored, so it is excluded from the calculation of the CP content and the ethylene content.

(6) Ethylene polymerization ratio The ethylene content in CP is determined by the following formula.
Ethylene content (% by weight) in CP = (W40 × A40 + W100 × A100) / [CP] where [CP] is the CP content (% by weight) determined previously.
From the value of the ethylene content (% by weight) in the CP obtained here, the molecular weight of ethylene and propylene is finally used to convert to mol%.

Hereinafter, in order to describe the present invention more specifically and clearly, the present invention will be described in contrast to Examples and Comparative Examples, and the rationality and significance of the requirements of the configuration of the present invention will be demonstrated.
In the following examples, the catalyst synthesis step and the polymerization step were all carried out under a purified nitrogen atmosphere, and the solvent was dehydrated with MS-4A (molecular sieve) and then degassed by bubbling with purified nitrogen. . The measurement and evaluation methods in the present invention are as follows.

(1) MFR measurement:
To 6 g of polymer, 6 g of an acetone solution (0.6 wt%) of a heat stabilizer (BHT) was added. Subsequently, after drying said polymer, it filled with the melt indexer (230 degreeC), and was left to stand on the conditions of a 2.16kg load for 5 minutes. Thereafter, the extrusion amount of the polymer was measured, converted into an amount per 10 minutes, and used as the MFR value (unit: g / 10 minutes).
(2) Measurement of melting point:
Use DSC (DuPont, TA2000 type or Seiko Instruments, DSC6200 type), and raise and lower the temperature up to 20-200 ° C at 10 ° C / min. It was determined from the measured value at the time of temperature increase.
(3) Cross separation (abbreviated as CFC)
According to the method described in detail in the paragraphs [0082] to [0091].

[Example-1]
(1) Metallocene Complex Synthesis of dichloro [dimethylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium Pentadiene (53.09 g, 662.5 mmol) and trimethylacetaldehyde (32.00 ml, 290.9 mmol) were dissolved in methanol (300 mL), and pyrrolidine (33.50 ml, 405.1 mmol) was added dropwise at 0 ° C. After dropping, the mixture was warmed to room temperature and stirred for 90 hours, and acetic acid (28.03 ml, 489.6 mmol) was added dropwise at 0 ° C. and stirred. Thereafter, distilled water was added to the reaction solution, followed by extraction with diethyl ether. The obtained organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The crude product was distilled under reduced pressure (90-100 ° C./0.15 mmHg) to give 3-methyl-6-tert-butylfulvene (16.53 g, 111.5 mmol).
The obtained fulvene (16.53 g, 111.5 mmol) was dissolved in diethyl ether (200 mL), and methyl lithium in diethyl ether (1.09 M, 100.00 mL) was added dropwise at −78 ° C. After dropping, the mixture was warmed to room temperature and stirred for 12 hours, and then the solvent was distilled off under reduced pressure to precipitate a solid. Tetrahydrofuran (344 mL) was added to dissolve the solid again, and then the mixture was added dropwise at −78 ° C. to a mixed solution of dimethyldichlorosilane (56.00 ml, 461.7 mmol) and diethyl ether (90 mL). After dropping, the mixture was warmed to room temperature and stirred for 66 hours, and then the solvent was distilled off under reduced pressure to dryness, followed by hexane extraction. After distilling off the solvent under reduced pressure, the crude product was distilled under reduced pressure (93-97 ° C./0.15 mmHg) and chlorodimethyl {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl. } Silane (3.72 g, 14.5 mmol) was obtained.
2-methylazulene (2.06 g, 14.5 mmol) was dissolved in hexane (49 mL), and a solution of phenyllithium in cyclohexane-diethyl ether (0.98 M, 16.00 mL) was added dropwise at 0 ° C. After dropping, the mixture was warmed to room temperature and stirred for 1 hour, tetrahydrofuran (32 mL) and N-methylimidazole (0.06 mL, 0.75 mmol) were added, and chlorodimethyl {2-methyl-4- (1,2) was added at 0 ° C. , 2-trimethylpropyl) cyclopentadienyl} silane (3.72 g, 14.5 mmol) was added dropwise. After dropping, the mixture was warmed to room temperature and stirred for 2 hours, and then distilled water was added to the reaction solution, and then the aqueous layer was removed. After drying the organic layer over magnesium sulfate, the solvent was distilled off under reduced pressure, and dimethyl {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-1). , 4-Dihydroazurenyl) silane crude product (5.93 g) was obtained.
The obtained ligand (5.93 g) was dissolved in diethyl ether (40 mL), and an n-butyllithium n-hexane solution (1.65 M, 16.5 mL) was added dropwise at 0 ° C. After stirring at room temperature for 2 hours, toluene (320 mL) was added, cooled to −78 ° C., and hafnium tetrachloride (4.33 g, 13.5 mmol) was added. The temperature was slowly raised and the mixture was stirred at room temperature for 2 hours. The obtained reaction solution was concentrated once, extracted with toluene, and concentrated again to dryness. This was washed with n-hexane, diisopropyl ether, diethyl ether, cyclohexane, and toluene in this order to obtain the desired dichloro [dimethylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl. } (2-methyl-4-phenyl-4H-azurenyl)] 0.54 g of hafnium (syn: anti = 45: 55) was obtained.
¹ H NMR (400 MHz, CDCl ₃ , anti isomer): δ 0.82 (s, 3H, Si (CH ₃ ) ₂ ), 0.82 (s, 9H, t-Bu), 0.98 (s, 3H, _{Si (CH 3) 2),} 1.22 (d, J = 6.8Hz, 3H, Cp-4-CHCH 3), 2.07 (s, 3H, Azu-2-CH 3), 2.34 ( _{s, 3H, Cp-2-} CH 3), 2.56 (q, J = 6.8Hz, 1H, Cp-4-CH), 5.05 (br, 1H, Azu-4-H), 5. 14 (d, J = 2.3 Hz, 1H, Cp-3-H), 5.67 (s, 1H, Azu-3-H), 5.83-5.98 (m, 2H, Azu-5H, 6H), 6.09-6.17 (m, 1H, Azu-7-H), 6.48 (d, J = 2.3 Hz, 1H, Cp-5-H), 6.78 ( , J = 11.6Hz, 1H, Azu -8-H), 7.28-7.30 (m, 1H, Ph-p-H), 7.36 (dd, J 1 = 14.1Hz, J 2 = 7.1 Hz, 2H, Ph-m-H), 7.45 (d, J = 7.3 Hz, 2H, Ph-o-H)
(2) Catalyst preparation Into a 5 L separable flask equipped with a stirring blade and a reflux apparatus, 1,698 g of pure water was added, and 501 g of 98% sulfuric acid was added dropwise. Further, 300 g of commercially available granulated montmorillonite (Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 19.5 μm) was added and stirred. Thereafter, the mixture was reacted at 90 ° C. for 2 hours. This slurry was washed with an apparatus in which an aspirator was connected to Nutsche and a suction bottle. A 900 mL aqueous solution of 324 g of lithium sulfate monohydrate was added to the recovered cake and reacted at 90 ° C. for 2 hours. This slurry was washed to pH> 4 with an apparatus in which an aspirator was connected to Nutsche and a suction bottle. The collected cake was dried at 120 ° C. overnight. As a result, 275 g of a chemically treated product was obtained.
5.0 g of the chemically treated montmorillonite obtained above was weighed in a flask having an internal volume of 1 L, 32 mL of heptane and 17.5 mL (12.5 mmol) of a heptane solution of triisobutylaluminum were added, and the mixture was stirred at room temperature for 1 hour. Then, the remaining liquid rate was washed to 1/100 with heptane, and finally the slurry amount was adjusted to 50 mL.

(3) Prepolymerization with propylene 0.85 mL of a triisobutylaluminum heptane solution was added to the montmorillonite heptane slurry prepared above and treated with triisobutylaluminum and stirred at room temperature for 10 minutes. Further, dichloro [dimethylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium synthesized in (1) ( 150 μmol) of heptane (30 ml) was added to the 1 L flask and stirred at room temperature for 60 minutes.
Next, 170 mL of heptane was further added to the above montmorillonite heptane slurry and introduced into a 1 L stirred autoclave, and propylene was supplied at a constant rate of 119 mmol / hr (5 g / hr) at 40 ° C. for 120 minutes. did. After the completion of the propylene supply, the temperature was raised to 60 ° C. and maintained for 2 hours, after which the remaining gas was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand, and the supernatant liquid was extracted. To the remaining solid, 4.3 mL (3.0 mmol) of a heptane solution of triisobutylaluminum was added at room temperature, stirred at room temperature for 10 minutes, and then dried under reduced pressure to recover 6.3 g of a solid catalyst.
The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 0.24.

(4) Block polymerization After the interior of the stirred autoclave with an internal volume of 3 L was sufficiently substituted with propylene, 2.76 mL (2.02 mmol) of triisobutylaluminum / n-heptane solution was added, and 90 mL of hydrogen and then 750 g of liquid propylene were introduced. The temperature was raised to 75 ° C. and the temperature was maintained. The prepolymerized catalyst prepared in the above (3) was slurried in normal heptane, and 50 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. The temperature inside the tank was maintained at 75 ° C., and after 1 hour from the catalyst addition, the remaining monomer was purged, and the inside of the tank was replaced five times with argon.
Thereafter, 0.7 MPa of propylene and then 1.3 MPa of ethylene were introduced, and the internal temperature was raised to 80 ° C. Thereafter, a mixed gas of propylene and ethylene prepared in advance was introduced, and the polymerization reaction was controlled for 30 minutes while adjusting the internal pressure to be 2.0 MPa so that the monomer composition ratio did not change during the polymerization. As a result, 13 g of a propylene-based block polymer having good particle properties was obtained.
From the results of CFC-IR, the propylene block copolymer obtained above has a rubber content (CP content) of 9.4% by weight, and the ethylene content in rubber (CP) is 65.1 mol%. The MFR was 14 (dg / min), and the weight average molecular weight of the CP part was 530,000.

[Example-2]
(1) Metallocene Complex Synthesis of dichloro [dimethylsilylene {2-methyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium methylcyclopentadiene ( 3.5 g, 43.4 mmol) and isobutyraldehyde (4.3 ml, 47.7 mmol) were dissolved in ethanol (40 ml), pyrrolidine (4 ml) was added under cooling, and the mixture was stirred overnight at room temperature. The reaction solution was poured into 1N hydrochloric acid-ice water and stirred, and then the organic layer was separated, dried over magnesium sulfate and concentrated to dryness. The obtained 6-isopropylfulvene compound (1.8 g, 13.4 mmol) was dissolved in diethyl ether (40 ml), and methyl lithium in diethyl ether (1.04 M, 12.9 ml) was added on an ice bath. After the temperature was increased, the mixture was stirred for a whole day and night, and the solvent was distilled off under reduced pressure. Tetrahydrofuran (30 ml) was again added and dissolved, and the mixture was added dropwise to a tetrahydrofuran solution of dimethyldichlorosilane (4 ml) with cooling at −70 ° C. The mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, the solvent was distilled off to dryness, followed by extraction with hexane to obtain a crude product of chlorodimethyl {2-methyl-4- (1,2-dimethylpropyl) cyclopentadienyl} silane (2.4 g). did.
2-Methylazulene (1.4 g, 9.8 mmol) was dissolved in hexane (50 mL), and phenylcyclohexane-diethyl ether solution (1.08 M, 9.1 mL) was added dropwise at 0 ° C. After dropping, the mixture was warmed to room temperature and stirred for about 2 hours. After suspending the suspended reaction solution, the supernatant was removed, hexane was added, and the mixture was stirred and further settled and the supernatant was removed twice. Tetrahydrofuran (40 mL) and N-methylimidazole (0.2 mL) were then removed. ), And a crude product of chlorodimethyl {2-methyl-4- (1,2-dimethylpropyl) cyclopentadienyl} silane (2.4 g) was added dropwise at 0 ° C. After dropping, the mixture was warmed to room temperature and stirred for 1.5 hours, and then distilled water was added to the reaction solution, and then the aqueous layer was removed. After drying the organic layer over magnesium sulfate, the solvent was distilled off under reduced pressure, and dimethyl {2-methyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-1,4). A crude product (4 g) of -dihydroazurenyl) silane was obtained.
The obtained ligand (4 g) was dissolved in diisopropyl ether (30 mL), and an n-butyllithium n-hexane solution (1.57 M, 12.0 mL) was added dropwise at 0 ° C. After stirring at room temperature for 1 hour, toluene (180 mL) was added, cooled to −40 ° C., hafnium tetrachloride (13.0 g, 9.4 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. The obtained reaction solution was concentrated once, extracted with toluene, and concentrated again to dryness. Wash with diisopropyl ether, extract with methylene chloride again to remove insoluble matter, wash with a small amount of toluene and cyclohexane in this order, and then add the desired dichloro [dimethylsilylene {2-methyl-4- (1,2-dimethylpropyl) cyclohexane. 0.2 g of pentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (syn: anti = 45: 55) was obtained.
¹ H NMR (400 MHz, CDCl ₃ ): δ 0.6-0.7 (m, 3H + 3H, Cp-4-CH (CH ₃ ) —CH (CH ₃ ) —CH ₃ anti, syn), 0, 7-1 _{.0 (m, 18H, Si (} CH 3) 2, Cp-4-CH (CH 3) -CH (CH 3) -CH 3, anti, syn), 1.12 (d, J = 7.1Hz, _{3H, Cp-4-CH (} CH 3) -CH (CH 3) -CH 3, anti), 1.18 (d, J = 7.1Hz, 3H, Cp-4-CH (CH 3) -CH ( _{CH 3) -CH 3, syn)} , 1.6-1.8 (m, 1H + 1H, Cp-4-CH (CH 3) -CH (CH 3) -CH 3, anti, syn), 2.08 ( _{s, 3H, Azu-2-} CH 3, anti), 2.21 (s, 3H, Azu-2-C _{3, syn), 2.34 (s} , 3H + 3H, Cp-2-CH 3, anti, syn), 2.8-2.9 (m, 1H, Cp-4-CH (CH 3) -CH (CH _{3) -CH 3, anti),} 2.9-3.0 (m, 1H, Cp-4-CH (CH 3) -CH (CH 3) -CH 3, syn), 4.99 (d, J = 4.0 Hz, 1H, Azu-4-H, syn), 5.06 (s, 1H, Azu-4-H, anti), 5.18 (s, 1H, Azu-3-H, anti), 5.26 (s, 1H, Azu-3-H, syn), 5.66 (s, 1H, Cp-3-H, anti), 5.67 (s, 1H, Cp-3-H, syn) 5.8-6.0 (m, 2H + 2H, Azu-5H, 6H, anti, syn), 6.0-6.2 (m, 1H, Azu-7) H, anti, syn), 6.23 (s, 1H, Cp-5-H, syn), 6.43 (s, 1H, Cp-5-H, anti), 6.61 (d, J = 11 .6 Hz, 1H, Azu-8-H, syn), 6.76 (d, J = 11.6 Hz, 1H, Azu-8-H, anti), 7.2-7.5 (m, 5H + 5H, arm) , Anti, syn)
(2) Prepolymerization and block polymerization Dichloro [dimethylsilylene {2-methyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] synthesized above A prepolymerized catalyst was prepared in the same manner as in (2) and (3) of Example 1 except that hafnium was used. The prepolymerization ratio was 0.27.
Subsequently, polymerization was carried out in the same manner as in Example 1 (4). As a result, 56 g of a propylene-based block polymer was obtained. The obtained propylene block copolymer has a rubber content (CP content) of 10.0% by weight and an ethylene content of rubber (CP) of 56.6 mol% based on the results of CFC-IR. , MFR was 17 (dg / min), and the weight average molecular weight of the CP part was 541,000.

[Example (reference example) -3]
(1) Metallocene complex Synthesis of dichloro [dimethylsilylene {2-methyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium 2,2- 3-methyl-2-cyclopentenone (9.00 mL, 91.8 mmol) was added dropwise at 0 ° C. to a diethyl ether solution (1.00 M, 100.00 mL) of dimethylpropylmagnesium chloride. After dropping, the mixture was warmed to room temperature and stirred for 66 hours, and then slowly dropped into a mixed solution of acetic acid (11.45 mL, 200.0 mmol) and distilled water (35 mL) at 0 ° C. After the dropwise addition, the temperature was raised to room temperature, and after stirring for a while, the mixture was again cooled to 0 ° C. and sodium carbonate solution (1.21 M, 50.00 mL) was added. After raising the temperature to room temperature and stirring for a while, the aqueous layer was removed. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product (7.10 g) of 2-methyl-4- (2,2-dimethylpropyl) cyclopentadiene.
The obtained crude product (7.10 g) of 2-methyl-4- (2,2-dimethylpropyl) cyclopentadiene was dissolved in diethyl ether (150 mL), and an n-hexane solution (1. 65M, 34.50 mL) was added dropwise at −78 ° C., and the mixture was warmed to room temperature and stirred for 19 hours, and then the solvent was distilled off under reduced pressure to precipitate a solid. Tetrahydrofuran (94.60 mL) was added to dissolve the solid again, and then the mixture was added dropwise to a mixed solution of dimethyldichlorosilane (30.00 mL, 247.3 mmol) and diethyl ether (50 mL) at −78 ° C. After dropping, the mixture was warmed to room temperature and stirred for 19 hours, and then the solvent was distilled off under reduced pressure to dryness, followed by extraction with hexane. After distilling off the solvent under reduced pressure, the crude product was distilled under reduced pressure (60-115 ° C./0.15 mmHg) and chlorodimethyl {2-methyl-4- (2,2-dimethylpropyl) cyclopentadienyl} silane. (3.49 g, 14.4 mmol) was obtained.
2-Methylazulene (2.04 g, 14.3 mmol) was dissolved in hexane (48 mL), and a solution of phenyllithium in cyclohexane-diethyl ether (1.08 M, 15.10 mL) was added dropwise at 0 ° C. After dropping, the mixture was warmed to room temperature and stirred for 2 hours, tetrahydrofuran (32 mL) and N-methylimidazole (0.06 mL, 0.75 mmol) were added, and chlorodimethyl {2-methyl-4- (2,2) was added at 0 ° C. -Dimethylpropyl) cyclopentadienyl} silane (3.49 g, 14.4 mmol) was added dropwise. After dropping, the mixture was warmed to room temperature and stirred for 2 hours, and then distilled water was added to the reaction solution, and then the aqueous layer was removed. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and dimethyl {2-methyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-1,4). -Dihydroazurenyl) silane crude product (5.79 g) was obtained.
The obtained ligand (5.79 g) was dissolved in diethyl ether (40 mL), and an n-butyllithium n-hexane solution (1.65 M, 16.5 mL) was added dropwise at 0 ° C. After stirring at room temperature for 2 hours, toluene (320 mL) was added, cooled to −78 ° C., and hafnium tetrachloride (4.32 g, 13.5 mmol) was added. The temperature was slowly raised and the mixture was stirred at room temperature for 2 hours. The obtained reaction solution was concentrated once, extracted with toluene, and concentrated again to dryness. This was washed with n-hexane, diisopropyl ether, diethyl ether, and cyclohexane in this order, and then extracted with toluene to obtain the desired dichloro [dimethylsilylene {2-methyl-4- (2,2-dimethylpropyl) cyclohexane. Pentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (syn: anti = 6: 94) was obtained in an amount of 0.56 g.
¹ H NMR (400 MHz, CDCl ₃ , anti isomer): δ 0.81 (s, 3H, Si (CH ₃ ) ₂ ), 0.84 (s, 9H, t-Bu), 0.97 (s, 3H, Si (CH ₃ ) ₂ ), 2.10 (s, 3H, Azu-2-CH ₃ ), 2.27 (d, J = 13.6 Hz, 1H, Cp-4-CH ₂ ), 2.33 ( _{s, 3H, Cp-2-} CH 3), 2.44 (d, J = 13.6Hz, 1H, Cp-4-CH 2), 5.07 (d, J = 4.0Hz, 1H, Azu- 4-H), 5.18 (d, J = 2.3 Hz, 1H, Cp-3-H), 5.65 (s, 1H, Azu-3-H), 5.91-5.99 (m _{, 2H, Azu-5H, 6H} ), 6.18 (dd, J 1 = 11.6Hz, J 2 = 5.0Hz, 1H, Azu-7-H), 6.34 (d J = 2.3 Hz, 1H, Cp-5-H), 6.74 (d, J = 11.6 Hz, 1H, Azu-8-H), 7.27-7.31 (m, 1H, Ph- _{p-H), 7.37 (dd} , J 1 = 8.2Hz, J 2 = 7.1Hz, 2H, Ph-m-H), 7.45 (d, J = 7.1Hz, 2H, Ph- oH)
(2) Prepolymerization and block polymerization Dichloro [dimethylsilylene {2-methyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] synthesized above A prepolymerized catalyst was prepared in the same manner as in (2) and (3) of Example 1 except that hafnium was used. The prepolymerization ratio was 0.31.
Subsequently, polymerization was carried out in the same manner as in Example 1 (4). As a result, 115 g of a propylene-based block polymer was obtained. From the result of CFC-IR, the resulting propylene block copolymer had a rubber content (CP content) of 6.9% by weight and an ethylene content in rubber (CP) of 49.4 mol%. , MFR was 59 (dg / min), and the weight average molecular weight of the CP part was 413,000.

[Comparative Example-1]
(This is a comparative example of a transition metal complex having four substituents in the cyclopentadienyl moiety.)
(1) Metallocene complex Dichloro [dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)] by the method described in JP-A-2005-336092 Hafnium was synthesized.
(2) Preliminary polymerization and block polymerization Examples except that dichloro [dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)] hafnium is used A prepolymerized catalyst was prepared in the same manner as in (2) and (3) of 1.
Subsequently, polymerization was carried out in the same manner as in Example 1 (4). As a result, 171 g of a propylene-based block polymer was obtained. From the result of CFC-IR, the obtained propylene-based block copolymer has a rubber content (CP content) of 13% by weight, and an ethylene content in rubber (CP) of 60.9 mol%. The weight average molecular weight of the part was 124,000.

[Comparative Example-2]
(This is a comparative example of a transition metal complex having three substituents in the cyclopentadienyl moiety.)
(1) Metallocene complex Dichloro [dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)] hafnium is synthesized by the method described in JP-A-2007-308486. did.
(2) Preliminary polymerization and block polymerization (Example 1) except that dichloro [dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)] hafnium is used. A prepolymerized catalyst was prepared in the same manner as 2) and (3).
Subsequently, polymerization was carried out in the same manner as in Example 1 (4). As a result, 84 g of a propylene-based block polymer was obtained. From the result of CFC-IR, the obtained propylene block copolymer has a rubber content (CP content) of 6.6% by weight, and an ethylene content in rubber (CP) of 52.0 mol%. The weight average molecular weight of the CP part was 320,000.

[Comparative Example-3]
(This is a comparative example of a transition metal complex having substituents at the 2-position and 4-position of the cyclopentadienyl moiety.)
(1) Metallocene complex Dichloro [dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)] hafnium is synthesized by the method described in JP-A-2007-308486. did.
(2) Prepolymerization and block polymerization (Example 1) except that dichloro [dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)] hafnium is used. A prepolymerized catalyst was prepared in the same manner as 2) and (3).
Subsequently, polymerization was carried out in the same manner as in Example 1 (4), and as a result, 86 g of a propylene-based block polymer was obtained. From the result of CFC-IR, the resulting propylene-based block copolymer had a rubber content (CP content) of 5.2% by weight and an ethylene content of rubber (CP) of 58.0 mol%. , MFR was 55.4 (dg / min), and the weight average molecular weight of the CP part was 380,000.

The results of the above examples and comparative examples are summarized and posted in Table 1.

(Consideration by comparison of results of Examples and Comparative Examples)
When comparing each of the above Examples and Comparative Examples, in the present invention, the same gas composition is used in Examples 1 to 3 than in the case of the transition metal compounds listed in the corresponding Comparative Examples 1 to 3. Higher ethylene content or higher molecular weight copolymers have been obtained. In particular, compared with Comparative Examples 1 to 3, Example 1 achieves a higher ethylene content and a higher molecular weight at the same time, and Example 2 achieves a higher molecular weight while maintaining a high ethylene content. Has been. Accordingly, in the present invention, when a novel transition metal compound having a specific structure represented by the general formula (I) and a catalyst comprising the same are used, ethylene or a carbon number of 4 is selected depending on the gas composition to be supplied. It has been shown that a catalyst can be provided that exhibits a balanced reactivity of -20 α-olefins and propylene and provides a high molecular weight copolymer, and the rationality and significance of the requirements in the present invention, and The superiority of the present invention over the prior art is shown.

As described above, the transition metal compound of the present invention can be used as an α-olefin polymerization catalyst as a catalyst component of an olefin polymerization catalyst or in combination with a promoter or the like. In particular, when the α-olefin polymerization catalyst of the present invention is used when copolymerizing propylene and ethylene or an α-olefin having 4 to 20 carbon atoms, propylene and the copolymerization monomer exhibit balanced reactivity. As a result, it is possible to perform the polymerization by rationally supplying a gas having a monomer ratio that does not substantially differ from the content in the copolymer, and at the same time, a catalytic function that brings about a high molecular weight is manifested. And the propylene / ethylene-alpha olefin copolymer obtained in this way can be used conveniently especially for an injection molded product and a film.
Therefore, the industrial value of the olefin polymerization catalyst and the α-olefin polymerization or copolymerization method using the transition metal compound according to the present invention is extremely large.

Claims (5)

The transition metal compound represented by the following general formula (I).

(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is a methyl group, R ³ is a secondary or tertiary alkyl group having 3 to 10 carbon atoms, and R ⁴ and R ⁵ are Each independently a hydrogen atom, hydrocarbon group, silicon-containing hydrocarbon group or halogenated hydrocarbon group, R ⁶ is a hydrocarbon group, halogenated hydrocarbon group or silicon-containing hydrocarbon group having 6 or more carbon atoms, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group.
Q is a silylene group which may have a substituent or a germylene group which may have a substituent, and X and Y are each independently a ligand which forms a σ bond with M. And M is a transition metal of Group 4 of the Periodic Table. )   An olefin polymerization catalyst component comprising the transition metal compound according to claim 1. An olefin polymerization catalyst comprising the following components (A) and (B) and optionally a component (C).
Component (A): transition metal compound according to claim 1 Component (B): an organoaluminum oxy compound, an ionic compound or Lewis capable of reacting with component (A) to convert component (A) into a cation Compound selected from acids Component (C): Fine particle carrier An olefin polymerization catalyst comprising the following components (A) and (D) and optionally a component (E).
Component (A): Transition metal compound according to claim 1 Component (D): Compound selected from ion-exchange layered compound or inorganic silicate Component (E): Organoaluminum compound Characterized in that the polymerization or copolymerization of α- olefins in the presence of an olefin polymerization catalyst according to claim 3 or 4, the polymerization or copolymerization process of α- olefins.