JP5089922B2 - Metallocene compound and olefin polymerization catalyst using the same - Google Patents

Description

  The present invention relates to a novel metallocene compound and an olefin polymerization catalyst using the same, and more specifically, a propylene-based block copolymer having a high molecular weight in the copolymer portion can be produced, and the copolymer monomers such as ethylene and α -It relates to a novel metallocene compound constituting an olefin polymerization catalyst, characterized by good olefin uptake efficiency.

Polyolefin resins are widely used as basic resin materials in the industry because of various excellent physical properties, ease of molding, good economy, and adaptability to environmental problems.
In particular, polypropylene resin is widely used as industrial material in various technical fields as a main material in polyolefin resin, and since it is an outstanding important raw material, further improvements in various performances are always required.

For example, polypropylene resin is excellent in rigidity and heat resistance, but lacks flexibility and impact resistance. Therefore, in order to improve flexibility and impact resistance, a propylene homopolymer such as ethylene-propylene rubber is used. A method of adding an elastomer, a method of producing a so-called block copolymer by multistage polymerization in which propylene and ethylene or α-olefin are subsequently copolymerized after homopolymerization of propylene are carried out.
Polypropylene has traditionally been produced industrially on a large scale by Ziegler catalysts, but later metallocene catalysts were developed. Metallocene catalysts have higher catalytic activity and unique stereoregularity compared to Ziegler catalysts. Since a polyolefin having a narrow molecular weight distribution can be produced, it has been attracting attention from Ziegler catalysts.

  Thus, improvements in the polypropylene resin mainly continued to improve the structure of metallocene compounds (metallocene complexes) in order to obtain higher molecular weight polymers or to increase the melting point, stereoregularity and particle properties of the polymers. ing. That is, a substituent is arranged on the conjugated 5-membered ring, and the conjugated ring is further linked by a bridging group, the transition metal atom and the auxiliary ligand are diversified, a cocatalyst and a support are employed, or the conjugated 5-membered Use an indenyl ring, a fluorenyl ring or an azulenyl ring in place of the ring, and make the conjugated ring an asymmetrical arrangement so that the conjugated ring is equipped with various specific substituents, and a plurality of substituents are further condensed. A number of improved catalysts have been disclosed and improvements in polypropylene resin and catalyst function have been demonstrated.

By the way, in order to improve the rigidity of the propylene-ethylene block copolymer, metallocene compounds that give polypropylene having a high melting point are disclosed (for example, refer to Patent Documents 1 and 2), and are composed of these metallocene compounds. When copolymerization of propylene and ethylene or α-olefin is carried out using a catalyst, there is a problem that the polymerization reactivity of ethylene or α-olefin is relatively low compared to the polymerization reactivity of propylene. . That is, in order to obtain a copolymer having a desired ethylene or α-olefin content, it is necessary to supply a gas having a monomer ratio that is greatly different from the content in the copolymer and to perform polymerization. In the extreme case, a copolymer having a desired content may not be produced.
For such problems, for example, it has been proposed that the polymerization reactivity of propylene and the polymerization reactivity of ethylene or α-olefin can be changed by changing the metallocene compound used (for example, Patent Document 3 and Non-Patent Document). No metallocene compound that satisfies both polymerization reactivity in a well-balanced manner has been known so far.
Further, 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-olefins must be exhibited. It is preferable that the content of each copolymer satisfies 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 polymerization reactivity of propylene and the polymerization reactivity of ethylene or α-olefin are balanced and within a certain range.

Furthermore, when a metallocene 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 portion is lowered. . For example, in order to obtain a high stereoregular olefin polymer with high activity, an indenyl skeleton complex in which a furyl group is substituted at the 2-position is exemplified (see Patent Document 4). The combined ethylene-propylene polymer component has a low molecular weight, and may not provide desired performance such as stickiness or high impact resistance, and it is difficult to obtain satisfactory results.
And in order to express high impact resistance in a propylene-ethylene block copolymer, it is also necessary for the molecular weight of the copolymer part to have a certain value or more. Metallocene catalysts that can be produced are also desired.

JP 11-240909 A (summary) JP 2000-95791 A (summary) WO 2004-87775 Publication Pamphlet (Summary and Claim 10) Japanese Patent Laying-Open No. 2004-2259 (Abstract and Claim 1)

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

  As is clear from the background art outlined in paragraphs 0005 to 0006, in the polypropylene resin material which is widely used and used in many industrial fields, when copolymerizing propylene and ethylene or α-olefin, Since the polymerization reactivity of α-olefin is not balanced with the polymerization reactivity of propylene, and there is a problem that it is difficult to obtain a high molecular weight of the copolymer part at that time, the present invention solves this problem. Accordingly, the present invention aims to develop a metallocene catalyst for olefin polymerization which exhibits a balanced polymerization reactivity of ethylene or α-olefin and propylene in the copolymerization of propylene and gives a copolymer portion having a high molecular weight.

In order to solve the problems of the present invention, the present inventors have developed various metallocene catalysts described above, and various ligand structures in the structure of transition metal compounds as metallocene compounds in metallocene polymerization catalysts. Considering empirical rules from the viewpoint of the reactivity of transition metal compounds derived from the basic skeleton, the steric effect of the substituents of the transition metal compounds and the electronic environment, and their influence on the coordination of the resulting polymer While searching for a technique for improving the balance between the polymerization reactivity of ethylene or α-olefin and the polymerization reactivity of propylene, and improving the molecular weight of the copolymer at that time, various investigations were conducted and experimental searches were conducted. Went.
In the process, when a metallocene complex having a specific specific steric and electronic environment structure is formed, it exhibits a balanced polymerization reactivity of ethylene or α-olefin and propylene. It is possible to recognize the fact that the catalytic function that brings about a high molecular weight in the part is manifested, and in the result of consideration of the model compound and experimental verification, a new metallocene compound that is very useful as a catalyst component was found, It came to create invention.

Thus, the metallocene metal complex (metallocene compound) constituting the basic constitution of the present invention is characterized by the chemical and steric and electronic environment structure of the ligand of the catalyst structure in the metallocene catalyst, with the requirement of a novel transition metal compound. And thus exhibiting a balanced polymerization reactivity of ethylene or α-olefin (α-olefin having about 4 to 20 carbon atoms) and propylene, and at the same time, high molecular weight of the copolymer part is also brought about The catalytic function is manifested.
The metallocene complex is composed of a novel transition metal compound having a structure represented by the following 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.

［式中、Ｍは、チタン、ジルコニウム、又はハフニウムであり、Ｙは、メチレン基、エチレン基、炭素数１〜６のアルキル基を有するテトラアルキルエチレン基、炭素数１〜６のアルキル基を有するジアルキルメチレン基、炭素数６〜１８のアリール基又は炭素数６〜１８のハロゲン化アリール基を骨格に含む２価の架橋基又は珪素原子、ゲルマニウム原子、酸素原子、窒素原子、燐原子もしくは硼素原子を含有する２価の架橋基であり、Ｘ¹とＸ²は、それぞれ独立して、Ｍとσ結合を形成する配位子である。
Ｒ¹とＲ¹¹は、互いに同じでも異なっていてもよく、水素、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数１〜６のハロゲン含有アルキル基、炭素数１〜６の珪素含有アルキル基、炭素数６〜１８のアリール基もしくは炭素数６〜１８のハロゲン含有アリール基、置換基を有していてもよい５員環を構成する複素環基（但し、５員環を構成する複素環基のヘテロ原子は直接アルカジエニル基と結合しない）である。そして、Ｒ¹とＲ¹¹の片方又は両方は、必ず、置換基を有していてもよい５員環を構成する複素環基である。
Ｒ⁴とＲ¹⁴は、互いに同じでも異なっていてもよく、水素、炭素数１〜６のアルキル基、炭素数１〜６のハロゲン含有アルキル基、炭素数１〜６の珪素含有アルキル基、炭素数２〜６のアルケニル基、炭素数６〜１８のアリール基もしくは炭素数６〜１８のハロゲン含有アリール基、置換基を有していてもよい５員環又は６員環を構成する複素環基又はアダマンチル基もしくは置換アダマンチル基である。そして、Ｒ^４とＲ^１４の片方又は両方は、必ず、アダマンチル基又は置換アダマンチル基である。
Ｒ², Ｒ³, Ｒ⁵, Ｒ^６,Ｒ⁷, Ｒ⁸, Ｒ⁹, Ｒ¹², Ｒ¹³, Ｒ¹⁵, Ｒ^１６,Ｒ¹⁷, Ｒ¹⁸, Ｒ¹⁹は、互いに同じでも異なっていてもよく、水素、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数１〜６のハロゲン含有アルキル基、炭素数１〜６の珪素含有アルキル基、炭素数６〜１８のアリール基又は炭素数６〜１８のハロゲン含有アリール基、置換基を有していてもよい５員環又は６員環を構成する複素環基である。また、隣接するＲ双方で６〜７員環を構成してもよく、６〜７員環が不飽和結合を含んでいてもよい。］

[Wherein, M is titanium, zirconium or hafnium, and Y has a methylene group, an ethylene group, a tetraalkylethylene group having an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Divalent methylene group, divalent methylene group, divalent bridging group having 6-18 carbon atoms or halogenated aryl group having 6-18 carbon atoms in the skeleton, or silicon atom, germanium atom, oxygen atom, nitrogen atom, phosphorus atom or boron atom And X ¹ and X ² are each independently a ligand that forms a σ bond with M.
R ¹ and R ¹¹ may be the same or different from each other, and are hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. A silicon-containing alkyl group having 6 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or a halogen-containing aryl group having 6 to 18 carbon atoms, and a heterocyclic group constituting a 5-membered ring which may have a substituent (provided that 5 The hetero atom of the heterocyclic group constituting the member ring is not directly bonded to the alkadienyl group). One or both of R ¹ and R ¹¹ is necessarily a heterocyclic group constituting a 5-membered ring which may have a substituent.
R ⁴ and R ¹⁴ may be the same or different from each other, and are hydrogen, an alkyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, a silicon-containing alkyl group having 1 to 6 carbon atoms, carbon Heterocyclic group constituting a alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or a halogen-containing aryl group having 6 to 18 carbon atoms, and optionally having a 5-membered ring or 6-membered ring Or it is an adamantyl group or a substituted adamantyl group. One or both of R ⁴ and R ¹⁴ are necessarily an adamantyl group or a substituted adamantyl group.
R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ may be the same or different from each other. Well, hydrogen, C1-C6 alkyl group, C2-C6 alkenyl group, C1-C6 halogen-containing alkyl group, C1-C6 silicon-containing alkyl group, C6-C18 An aryl group, a halogen-containing aryl group having 6 to 18 carbon atoms, or a heterocyclic group constituting a 5-membered ring or 6-membered ring which may have a substituent. Moreover, 6-7 membered ring may be comprised by both adjacent R, and the 6-7 membered ring may contain the unsaturated bond. ]

As described above, the metallocene compound of the present invention necessarily has a bulky adamantyl group or substituted adamantyl group at the p-position of the phenyl substituent at the 4-position of one or both indenyl rings, and one or both of the indenyl rings. A novel compound characterized by having a heterocyclic group or a substituted heterocyclic group at the 2-position, and having a plurality of sterically and electronically environmentally specific substituents on the indenyl ring, A complex having a steric and electronic environment-specific structure is formed.
By using the metallocene compound of the present invention as a catalyst component for olefin polymerization, when a propylene-based block copolymer is produced, the efficiency of incorporating ethylene or α-olefin into the copolymer is higher than that of a conventional catalyst, Further, the molecular weight of the copolymer part is increased, and as demonstrated by the comparison of Examples and Comparative Examples described below, the copolymer part has a balanced polymerization reactivity of ethylene or α-olefin and propylene. It is possible to realize a metallocene catalyst for α-olefin polymerization that provides a high molecular weight.

As an additional requirement in the present invention, Y in the chemical formula [I] is a specific divalent bridging group of R ²⁰ ₂ A (A is germanium or silicon), M is zirconium or hafnium, One or both of R ¹ and R ¹¹ is a furyl group or a thienyl group which may have a substituent.
Further, the present invention is based on “component (A): metallocene compound, component (B): compound that reacts with component (A) to form an ion pair or ion-exchangeable layered silicate component (C): organoaluminum compound”. The component (B) is an ion-exchange layered silicate, the olefin is propylene, and the olefin polymerization catalyst is further used for polymerization or copolymerization of the olefin. It is also a method for polymerizing olefins.

  By the way, as described in paragraph 0013, the metallocene compound disclosed in the present invention always has a bulky adamantyl group or substituted adamantyl group at the p-position of the phenyl substituent at the 4-position of at least one indenyl ring. A novel compound having a heterocyclic group or a substituted heterocyclic group in the 2-position of at least one indenyl ring, and a plurality of sterically and electronically specific substituents in the indenyl ring. And forms a complex having a chemical, steric and electronic environment-specific structure. In addition to each patent document and non-patent document described in the background art, other patent documents are described in detail. Even after careful examination, metallocene compounds in which an adamantyl group is simply arranged on the indenyl ring (Claims 1 and 9 of JP 2002-535416 A) or cyclope A metallocene compound in which a heterocyclic group is simply arranged on the tadienyl ring (Claims 9 and 12 of JP-T-2002-516359) is only slightly seen, suggesting or presenting a metallocene compound having a unique structure in the present invention. I can't find any remarks on the literature.

  In the above, the background of the creation of the present invention and the basic configuration and features of the invention have been described generally. Here, when overviewing the overall configuration of the present invention, the present invention has the following invention units. It consists of a group. The metallocene compound represented by the general formula [I] is constituted as the basic invention [1]. [2] Each of the following inventions adds an additional requirement to the basic invention or shows an embodiment thereof. is there. All invention units are collectively referred to as an invention group.

［式中、Ｍは、チタン、ジルコニウム、又はハフニウムであり、Ｙは、メチレン基、エチレン基、炭素数１〜６のアルキル基を有するテトラアルキルエチレン基、炭素数１〜６のアルキル基を有するジアルキルメチレン基、炭素数６〜１８のアリール基又は炭素数６〜１８のハロゲン化アリール基を骨格に含む２価の架橋基又は珪素原子、ゲルマニウム原子、酸素原子、窒素原子、燐原子もしくは硼素原子を含有する２価の架橋基であり、Ｘ¹とＸ²は、それぞれ独立して、Ｍとσ結合を形成する配位子である。
Ｒ¹とＲ¹¹は、互いに同じでも異なっていてもよく、水素、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数１〜６のハロゲン含有アルキル基、炭素数１〜６の珪素含有アルキル基、炭素数６〜１８のアリール基もしくは炭素数６〜１８のハロゲン含有アリール基、置換基を有していてもよい５員環を構成する複素環基（但し、５員環を構成する複素環基のヘテロ原子は直接アルカジエニル基と結合しない）である。そして、Ｒ¹とＲ¹¹の片方又は両方は、必ず、置換基を有していてもよい５員環を構成する複素環基である。
Ｒ⁴とＲ¹⁴は、互いに同じでも異なっていてもよく、水素、炭素数１〜６のアルキル基、炭素数１〜６のハロゲン含有アルキル基、炭素数１〜６の珪素含有アルキル基、炭素数２〜６のアルケニル基、炭素数６〜１８のアリール基もしくは炭素数６〜１８のハロゲン含有アリール基、置換基を有していてもよい５員環又は６員環を構成する複素環基又はアダマンチル基もしくは置換アダマンチル基である。そして、Ｒ^４とＲ^１４の片方又は両方は、必ず、アダマンチル基又は置換アダマンチル基である。
Ｒ², Ｒ³, Ｒ⁵, Ｒ^６,Ｒ⁷, Ｒ⁸, Ｒ⁹, Ｒ¹², Ｒ¹³, Ｒ¹⁵, Ｒ^１６,Ｒ¹⁷, Ｒ¹⁸, Ｒ¹⁹は、互いに同じでも異なっていてもよく、水素、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数１〜６のハロゲン含有アルキル基、炭素数１〜６の珪素含有アルキル基、炭素数６〜１８のアリール基又は炭素数６〜１８のハロゲン含有アリール基、置換基を有していてもよい５員環又は６員環を構成する複素環基である。また、隣接するＲ双方で６〜７員環を構成してもよく、６〜７員環が不飽和結合を含んでいてもよい。］
［２］Ｙが、Ｒ²⁰ _２Ａ（Ａは、ゲルマニウム又は珪素であり、Ｒ²⁰は、互いに同じでも異なっていてもよく、水素、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数１〜６のハロゲン含有アルキル基、炭素数６〜１８のアリール基又は炭素数６〜１８のハロゲン含有アリール基である。隣接するＲ²⁰双方でＡを含む４〜７員環を構成してもよく、５〜７員環で不飽和結合を含んでいてもよい。）で示される２価の架橋基であることを特徴とする、［１］におけるメタロセン化合物。
［３］一般式［Ｉ］中において、Ｍは、ジルコニウム又はハフニウムであり、Ｒ^１とＲ^１１の片方又は両方が、置換基を有していてもよいフリル基又はチエニル基であることを特徴とする、［１］又は［２］におけるメタロセン化合物。
［４］下記の（Ａ）、（Ｂ）、（Ｃ）の各成分を含むオレフィン重合用触媒。
成分（Ａ）：［１］〜［３］のいずれかにおけるメタロセン化合物
成分（Ｂ）：成分（Ａ）と反応してイオン対を形成する化合物又はイオン交換性層状珪酸塩
成分（Ｃ）：有機アルミニウム化合物
［５］成分（Ｂ）が、イオン交換性層状珪酸塩であり、オレフィンがプロピレンであることを特徴とする、［４］におけるオレフィン重合用触媒。
［６］［４］又は［５］におけるオレフィン重合用触媒を使用してオレフィンの重合又は共重合を行うことを特徴とする、オレフィンの重合方法。 [1] A metallocene compound represented by the following general formula [I].

[Wherein, M is titanium, zirconium or hafnium, and Y has a methylene group, an ethylene group, a tetraalkylethylene group having an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Divalent methylene group, divalent methylene group, divalent bridging group having 6-18 carbon atoms or halogenated aryl group having 6-18 carbon atoms in the skeleton, or silicon atom, germanium atom, oxygen atom, nitrogen atom, phosphorus atom or boron atom And X ¹ and X ² are each independently a ligand that forms a σ bond with M.
R ¹ and R ¹¹ may be the same or different from each other, and are hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. A silicon-containing alkyl group having 6 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or a halogen-containing aryl group having 6 to 18 carbon atoms, and a heterocyclic group constituting a 5-membered ring which may have a substituent (provided that 5 The hetero atom of the heterocyclic group constituting the member ring is not directly bonded to the alkadienyl group). One or both of R ¹ and R ¹¹ is necessarily a heterocyclic group constituting a 5-membered ring which may have a substituent.
R ⁴ and R ¹⁴ may be the same or different from each other, and are hydrogen, an alkyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, a silicon-containing alkyl group having 1 to 6 carbon atoms, carbon Heterocyclic group constituting a alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or a halogen-containing aryl group having 6 to 18 carbon atoms, and optionally having a 5-membered ring or 6-membered ring Or it is an adamantyl group or a substituted adamantyl group. One or both of R ⁴ and R ¹⁴ are necessarily an adamantyl group or a substituted adamantyl group.
R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ may be the same or different from each other. Well, hydrogen, C1-C6 alkyl group, C2-C6 alkenyl group, C1-C6 halogen-containing alkyl group, C1-C6 silicon-containing alkyl group, C6-C18 An aryl group, a halogen-containing aryl group having 6 to 18 carbon atoms, or a heterocyclic group constituting a 5-membered ring or 6-membered ring which may have a substituent. Moreover, 6-7 membered ring may be comprised by both adjacent R, and the 6-7 membered ring may contain the unsaturated bond. ]
[2] Y is R ²⁰ ₂ A (A is germanium or silicon, R ²⁰ may be the same as or different from each other, and is hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 2 to 6 carbon atoms. alkenyl group, a halogen-containing alkyl group having 1 to 6 carbon atoms, a halogen-containing aryl group having 6 to 18 aryl group or a carbon number of 6 to 18 carbon atoms. 4-7 membered ring containing adjacent R ²⁰ both the a The metallocene compound according to [1], wherein the metallocene compound is a divalent bridging group represented by the following formula:
[3] In general formula [I], M is zirconium or hafnium, and one or both of R ¹ and R ¹¹ are a furyl group or a thienyl group which may have a substituent. The metallocene compound in [1] or [2].
[4] An olefin polymerization catalyst containing the following components (A), (B), and (C).
Component (A): Metallocene compound in any one of [1] to [3] Component (B): Compound that reacts with component (A) to form an ion pair or ion-exchangeable layered silicate Component (C): Organic Aluminum compound [5] The catalyst for olefin polymerization according to [4], wherein the component (B) is an ion-exchange layered silicate and the olefin is propylene.
[6] An olefin polymerization method, wherein the olefin polymerization or copolymerization is performed using the olefin polymerization catalyst according to [4] or [5].

  In the present invention, a novel transition metal compound whose structure is represented by the above general formula [I] is employed as the metallocene complex, and is used as a catalyst component of an olefin polymerization catalyst. Since it forms a polymerization catalyst, when copolymerizing propylene and ethylene or α-olefin, propylene and copolymerization monomer exhibit a balanced polymerization reactivity, and as a result, in the copolymer Thus, it is possible to perform the polymerization by rationally supplying a gas having a monomer ratio that does not differ substantially from the content of the catalyst, and in this case, a catalytic function that brings about a high molecular weight in the copolymer portion is manifested.

  The outline of the present invention and the basic configuration and features of the present invention have been described above. In the following, the embodiments of the present invention are carried out in order to explain the entire invention group of the present invention in detail. Detailed description will be given in detail as the best mode for the above.

1. Metallocene Compound Used for Olefin Polymerization Catalyst Component (1) Structure of Metallocene Compound The transition metal compound forming the metallocene complex in the metallocene catalyst of the present invention is a novel metallocene compound represented by the following general formula [I].

［式中、Ｍは、チタン、ジルコニウム、又はハフニウムであり、Ｙは、メチレン基、エチレン基、炭素数１〜６のアルキル基を有するテトラアルキルエチレン基、炭素数１〜６のアルキル基を有するジアルキルメチレン基、炭素数６〜１８のアリール基又は炭素数６〜１８のハロゲン化アリール基を骨格に含む２価の架橋基又は珪素原子、ゲルマニウム原子、酸素原子、窒素原子、燐原子もしくは硼素原子を含有する２価の架橋基であり、Ｘ¹とＸ²は、それぞれ独立して、Ｍとσ結合を形成する配位子である。
Ｒ¹とＲ¹¹は、互いに同じでも異なっていてもよく、水素、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数１〜６のハロゲン含有アルキル基、炭素数１〜６の珪素含有アルキル基、炭素数６〜１８のアリール基もしくは炭素数６〜１８のハロゲン含有アリール基、置換基を有していてもよい５員環を構成する複素環基（但し、５員環を構成する複素環基のヘテロ原子は直接アルカジエニル基と結合しない）である。そして、Ｒ¹とＲ¹¹の片方又は両方は、必ず、置換基を有していてもよい５員環を構成する複素環基である。
Ｒ⁴とＲ¹⁴は、互いに同じでも異なっていてもよく、水素、炭素数１〜６のアルキル基、炭素数１〜６のハロゲン含有アルキル基、炭素数１〜６の珪素含有アルキル基、炭素数２〜６のアルケニル基、炭素数６〜１８のアリール基もしくは炭素数６〜１８のハロゲン含有アリール基、置換基を有していてもよい５員環又は６員環を構成する複素環基又はアダマンチル基もしくは置換アダマンチル基である。そして、Ｒ^４とＲ^１４の片方又は両方は、必ず、アダマンチル基又は置換アダマンチル基である。
Ｒ², Ｒ³, Ｒ⁵, Ｒ^６,Ｒ⁷, Ｒ⁸, Ｒ⁹, Ｒ¹², Ｒ¹³, Ｒ¹⁵, Ｒ^１６,Ｒ¹⁷, Ｒ¹⁸, Ｒ¹⁹は、互いに同じでも異なっていてもよく、水素、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、炭素数１〜６のハロゲン含有アルキル基、炭素数１〜６の珪素含有アルキル基、炭素数６〜１８のアリール基又は炭素数６〜１８のハロゲン含有アリール基、置換基を有していてもよい５員環又は６員環を構成する複素環基である。また、隣接するＲ双方で６〜７員環を構成してもよく、６〜７員環が不飽和結合を含んでいてもよい。］

[Wherein, M is titanium, zirconium or hafnium, and Y has a methylene group, an ethylene group, a tetraalkylethylene group having an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Divalent methylene group, divalent methylene group, divalent bridging group having 6-18 carbon atoms or halogenated aryl group having 6-18 carbon atoms in the skeleton, or silicon atom, germanium atom, oxygen atom, nitrogen atom, phosphorus atom or boron atom And X ¹ and X ² are each independently a ligand that forms a σ bond with M.
R ¹ and R ¹¹ may be the same or different from each other, and are hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. A silicon-containing alkyl group having 6 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or a halogen-containing aryl group having 6 to 18 carbon atoms, and a heterocyclic group constituting a 5-membered ring which may have a substituent (provided that 5 The hetero atom of the heterocyclic group constituting the member ring is not directly bonded to the alkadienyl group). One or both of R ¹ and R ¹¹ is necessarily a heterocyclic group constituting a 5-membered ring which may have a substituent.
R ⁴ and R ¹⁴ may be the same or different from each other, and are hydrogen, an alkyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, a silicon-containing alkyl group having 1 to 6 carbon atoms, carbon Heterocyclic group constituting a alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or a halogen-containing aryl group having 6 to 18 carbon atoms, and optionally having a 5-membered ring or 6-membered ring Or it is an adamantyl group or a substituted adamantyl group. One or both of R ⁴ and R ¹⁴ are necessarily an adamantyl group or a substituted adamantyl group.
R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ may be the same or different from each other. Well, hydrogen, C1-C6 alkyl group, C2-C6 alkenyl group, C1-C6 halogen-containing alkyl group, C1-C6 silicon-containing alkyl group, C6-C18 An aryl group, a halogen-containing aryl group having 6 to 18 carbon atoms, or a heterocyclic group constituting a 5-membered ring or 6-membered ring which may have a substituent. Moreover, 6-7 membered ring may be comprised by both adjacent R, and the 6-7 membered ring may contain the unsaturated bond. ]

(2) Characteristics of metallocene compound As described in paragraph 0013, the metallocene compound of the present invention is characterized by a bulky adamantyl group or substituted adamantyl group at the p-position of the phenyl substituent at the 4-position of one or both indenyl rings. A plurality of substituents that are sterically and electronically specific to the indenyl ring, which is a novel compound that necessarily has a group and has a heterocyclic group or a substituted heterocyclic group at the 2-position of one or both indenyl rings. To form a complex having a chemical, steric and electronic environment-specific structure.
By using the metallocene compound of the present invention as a catalyst component for olefin polymerization, when a propylene-based block copolymer is produced, the efficiency of incorporating ethylene or α-olefin into the copolymer is higher than that of a conventional catalyst, In addition, the molecular weight of the copolymer portion is increased.

(3) Cross-linking group, substituent and others M is a Group 4 transition metal of titanium, zirconium and hafnium, preferably zirconium or hafnium.

  Y is a divalent group that bridges two indenyl groups, and preferred examples include dimethylsilylene, diethylsilylene, di-n-propylsilylene, dii-propylsilylene, din-butylsilylene, methylethylsilylene. Methyl n-butylsilylene, ethyl n-butylsilylene, divinylsilylene, diphenylsilylene, ditolylsilylene, silacyclobutylene, silacyclopentylene, silafluorene, dimethylgermylene, diethylgermylene, di-n-propylgermylene, Examples include di-propylgermylene, di-n-butylgermylene, methylethylgermylene, methyln-butylgermylene, ethyln-butylgermylene, divinylgermylene, and the like. Among these, dimethylsilylene, diethylsilylene , Dimethylgermylene, di Ethylgermylene is particularly preferred.

Specific examples of the alkyl group having 1 to 6 carbon atoms in the general formula [I] include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, Examples thereof include n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.
Specific examples of the alkenyl group having 2 to 6 carbon atoms include vinyl, propenyl, allyl, butenyl, cyclohexenyl and the like.
The aryl group having 6 to 18 carbon atoms may be substituted with an alkyl group. Specific examples include phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, t-butylphenyl, 1-naphthyl, 2-naphthyl and acenaphthyl. , Phenanthryl, anthryl and the like.
Examples of the halogen atom of the halogen-containing alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the substituent include fluoromethyl, difluoromethyl, trifluoromethyl, and chloromethyl. , Dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoro Propyl, nonafluorobutyl, 5-chloropentyl, 5,5,5-trichloropentyl, 5-fluoropentyl, 5,5,5-trifluoropentyl, 6-chlorohexyl, 6,6,6-trichlorohexyl, 6 -Fluorohexyl, 6,6,6-trifluorohex Mention may be made of Le.
Specific examples of the silicon-containing alkyl group having 1 to 6 carbon atoms include trimethylsilyl, triethylsilyl, t-butyldimethylsilyl and the like.
Specific examples of the halogen-containing aryl group having 6 to 18 carbon atoms include 2-, 3-, 4-substituted fluorophenyl, 2-, 3-, 4-substituted chlorophenyl, 2-, 3-, 4- Each substituted bromophenyl, 2,4-, 2,5-, 2,6-, 3,5-substituted difluorophenyl, 2,4-, 2,5-, 2,6-, 3,5- Examples include substituted dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, and the like.

  The heterocyclic group constituting the 5-membered ring or 6-membered ring which may have a substituent is a hetero atom which is not directly bonded to the alkadienyl group. Specific examples of the heterocyclic ring include pyrrolidyl, pyridyl, Pyrimidyl, quinolyl, isoquinolyl, carbazolyl, furyl, thienyl, thianofuryl, imidazolyl, pyrazolyl, pyrrolyl, oxazolyl, thiazolyl, isothiazolyl, isoxazolyl, and these heterocycles having an alkyl group having 1 to 6 carbon atoms and an alkenyl having 2 to 6 carbon atoms A substituent of a group, a halogen-containing alkyl group having 1 to 6 carbon atoms, a silicon-containing alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms It may be. Preferably, it is a heterocyclic ring containing a sulfur atom or an oxygen atom having a 5-membered ring structure, more preferably a furyl group or a thienyl group which may have a substituent, and specific examples of the furyl group or the thienyl group Examples include 2-furyl, 3-furyl, 2- (5-methylfuryl), 3- (5-methylfuryl), 3- (5-t-butylfuryl), 3- (5-trimethylsilylfuryl), 3 -(5-triethylsilylfuryl), 3- (5-phenylfuryl), 3- (5-tolylfuryl), 3- (5-fluorophenylfuryl), 3- (5-chlorophenylfuryl), 2- (4 5-dimethylfuryl), 2- (3,5-dimethylfuryl), 2-benzofuryl, 2- (5-methylthienofuran), 2-thienyl, 3-thienyl, 2- (5-methylthienyl), 3- (5-me Tilthienyl), 3- (5-t-butylthienyl), 3- (5-trimethylsilylthienyl), 3- (5-triethylsilylthienyl), 3- (5-phenylthienyl), 3- (5-tolylthienyl) , 3- (5-fluorophenylthienyl), 3- (5-chlorophenylthienyl), 2- (4,5-dimethylthienyl), 2- (3,5-dimethylthienyl), 2-benzothienyl, etc. Can do.

  Specific examples of the adamantyl group or the substituted adamantyl group include 1-adamantyl, 2-adamantyl, 1- (2-methyladamantyl), 1- (3-methyladamantyl), 1- (4-methyladamantyl), 1- ( 2-phenyladamantyl), 1- (3-phenyladamantyl), 1- (4-phenyladamantyl), 1- (2-chloroadamantyl), 1- (3-chloroadamantyl), 1- (4-chloroadamantyl) 1- (2-fluoroadamantyl), 1- (3-fluoroadamantyl), 1- (4-fluoroadamantyl), 1- (3,5-dimethyladamantyl), 1- (3,5,7-trimethyladamantyl) ), 1- (3,5,7-triphenyladamantyl), 1- (3,5,7-trichloroadamantyl), 1- (3 5,7-trifluoro-adamantyl) and the like.

Specific examples of X ¹ and X ² include chlorine, methyl, i-butyl, phenyl, benzyl, dimethylamino, diethylamino and the like.

(4) Synthesis of Metallocene Compound The novel metallocene compound of the present invention can be synthesized by any method with respect to the substituents or bonding modes.
An example of a typical synthetic route is as shown in the following reaction formula.

The starting material 1 can be synthesized by the method described in J. Org. Chem. 1988, 53, 729-733, Synthesis, 1998, 148-152 and Synthesis, 1999, 7, 1246-1250.
After lithiation of 1 with alkyllithium, 2 is obtained by reacting with trialkoxyborane and hydrolysis. 3 is obtained by performing a coupling reaction of 2 and 4-bromoindene in the presence of a palladium catalyst or the like. The bromination of 3 to 4 can be carried out by the method described in the literature (J. Org. Chem. 1982, 47, 705-709). 5 is obtained by conducting a coupling reaction of 4 and furylboranoic acid in the presence of a palladium catalyst or the like. 5 is obtained by reaction with YCl ₂ such as dimethyldichlorosilane. After lithiation of 6 with alkyllithium, the desired 7 is obtained by reaction with MX ¹ X ² Cl ₂ .

Furthermore, the synthesis | combination of the complex which introduce | transduced the substituent can be synthesize | combined by using a corresponding substitution raw material, and using a substituted furylboranoic acid, the thienylboranoic acid which may be substituted, etc. is used instead of a furylboranoic acid. Can introduce the corresponding 2-position substituent (R ¹ R ¹¹ ). When the 2-position substituent (R ¹ R ¹¹ ) is an alkyl group or the like, the substituent may be introduced into 4-bromoindene first.
The synthesis of metallocene compounds with different substituents on the two indenyl rings can be bridged by reacting different substituted indenes with YCl ₂ in turn. A crosslinking aid such as an amine compound (for example, methylimidazole) may be present during crosslinking.

(5) Specific examples of metallocene compounds Specific examples of metallocene compounds according to the present invention are described below. Since the present invention is basically a novel metallocene compound invention, specific examples are described in detail while avoiding complicated description.
Since all of the metallocene exemplified compounds listed are chemical compounds in chemical structure, those synthesis methods can be easily inferred from the synthesis methods of the metallocene compounds of the present invention described in paragraphs 0029 to 0031 above, and the present compounds as metallocene catalysts. It can also be said that it has the unique properties of the invention.
The metallocene exemplified compounds to be listed are described in each paragraph for each group having a common characteristic of the chemical structure.

In the metallocene complex represented by the general formula [I], specific examples in which A in Y is silicon, X ¹ and X ² are chlorine, M is zirconium, and R ¹ is a substituted furyl group are listed below.
(1) Dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (2) Dimethylsilylenebis (2- (2- ( 5-t-butylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (3) dimethylsilylenebis (2- (2- (5-phenylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (4) dimethylsilylenebis (2- (2- (4,5-benzofuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (5) Dimethylsilylenebis (2- (2- (4,5-dimethylfuryl))-4- (4- (1-adamantyl) Phenyl) - indenyl) zirconium dichloride (6) dimethylsilylene-bis (2- (2- (3,5-dimethyl-furyl)) - 4- (4- (1-adamantyl) phenyl) - indenyl) zirconium dichloride

(7) Dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4- (2-adamantyl) phenyl) -indenyl) zirconium dichloride (8) Dimethylsilylenebis (2- (2- ( 5-methylfuryl))-4- (4- (1- (3-methyladamantyl)) phenyl) -indenyl) zirconium dichloride (9) dimethylsilylenebis (2- (2- (5-methylfuryl))-4 -(4- (1- (3,5-dimethyladamantyl)) phenyl) -indenyl) zirconium dichloride (10) dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4- (1 -(3,5,7-trimethyladamantyl)) phenyl) -indenyl) zirconium dichloride

(11) Dimethylsilylenebis (2- (2- (5-t-butylfuryl))-4- (4- (2-adamantyl) phenyl) -indenyl) zirconium dichloride (12) Dimethylsilylenebis (2- (2- (5-t-butylfuryl))-4- (4- (1- (3-methyladamantyl)) phenyl) -indenyl) zirconium dichloride (13) dimethylsilylenebis (2- (2- (5-t-butylfuryl)) ) -4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -indenyl) zirconium dichloride (14) dimethylsilylenebis (2- (2- (5-t-butylfuryl))-4- ( 4- (1- (3,5,7-trimethyladamantyl)) phenyl) -indenyl) zirconium dichloride

(15) Dimethylsilylenebis (2- (2- (5-phenylfuryl))-4- (4- (2-adamantyl) phenyl) -indenyl) zirconium dichloride (16) Dimethylsilylenebis (2- (2- ( 5-phenylfuryl))-4- (4- (1- (3-methyladamantyl)) phenyl) -indenyl) zirconium dichloride (17) dimethylsilylenebis (2- (2- (5-phenylfuryl))-4 -(4- (1- (3,5-dimethyladamantyl)) phenyl) -indenyl) zirconium dichloride (18) dimethylsilylenebis (2- (2- (5-phenylfuryl))-4- (4- (1 -(3,5,7-trimethyladamantyl)) phenyl) -indenyl) zirconium dichloride

(19) Dimethylsilylenebis (2- (2- (4,5-dimethylfuryl))-4- (4- (2-adamantyl) phenyl) -indenyl) zirconium dichloride (20) Dimethylsilylenebis (2- (2 -(4,5-dimethylfuryl))-4- (4- (1- (3-methyladamantyl)) phenyl) -indenyl) zirconium dichloride (21) dimethylsilylenebis (2- (2- (4,5- Dimethylfuryl))-4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -indenyl) zirconium dichloride (22) dimethylsilylenebis (2- (2- (4,5-dimethylfuryl)) -4- (4- (1- (3,5,7-trimethyladamantyl)) phenyl) -indenyl) zirconium dichloride

(23) Dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4- (2-adamantyl) phenyl) -5-methyl-indenyl) zirconium dichloride (24) Dimethylsilylenebis (2- (2- (5-Methylfuryl))-4- (4- (2-adamantyl) phenyl) -7-methyl-indenyl) zirconium dichloride

(25) Dimethylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (4- (4- (1-adamantyl) phenyl) -indenyl) Zirconium dichloride (26) dimethylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (4- (1-adamantyl) ) Phenyl) -indenyl) zirconium dichloride (27) dimethylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-ethyl-4- ( 4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (28) dimethylsilylene (2- (2- (5-methylfuryl))- - (4- (1-adamantyl) phenyl) - indenyl) (2-n-butyl-4- (4- (1-adamantyl) phenyl) - indenyl) zirconium dichloride

(29) Dimethylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (4-t-butylphenyl)- Indenyl) zirconium dichloride (30) dimethylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (3,5- Di-t-butylphenyl) -indenyl) zirconium dichloride (31) dimethylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl -4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (32) dimethylsilylene (2- (2- (5-methylfuryl))-4- (4 (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (3,5-dichlorophenyl) -indenyl) zirconium dichloride (33) dimethylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (1-naphthyl) -indenyl) zirconium dichloride (34) dimethylsilylene (2- (2- (5-methylfuryl))-4 -(4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (2-naphthyl) -indenyl) zirconium dichloride (35) dimethylsilylene (2- (2- (5-methylfuryl))- 4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (9-phenanthryl) -indenyl ) Zirconium dichloride

(36) Diethylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (4-t-butylphenyl)- Indenyl) zirconium dichloride (37) diethylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (3,5- Di-t-butylphenyl) -indenyl) zirconium dichloride (38) diethylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl -4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (39) diethylsilylene (2- (2- (5-methylfuryl))-4- (4 (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (3,5-dichlorophenyl) -indenyl) zirconium dichloride (40) diethylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (1-naphthyl) -indenyl) zirconium dichloride (41) diethylsilylene (2- (2- (5-methylfuryl))-4 -(4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (2-naphthyl) -indenyl) zirconium dichloride (42) diethylsilylene (2- (2- (5-methylfuryl))- 4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (9-phenanthryl) -indenyl ) Zirconium dichloride

(43) Di-n-butylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (4-t-butyl) Phenyl) -indenyl) zirconium dichloride (44) di-n-butylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4) -(3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (45) di-n-butylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl)) Phenyl) -indenyl) (2-methyl-4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (46) di-n-butylsilylene (2- (2- (5-methylfree)) ))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (3,5-dichlorophenyl) -indenyl) zirconium dichloride (47) di-n-butylsilylene (2- (2 -(5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (1-naphthyl) -indenyl) zirconium dichloride (48) di-n-butylsilylene ( 2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (2-naphthyl) -indenyl) zirconium dichloride (49) di n -Butylsilylene (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) (2-methyl-4- (9 Phenanthryl) - indenyl) zirconium dichloride

(50) Dimethylsilylene (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) (2-methyl-4- (4- (1-adamantyl) phenyl)- Indenyl) zirconium dichloride (51) dimethylsilylene (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) (2-methyl-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (52) dimethylsilylene (2- (2- (5-methylfuryl))-4- (3,5-dimethylphenyl) -indenyl) (2-methyl-4 -(4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (53) dimethylsilylene (2- (2- (5-methylfuryl))-4- (3 5-dichlorophenyl) -indenyl) (2-methyl-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (54) dimethylsilylene (2- (2- (5-methylfuryl))-4- (1-naphthyl) -indenyl) (2-methyl-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (55) dimethylsilylene (2- (2- (5-methylfuryl))-4 -(2-Naphtyl) -indenyl) (2-methyl-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (56) dimethylsilylene (2- (2- (5-methylfuryl))- 4- (4- (9-phenanthryl) -indenyl) (2-methyl-4- (1-adamantyl) phenyl) -indenyl ) Zirconium dichloride

(57) Dimethylsilylenebis (2- (3- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (58) Dimethylsilylenebis (2- (3- ( 5-t-butylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (59) dimethylsilylenebis (2- (3- (5-phenylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (60) dimethylsilylenebis (2- (3- (4,5-dimethylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium Dichloride

(61) Dimethylsilylenebis (2- (3- (2,5-dimethylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (62) Dimethylsilylenebis (2- (2 -(5-chlorofuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (63) dimethylsilylenebis (2- (2- (5-fluorofuryl))-4- (4 -(1-adamantyl) phenyl) -indenyl) zirconium dichloride (64) dimethylsilylenebis (2- (3- (2-chloro-5-methylfuryl))-4- (4- (1-adamantyl) phenyl)- Indenyl) zirconium dichloride (65) dimethylsilylene bis (2- (3- (2-fluoro-5-methylfuryl))- - (4- (1-adamantyl) phenyl) - indenyl) zirconium dichloride

In these exemplified metallocene compounds represented by the general formula [I], one or both of two chlorine atoms corresponding to X ¹ and X ² are fluorine atom, bromine atom, iodine atom, methyl group, phenyl group, benzyl group , A complex in place of dimethylamino group, diethylamino group, etc., a complex of germanium bridge instead of silylene bridge corresponding to A in Y, M is hafnium instead of zirconium, R ¹ is substituted instead of substituted furyl group The thing of a thienyl group can also be illustrated.

2. Olefin Polymerization Catalyst The metallocene 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 the olefin polymerization catalyst described.

(1) Components of Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention includes the following components (A), (B) and (C).
Component (A): Metallocene complex represented by general formula [I] Component (B): Compound or ion-exchange layered silicate that reacts with component (A) to form an ion pair, preferably ion-exchange layered silicate Component (C): Organoaluminum compound

(2) About each component The metallocene complex represented by the general formula [I] of the component (A) may use two or more compounds represented by the same or different general formula [I].

  Examples of the component (B) compound that reacts with the component (A) to form an ion pair include an aluminum oxy compound, a boron compound, and an ion-exchange layered silicate, preferably an ion-exchange layered silicate. is there. These components (B) may be used alone or in combination of two or more.

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、各群内及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ＲｂＢ（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、Ｒｂ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 the aluminum oxy compound, it is well known that the aluminum oxy compound can activate the metallocene complex, and specific examples of such a compound include compounds represented by the following general formulas.

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 of the general formula is 10: 1 to 1: of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula RbB (OH) _2. 1 (molar ratio) reaction. In the general formula, Rb represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

  The boron compound may be a complex of a cation such as a carbonium cation or an ammonium cation with an organic boron compound such as triphenylboron, tris (3,5-difluorophenyl) boron, or tris (pentafluorophenyl) boron, or various types. Organic boron compounds such as tris (pentafluorophenyl) boron.

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 clay minerals, and often contain impurities other than ion-exchange layered silicates (such as quartz and cristobalite). 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 Montmorillonite, Sauconite, Beidellite, Nontronite, Saponite, Hectorite, Stevensite and other smectite groups; Vermiculite and other vermiculite groups; Pyrophyllite such as phyllite and talc-Talc group; Chlorite group such as magnesium chlorite 2: 1 Ribbon type minerals 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.
Silicates can change the solid acid strength by salt treatment and / or acid treatment. In the salt treatment, the surface area and interlayer distance can be changed by forming an ion complex, a molecular complex, an organic derivative, or the like. That is, by utilizing ion exchange properties and replacing exchangeable ions between layers with other large and bulky ions, a layered material in a state where the layers are expanded can be obtained.

The salt used for the ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of 1 to 14 atoms, and preferably selected from the group consisting of 1 to 14 atoms. And a compound comprising a cation containing at least one atom and an anion derived from at least one atom or atomic group selected from the group consisting of a halogen atom, an inorganic acid and an organic acid. Is a cation containing at least one atom selected from the group consisting of group 2 to 14 atoms, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₃ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ A _{C 2 H 4 O 4, C} 6 H 5 O 7 compound comprising at least one anion selected from the group consisting of. Two or more of these salts may be used simultaneously.
The acid used for the ion exchange is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and oxalic acid, and two or more of these may be used simultaneously. As a method of combining the salt treatment and the acid treatment, a method of performing the acid treatment after performing the salt treatment, a method of performing the salt treatment after performing the acid treatment, a method of performing the salt treatment and the acid treatment simultaneously, and performing a salt treatment. There is a method of performing salt treatment and acid treatment at the same time later.
The acid treatment has an effect of eluting part of cations such as Al, Fe, Mg, Li having a crystal structure in addition to the effect of ion exchange and removing impurities on the surface.

The treatment conditions with salts and acids are not particularly limited. However, usually, the salt and acid concentrations are 0.1 to 30% by weight, the treatment temperature is selected from the room temperature to the boiling point of the solvent used, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out under conditions for eluting parts. In addition, salts and acids are generally used in an aqueous solution.
When performing the above-described salt treatment and / or acid treatment, shape control may be performed by pulverization or granulation before treatment, between treatments, and after treatment. Further, other chemical treatments such as alkali treatment, organic compound treatment, and organometallic treatment may be used in combination.

As the component (B) thus obtained, the pore volume having a radius of 20 mm or more measured by a mercury intrusion method is preferably 0.1 cc / g or more, particularly 0.3 to 5 cc / g. When the component (B) is treated in an aqueous solution, it contains adsorbed water and interlayer water. Here, the adsorbed water is water adsorbed on the surface or crystal fracture surface of the ion-exchange layered compound or inorganic silicate, and the interlayer water is water existing between the crystal layers.
The silicate is preferably used after removing adsorbed water and interlayer water as described above. The dehydration method is not particularly limited, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. The heating temperature is a temperature range in which the adsorbed water and interlayer water do not remain, and is usually 100 ° C. or higher, preferably 150 ° C. or higher, but high temperature conditions that cause structural destruction are not preferable. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the weight loss of the component (B) after dehydration and drying is preferably 3% by weight or less as a value when sucked for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. In the present invention, when a silicate having a weight loss adjusted to 3% by weight or less is used, the same weight loss state is maintained even when contacting the component (A) and the component (C). It is preferable to handle them.

An example of the organoaluminum compound of component (C) 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 of the present invention, an aluminoxane such as methylaluminoxane can be used as the component (C) in addition to the organoaluminum compound represented by the above general formula. In addition, as the component (C), two or more of the above organoaluminum compounds may be used in combination, or the organoaluminum compound represented by the above general formula and an aluminoxane may be used in combination.

(3) Catalyst preparation method In the preparation method of the catalyst for olefin polymerization of the present invention, the contact method of the component (A) and the component (B) with the optional component (C) is not particularly limited, but the following method is used. Can be illustrated.
(1) Method of adding component (C) after contacting component (A) and component (B) (2) Adding component (B) after contacting component (A) and component (C) Method (3) Method of adding component (A) after contacting component (B) and component (C) (4) Each component (A), (B), (C) is contacted simultaneously.
Furthermore, you may use as a mixture with a different kind of component in each component, and you may change the order separately and may make it contact. In addition, you may perform this contact at the time of the prepolymerization by an olefin or the polymerization of an olefin not only at the time of catalyst preparation. A carrier may be allowed to coexist or contact as an optional component during or after the contact of each of the above components.
The contact of each of the components (A), (B), and (C) is preferably performed in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, and xylene in an inert gas such as nitrogen. The contact can be performed at a temperature between −20 ° C. and the boiling point of the solvent, and is preferably performed at a temperature between room temperature and the boiling point of the solvent.

In the olefin polymerization catalyst used in the present invention, the optional carrier is a particulate carrier made of an inorganic or organic compound and having a particle size of usually 5 μm to 5 mm, preferably 10 μm to 2 mm.
Examples of the inorganic carrier, for _{example, SiO 2, Al 2 O 3} , MgO, ZrO, TiO 2, B 2 O 3, oxides such as _{ZnO, SiO 2 -MgO, SiO 2} -Al 2 O 3, SiO 2 Examples include composite oxides such as —TiO ₂ , 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 aromatics such as styrene and divinylbenzene. Examples thereof include porous polymer fine particle carriers made of unsaturated 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 is suitable.

  In the polymerization catalyst of the present invention, the component (A), the component (B) and the component (C) are used in an optimum amount ratio in each combination. When component (B) is an aluminum oxy compound, the molar ratio of Al / metallocene compound 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 a boron compound 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, and more preferably 1 to 50. When using an ion exchange layered compound, it is 0.001-10 mmol of transition metal complexes per 1g of components, Preferably it is the range of 0.001-1 mmol. The amount of the component (C) used is an Al / metallocene compound molar ratio of 0.1 to 100,000, preferably 1 to 10,000. These use ratios show examples of normal ratios, and the present invention is not limited by the range of the use ratios described above as long as the catalyst meets the purpose.

  Before using a polyolefin production catalyst comprising a transition metal complex and a cocatalyst as a catalyst for olefin polymerization (main polymerization), ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4- A prepolymerization treatment for preliminarily polymerizing a small amount of an olefin such as methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane or styrene may be performed. A known method can be used as the prepolymerization method.

3. Olefin Polymerization Method (1) Polymerization Method As a polymerization process to which the olefin polymerization catalyst of the present invention is applied, a known olefin polymerization process can be used, and aliphatic hydrocarbons such as butane, pentane, hexane, heptane, isooctane, Slurries for polymerizing olefins in an inert solvent such as cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, gasoline fractions and hydrogenated diesel oil fractions. A polymerization method can be employed. In addition, a bulk polymerization method using olefins themselves as a solvent, or a gas phase polymerization method in which polymerization of olefins is performed in a gas phase can be employed. And the polymerization process which combined 2 or more types of these processes is also employable.
As a combination of the polymerization processes, a combination in which the first stage is performed by a gas phase polymerization method or a bulk polymerization method and the subsequent second stage is performed by a gas phase polymerization method is most preferable. It is also possible to use a solution polymerization method.

(2) Polymerization conditions The polymerization conditions using the olefin polymerization catalyst of the present invention are -50 to 150 ° C, preferably 20 to 120 ° C, more preferably 40 to 100 ° C as the polymerization temperature, and atmospheric pressure to 9 as the polymerization pressure. 0.9 MPa (gauge pressure), preferably 0.4 to 5.0 MPa (gauge pressure).
Further, if necessary, a chain transfer agent such as hydrogen may be introduced to adjust the molecular weight of the resulting olefin polymer.
After the completion of the polymerization reaction, unreacted monomers and hydrogen are separated from the polymerization system, and a catalyst deactivation treatment is performed to obtain an olefin polymer.

(3) Polymerization monomer In the present invention, “olefin” refers to an olefin having 2 to 20 carbon atoms, specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, Examples include 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene, styrene, vinylcyclohexane, diene, triene, and cyclic olefin.
In the present invention, “olefin other than propylene” similarly refers to olefins having 2 to 20 carbon atoms, specifically, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1 -Octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene and the like, and a mixture of two or more of these. In the present invention, the most preferably used olefin other than propylene is ethylene, 1-butene, or a mixture of ethylene and 1-butene.

4). Analysis of characteristic values of polymerized olefin 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, And the alpha olefin polymerization rate in CP is calculated | required with 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 sorter CFC T-100 manufactured by Dia Instruments Co., Ltd.
(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 the temperature 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) Sorting method:
The fractionation temperature at the time of temperature-raising elution fractionation is 40, 100, and 140 ° C., and the fraction is separated into three fractions in total. 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 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.
The standard polystyrenes used are all 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-purpose 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
The ethylene content distribution (distribution of ethylene content along the molecular weight axis) of each eluted component is the ratio of the absorbance of 2956 cm ⁻¹ and the absorbance of 2927 cm ⁻¹ obtained by GPC-IR, and is obtained by using polyethylene, polypropylene, or 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 formula (I), W40 and W100 are the elution ratios (unit: 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 directly contributes to the content of CP derived from fraction 1 in the 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 of fractions 1 to 3, A100, A140, the ethylene content of the 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, B40 can reasonably explain the effect of improving the material properties when the ethylene content corresponding to the peak position of the differential molecular weight distribution curve of fraction 1 is used. I understood. 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. Is closer to the actual situation, and almost no error occurs in the 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 at 40 ° C. (for example, most of CP, or components having extremely low molecular weight and atactic components among propylene polymer components (PP)) are fractionated. It has the meaning that it is a temperature condition necessary and sufficient to do. 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 an extremely high molecular weight and extremely high ethylene crystallinity in CP) The temperature is necessary and sufficient to elute only the component) and 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] However, [CP] is the CP content (% by weight) obtained 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 explain 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 constitution of the present invention and superiority over the prior art will be described. Demonstrate.
In the following examples, the complex synthesis step, the catalyst synthesis step, and the polymerization step were all performed in a purified nitrogen atmosphere, and the solvent was dehydrated and then degassed by bubbling with purified nitrogen.

(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 for 5 minutes on the conditions of a 2.16 kg load. 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:
Using DSC (TA2000 model manufactured by DuPont or DSC6200 model manufactured by Seiko Instruments Inc.), the temperature is raised and lowered once from 20 to 200 ° C. at 10 ° C./min, and then the second time at 10 ° C./min. It was determined from the measured value at the time of temperature rise.

[Example-1]
Synthesis of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (1) 4- (4- (1-adamantyl) phenyl ) -Indene synthesis To a 500 ml glass reaction vessel, 10 g (34 mmol) of 1- (4-bromophenyl) adamantane and 250 ml of dimethoxyethane (DME) were added and cooled to -40 ° C in a dry ice-methanol bath. To this, 47 ml (68 mmol) of a 1.45 mol / L t-butyllithium-n-pentane solution was added dropwise and stirred as it was for 3 hours. While being cooled at −40 ° C., 8 ml (35 mmol) of triisopropyl borate was added dropwise. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After hydrolyzing by adding 30 ml of distilled water to the reaction solution, 50 ml of an aqueous solution of 6 g of sodium carbonate, 6 g (31 mmol) of 4-bromoindene and 2 g (1.7 mmol) of tetrakistriphenylphosphinopalladium were added in this order to remove the low boiling point content. And heated at 80 ° C. for 5 hours.
After allowing to cool, the reaction solution was poured into 500 ml of distilled water, transferred to a separatory funnel and extracted three times with diethyl ether. The ether layer was washed with saturated brine, filtered through celite, and dried over sodium sulfate. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 8.9 g (yield 88%) of 4- (4- (1-adamantyl) phenyl) -indene as pale yellow crystals. .

(2) Synthesis of 2-bromo-4- (4- (1-adamantyl) phenyl) -indene 8.9 g (27 mmol) of 4- (4- (1-adamantyl) phenyl) -indene in a 500 ml glass reaction vessel Then, 2 ml of distilled water and 150 ml of DMSO were added, and 6 g (33 mmol) of N-bromosuccinimide was gradually added thereto. The mixture was stirred at room temperature for 2 hours, poured into 300 ml of ice water, and extracted three times with 100 ml of toluene. The toluene layer was washed with saturated brine, 0.5 g (3 mmol) of p-toluenesulfonic acid was added, and the mixture was heated to reflux for 6 hours while removing moisture. The reaction mixture was allowed to cool, washed with saturated brine, and dried over sodium sulfate. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column. )

(3) Synthesis of 2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indene In a 500 ml glass reaction vessel, 1.9 g (24 mmol) of 2-methylfuran , 100 ml of DME was added and cooled to −40 ° C. in a dry ice-methanol bath. To this, 15 ml (24 mmol) of a 1.58 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred as it was for 3 hours. While being cooled to −40 ° C., 6 ml (26 mmol) of triisopropyl borate was added dropwise. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
The reaction solution was hydrolyzed by adding 10 ml of distilled water, 30 ml of an aqueous solution of 5 g of sodium carbonate, 7.7 g (19 mmol) of 2-bromo-4- (4- (1-adamantyl) phenyl) -indene, tetrakistriphenylphosphino Palladium 2 g (1.7 mmol) was sequentially added to remove the low boiling point, and then heated at 80 ° C. for 3 hours.
After allowing to cool, the reaction solution was poured into 300 ml of distilled water, transferred to a separatory funnel and extracted three times with diethyl ether. The ether layer was washed with saturated brine, filtered through Celite, and dried over sodium sulfate. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to give pale yellow 2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indene. 5.0 g of crystals (yield 65%) were obtained.

(4) Synthesis of dimethylbis (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) silane In a 300 ml glass reaction vessel, 2- (2- (5-Methylfuryl))-4- (4- (1-adamantyl) phenyl) -indene (5.0 g, 12 mmol) and THF (100 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. To this was added dropwise 7.8 ml (12 mmol) of a 1.58 mol / L n-butyllithium-hexane solution, and the mixture was stirred as it was for 3 hours. While cooling at −70 ° C., 50 μl (0.6 mmol) of 1-methylimidazole and 0.7 ml (6 mmol) of dimethyldichlorosilane were sequentially added, and the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel and washed with brine until neutral, and sodium sulfate was added to dry the reaction solution. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column. Dimethylbis (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl ) 4.4 g (82% yield) of a light red solid of silane was obtained.

(5) Synthesis of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride Into a 200 ml glass reaction vessel, dimethylbis ( 2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) silane (3.9 g, 4.5 mmol) and diethyl ether (100 ml) were added, and the mixture was added in a dry ice-methanol bath. Cooled to -70 ° C. To this was added dropwise 5.7 ml (9.0 mmol) of a 1.58 mol / L n-butyllithium-n-hexane solution. After dropping, the temperature was returned to room temperature and stirred for 2 hours. The solvent of the reaction solution was distilled off under reduced pressure, 100 ml of toluene and 10 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 1.0 g (4.3 mmol) of zirconium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallized from dichloromethane-hexane, and dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride. Was obtained as yellow-orange crystals (yield 45%).
¹ H-NMR value (CDCl ₃ ) Racemate: δ 1.14 (s, 6H), δ 1.76 (t, 12H), δ 1.93 (s, 12H), δ 2.09 (s, 6H), δ2. 42 (s, 6H), δ 6.05 (d, 2H), δ 6.26 (d, 2H), δ 6.79 (dd, 2H), δ 6.91 (d, 2H), δ 7.08 (s, 2H) ), Δ 7.31 (d, 2H), δ 7.41 (d, 4H), δ 7.59 (d, 4H).

(6) Chemical treatment of ion-exchange layered silicate Acid treatment: 1130 g of distilled water and 750 g of 96% sulfuric acid are added to a separable flask, the internal temperature is kept at 90 ° C., and granulated montmorillonite made by Mizusawa Chemical Co., Ltd. Benclay SL (average particle size 19 μm, 300 g) was added and reacted for 2 hours. The suspension was cooled to room temperature in 1 hour and washed with distilled water to pH = 4. The washing magnification at this time was 1/10000 or less.
Salt treatment: 210 g of lithium sulfate monohydrate was dissolved in 520 g of distilled water in a separable flask, and filtered acid-treated clay was added thereto and stirred at room temperature for 120 minutes. The slurry was filtered, 3000 ml of distilled water was added to the obtained solid, and the mixture was stirred for 5 minutes at room temperature. The slurry was filtered. To the obtained solid, 2500 ml of distilled water was added, stirred for 5 minutes, and then filtered again. This operation was repeated four more times. The obtained solid was pre-dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, followed by drying under reduced pressure at 200 ° C. for 2 hours to obtain chemically treated montmorillonite. Obtained.
The composition of this chemically treated montmorillonite is Al: 7.5 wt%, Si: 37.6 wt%, Mg: 1.22 wt%, Fe: 1.60 wt%, Li: 0.22 wt%, and Al / Si = 0. It was 207 [mol / mol].

(7) Preparation of catalyst using dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride (Catalyst A)
10.0 g of the chemically treated montmorillonite obtained above was weighed into a 1 L flask, 65 ml of heptane and 35 ml (25 mmol) of a heptane solution of triisobutylaluminum were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the residue was washed with heptane to a residual liquid ratio of 1/100, and finally the amount of slurry was adjusted to 100 ml. To this, 1.67 ml (1.2 mmol) of a heptane solution of triisobutylaluminum was added and stirred for 10 minutes at room temperature. Further, a solution of 314 mg (305 μmol) of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride in 60 ml of toluene was added at room temperature. Stir for minutes.
Next, 340 ml of heptane was added to the above heptane slurry, introduced into a stirring autoclave having an internal volume of 1 L, and propylene was supplied at 40 ° C. at a constant rate of 10 g / hour for 120 minutes. After completion of the propylene supply, the temperature was raised to 50 ° C. and maintained for 2 hours. Thereafter, the residual 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, 8.5 ml (6.0 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 29.1 g of a solid catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.81.

[Example-2]
(Propylene-propylene / ethylene block copolymerization with catalyst A)
After sufficiently replacing the inside of the stirred autoclave with an internal volume of 3 L with propylene, 2.76 ml (2.02 mmol) of an n-heptane solution of triisobutylaluminum was added, and 400 ml of hydrogen and then 750 g of liquid propylene were introduced. The temperature was raised to 65 ° C. and the temperature was maintained. Catalyst A was slurried in n-heptane, and 30 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. The temperature inside the tank was maintained at 65 ° C., and after 1 hour from the addition of the catalyst, the remaining monomer was purged, and the inside of the tank was replaced with argon. Stirring was stopped, and while flowing argon, a Teflon (registered trademark) tube was inserted into the tank, and a small amount of polypropylene was extracted. The extracted amount was 13.6 g.
Thereafter, propylene was introduced to 0.76 MPa at an internal temperature of 60 ° C., and then ethylene was introduced to 1.8 MPa to raise the internal temperature to 80 ° C. Thereafter, a pre-prepared mixed gas of propylene and ethylene 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 significantly during the polymerization. As a result, 215.6 g of propylene-propylene • ethylene block copolymer having good particle properties was obtained. The average gas mol composition in the tank during the polymerization of propylene and ethylene was propylene / ethylene = 33/67.
From the result of CFC-IR, the block copolymer obtained above had a rubber content (CP content) of 15.4 wt%, and the ethylene content in rubber (CP) was 50.4 wt% (60.4 mol). %) And the weight average molecular weight (Mw) of the CP part was 226,000, and the MFR was 113 (dg / min). Moreover, Tm of propylene homopolymer collected separately was 154 ° C. and MFR was 224 (dg / min).

[Example-3]
(Propylene-propylene / ethylene block copolymerization with catalyst A)
The same operation as in Example-2 was performed except that the average gas mol composition in the tank at the time of propylene / ethylene polymerization was adjusted to be propylene / ethylene = 41/59. As a result, 218.4 g of propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above had a CP content of 10.7 wt%, an ethylene content in CP of 39.0 wt% (49.0 mol%), and an MFR of 208 (Dg / min), and the weight average molecular weight (Mw) of the CP part was 155,000. The amount of the separately collected propylene homopolymer was 15.2 g. Tm was 154 ° C. and MFR was 290 (dg / min).

[Comparative Example-1]
Preparation of catalyst using dimethylsilylenebis (2-methyl-4-phenyl-indenyl) zirconium dichloride (Catalyst B)
Dimethylsilylenebis (2-methyl-4-phenyl-indenyl) instead of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4- (1-adamantyl) phenyl) -indenyl) zirconium dichloride ) Zirconium dichloride (synthesized with reference to the method described in Organometallics 1994, 13, 954-963, and a racemate (purity 99% or more) was used for catalyst preparation) Example -1 except that 186 mg (300 μmol) was used -Catalyst B was obtained in the same manner as (7). The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.11.

[Comparative Example-2]
Propylene-propylene / ethylene block copolymerization with catalyst B After the inside of the stirred autoclave with an internal volume of 3 L was sufficiently substituted with propylene, 2.76 ml (2.02 mmol) of n-heptane solution of triisobutylaluminum was added, 90 ml of hydrogen and then 750 g of liquid propylene were introduced, and the temperature was raised to 65 ° C. to maintain the temperature. Catalyst B was slurried in n-heptane, and 30 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. The temperature inside the tank was maintained at 65 ° C., and after 1 hour from the addition of the catalyst, the remaining monomer was purged, and the inside of the tank was replaced with argon. Stirring was stopped, and while flowing argon, a Teflon (registered trademark) tube was inserted into the tank, and a small amount of polypropylene was extracted. The extracted amount was 51.1 g.
Thereafter, propylene was introduced to 0.53 MPa at an internal temperature of 40 ° C., and then ethylene was introduced to 1.4 MPa to raise the internal temperature to 65 ° C. Thereafter, a pre-prepared mixed gas of propylene and ethylene was introduced, and the polymerization reaction was controlled for 30 minutes while adjusting the internal pressure to 1.5 MPa so that the monomer composition ratio did not change significantly during the polymerization. As a result, 237.1 g of a propylene-propylene • ethylene block copolymer was obtained. The average gas mol composition in the tank during propylene / ethylene polymerization was propylene / ethylene = 35/65.
From the results of CFC-IR, the block copolymer obtained above had a CP content of 53.9 wt%, an ethylene content in CP of 35.7 wt% (45.4 mol%), and an MFR of 20 (Dg / min), and the weight average molecular weight (Mw) of the CP part was 55,000. Moreover, Tm of the propylene homopolymer collected separately was 149 ° C., and MFR was 0.39 (dg / min).

[Comparative Example-3]
Propylene-propylene / ethylene block copolymerization with catalyst B
The same operation as in Comparative Example-2 was performed except that the average gas mol composition in the tank at the time of propylene / ethylene polymerization was adjusted to be propylene / ethylene = 46/54. As a result, 204.7 g of a propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above had a CP content of 30.0 wt%, an ethylene content in CP of 23.8 wt% (31.9 mol%), and an MFR of 6 .4 (dg / min), and the weight average molecular weight (Mw) of the CP part was 48,000. The amount of the separately collected propylene homopolymer was 51.5 g. Tm was 149 ° C. and MFR was 0.46 (dg / min).
As a result of the above, Table 1 collectively shows the polymerization results described in each Example and each Comparative Example.

[Consideration by comparison of results of Examples and Comparative Examples]
As described above, by using the metallocene catalyst using the metallocene compound of the present invention, the ethylene incorporation efficiency of the copolymer portion (CP) in the polyolefin block copolymer (the ethylene in the CP relative to the amount of ethylene gas supplied). It has been clarified that a block copolymer having a copolymer part (rubber component) having a molecular weight of a much higher content than that of the conventional catalyst and a much higher molecular weight than that of the conventional catalyst can be produced. Yes.
Therefore, the rationality and significance of the configuration requirements in the present invention, and the superiority of the present invention over the prior art are clarified.

Claims (5)

A metallocene compound represented by the following general formula [I].

[ Wherein , M is titanium, zirconium, or hafnium, Y is R ²⁰ ₂ A (A is germanium or silicon, and R ²⁰ may be the same as or different from each other, hydrogen, carbon number An alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms, A divalent bridging group represented by the following formula: a 4- to 7-membered ring containing A may be formed on both adjacent R ^{20 s} , and an unsaturated bond may be contained on a 5- to 7-membered ring ; ¹ and X ² are each independently any one of fluorine, chlorine, bromine, iodine, methyl, i-butyl, phenyl, benzyl, dimethylamino, and diethylamino .
R ¹ and R ¹¹ may be the same or different from each other, and are hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. -6 silicon-containing alkyl group, aryl group having 6-18 carbon atoms or halogen-containing aryl group having 6-18 carbon atoms, alkyl group having 1-6 carbon atoms, alkenyl group having 2-6 carbon atoms, carbon number 1 to 6 halogen-containing alkyl group, 1 to 6 silicon-containing alkyl group, 6 to 18 aryl group, or 6 to 18 halogen-containing aryl group. And a heterocyclic group constituting a 5-membered ring (however, a heteroatom of the heterocyclic group constituting the 5-membered ring is not directly bonded to the alkadienyl group). One or both of R ¹ and R ¹¹ are always an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is a heterocyclic group constituting a 5-membered ring which may have any substituent of a silicon-containing alkyl group, an aryl group having 6 to 18 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms .
R ⁴ and R ¹⁴ may be the same or different from each other, and are hydrogen, an alkyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, a silicon-containing alkyl group having 1 to 6 carbon atoms, carbon C2-C6 alkenyl group, C6-C18 aryl group or C6-C18 halogen-containing aryl group, C1-C6 alkyl group, C2-C6 alkenyl group, C1-C1 A halogen-containing alkyl group having 6 to 6 carbon atoms, a silicon-containing alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms. Further, it may be a heterocyclic group constituting a 5-membered ring or 6-membered ring, an adamantyl group or an adamantyl group substituted with any of a methyl group, a phenyl group and a halogen . One or both of R ⁴ and R ¹⁴ is always an adamantyl group or an adamantyl group substituted with any of a methyl group, a phenyl group, and a halogen .
R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ may be the same or different from each other. Well, hydrogen, C1-C6 alkyl group, C2-C6 alkenyl group, C1-C6 halogen-containing alkyl group, C1-C6 silicon-containing alkyl group, C6-C18 An aryl group or a C6-C18 halogen-containing aryl group, or a C1-C6 alkyl group, a C2-C6 alkenyl group, a C1-C6 halogen-containing alkyl group, a C1-C6 Heterocycle constituting a 5-membered ring or 6-membered ring which may have any substituent of a silicon-containing alkyl group, an aryl group having 6 to 18 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms It is a group. Moreover, 6-7 membered ring may be comprised by both adjacent R, and the 6-7 membered ring may contain the unsaturated bond. ] In general formula [I], M is zirconium or hafnium, and one or both of R ¹ and R ¹¹ is a furyl group or a thienyl group substituted with any of a methyl group, a phenyl group, and a halogen. The metallocene compound according to claim 1, wherein An olefin polymerization catalyst containing the following components (A), (B), and (C).
Component (A): Metallocene compound described in claim 1 or claim 2 (B): Compound that reacts with component (A) to form an ion pair or ion-exchange layered silicate component (C): Organic Aluminum compound The catalyst for olefin polymerization according to claim 3, wherein the component (B) is an ion-exchange layered silicate and the olefin is propylene. An olefin polymerization method, wherein the olefin polymerization or copolymerization is carried out using the olefin polymerization catalyst according to claim 3 or 4 .