JP5271464B2 - Metallocene compound and olefin polymerization catalyst using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a metallocene catalyst for olefin polymerization, which produces a high-melting polypropylene resin, exhibits reactivity having a balanced reactivity between propylene and a copolymerizable monomer and provides a high-molecular-weight copolymer part in copolymerizing propylene with ethylene or an &alpha;-olefin. <P>SOLUTION: The metallocene compound is represented by formula [I]. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a novel metallocene compound and an olefin polymerization catalyst using the same, and more specifically, a polypropylene having a high melting point can be produced, and a propylene block copolymer having a high molecular weight in a copolymer part. A novel metallocene compound that forms a polymer for olefin polymerization and is capable of producing a polymer, has good uptake efficiency of ethylene and α-olefin as a copolymerization monomer, and can further produce a polymer with good particle properties It is.

Polyolefin resins are excellent in physical properties, molding processability, basic performance such as economy and adaptability to environmental problems, and are therefore frequently used as basic resin materials in the industry.
In particular, polyethylene resins and polypropylene resins are widely used as industrial materials in various technical fields as main raw materials in polyolefin resins, and since they are outstanding and important raw materials, further improvements in various performances are always required.

For example, polypropylene resin is excellent in rigidity and heat resistance, but generally lacks flexibility and impact resistance. Therefore, in order to improve flexibility and impact resistance, propylene homopolymer and ethylene-propylene rubber are used. Have been widely implemented for a long time, such as a method of adding an elastomer component to form a composition and a method of producing a so-called block copolymer by multistage polymerization in which propylene and ethylene or α-olefin are copolymerized after homopolymerization of propylene. Has been.
Polypropylene resin has been produced industrially on a large scale with Ziegler catalysts. Metallocene catalysts have been developed since then, and metallocene catalysts have higher catalytic activity than Ziegler catalysts and have a unique stereoregulation. Therefore, it is more important than Ziegler catalysts because it can produce polypropylene resins and the like having a narrow molecular weight distribution.

As a major improvement in polypropylene resin, the copolymerization performance of propylene is further improved in order to obtain a higher molecular weight polymer or to further increase the melting point, stereoregularity and particle properties of the polymer. In order to do so, improvements in the complex structure of metallocene catalysts have been continued.
That is, in the metallocene complex, 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, and a cocatalyst and a support are employed. Alternatively, an indenyl ring or a fluorenyl ring is used instead of the conjugated 5-membered ring, and the conjugated ring is asymmetrically arranged so that the conjugated ring is provided with various specific substituents, and a plurality of substituents are further condensed. A number of improved catalysts have been developed and the results of improvements in polypropylene resin and catalyst function have been clarified.

And in the propylene-ethylene block copolymer which improves the softness | flexibility and impact resistance of polypropylene resin, in order to improve the rigidity of a copolymer, the metallocene compound which provides the polypropylene component which has high melting | fusing point is disclosed. (See, for example, Patent Documents 1 and 2), when copolymerization of propylene and ethylene or α-olefin is carried out using a catalyst comprising these metallocene compounds, the reactivity of ethylene or α-olefin is reduced to that of propylene. The problem is that it is relatively low compared to reactivity. In other words, in order to obtain a copolymer having a desired ethylene or α-olefin content, it is necessary to supply a gas raw material with a monomer ratio greatly different from the content in the copolymer and polymerize. There is a problem in the process, and in a more extreme case, a copolymer having a desired copolymer component content may not be produced.
For such problems, for example, it has been proposed that the reactivity of propylene and the reactivity of ethylene or α-olefin can be changed by changing the metallocene compound used (for example, Patent Document 3 and Non-Patent Document 1). No metallocene compound that satisfies both 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. Each content of the copolymer preferably satisfies a specific range (for example, see Non-Patent Document 2). Therefore, the performance of the catalyst in the production process requires that the reactivity of propylene and the 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 highly 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). Since the ethylene-propylene polymer component of the polymer has a low molecular weight, it may be difficult to obtain satisfactory results because it may not provide the desired performance such as stickiness and high impact resistance.
Therefore, in order to develop high impact resistance in the propylene-ethylene block copolymer, it is necessary that the molecular weight of the copolymer portion has a certain value or more, and a copolymer portion having a higher molecular weight is required. Metallocene catalysts that can be produced are also desired.

JP 11-240909 A (summary) JP 2000-95791 A (summary) WO 2004-87775 gazette (summary and claim 10) JP 2004-2259 A (Abstract and Claims 1 and 2 of Claims)

Journal of the American Chemical Society 2001 123 123 9,555 Polymer 2001 Volume 42 Page 9,611

  In view of the background art outlined in paragraphs 0005 to 0006, in polypropylene resin materials that are widely used and widely used in many industrial fields, polypropylene resins having superior physical properties such as a high melting point can be produced. When copolymerizing propylene and ethylene or α-olefin, the polymerization reactivity of ethylene or α-olefin is balanced with the polymerization reactivity of propylene, and at that time, a high molecular weight of the copolymer portion is obtained. In order to solve such a problem, the present invention can produce a high melting point polypropylene resin, and in the copolymerization of propylene with ethylene or α-olefin. Providing a balanced reactivity of propylene and giving high molecular weight copolymer parts In which it aims to develop olefin polymerization metallocene catalysts.

In order to solve the problems of the present invention, the present inventors developed a novel metallocene catalyst as described above, and the complex structure of the transition metal compound as the metallocene compound in the metallocene polymerization catalyst is attributed to its basic skeleton. Polypropylene resin obtained in consideration of empirical rules from the viewpoint of the reactivity of transition metal compounds, the steric effect and electronic environment of the substituents of transition metal compounds, and their influence on the coordination of the resulting polymer Searching for various methods and conducting experimental searches for high melting point, improving the balance between ethylene or α-olefin reactivity and propylene reactivity and improving the molecular weight of the copolymer part It was.
By the way, the present inventors have previously developed a metallocene catalyst for olefin polymerization that exhibits a balanced reactivity of ethylene or α-olefin and propylene in the copolymerization of propylene and gives a high molecular weight copolymer portion. In addition, in the complex structure of the transition metal compound as the metallocene compound in the metallocene polymerization catalyst, the same investigation as described above was conducted, and a 5-membered heterocyclic group was present at the 2-position of the indenyl ring and the para-position at the 4-position. When a novel metallocene complex having a specific specific steric and electronic environment structure with a substituted adamantyl group phenyl group is formed, it exhibits a balanced reactivity of ethylene or α-olefin and propylene. At this time, the fact that a catalytic function that brings about a high molecular weight to the copolymer portion is revealed is found, and the invention has been put forward as a prior invention. It has just been requested (Japanese Patent Application No. 2006-164340).

  Based on the results of the invention of the prior application, the present inventors conducted the above-mentioned various considerations and experimental searches, and newly developed a metallocene complex having a specific specific steric and electronic environment structure. In addition, a high melting point of the polypropylene resin can be achieved, and at the same time, a balanced reactivity of ethylene or α-olefin and propylene is exhibited, and at that time, a catalytic function that brings a high molecular weight to the copolymer part. As a result of further consideration of model compounds and experimental demonstrations, we have found new metallocene compounds that are very useful as catalyst components and led to the creation of the present invention. It was.

Thus, the metallocene metal complex 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, which requires a novel transition metal compound. Can produce a polypropylene resin having a higher melting point, exhibiting a balanced reactivity of ethylene or α-olefin (α-olefin having about 4 to 20 carbon atoms) and propylene, and a copolymer at that time Catalytic functions that bring about even higher molecular weights are 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 a catalyst for olefin polymerization.

［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のアリール基若しくは炭素数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、燐原子若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、炭素数６〜１８のアリール基、炭素数６〜１８のハロゲン含有アリール基、又は置換基を有していてもよい５員環若しくは６員環で構成する複素環基（但し、５員環若しくは６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。
Ｒ³，Ｒ⁵，Ｒ¹³，Ｒ¹⁵は、互いに同じでも異なっていてもよく、塩素、フッ素、炭素数１〜６のアルキル基、炭素数１〜６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である。
Ｒ², Ｒ⁴, Ｒ⁶, Ｒ⁷, Ｒ⁸, Ｒ⁹, Ｒ¹², Ｒ¹⁴, Ｒ¹⁶,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１〜６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、炭素数６〜１８のハロゲン含有アリール基、又は置換基を有していてもよい５員環若しくは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. A divalent methylene group, a divalent methylene group, a divalent bridging group containing 6-18 carbon atoms or a halogenated aryl group having 6-18 carbon atoms in the skeleton, or a silicon atom, germanium atom, oxygen atom, nitrogen atom, phosphorus atom or boron It is a divalent bridging group containing an 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 as or different from each other, and a 6- to 18-carbon aryl group, a 6- to 18-halogen-containing aryl group, or a 5-membered ring which may have a substituent, A heterocyclic group composed of a 6-membered ring (provided that a hetero atom of a 5-membered ring or a heterocyclic group constituting a 6-membered ring is not directly bonded to an 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 ³ , R ⁵ , R ¹³ and R ¹⁵ may be the same or different from each other, and are chlorine, fluorine, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. A halogen-containing alkyl group, 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.
R ² , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ may be the same as or different from each other, and represent hydrogen, carbon number An alkyl group having 1 to 6 carbon atoms, an alkenyl 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, an aryl group having 6 to 18 carbon atoms, and 6 carbon atoms It is a heterocyclic group constituting a 18-halogen-containing aryl group or a 5-membered or 6-membered ring optionally having 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 always has a specific substituent at the 3,5-position of the phenyl substituent at the 4-position of both indenyl rings (R ³ , R ⁵ , R ¹³ , R ¹⁵ ), The 2-position of the indenyl ring is an aryl group, a halogen-containing aryl group, a heterocyclic group or a substituted heterocyclic group (R ¹ , R ¹¹ ), and one or both of the 2-positions are a heterocyclic group or a substituted heterocyclic ring It is a novel compound characterized by necessarily having a group, and a plurality of sterically and electronically environment-specific substituents are arranged on the indenyl ring to form a chemically, sterically and electronically environment-specific structure. Forming a complex.
By using the metallocene compound of the present invention as a catalyst component for olefin polymerization, a polypropylene resin having a higher melting point can be produced, and when a propylene-based block copolymer is produced, the molecular weight of the copolymer portion is higher than that of the conventional catalyst. The higher the incorporation efficiency of ethylene or α-olefin into the copolymer, and the balanced reactivity of ethylene or α-olefin and propylene as demonstrated by the comparison of Examples and Comparative Examples below. Thus, it is possible to realize a metallocene catalyst for olefin polymerization, which can produce a polymer having a high molecular weight of a copolymer part and additionally having a good particle property.
Furthermore, in the present invention, incidentally, in the metallocene compound of the present invention, the 2-position substituent of the indenyl ring is converted to an aryl group, a halogen-containing aryl group, a heterocyclic group or a substituted heterocyclic group. In this case, a racemate is produced with a selectivity of 85% or more and separation is easy, so that a complex can be obtained in a high yield.

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, R ¹ and R ¹¹ are a furyl group or a thienyl group which may have a substituent, and X ¹ and X ² may be the same or different, and are a halogen atom or an alkyl having 1 to 6 carbon atoms. It is a group. In the present invention, “component (A): metallocene compound, component (B): compound that reacts with component (A) to form an ion pair, or an ion-exchange layered silicate or inorganic silicate component (C): Comprising an organoaluminum compound ", preferably the component (B) is an ion-exchange layered silicate, the olefin is propylene, and further using such an olefin polymerization catalyst It is also an olefin polymerization method characterized by performing polymerization or copolymerization.

By the way, as disclosed in the present invention, the phenyl substituent in the 4-position of both indenyl rings always has a specific substituent at the 3,5-position, and the 2-position of the indenyl ring is an aryl group, It is a halogen-containing aryl group, heterocyclic group or substituted heterocyclic group, and one or both of the 2-positions is a novel compound characterized by having a heterocyclic group or a substituted heterocyclic group. A metallocene compound having a chemical, steric, and electronic environment specific structure by arranging a plurality of substituents specific to the environment and the electronic environment is disclosed in each patent document and non-patent document described in the background art. Even if we scrutinize literatures and other patent literatures, we cannot find them.
As a related metallocene compound, a compound having an indenyl skeleton in which a furyl group is substituted at the 2-position and a phenyl group is arranged at the 4-position is disclosed in Patent Document 4 (Claim 2 of JP-A-2004-2259). Although illustrated, nothing is described about the substituent at the 3,5-position of the phenyl group.
In other patent documents, metallocene compounds having a phenyl group at the 4-position of the indenyl ring and having substituents at both the 3- and 5-positions of the phenyl group are merely described (Japanese Patent Publication No. 2004-502698). Japanese Patent Publication No. 2004-502699 and each claim 2), nothing which simultaneously has a heterocyclic group constituting a 5-membered ring at the 2-position of indenyl is disclosed.

  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], and [2] each of the following inventions adds an additional requirement to the basic invention or shows an embodiment thereof. . 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のアリール基若しくは炭素数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、燐原子若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、炭素数６〜１８のアリール基、炭素数６〜１８のハロゲン含有アリール基、又は置換基を有していてもよい５員環若しくは６員環で構成する複素環基（但し、５員環若しくは６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。
Ｒ³，Ｒ⁵，Ｒ¹³，Ｒ¹⁵は、互いに同じでも異なっていてもよく、塩素、フッ素、炭素数１〜６のアルキル基、炭素数１〜６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である。
Ｒ², Ｒ⁴, Ｒ⁶, Ｒ⁷, Ｒ⁸, Ｒ⁹, Ｒ¹², Ｒ¹⁴, Ｒ¹⁶,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１〜６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、炭素数６〜１８のハロゲン含有アリール基、又は置換基を有していてもよい５員環若しくは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］一般式［Ｉ］中において、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１〜６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Ｒ¹¹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］一般式［Ｉ］中において、Ｘ¹とＸ²は、同じでも異なっていてもよく、ハロゲン原子、又は炭素数１〜６のアルキル基であることを特徴とする、［１］〜［３］のいずれかにおけるメタロセン化合物。
［５］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］〜［４］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若しくは無機珪酸塩
成分（Ｃ）：有機アルミニウム化合物
［６］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を必須とすることを特徴とする、［５］におけるオレフィン重合用触媒。
［７］［５］又は［６］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. A divalent methylene group, a divalent methylene group, a divalent bridging group containing 6-18 carbon atoms or a halogenated aryl group having 6-18 carbon atoms in the skeleton, or a silicon atom, germanium atom, oxygen atom, nitrogen atom, phosphorus atom or boron It is a divalent bridging group containing an 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 as or different from each other, and a 6- to 18-carbon aryl group, a 6- to 18-halogen-containing aryl group, or a 5-membered ring which may have a substituent, A heterocyclic group composed of a 6-membered ring (provided that a hetero atom of a 5-membered ring or a heterocyclic group constituting a 6-membered ring is not directly bonded to an 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 ³ , R ⁵ , R ¹³ and R ¹⁵ may be the same or different from each other, and are chlorine, fluorine, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. A halogen-containing alkyl group, 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.
R ² , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ may be the same as or different from each other, and represent hydrogen, carbon number An alkyl group having 1 to 6 carbon atoms, an alkenyl 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, an aryl group having 6 to 18 carbon atoms, and 6 carbon atoms It is a heterocyclic group constituting a 18-halogen-containing aryl group or a 5-membered or 6-membered ring optionally having 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] In general formula [I], Y is R ²⁰ ₂ A (A is germanium or silicon, R ²⁰ may be the same as or different from each other, hydrogen, alkyl having 1 to 6 carbon atoms, group, an alkenyl group having 1 to 6 carbon atoms, 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. in the adjacent R ²⁰ both A 4- to 7-membered ring containing A may be formed, and a 5- to 7-membered ring may contain an unsaturated bond. ] The metallocene compound in this.
[3] In the general formula [I], M is zirconium or hafnium, and R ¹ and R ¹¹ are a furyl group or a thienyl group which may have a substituent, Metallocene compound in [1] or [2].
[4] In the general formula [I], X ¹ and X ² may be the same or different and are a halogen atom or an alkyl group having 1 to 6 carbon atoms, The metallocene compound according to any one of [3].
[5] An olefin polymerization catalyst containing the following components (A), (B), and (C).
Component (A): Metallocene compound in any one of [1] to [4] Component (B): Compound that reacts with component (A) to form an ion pair or ion-exchangeable layered silicate or inorganic silicate Component ( C): Organoaluminum compound [6] The catalyst for olefin polymerization according to [5], wherein the component (B) is an ion-exchange layered silicate and the olefin essentially requires propylene.
[7] A method for polymerizing olefins, wherein the olefin polymerization or copolymerization is carried out using the olefin polymerization catalyst according to [5] or [6].

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. Forms a catalyst for polymerization, can produce high melting point polypropylene resin, and when propylene is copolymerized with ethylene or α-olefin, propylene and copolymerized monomer have a balanced reactivity As a result, it is realized that a gas having a monomer ratio that is not substantially different from the content in the copolymer is rationally supplied in the production process for polymerization, and in that case, the copolymer portion has a high molecular weight. The catalytic function that brings about
In addition, it is possible to produce a polymer having good particle properties, and furthermore, when complexed, a racemate is produced with a selectivity of 85% or more and separation is easy, so that the complex can be produced in a high yield. Can be obtained.

  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のアリール基若しくは炭素数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、燐原子若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、炭素数６〜１８のアリール基、炭素数６〜１８のハロゲン含有アリール基、又は置換基を有していてもよい５員環若しくは６員環で構成する複素環基（但し、５員環若しくは６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。
Ｒ³，Ｒ⁵，Ｒ¹³，Ｒ¹⁵は、互いに同じでも異なっていてもよく、塩素、フッ素、炭素数１〜６のアルキル基、炭素数１〜６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である。
Ｒ², Ｒ⁴, Ｒ⁶, Ｒ⁷, Ｒ⁸, Ｒ⁹, Ｒ¹², Ｒ¹⁴, Ｒ¹⁶,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１〜６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、炭素数６〜１８のハロゲン含有アリール基、又は置換基を有していてもよい５員環若しくは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. A divalent methylene group, a divalent methylene group, a divalent bridging group containing 6-18 carbon atoms or a halogenated aryl group having 6-18 carbon atoms in the skeleton, or a silicon atom, germanium atom, oxygen atom, nitrogen atom, phosphorus atom or boron It is a divalent bridging group containing an 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 as or different from each other, and a 6- to 18-carbon aryl group, a 6- to 18-halogen-containing aryl group, or a 5-membered ring which may have a substituent, A heterocyclic group composed of a 6-membered ring (provided that a hetero atom of a 5-membered ring or a heterocyclic group constituting a 6-membered ring is not directly bonded to an 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 ³ , R ⁵ , R ¹³ and R ¹⁵ may be the same or different from each other, and are chlorine, fluorine, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. A halogen-containing alkyl group, 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.
R ² , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ may be the same as or different from each other, and represent hydrogen, carbon number An alkyl group having 1 to 6 carbon atoms, an alkenyl 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, an aryl group having 6 to 18 carbon atoms, and 6 carbon atoms It is a heterocyclic group constituting a 18-halogen-containing aryl group or a 5-membered or 6-membered ring optionally having 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) Features of the metallocene compound The feature of the metallocene compound of the present invention is that, in the 3rd and 5th positions of the phenyl substituent at the 4-position of one or both indenyl rings, chlorine, fluorine, an alkyl group having 1 to 6 carbon atoms, An alkenyl 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, an aryl group having 6 to 18 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms The 2-position of the indenyl ring is necessarily an aryl group, a halogen-containing aryl group, a heterocyclic group or a substituted heterocyclic group, and one or both of the 2-positions are a heterocyclic group or a substituted group. A novel compound that necessarily has a heterocyclic group, and has a plurality of substituents that are sterically and electronically specific in the indenyl ring, and has a structure that is chemically, sterically and electronically specific. form To do.
By using the metallocene compound of the present invention as a catalyst component for olefin polymerization, a polypropylene having a high melting point can be produced, and when a propylene-based block copolymer is produced, the molecular weight of the copolymer portion is higher than that of the conventional catalyst. In addition, the incorporation efficiency of ethylene or α-olefin in the copolymer is increased. In addition, a polymer having good particle properties can be produced.
In general, isomers such as racemates and meso isomers are formed at about 1: 1 during complex synthesis. Usually, however, racemic isomers are used as propylene polymerization catalysts, and racemates are obtained from racemic / meso isomer mixtures. It is necessary to separate. However, in the metallocene compound of the present invention, when the 2-position substituent of the indenyl ring is an aryl group, a halogen-containing aryl group, a heterocyclic group or a substituted heterocyclic group, the racemate is 85% or more when complexed. The complex can be obtained in a high yield because it is produced with the selectivity of and is easily separated.

(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 is preferably crosslinked with silicon or germanium atoms. Preferred examples include dimethylsilylene, diethylsilylene, di-n-propylsilylene, dii -Propylsilylene, di-n-butylsilylene, methylethylsilylene, methyln-butylsilylene, ethyl n-butylsilylene, divinylsilylene, diphenylsilylene, ditolylsilylene, silacyclobutylene, silacyclopentylene, silafluorene, dimethyl gel Mylene, diethylgermylene, di-n-propylgermylene, dii-propylgermylene, din-butylgermylene, methylethylgermylene, methyln-butylgermylene, ethyln-butylgermylene, divinylgermylene, etc. I can mention Dimethylsilylene, diethyl silylene, dimethyl gel Mi Ren, diethyl gel Mi Ren 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 include n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.
Specific examples of the alkenyl group having 1 to 6 carbon atoms include vinyl, propenyl, allyl, butenyl, and cyclohexenyl.
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, Examples include acenaphthyl, phenanthryl, anthryl.
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- Each substituted dichlorophenyl, 2,4,6-, 2,3,4-, 2,4,5-, 3,4,5-substituted trifluorophenyl, 2,4,6-, 2,3, Examples include 4-, 2,4,5-, 3,4,5-substituted 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 alkenyl having 1 to 6 carbon atoms A substituent of a group, a C1-C6 halogen-containing alkyl group, a C1-C6 silicon-containing alkyl group, a C6-C18 aryl group, or a C6-C18 halogen-containing aryl group And may have a 5- to 7-membered ring formed by both adjacent atoms, and have an unsaturated bond in it. It may be.

Preferably, it is a heterocyclic ring containing a sulfur atom or 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 -Methylthienyl), 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 be mentioned.

Specific examples of X ¹ and X ² include chlorine, bromine, iodine, methyl, ethyl, n-propyl, n-butyl, i-butyl, phenyl, benzyl, dimethylamino, diethylamino, preferably Chlorine, bromine, iodine, methyl and ethyl.

(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 the mode of bonding. A typical synthesis route is as shown in the following reaction formula. An example of a synthetic route for a metallocene compound is shown below.

Starting material 1 can be purchased as a reagent, and 1 can be lithiated with alkyllithium, then reacted with trialkoxyborane and hydrolyzed to yield 2. 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 the 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 the corresponding substitution raw material, and instead of a furyl boric acid, phenyl boronic acid, a substituted furyl boric acid, or the thienyl boric acid which may be substituted etc. Can be used to introduce the corresponding 2-position substituent (R ¹ , R ¹¹ ).
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 0030 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 the common characteristics 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- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (2) Dimethylsilylenebis (2- (2- (5- t-butylfuryl))-4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (3) dimethylsilylenebis (2- (2- (5-phenylfuryl))-4- (3,5-dimethylphenyl) ) -Indenyl) zirconium dichloride (4) dimethylsilylenebis (2- (2- (4,5-benzofuryl))-4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (5) dimethylsilylenebis (2 -(2- (4,5-dimethylfuryl))-4- (3,5-dimethylphenyl) -indenyl) zirconium di Roraido (6) dimethylsilylene-bis (2- (2- (3,5-dimethyl-furyl)) - 4- (3,5-dimethylphenyl) - indenyl) zirconium dichloride

(7) Dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (8) Dimethylsilylenebis (2- (2 -(5-t-butylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (9) dimethylsilylenebis (2- (2- (5-phenylfuryl))-4 -(3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (10) dimethylsilylenebis (2- (2- (4,5-benzofuryl))-4- (3,5-di-t- Butylphenyl) -indenyl) zirconium dichloride (11) dimethylsilylenebis (2- (2- (4,5-dimethylfuryl))-4- (3,5-di-t-butylphenyl) Le) - indenyl) zirconium dichloride (12) dimethylsilylene-bis (2- (2- (3,5-dimethyl-furyl)) - 4- (3,5-di -t- butyl-phenyl) - indenyl) zirconium dichloride

(13) Dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-di-chlorophenyl) -indenyl) zirconium dichloride (14) Dimethylsilylenebis (2- (2- (5 -T-butylfuryl))-4- (3,5-di-chlorophenyl) -indenyl) zirconium dichloride (15) dimethylsilylenebis (2- (2- (5-phenylfuryl))-4- (3,5- Di-chlorophenyl) -indenyl) zirconium dichloride (16) dimethylsilylenebis (2- (2- (4,5-benzofuryl))-4- (3,5-di-chlorophenyl) -indenyl) zirconium dichloride (17) dimethyl Silylenebis (2- (2- (4,5-dimethylfuryl))-4- (3,5-di-chlorophenyl) -indene Le) zirconium dichloride (18) dimethylsilylene-bis (2- (2- (3,5-dimethyl-furyl)) - 4- (3,5-di - chlorophenyl) - indenyl) zirconium dichloride

(19) Dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-di-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (20) Dimethylsilylenebis (2- (2- (5-t-butylfuryl))-4- (3,5-di-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (21) dimethylsilylenebis (2- (2- (5-phenylfuryl))-4- ( 3,5-di-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (22) dimethylsilylenebis (2- (2- (4,5-benzofuryl))-4- (3,5-di-trimethylsilyl-phenyl)- Indenyl) zirconium dichloride (23) dimethylsilylenebis (2- (2- (4,5-dimethylfuryl) ) -4- (3,5-di-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (24) dimethylsilylenebis (2- (2- (3,5-dimethylfuryl))-4- (3,5-di -Trimethylsilyl-phenyl) -indenyl) zirconium dichloride

(25) Dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-di-trifluoromethyl-phenyl) -indenyl) zirconium dichloride (26) Dimethylsilylenebis (2- ( 2- (5-t-butylfuryl))-4- (3,5-di-trifluoromethyl-phenyl) -indenyl) zirconium dichloride (27) dimethylsilylenebis (2- (2- (5-phenylfuryl)) -4- (3,5-di-trifluoromethyl-phenyl) -indenyl) zirconium dichloride (28) dimethylsilylenebis (2- (2- (4,5-benzofuryl))-4- (3,5-di -Trifluoromethyl-phenyl) -indenyl) zirconium dichloride (29) dimethylsilylenebis (2- (2- (4,5-dimethyl) Furyl))-4- (3,5-di-trifluoromethyl-phenyl) -indenyl) zirconium dichloride (30) dimethylsilylenebis (2- (2- (3,5-dimethylfuryl))-4- (3 , 5-Di-trifluoromethyl-phenyl) -indenyl) zirconium dichloride

(31) Dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dimethyl-4-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (32) Dimethylsilylenebis (2- ( 2- (5-t-Butylfuryl))-4- (3,5-dimethyl-4-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (33) dimethylsilylenebis (2- (2- (5-phenylfuryl)) -4- (3,5-dimethyl-4-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (34) dimethylsilylenebis (2- (2- (4,5-benzofuryl))-4- (3,5-dimethyl) -4-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (35) dimethylsilylene (2- (2- (4,5-dimethylfuryl))-4- (3,5-dimethyl-4-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (36) dimethylsilylenebis (2- (2- ( 3,5-dimethylfuryl))-4- (3,5-dimethyl-4-trimethylsilyl-phenyl) -indenyl) zirconium dichloride

(37) Dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dichloro-4-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (38) Dimethylsilylenebis (2- ( 2- (5-t-butylfuryl))-4- (3,5-dichloro-4-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (39) dimethylsilylenebis (2- (2- (5-phenylfuryl)) -4- (3,5-dichloro-4-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (40) dimethylsilylenebis (2- (2- (4,5-benzofuryl))-4- (3,5-dichloro -4-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (41) dimethylsilylene (2- (2- (4,5-dimethylfuryl))-4- (3,5-dichloro-4-trimethylsilyl-phenyl) -indenyl) zirconium dichloride (42) dimethylsilylenebis (2- (2- ( 3,5-dimethylfuryl))-4- (3,5-dichloro-4-trimethylsilyl-phenyl) -indenyl) zirconium dichloride

(43) Dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (2,3,5-trimethylphenyl) -indenyl) zirconium dichloride (44) Dimethylsilylenebis (2- (2- ( 5-t-butylfuryl))-4- (2,3,5-trimethylphenyl) -indenyl) zirconium dichloride (45) dimethylsilylenebis (2- (2- (5-phenylfuryl))-4- (2, 3,5-trimethylphenyl) -indenyl) zirconium dichloride (46) dimethylsilylenebis (2- (2- (4,5-benzofuryl))-4- (2,3,5-trimethylphenyl) -indenyl) zirconium dichloride (47) Dimethylsilylenebis (2- (2- (4,5-dimethylfuryl))-4- (2,3,5-trimethyl) Phenyl) - indenyl) zirconium dichloride (48) dimethylsilylene-bis (2- (2- (3,5-dimethyl-furyl)) - 4- (2,3,5-trimethylphenyl) - indenyl) zirconium dichloride

(49) Dimethylsilylene (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) (2-phenyl-4- (3,5-di-) t-butylphenyl) -indenyl) zirconium dichloride (50) dimethylsilylene (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) (2- ( 4-t-butylphenyl) -4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (51) dimethylsilylene (2- (2- (5-methylfuryl))-4- (3 , 5-Di-t-butylphenyl) -indenyl) (2- (4-trifluoromethylphenyl) -4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (52) dichloride Tylsilylene (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) (2- (4-chlorophenyl) -4- (3,5-di-) t-butylphenyl) -indenyl) zirconium dichloride (53) dimethylsilylene (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) (2- ( 3,5-di-t-butylphenyl) -4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (54) dimethylsilylene (2- (2- (5-methylfuryl))- 4- (3,5-di-t-butylphenyl) -indenyl) (2- (2,5-di-fluorophenyl) -4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride

(55) Diethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (56) di-n-propylsilylenebis (2- (2 -(5-Methylfuryl))-4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (57) di-i-propylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (58) di-n-butylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dimethylphenyl) -indenyl) Zirconium dichloride (59) diphenylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dimethylphenyl) -indeni ) Zirconium dichloride

(60) Diethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (61) di-n-propylsilylenebis ( 2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (62) di-i-propylsilylenebis (2- (2- (5 -Methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (63) di-n-butylsilylenebis (2- (2- (5-methylfuryl))-4 -(3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (64) diphenylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-di- - butylphenyl) - indenyl) zirconium dichloride

(65) Diethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dichlorophenyl) -indenyl) zirconium dichloride (66) di-n-propylsilylenebis (2- (2- (5-Methylfuryl))-4- (3,5-dichlorophenyl) -indenyl) zirconium dichloride (67) di-i-propylsilylenebis (2- (2- (5-methylfuryl))-4- (3 , 5-dichlorophenyl) -indenyl) zirconium dichloride (68) di-n-butylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dichlorophenyl) -indenyl) zirconium dichloride (69 ) Diphenylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dichlorophenyl) -5-methyl -Indenyl) zirconium dichloride

(70) Dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dimethylphenyl) -5-methyl-indenyl) zirconium dichloride (71) Dimethylsilylenebis (2- (2 -(5-Methylfuryl))-4- (3,5-di-t-butylphenyl) -5-methyl-indenyl) zirconium dichloride (72) dimethylsilylenebis (2- (2- (5-methylfuryl)) ) -4- (3,5-dichlorophenyl) -5-methyl-indenyl) zirconium dichloride

(73) Dimethylsilylenebis (2- (2- (3,5-dimethylfuryl))-4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (74) Dimethylsilylenebis (2- (2- ( 3,5-dimethylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (75) dimethylsilylenebis (2- (2- (3,5-dimethylfuryl))- 4- (3,5-dichlorophenyl) -indenyl) zirconium dichloride

(76) Dimethylsilylenebis (2- (3- (2,5-dimethylfuryl))-4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (77) Dimethylsilylenebis (2- (3- ( 2,5-dimethylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (78) dimethylsilylenebis (2- (3- (2,5-dimethylfuryl))- 4- (3,5-dichlorophenyl) -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 , Complexes substituted for dimethylamino group, diethylamino group, etc., complexes of germylene 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 that reacts with component (A) to form an ion pair, ion-exchangeable layered silicate or inorganic silicate, preferably ion Exchangeable layered silicate component (C): organoaluminum compound

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

上記の各一般式中において、Ｒ^ａは、水素原子又は炭化水素基、好ましくは炭素数１〜１０、特に好ましくは炭素数１〜６の炭化水素基を示す。また、複数のＲ^ａは、それぞれ同一でも異なっていてもよい。また、ｐは０〜４０、好ましくは２〜３０の整数を示す。
一般式のうち、一番目及び二番目の式で表される化合物は、アルミノキサンとも称される化合物であって、これらの中では、メチルアルミノキサン又はメチルイソブチルアルミノキサンが好ましい。上記のアルミノキサンは、各群内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Ｒ^ｂＢ（ＯＨ）_２で表されるアルキルボロン酸との１０：１〜１：１（モル比）の反応により得ることができる。一般式中、Ｒ^ｂは、炭素数１〜１０、好ましくは炭素数１〜６の炭化水素基を示す。

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

  The 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, Palygorskite, etc.

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. For example, a layered substance in a state where the layers are expanded can be obtained by replacing the exchangeable ions between the layers with other large and bulky ions using ion exchange.

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 , C _A compound comprising at least one anion selected from the group consisting of ₂ H ₄ O ₄ and C ₆ H ₅ O ₇ . 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. 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.
Further, different components may be used as a mixture in each component, or the components may be contacted in different orders. 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 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 thereof 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.
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 used amounts of 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 limited by the range of use ratios described above as long as the catalyst meets the purpose of the present invention. Must not.

  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, The α-olefin polymerization ratio in CP is determined by the following method.
In addition, although the following examples are when ethylene is used as the α-olefin in the CP, α-olefins other than ethylene are obtained using a method according to the following example.

(1) Analytical device to be used (i) Cross 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 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, so 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) / [content of copolymer component (% by weight)] (III)

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

(6) Ethylene polymerization ratio The ethylene content in CP is determined by the following formula.
Ethylene content (% by weight) in CP = (W40 × A40 + W100 × A100) / [CP] 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 describe the present invention more specifically and clearly, the present invention will be described in contrast to Examples and Comparative Examples, and the rationality and significance of the requirements of the configuration of the present invention and the 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 on the conditions of a 2.16kg load for 5 minutes. Thereafter, the extrusion amount of the polymer was measured, converted into an amount per 10 minutes, and used as the MFR value (unit: g / 10 minutes).

(2) Measurement of melting point:
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- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (1) Synthesis of 4- (3,5-dimethylphenyl) indene To a 500 ml glass reaction vessel, 13.6 g (74 mmol) of 1-bromo-3,5-dimethylbenzene and 100 ml of dimethoxyethane (DME) were added and cooled to −40 ° C. in a dry ice-methanol bath. To this, 101 ml (147 mmol) of a 1.46 mol / L t-butyllithium-n-pentane solution was added dropwise and stirred as it was for 4 hours. With cooling at −40 ° C., 20.4 ml (88 mmol) of triisopropyl borate was added dropwise. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After 20 ml of distilled water was added to the reaction solution for hydrolysis, 20 ml of an aqueous solution of 19.5 g of sodium carbonate, 11.5 g (59 mmol) of 4-bromoindene and 5.0 g (3.4 mmol) of tetrakistriphenylphosphinopalladium were added in order. After removing the low boiling point, the mixture was heated at 80 ° C. for 7 hours.
After allowing to cool, the reaction solution was poured into 100 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 obtain 10.7 g of light yellow crystals of 4- (3,5-dimethylphenyl) indene (yield 82%).

(2) Synthesis of 2-bromo-4- (3,5-dimethylphenyl) indene In a 500 ml glass reaction vessel, 10.7 g (49 mmol) of 4- (3,5-dimethylphenyl) -indene, 5 ml of distilled water, 200 ml of DMSO was added, and 11.3 g (63 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, 1.4 g (7.4 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, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 10.2 g (yield 69%) of 2-bromo-4- (3,5-dimethylphenyl) indene as pale yellow crystals. It was.

(3) Synthesis of 2- (2- (5-methylfuryl))-4- (3,5-dimethylphenyl) indene In a 500 ml glass reaction vessel, 4.2 g (51 mmol) of 2-methylfuran, 100 ml of DME And cooled to −40 ° C. in a dry ice-methanol bath. To this was added dropwise 33.5 ml (51 mmol) of a 1.52 mol / L n-butyllithium-n-hexane solution, and the mixture was stirred as such for 2 hours. While being cooled to −40 ° C., 13.0 ml (56 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 20 ml of distilled water, 50 ml of an aqueous solution of 11.9 g of sodium carbonate, 10.2 g (34 mmol) of 2-bromo-4- (3,5-dimethylphenyl) indene, tetrakistriphenylphosphinopalladium. After adding 3.0 g (2.6 mmol) in order and removing a low boiling point, it heated at 80 degreeC for 3 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. 2. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to give pale yellow crystals of 2- (2- (5-methylfuryl))-4- (3,5-dimethylphenyl) indene. 0 g (yield 30%) was obtained.

(4) Synthesis of dimethylbis (2- (2- (5-methylfuryl))-4- (3,5-di-methylphenyl) -indenyl) silane In a 300 ml glass reaction vessel, 2- (2- (5-Methylfuryl))-4- (3,5-di-methylphenyl) -indene (3.0 g, 10 mmol) and THF (50 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. 6.4 ml (10 mmol) of a 1.57 mol / L n-butyllithium-hexane solution was added dropwise thereto, and the mixture was stirred as it was for 2 hours. While cooling at −70 ° C., 0.5 ml (0.05 mmol) of 1-methylimidazole and 0.64 g (5.0 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, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column. Dimethylbis (2- (2- (5-methylfuryl))-4- (3,5-di-methylphenyl) -indenyl ) 2.6 g (yield 40%) of a light red solid of silane was obtained.

(5) Synthesis of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride Into a 200 ml glass reaction vessel, dimethylbis (2- 2.6 g (4.0 mmol) of (2- (5-methylfuryl))-4- (3,5-di-methylphenyl) -indenyl) silane and 50 ml of diethyl ether were added, and -70 in a dry ice-methanol bath. Cooled to ° C. To this, 5.1 ml (8.0 mmol) of a 1.57 mol / L n-butyllithium-n-hexane solution was added dropwise. 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, 50 ml of toluene and 5 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 0.91 g (3.9 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 racemic dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride. 0.5 g (yield 14%) of the product (purity 99% or more) was obtained as red-orange crystals.
¹ H-NMR value (CDCl ₃ ) Racemate: δ 1.12 (s, 6H), δ 2.32 (s, 12H), δ 2.42 (s, 6H), δ 6.06 (d, 2H), δ 6. 27 (d, 2H), δ 6.78 (dd, 2H), δ 6.90 (d, 2H), δ 6.96 (s, 2H) δ 7.04 (s, 2H), δ 7.26 (s, 4H) , Δ 7.29 (d, 2H).

(6) Chemical treatment of ion-exchange layered silicate Acid treatment: 1,130 g of distilled water and 750 g of 96% sulfuric acid are added to a separable flask, and the internal temperature is kept at 90 ° C., where there is a granulated montmorillonite, Mizusawa Chemical Benclay SL (average particle size 19 μm, 300 g) was added and allowed to react 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 / 10,000 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, followed by stirring at room temperature for 120 minutes. The slurry was filtered, 3,000 ml of distilled water was added to the obtained solid, and the mixture was stirred at room temperature for 5 minutes. 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- (3,5-dimethylphenyl) -indenyl) zirconium dichloride (referred to as catalyst A)
10.1 g of the chemically treated montmorillonite obtained above was weighed in a flask having an internal volume of 1 L, 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 slurry amount 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, dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride 245 mg (300 μmol) in 60 ml of toluene was added and stirred at room temperature for 60 minutes. did.
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 18.7 g of a solid catalyst. The prepolymerization magnification (the value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 0.81.

[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 300 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 50 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. The temperature inside the tank was maintained at 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 10.0 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, 161 g of propylene-propylene • ethylene block copolymer having good particle properties was obtained. The average gas mol composition in the tank during polymerization of propylene and ethylene was propylene / ethylene = 38/62.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 12 wt%, and the ethylene content in rubber (CP) is 41 wt% (51 mol%). The weight average molecular weight (Mw) was 150,000, and MFR was 250 (dg / min). Moreover, Tm of propylene homopolymer collected separately was 155 ° C. and MFR was 380 (dg / min).

[Example-3]
(Propylene-propylene / ethylene block copolymerization with catalyst A)
The same operation as in Example-2 was carried out except that the average gas mol composition in the tank at the time of propylene / ethylene polymerization was adjusted to be propylene / ethylene = 29/71. As a result, 155 g of propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above has a CP content of 22 wt%, an ethylene content in CP of 53 wt% (63 mol%), and an MFR of 8.2 (dg / min). ), And the weight average molecular weight (Mw) of the CP part was 190,000. The amount of the separately collected propylene homopolymer was 9.0 g. Tm was 156 ° C. and MFR was 18 (dg / min).

[Example-4]
Synthesis of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (1) 4- (3,5-di- Synthesis of t-butylphenyl) indene To a 500 ml glass reaction vessel, 9.8 g (36 mmol) of 1-bromo (3,5-di-t-butyl) benzene and 100 ml of dimethoxyethane (DME) were added and dried ice- It cooled to -40 degreeC with the methanol bath. To this, 50 ml (73 mmol) of a 1.46 mol / L t-butyllithium-n-pentane solution was added dropwise and stirred as it was for 4 hours. While cooling at −40 ° C., 10 ml (44 mmol) of triisopropyl borate was added dropwise. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After 20 ml of distilled water was added to the reaction solution for hydrolysis, 10 ml of an aqueous solution of 12 g of sodium carbonate, 5.5 g (28 mmol) of 4-bromoindene and 2.0 g (1.7 mmol) of tetrakistriphenylphosphinopalladium were added in this order. After removing the boiling component, the mixture was heated at 80 ° C. for 7 hours.
After allowing to cool, the reaction solution was poured into 100 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, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 8.1 g (yield 94%) of 4- (3,5-di-t-butylphenyl) indene as pale yellow crystals. .

(2) Synthesis of 2-bromo-4- (3,5-di-t-butylphenyl) indene In a 500 ml glass reaction vessel, 8.1 g of 4- (3,5-di-t-butylphenyl) indene ( 27 mmol), 2.0 ml of distilled water and 150 ml of DMSO were added, and N
-5.4 g (30 mmol) of bromosuccinimide was gradually added. 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, 0.7 g (3.7 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 to give 8.0 g of light yellow crystals of 2-bromo-4- (3,5-di-t-butylphenyl) indene (yield 79). %).

(3) Synthesis of 2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) indene In a 500 ml glass reaction vessel, 2.6 g (31 mmol) of 2-methylfuran ), 100 ml of DME was added, and the mixture was cooled to −40 ° C. in a dry ice-methanol bath. 20 ml (31 mmol) of a 1.52 mol / L n-butyllithium-n-hexane solution was added dropwise thereto, and the mixture was stirred as it was for 2 hours. While cooling to −40 ° C., 7.6 ml (33 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, then 30 ml of an aqueous solution of 7.0 g of sodium carbonate, 8.0 g (21 mmol) of 2-bromo-4- (3,5-di-t-butylphenyl) indene, tetrakistri After adding 3.0 g (2.6 mmol) of phenylphosphinopalladium in order and removing a low boiling point, it heated at 80 degreeC for 3 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 with a silica gel column to give 2- (2- (5-methylfuryl))-4- (3,5-di-tert-butylphenyl) indene 6.2 g (yield 80%) of yellow crystals were obtained.

(4) Synthesis of dimethylbis (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) silane In a 300 ml glass reaction vessel, 2- ( 6.2 g (16 mmol) of 2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indene and 100 ml of THF were added, and the mixture was cooled to −70 ° C. in a dry ice-methanol bath. To this was added dropwise 10.6 ml (16 mmol) of a 1.52 mol / L n-butyllithium-hexane solution, and the mixture was stirred as it was for 2 hours. While cooling at -70 ° C, 0.65 ml (0.05 mmol) of 1-methylimidazole and 1.0 g (7.7 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- (3,5-di-t-butylphenyl) -5.9 g (92% yield) of a light red solid of indenyl) silane.

(5) Synthesis of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride Into a 200 ml glass reaction vessel, dimethyl Bis (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) silane (5.9 g, 7.2 mmol) and diethyl ether (100 ml) were added, and dry ice was added. -It cooled to -70 degreeC with the methanol bath. To this, 9.5 ml (14 mmol) of a 1.52 mol / L n-butyllithium-n-hexane solution was added dropwise. 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 1.67 g (7.2 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 dimethylsilylene bis (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) A racemic form of zirconium dichloride (purity 97% or more) was obtained as reddish orange crystals (2.6 g, yield 37%).
¹ H-NMR value (CDCl ₃ ) Racemate: δ 1.13 (s, 6H), δ 1.31 (s, 36H), δ 2.40 (s, 6H), δ 6.03 (d, 2H), δ 6. 24 (d, 2H), δ 6.81 (dd, 2H), δ 6.94 (d, 2H), δ 7.05 (s, 2H), δ 7.34 (d, 2H), δ 7.38 (s, 2H ), Δ 7.54 (s, 4H).

(6) Catalyst preparation using dimethylsilylene bis (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride (referred to as catalyst B)
10.3 g of the chemically treated montmorillonite obtained above was weighed in a flask having an internal volume of 1 L, 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 slurry amount 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 296 mg (300 μmol) of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-di-t-butylphenyl) -indenyl) zirconium dichloride in 60 ml of toluene was added to room temperature. For 60 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 triisobutylaluminum heptane solution was added at room temperature, stirred at room temperature for 10 minutes, and then dried under reduced pressure to recover 24.1 g of a solid catalyst. The prepolymerization ratio was 1.27.

[Example-5]
(Propylene-propylene / ethylene block copolymerization with catalyst B)
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 300 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 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 15 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, 186 g of a 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 = 39/61.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 0.9 wt% (low activity), and the ethylene content in rubber (CP) is 38 wt% (48 mol). %) And the weight average molecular weight (Mw) of the CP part was 180,000, and the MFR was 9.3 (dg / min). Moreover, Tm of the propylene homopolymer collected separately was 158 ° C., and MFR was 9.6 (dg / min).

[Example-6]
(Propylene-propylene / ethylene block copolymerization with catalyst B)
The same operation as in Example-5 was carried out except that the average gas mol composition in the tank at the time of propylene / ethylene polymerization was adjusted to be propylene / ethylene = 29/71. As a result, 153 g of propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above has a CP content of 3.2 wt%, an ethylene content in CP of 41 wt% (51 mol%), and an MFR of 4.7 (dg / Min), and the weight average molecular weight (Mw) of the CP part was 240,000. Further, the amount of the separately collected propylene homopolymer was 16 g. Tm was 159 ° C. and MFR was 3.4 (dg / min).

[Comparative Example-1]
Preparation of catalyst using dimethylsilylene bis (2-methyl-4-phenyl-indenyl) zirconium dichloride (referred to as catalyst C)
Dimethylsilylenebis (2-methyl-4-phenyl-indenyl) zirconium instead of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (3,5-dimethylphenyl) -indenyl) zirconium dichloride Dichlorochloride (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 The same procedure as in 7) was performed to obtain catalyst C. The prepolymerization ratio was 2.11.

[Comparative Example-2]
Propylene-propylene / ethylene block copolymerization with catalyst C 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 n-heptane solution of triisobutylaluminum was added, 300 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 C 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 15 g.
Thereafter, propylene was introduced to 0.85 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, 249 g of a propylene-propylene • ethylene block copolymer was obtained. The average gas mol composition in the tank at the time of propylene / ethylene polymerization was propylene / ethylene = 44/56.
From the results of CFC-IR, the block copolymer obtained above has a CP content of 63 wt%, an ethylene content in CP of 24 wt% (32 mol%), and an MFR of 118 (dg / min), The weight average molecular weight (Mw) of the CP part was 62,000. Moreover, Tm of propylene homopolymer collected separately was 150 ° C., and MFR was 3.2 (dg / min).

[Comparative Example-3]
Propylene-propylene / ethylene block copolymerization with catalyst C 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 n-heptane solution of triisobutylaluminum was added, 300 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 C was slurried in n-heptane, and 20 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 amount extracted was 10 g.
Thereafter, propylene was introduced to 0.63 MPa at an internal temperature of 40 ° C., and then ethylene was introduced to 1.8 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 be 2.0 MPa so that the monomer composition ratio did not change significantly during the polymerization. As a result, 79 g of propylene-propylene • ethylene block copolymer was obtained. The average gas mol composition in the tank at the time of propylene / ethylene polymerization was propylene / ethylene = 28/72.
From the results of CFC-IR, the block copolymer obtained above has a CP content of 21 wt%, an ethylene content in CP of 39 wt% (49 mol%), and an MFR of 70 (dg / min). The weight average molecular weight (Mw) of the CP part was 53,000. Moreover, Tm of the propylene homopolymer collected separately was 149 ° C., and MFR was 38 (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, a polypropylene having a higher melting point than before can be obtained.
And by comparison with each example and each comparative example, the ethylene incorporation efficiency of the copolymer portion (CP) in the polyolefin block copolymer is much higher than that of the conventional catalyst, and moreover than the conventional catalyst. It has been shown that block copolymers having very high molecular weight copolymer parts (rubber components) can be produced. Moreover, in each Example of this invention, the polymer with favorable particle property is produced | generated.
Accordingly, 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 (7)

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. A divalent methylene group, a divalent methylene group, a divalent bridging group containing 6-18 carbon atoms or a halogenated aryl group having 6-18 carbon atoms in the skeleton, or a silicon atom, germanium atom, oxygen atom, nitrogen atom, phosphorus atom or boron It is a divalent bridging group containing an atom, and X ¹ and X ² are each independently a ligand that forms a σ bond with M.
R ¹ and R ¹¹ are the same as each other, and a heterocyclic group constituting a 5-membered ring which may have a substituent (however, the heteroatom of the heterocyclic group constituting the 5-membered ring is directly an alkadienyl group and Do not combine).
R ³ , R ⁵ , R ¹³ and R ¹⁵ may be the same or different from each other, and are chlorine, fluorine, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. A halogen-containing alkyl group, 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.
R ² , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ may be the same or different from each other, and may be hydrogen, carbon number An alkyl group having 1 to 6 carbon atoms, an alkenyl 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, an aryl group having 6 to 18 carbon atoms, and 6 carbon atoms It is a heterocyclic group constituting a 18-halogen-containing aryl group or a 5-membered or 6-membered ring optionally having 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. ] In the general formula [I], Y is R ²⁰ ₂ A (A is germanium or silicon, and R ²⁰ may be the same as or different from each other, and may be hydrogen, an alkyl group having 1 to 6 carbon atoms, carbon number 1-6 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. including a at adjacent ^{R 20} both The divalent bridging group represented by (4) may comprise a 4- to 7-membered ring and may contain an unsaturated bond in the 5- to 7-membered ring. Metallocene compounds. In the general formula [I], M is zirconium or hafnium, and R ¹ and R ¹¹ are a furyl group or a thienyl group which may have a substituent, or The metallocene compound according to claim 2. In the general formula [I], X ¹ and X ² may be the same or different, and are a halogen atom or an alkyl group having 1 to 6 carbon atoms. The metallocene compound described in any one of the above. An olefin polymerization catalyst containing the following components (A), (B), and (C).
Component (A): Metallocene compound according to any one of claims 1 to 4 Component (B): Compound that reacts with component (A) to form an ion pair, ion-exchangeable layered silicate or inorganic silicic acid Salt component (C): Organoaluminum compound 6. The catalyst for olefin polymerization according to claim 5, wherein the component (B) is an ion-exchange layered silicate and the olefin essentially comprises propylene. An olefin polymerization method, wherein the olefin polymerization or copolymerization is performed using the olefin polymerization catalyst according to claim 5 or 6.