JP2007320935A - Metallocene compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metallocene-based catalyst which is used for polymerizing α-olefins and exhibits reactivity having a good balance between propylene and ethylene or an α-4 to 20C olefin. <P>SOLUTION: This metallocene compound is represented by dichloro[dimethylsilylene(2-indenyl)(2-methyl-4-phenyl-4H-1-azulenyl)]hafnium. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a metallocene compound, and particularly relates to a metallocene compound, a catalyst component including the compound, a catalyst for olefin polymerization including the same, and an α-olefin polymerization method using the catalyst. The olefin polymerization catalyst has a balanced reactivity of ethylene or an α-olefin having 4 to 20 carbon atoms and propylene, and a higher ethylene or an α-olefin copolymer having the α-olefin content. Generate. The present invention relates to a novel metallocene compound capable of forming such a useful metallocene catalyst.

  Polypropylene-based resin materials have a great number of excellent performances mainly with respect to moldability, various physical properties, economy, adaptability to environmental problems, and the like, and are therefore widely used and used as industrial materials. Due to its importance in the industrial field, further improvements in performance are constantly demanded, for example, propylene homopolymers and elastomers such as ethylene-propylene rubber to improve flexibility and impact resistance. And a method of producing a so-called block copolymer by multistage polymerization in which propylene and ethylene or an α-olefin having 4 to 20 carbon atoms are subsequently copolymerized after homopolymerization of propylene.

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

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

  Metallocene catalysts generally have higher polymerization activity than Ziegler catalysts, and can produce polymers having a narrow molecular weight distribution and uniformity of copolymer composition distribution, but the synthesis is complicated. Many problems to be improved, such as the need to further increase and improve the polymerization activity, the molecular weight and stereoregularity of the polymer, as well as economic problems due to the use of metallocene compounds and organoaluminum oxy compounds (MAO) Is inherent.

  For metallocene catalysts, various improvements have been made from various viewpoints. For example, in order to improve the rigidity of a propylene-ethylene block copolymer, a metallocene compound that provides a polypropylene having a high melting point. Is disclosed (for example, see Patent Documents 4 and 5). When a catalyst comprising these metallocene compounds is used to copolymerize propylene and ethylene or an α-olefin having 4 to 20 carbon atoms, ethylene is obtained. Alternatively, the reactivity of the α-olefin having 4 to 20 carbon atoms is relatively low compared to the reactivity of propylene. In other words, in order to obtain a copolymer having a desired ethylene content or an α-olefin content of 4 to 20 carbon atoms, it is necessary to perform polymerization by supplying a gas having a monomer ratio greatly different from the content in the copolymer. Thus, there is a problem in production, and in a more extreme case, a copolymer having a desired content may not be produced. Increasing the ethylene partial pressure can solve some problems, but such operations are not only complicated, but due to restrictions on industrial plant equipment, the ethylene partial pressure cannot be increased beyond a certain level. For this reason, there are industrial restrictions and it is not advantageous.

  For such problems, for example, it has been proposed that the reactivity of propylene and the reactivity of ethylene or an α-olefin having 4 to 20 carbon atoms can be changed by changing the metallocene compound used (for example, patents). Metallocene compounds satisfying both the reactivity in a well-balanced manner have not been known so far, and in particular, copolymerization of propylene and ethylene or an α-olefin having 4 to 20 carbon atoms is not particularly known. When it is carried out in a phase, a metallocene compound that satisfies the above-described reactivity in a well-balanced manner has not yet been known.

  For example, in order to express 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 a carbon number of 4 to The content of each of the 20 α-olefin copolymers preferably satisfies a specific range (for example, see Non-Patent Document 2). Therefore, in terms of the performance of the catalyst in production, it is necessary that the reactivity of propylene and the reactivity of ethylene or an α-olefin having 4 to 20 carbon atoms are balanced and within a certain range.

Meanwhile, there is a document disclosing a metallocene compound similar to the present invention, for example, metallocene compounds of the pseudo-C ₂ symmetry crosslinked with 1-position and the 1-position and hydroazulenyl group indenyl group are disclosed in Patent Documents 7 and 8 ing. However, the crosslinking position is different from the metallocene compound of the present invention. Patent Document 9 discloses a metallocene compound in which the 1-position of the indenyl group and the 2-position of the indenyl group are bridged. However, the hydroazurenyl group is not shown, and there is no description about the fact that the reactivity between propylene and ethylene or an α-olefin having 4 to 20 carbon atoms is greatly different due to slightly different crosslinking positions. . In addition, Patent Document 10 has a broad description conceptually including the metallocene compound of the present invention, but the metallocene compound according to the claims of the present application is not explicitly described. There is no description as an example synthesized and confirmed.

JP-A-4-337308 Japanese Patent Laid-Open No. 11-228648 JP-A-11-240929 Japanese Patent Laid-Open No. 11-240909 Japanese Patent Laid-Open No. 2000-95791 WO2004-87775 pamphlet Journal of the American Chemical Society 2001, 123, 9555 Polymer 2001, 42, 9611 JP 2003-292700 A Japanese Patent Laid-Open No. 2004-155739 JP 2001-64322 A Japanese Patent Laid-Open No. 11-292934

  In view of the background technology outlined above, metallocene polymerization catalysts that are important and essential for industrial production of polypropylene resin materials that are widely used and used in many industrial fields are still problematic. One of the important problems is that when propylene is copolymerized with ethylene or an α-olefin having 4 to 20 carbon atoms, the reaction of ethylene or the α-olefin having 4 to 20 carbon atoms is performed. There is a problem that the property cannot be balanced with the reactivity of propylene. The present invention aims to solve this problem and to develop a metallocene-based catalyst for polymerization of α-olefin that exhibits a balanced reactivity of ethylene or an α-olefin having 4 to 20 carbon atoms and propylene. .

  In order to solve the problems of the present invention, the inventors of the present invention have proposed that the metallocene compound in the metallocene polymerization catalyst has a ligand structure, the symmetry of the metallocene compound resulting from the basic skeleton, and polymer formation at the catalytic activity point. Reactivity of ethylene or α-olefins having 4 to 20 carbon atoms while taking into account the empirical rules from the viewpoints of the mechanism of the reaction, the steric effect of the substituent of the metallocene compound and the influence of the resulting polymer on the coordination monomer, etc. In order to find a method for improving the balance between the reactivity of propylene and propylene, we conducted a multifaceted investigation and experimental search.

  In the process, when a metallocene compound having a specific steric structure is formed, the fact that a catalytic function exhibiting balanced reactivity of ethylene or an α-olefin having 4 to 20 carbon atoms and propylene is manifested. As a result of consideration of model compounds and experimental verification, a new metallocene compound that is very useful as a catalyst component was found and the present invention was created.

That is, the gist of the present invention resides in the metallocene compound represented by the following general formula (I).

(Wherein, R ^1, R ^2, R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group, any of R ^1, R ² One of them is a hydrogen atom, R ³ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 6 carbon atoms, and R ⁴ represents a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing group. represents a hydrocarbon group, n is 0 or an 2 times or less an integer number of carbon atoms in R ^3, when n is 2 or more, R ⁴ to each other to form a ring structure at an arbitrary position R ⁷ represents a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing hydrocarbon group having 6 or more carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen Represents an atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group, Q represents a bridging group, and X and Y are Each independently represents a ligand that forms a σ bond with M, and M represents a transition metal of Groups 4 to 6 of the periodic table.)

Another aspect of the present invention resides in a metallocene compound represented by the following general formula (II).

(Wherein, R ^1, R ^2, R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group, any of R ^1, R ² One of them is a hydrogen atom, R ³ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 6 carbon atoms, and R ⁴ represents a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing group. represents a hydrocarbon group, m represents an integer of 0 to 4, when m is 2 or more, may be R ⁴ to each other to form a ring structure at an arbitrary position .R ^7, the carbon Represents a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing hydrocarbon group having a number of 6 or more, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a hydrocarbon group or a silicon-containing group. Represents a hydrocarbon group or a halogenated hydrocarbon group, Q represents a bridging group, and X and Y each independently represent M It represents a ligand forming a σ bond, M represents a 4-6 transition metals of the periodic table.)

  Another aspect of the present invention resides in an olefin polymerization catalyst component comprising the metallocene compound described above.

Moreover, the place made into the other summary of this invention exists in the catalyst for olefin polymerization characterized by including the following component (A) and (B) and component (C) arbitrarily.
Component (A): selected from the group consisting of the metallocene compound component (B): an organoaluminum oxy compound, an ionic compound capable of reacting with the component (A) to convert the component (A) into a cation, or a Lewis acid Compound component (C): fine particle carrier

Moreover, the place made into the other summary of this invention exists in the catalyst for olefin polymerization characterized by including the following component (A) and (D) and component (E) arbitrarily.
Component (A): The metallocene compound component (D): a compound component selected from the group consisting of an ion-exchange layered compound or an inorganic silicate (E): an organoaluminum compound

  Another aspect of the present invention resides in an α-olefin polymerization method, wherein the α-olefin is polymerized using the olefin polymerization catalyst.

  Another aspect of the present invention is that an α-olefin is obtained by copolymerizing propylene and ethylene or an α-olefin having 4 to 20 carbon atoms using the olefin polymerization catalyst. In the polymerization method.

  In the present invention, as the metallocene compound, a novel metallocene compound whose structural formula is represented by the general formula (I) or (II) is adopted, used as a catalyst component for olefin polymerization, and combined with a cocatalyst or the like. To form an α-olefin polymerization catalyst. When copolymerizing propylene and ethylene or an α-olefin having 4 to 20 carbon atoms, propylene and the copolymerization monomer exhibit balanced reactivity, and as a result, the content and substantial content in the copolymer are substantially reduced. Thus, a catalytic function that realizes the polymerization by rationally supplying a gas having a monomer ratio not different from the above is revealed.

  The reason is not necessarily clear, but the metallocene compound represented by the general formula (I) or (II) in the present invention has a structure in which a ring structure is formed at positions 3 and 4 of the cyclopentadienyl ring portion. Basically, it has a sterically bulky substituent such as a branched alkyl group or aromatic ring at the 4-position of the hydroazurenyl ring, and has a chemical, steric and electronic environment-specific structure. However, the reason can be estimated as follows.

In a metallocene compound having C ₂ symmetry (symmetry having a two-fold rotation axis) as typically shown in the above-mentioned Patent Document 4, the two-dimensional coordination field has the same steric and electronic environment. It is. In this case, the reactivity ratio of the monomer to be copolymerized, such as propylene and ethylene or an α-olefin having 4 to 20 carbon atoms, is determined in a coordination field environment determined by the ligand structure of the metallocene compound.

On the other hand, in the metallocene compound having no C ₂ symmetry as shown in the general formula (I) or (II) in the present invention, two coordination fields are sterically and electronically due to the low symmetry. The environment is not the same. In this case, the reactivity ratio of the monomer copolymerized with propylene is different in each coordination field. In such a coordination field environment, for example, the reaction of propylene is relatively large in one coordination field, and in the extreme, only propylene can selectively react. It is presumed that the reactivity of the monomer to be polymerized becomes relatively large, and in the extreme, only the copolymerization monomer can selectively react.

  This indicates that the reactivity in each coordination field can be freely changed by arbitrarily changing the substituent in the metallocene compound. As a result, it is considered that the reactivity ratio of propylene and ethylene or the monomer to be copolymerized such as C 4-20 α-olefin as the catalyst performance can be in a desired balanced range.

  The outline of the present invention and the basic configuration and features of the invention have been described above. In the following, the best mode for carrying out the invention will be described in order to explain the entire invention group of the present application in detail. Describe in detail.

1. Metallocene Compound (1) Structure of Metallocene Compound The metallocene compound of the present invention is a novel transition metal compound represented by the following general formula (I).

(Wherein, R ^1, R ^2, R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group, any of R ^1, R ² One of them is a hydrogen atom, R ³ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 6 carbon atoms, and R ⁴ represents a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing group. represents a hydrocarbon group, n is 0 or an 2 times or less an integer number of carbon atoms in R ^3, when n is 2 or more, R ⁴ to each other to form a ring structure at an arbitrary position R ⁷ represents a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing hydrocarbon group having 6 or more carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen Represents an atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group, Q represents a bridging group, and X and Y are Each independently represents a ligand that forms a σ bond with M, and M represents a transition metal of Groups 4 to 6 of the periodic table.)

(2) Features of metallocene compounds The features of the metallocene compounds of the present invention as complex ligands are the basic features of the chemical structure and the specificity of the steric arrangement as substituents. In addition, a ring structure is further formed on the cyclopentadienyl skeleton, and a bulky substituent is arranged at the 4-position on the hydroazurenyl skeleton to have a unique and novel structure. Further, in the metallocene compound of the present invention, the condensed cyclopentadienyl skeleton and the hydroazurenyl skeleton are bonded via the bonding group Q at the 2-position of the former skeleton and the 1-position of the latter skeleton. Therefore, this metallocene compound has two isomers with respect to the plane including M, X and Y in terms of relative positions. That is, there are usually an isomer (a) called an anti isomer and an isomer (b) called a syn isomer. In comparing both isomers, in order to produce a high molecular weight α-olefin polymer, the above isomer (a) is used from the viewpoint of regulating the growth direction of the polymer chain and the coordination direction of the monomer. That is, it is preferable to use a compound in which two ligands facing each other across a plane including M, X, and Y are not in an entity-mirror relationship with respect to the plane.

(3) Substituent of metallocene compound In general formula (I), R ¹ , R ² , R ⁵ and R ⁶ are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon. It is a group. When these are a hydrocarbon group, a silicon-containing hydrocarbon group, or a halogenated hydrocarbon group, the number of carbon atoms is preferably 1-6. A hydrogen atom is also preferred. More preferably, they are a C1-C3 group or a hydrogen atom.

  Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and other alkyl groups or cycloalkyl groups, vinyl group, propenyl group, cyclohexenyl group and other alkenyl groups or cycloalkenyl groups, phenyl group, tolyl group, dimethyl group Examples thereof include aryl groups such as phenyl group, ethylphenyl group, trimethylphenyl group, t-butylphenyl group, 1-naphthyl group, 2-naphthyl group, acenaphthyl group, phenanthryl group and anthryl group.

  Specific examples of the silicon-containing hydrocarbon group preferably include a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group, and an alkylsilylalkyl group such as a bis (trimethylsilyl) methyl group.

  In the halogenated hydrocarbon group, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. And as a halogenated hydrocarbon group, when a halogen atom is a fluorine atom, the compound which substituted the fluorine atom in the arbitrary positions of said hydrocarbon group is mentioned, for example. Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2 -Trifluoroethyl group, 2,2,1,1-tetrafluoroethyl group, pentafluoroethyl group, pentachloroethyl group, pentafluoropropyl group, nonafluorobutyl group, trifluorovinyl group, 2-, 3-, 4-substituted fluorophenyl groups, 2-, 3-, 4-substituted chlorophenyl groups, 2-, 3-, 4-substituted bromophenyl groups, 2,4-, 2,5-, 2, 6-, 3,5-substituted difluorophenyl groups, 2,4-, 2,5-, 2,6-, 3,5-substituted dichlorophenyl groups, 2,4,6-to Fluorophenyl group, a 2,4,6-trichlorophenyl group, pentafluorophenyl group, etc. pentachlorophenyl group.

In these, as R < ¹ > and R < ² >, C1-C6 alkyl groups, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, or C6-C12, such as a phenyl group, Aryl groups are preferred. However, ^one of R ¹ and R ² is a hydrogen atom. R ⁵ is preferably an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, and R ⁶ is preferably a hydrogen atom.

R ³ is a saturated or unsaturated divalent hydrocarbon group having 3 to 6 carbon atoms. Specific examples of the condensed cyclopentadienyl structure formed from the cyclopentadienyl moiety to which R ³ is bonded and R ³ include the following partial structures (a) to (i), among which (c), (E) and (f) are preferable. Further, R ⁴ may be substituted on these partial structures (a) to (i).

R ⁴ is a hydrocarbon group, a halogenated hydrocarbon group, or a silicon-containing hydrocarbon group, and the carbon number thereof is usually 1 to 12, preferably 1 to 6. n represents an integer of 0 or less than twice the number of carbon atoms of R ³ . And when n is two or more, R < ⁴ > may couple | bond together in arbitrary positions and may form the ring structure. Specific examples of the hydrocarbon group, the halogenated hydrocarbon group, and the silicon-containing hydrocarbon group include the same as the specific examples given for R ¹ , R ² , R ^5, and R ⁶ . Alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group and butyl group, aryl groups having 6 to 12 carbon atoms such as phenyl group, trialkylsilyl groups such as trimethylsilyl group, 2-3 Preferred are halogenated aryl groups such as-, 4-substituted chlorophenyl groups.

Specific examples of R ⁴ bonded to each other at any position to form a ring structure include the following partial structures (j) to (n).

R ⁷ represents a hydrocarbon group having 6 or more carbon atoms, preferably 6 to 12 carbon atoms, a halogenated hydrocarbon group, or a silicon-containing hydrocarbon group. Specific examples of the hydrocarbon group include phenyl, tolyl, dimethylphenyl, mesityl, ethylphenyl, diethylphenyl, triethylphenyl, i-propylphenyl, dii-propylphenyl, tri i-propylphenyl group, n-butylphenyl group, di-n-butylphenyl group, tri-n-butylphenyl group, t-butylphenyl group, di-t-butylphenyl group, tri-t-butylphenyl group, biphenylyl group, p -Aryl group of terphenyl group, m-terphenyl group, naphthyl group, anthryl group, phenanthryl group, etc. are mentioned.

  In the above halogenated hydrocarbon substituent, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated hydrocarbon substituent is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group. Specifically, fluorodimethylphenyl group, (fluoromethyl) methylphenyl group, ethylfluorophenyl group, diethylfluorophenyl group, triethylfluorophenyl group, fluoro i-propylphenyl group, fluorodi i-propylphenyl group, (fluoro i -Propyl) i-propylphenyl group, fluorotri-i-propylphenyl group, n-butylfluorophenyl group, di-n-butylfluorophenyl group, (fluorobutyl) butylphenyl group, tri-n-butylfluorophenyl group, t- Butylfluorophenyl group, di-t-butylfluorophenyl group, tri-t-butylfluorophenyl group, fluorobiphenylyl group, fluoro p-terphenyl group, fluoro m-terphenyl group, fluoronaphthyl group, fluoroanthryl group, fluoro And phenanthryl groups.

  Specific examples of the silicon-containing hydrocarbon substituent having 6 or more carbon atoms include silyl such as trimethylsilylphenyl group, triethylsilylphenyl group, isopropyldimethylsilylphenyl group, t-butyldimethylsilylphenyl group, and phenyldimethylsilylphenyl group. And group-substituted aryl groups.

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are not particularly bulky groups, and are preferably hydrogen atoms, hydrocarbon groups having 1 to 6 carbon atoms, halogenated hydrocarbon groups or silicon-containing hydrocarbon groups. Specific examples of the hydrocarbon group include alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group and n-butyl group, alkenyl groups such as vinyl group, propenyl group and cyclohexenyl group. It is done.

  The halogenated hydrocarbon group is a compound in which a halogen atom is substituted at an arbitrary position of the above hydrocarbon group. Halogen is preferably fluorine, chlorine or bromine, among which fluorine or chlorine is preferred. Specific examples of the halogenated hydrocarbon include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, and a dichloromethyl group.

Specific examples of silicon-containing hydrocarbon groups include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group and t-butyldimethylsilyl group, trialkylsilylmethyl groups such as trimethylsilylmethyl group and triethylsilylmethyl group, dimethylphenylsilyl Examples thereof include di (alkyl) (aryl) silylmethyl groups such as methyl group and dimethyltolylsilylmethyl group. Among these, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are particularly preferably hydrogen atoms.

  In general formula (I), Q is a bridging group that connects two cyclopentadienyl rings. Q is a bridging group, and specific examples thereof are a divalent hydrocarbon group, or a silylene group, an oligosilylene group, or a germylene group, which may have a hydrocarbon group as a substituent, Preferably, it is any one of a divalent hydrocarbon group having 1 to 20 carbon atoms, or a silylene group, an oligosilylene group, or a germylene group, which may have a hydrocarbon group having 1 to 20 carbon atoms. When two hydrocarbon groups are present on the above-mentioned silylene group, oligosilylene group or germylene group, they may be bonded to each other to form a ring structure.

  Specific examples of the bridging group Q include a methylene group, a dimethylmethylene group, a 1,2-ethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,2-cyclohexylene group, and a 1,4. -Alkylene group such as cyclohexylene group; arylalkylene group such as diphenylmethylene; silylene group; dimethylsilylene group, diethylsilylene group, di (n-propyl) silylene group, alkylsilylene group such as di (i-propyl) silylene An arylsilylene group such as a diphenylsilylene group; an alkyl oligosilylene group such as tetramethyldisilylene; a germylene group; an alkyl in which silicon of the above-mentioned divalent hydrocarbon group having 1 to 20 carbon atoms is substituted with germanium A germylene group; an arylgermylene group; Among these, an alkylene group having 1 to 20 carbon atoms, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, a dimethylmethylene group, 1,2-ethylene group, dimethylsilylene group, diethylsilylene group, dimethylgermylene group and diethylgermylene group are particularly preferred.

  X and Y are ligands that form a σ bond with M, and are not particularly limited, but preferred X and Y are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substitution having 1 to 20 carbon atoms. Examples thereof include an amino group and a nitrogen-containing hydrocarbon group. Among these, a chlorine atom, a methyl group, an i-butyl group, a phenyl group, a benzyl group, a dimethylamino group or a diethylamino group is particularly preferable.

  M represents a transition metal of Groups 4 to 6 of the periodic table, preferably a transition metal of Group 4 of titanium, zirconium and hafnium, more preferably zirconium or hafnium.

(4) Synthesis of metallocene compound The metallocene compound of the present invention can be synthesized by any method with respect to the substituent or the mode of bonding. A typical synthesis route is as shown in the following reaction formula. For example, when R ³ has 4 carbon atoms and has an indenyl group as a condensed ring with a cyclopentadienyl moiety, it can be synthesized as follows.

When bromoindene (1) having an R ⁴ group is selectively Grignarded at the 2-position of the indenyl group using magnesium and reacted with dichlorodimethylsilane, a chlorosilylated indenyl derivative (2) is obtained. It is done. On the other hand, when a lithium reagent having an R ⁷ group is reacted with azulene (3) having an R ⁵ group, (4) in which the R ⁷ group is added to the 4-position of the azulenyl moiety is obtained. When this is reacted with (2) as it is, a bridging ligand (5) is obtained. Subsequently, after deprotonation by a known method, reaction with zirconium tetrachloride or the like gives the desired metallocene compound (6 ) Can be synthesized. It is obvious that other metallocene compounds of the present invention can be easily synthesized based on such a synthesis route.

(5) Specific examples of metallocene compounds Preferred specific examples of the metallocene compounds of the present invention are shown below. Hafnium dichloride is selected as a representative, and examples of the names are given in the compounds of the structural formula shown below. The compound of this structural formula is called dichloro {dimethylsilylene (2-indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium. Also referred to as dimethylsilylene (2-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl) hafnium dichloride.

  By the way, since the present invention has a novel metallocene compound as a main component, it is basically necessary to exemplify a large number of compounds. However, in order to make the specification concise and concise, the illustration is complicated. The main representative examples are kept away from the description. Accordingly, compounds other than the compounds listed below are also included as long as they are included in the claims of the present application. For example, in the following specific examples, it should be understood that titanium or zirconium is substituted for hafnium, germanium is substituted for silylene, 4- (1-naphthyl) is substituted for 4-phenyl, and the like. . In addition, other compounds having other X and Y instead of dichloride are also exemplified. That is, one or both of the two chlorine atoms corresponding to the X and Y parts of the general formula (I) are fluorine atom, bromine atom, iodine atom, methyl group, phenyl group, benzyl group, dimethylamino group, diethylamino group, etc. The compound replaced with can also be illustrated. In the following examples, highly similar compounds are summarized in paragraphs (1) to (8).

(1) Dichloro {methylene (2-indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium (1) Dichloro {dimethylmethylene (2-indenyl) (2-methyl-4-phenyl-4H -1-azulenyl)} hafnium (1) dichloro {ethylene (2-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium (1) dichloro {dimethylsilylene (2-indenyl) (2- Methyl-4-phenyl-4H-1-azurenyl)} hafnium (1) dichloro {diethylsilylene (2-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium (1) dichloro {diphenylsilylene (2-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium (1) di Rollo {dimethyl gel Mi Len (2-indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium

(2) Dichloro {dimethylsilylene (2-indenyl) (2-ethyl-4-phenyl-4H-1-azulenyl)} hafnium (2) dichloro {dimethylsilylene (2-indenyl) (4-phenyl-2-n- Propyl-4H-1-azulenyl)} hafnium (2) dichloro {dimethylsilylene (2-indenyl) (4-phenyl-2-i-propyl-4H-1-azurenyl)} hafnium

(3) Dichloro {dimethylsilylene (2-indenyl) (2-methyl-4- (1-naphthyl) -4H-1-azulenyl)} hafnium (3) dichloro {dimethylsilylene (2-indenyl) (2-methyl- 4- (2-naphthyl) -4H-1-azulenyl)} hafnium (3) dichloro {dimethylsilylene (2-indenyl) (4- (4-fluorophenyl) -2-methyl-4H-1-azulenyl)} hafnium (3) Dichloro {dimethylsilylene (2-indenyl) (4- (4-chlorophenyl) -2-methyl-4H-1-azulenyl)} hafnium (3) dichloro {dimethylsilylene (2-indenyl) (2-methyl- 4- (4-Methylphenyl) -4H-1-azulenyl)} hafnium (3) dichloro {dimethylsilylene (2-indenyl) ) (4- (4-t-butylphenyl) -2-methyl-4H-1-azulenyl)} hafnium (3) dichloro {dimethylsilylene (2-indenyl) (2-methyl-4- (4-trimethylsilylphenyl)] -4H-1-azulenyl)} hafnium (3) dichloro {dimethylsilylene (2-indenyl) (2-methyl-4- (4-trimethylsilyl-3-methylphenyl) -4H-1-azurenyl)} hafnium (3) Dichloro {dimethylsilylene (2-indenyl) (2-methyl-4- (4-trimethylsilyl-3-chlorophenyl) -4H-1-azulenyl)} hafnium (3) dichloro {dimethylsilylene (2-indenyl) (4- ( 4-biphenylyl) -2-methyl-4H-1-azulenyl)} hafnium (3) dichloro {dimethylsilane Len (2-indenyl) (4- (2-fluoro-4-biphenylyl) -2-methyl-4H-1-azulenyl)} hafnium (3) dichloro {dimethylsilylene (2-indenyl) (4- (4-chloro -1-naphthyl) -2-methyl-4H-1-azulenyl)} hafnium (3) dichloro {dimethylsilylene (2-indenyl) (4- (4-chloro-2-naphthyl) -2-methyl-4H-1 -Azulenyl)} hafnium

(4) Dichloro {dimethylsilylene (1-methyl-2-indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium (4) dichloro {dimethylsilylene (4-methyl-2-indenyl) ( 2-methyl-4-phenyl-4H-1-azulenyl)} hafnium (4) dichloro {dimethylsilylene (5-methyl-2-indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium ( 4) Dichloro {dimethylsilylene (4,7-dimethyl-2-indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium (4) dichloro {dimethylsilylene (5,6-dimethyl-2- Indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium (4) dichloro {dimethylsilylene ( -Benzo [e] indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium (4) dichloro {dimethylsilylene (6,7-dihydro-5H-2-indacenyl) (2-methyl-4 -Phenyl-4H-1-azulenyl)} hafnium

(5) Dichloro {ethylene (4,5,6,7-tetrahydro-2-indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium (5) dichloro {dimethylsilylene (4,5, 6,7-tetrahydro-2-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium (5) dichloro {dimethylgermylene (4,5,6,7-tetrahydro-2-indenyl) (2-Methyl-4-phenyl-4H-1-azurenyl)} hafnium

(6) Dichloro {ethylene (4H-2-pentalenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium (6) dichloro {dimethylsilylene (4H-2-pentalenyl) (2-methyl-4 -Phenyl-4H-1-azulenyl)} hafnium (6) dichloro {dimethylgermylene (4H-2-pentalenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium (6) dichloro {ethylene ( 5,6-dihydro-4H-2-pentalenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium (6) dichloro {dimethylsilylene (5,6-dihydro-4H-2-pentalenyl) ( 2-methyl-4-phenyl-4H-1-azulenyl)} hafnium (6) dichloro {dimethylgermylene (5,6- Hydro-4H-2-pentalenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium

(7) Dichloro {ethylene (4-methyl-4H-2-azurenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium (7) Dichloro {dimethylsilylene (4-methyl-4H-2- Azulenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium (7) dichloro {dimethylgermylene (4-methyl-4H-2-azurenyl) (2-methyl-4-phenyl-4H-1) -Azurenyl)} hafnium (7) dichloro {dimethylsilylene (4-iso-propyl-4H-2-azurenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium (7) dichloro {dimethylsilylene ( 4-phenyl-4H-2-azulenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium

(8) Dichloro {ethylene (4-methyl-5,6,7,8-tetrahydro-4H-2-azurenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium (8) dichloro {dimethyl Silylene (4-methyl-5,6,7,8-tetrahydro-4H-2-azurenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium (8) dichloro {dimethylgermylene (4- Methyl-5,6,7,8-tetrahydro-4H-2-azurenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium

  By the way, in general, in the technical field of olefin polymerization catalysts, it is known that the catalytic action is greatly influenced by the metal species of the transition metal compound as the catalyst component, and only the metal species of certain transition metal catalysts are used. There is no theoretical guarantee that other different catalysts have equivalent catalysis. However, it has been confirmed by experiments that when the metallocene catalyst component is zirconium, titanium and hafnium of Group 4 of the periodic table, almost the same catalytic action is shown, and is well known to those skilled in the art. (See, for example, Japanese Patent Laid-Open Nos. 60-130604 and 4-100808). Accordingly, the above examples of the metallocene compounds in this specification are rational and are not merely an enumeration.

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

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

(B-1) It is well known that organoaluminum oxy compounds can activate metallocene compounds. Specific examples of such compounds include compounds represented by the following general formulas (III) to (V). Can be mentioned.

In each of the above general formulas, R ^a represents a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly preferably a hydrocarbon group having 1 to 6 carbon atoms. Moreover, several ^Ra may be same or different, respectively. P represents an integer of 0 to 40, preferably 2 to 30. The compounds represented by the general formulas (III) and (IV) are 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 general formula (V) is 10: 1 of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula R ^b B (OH) _2. It can be obtained by a reaction of ˜1: 1 (molar ratio). In the general formula (V), R ^b represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

The compound (B-2) is an ionic compound or a Lewis acid capable of reacting with the component (A) to convert the component (A) into a cation. Examples of such an ionic compound include carbonium. Examples thereof include complexes of cations such as cations and ammonium cations with organic boron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron, and tris (pentafluorophenyl) boron. Examples of the Lewis acid as described above include various organic boron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halide compounds such as aluminum chloride and magnesium chloride are exemplified.

  In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with a component (A) and can convert a component (A) into a cation. Examples of the metallocene catalyst using the non-coordinating boron compound described above are disclosed in JP-A-3-234709 and JP-A-5-247128.

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

  In the olefin polymerization catalyst (i) of the present invention, the fine particle carrier (C) can optionally be used as the component (C). Such a fine particle carrier is made of an inorganic or organic compound and is usually in the form of fine particles having a particle diameter of 5 μm to 5 mm, preferably 10 μm to 2 mm.

The inorganic carrier, _{e.g., 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 -TiO ₂ , composite oxides such as SiO ₂ —Cr ₂ O ₃ and SiO ₂ —Al ₂ O ₃ —MgO. Examples of organic carriers include (co) polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturation such as styrene and divinylbenzene. Examples thereof include porous polymer fine particle carriers made of hydrocarbon (co) polymers. The specific surface area of these particles is usually 20~1,000m ² / g, preferably 50~700m ² / g, pore volume is usually 0.1 cm ³ / g or more, preferably 0.3 cm ³ / g or more, more preferably 0.8 cm ³ / g or more.

  The olefin polymerization catalyst (i) of the present invention includes, as an optional component other than the fine particle carrier, for example, active hydrogen-containing compounds such as water, methanol, ethanol and butanol, electron donating compounds such as ethers, esters and amines, boric acid Alkoxy-containing compounds such as phenyl, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane, and diphenyldimethoxysilane can be included. Examples of optional components other than the above include tri-lower alkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum, halogen-containing alkylaluminum such as diethylaluminum chloride, diisobutylaluminum chloride and methylaluminum sesquichloride, and diethylaluminum hydride. Alkyl-containing alkylaluminums such as alkylaluminum hydride, diethylaluminum ethoxide, dimethylaluminum butoxide, and aryloxy-containing alkylaluminums such as diethylaluminum phenoxide.

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

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

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

  Component (D) is selected from the group consisting of ion-exchangeable layered compounds or inorganic silicates, and component (E) is an organoaluminum compound. Of the component (D), the ion-exchange layered compound occupies most of the clay mineral, and is preferably an ion-exchange layered silicate.

  An ion-exchange layered silicate (hereinafter, sometimes simply referred to as “silicate”) has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other and have a binding force. Refers to a silicate compound in which the ions to be exchanged are exchangeable. Most silicates are naturally produced mainly as clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. You may go out. Various known silicates can be used. Specifically, the following layered silicates described in “Clay Mineralogy” by Asakura Shoten (1995) by Haruo Shiramizu are given as typical examples.

  2: 1 type minerals include smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite and stevensite; vermiculites such as vermiculite; mica such as mica, illite, sericite and sea chlorite Group: Pyrophyllite-talc group such as pyrophyllite, talc; Chlorite group such as magnesium chlorite. On the other hand, examples of 2: 1 ribbon type minerals include sepiolite and palygorskite.

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

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

  In the olefin polymerization catalyst (ii) of the present invention, an aluminoxane such as methylaluminoxane can be used as the component (E) in addition to the organoaluminum compound represented by the above general formula. Moreover, said organoaluminum compound and aluminoxane can also be used together.

The olefin polymerization catalyst (ii) of the present invention can be prepared by the same method as in the case of the olefin polymerization catalyst (i). At this time, the contact method of the component (A) and the component (D) with the optional component (E) is not particularly limited, but the following method can be exemplified.
(1) Method of contacting component (A) and component (D) (2) Method of adding optional component (E) after contacting component (A) and component (D) (3) Component (A ) And the optional component (E) are contacted and then the component (D) is added (4) The component (D) and the optional component (E) are contacted and then the component (A) is added (5) ) Each component (A), (D), (E) is contacted simultaneously.

  The above contact operation may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin. During or after the contact of each of the above components, a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may coexist or contact. Moreover, you may perform contact of said each component in inert hydrocarbon solvents, such as pentane, hexane, heptane, toluene, and xylene, in inert gas, such as nitrogen. The contact is preferably performed at a temperature between −20 ° C. and the boiling point of the solvent, particularly at a temperature between room temperature and the boiling point of the solvent.

(3) Use amount of catalyst component The other component (A) and the use amount of component (B) or component (D) are used in an optimal amount ratio in each combination. When component (B) is an organoaluminum oxy compound, the molar ratio of Al / transition metal is usually from 10 to 100,000, more preferably from 100 to 20,000, particularly from 100 to 10,000. On the other hand, when an ionic compound or Lewis acid is used as the component (B), the molar ratio of the transition metal to the transition metal is 0.1 to 1,000, preferably 0.5 to 100, more preferably 1 to 50. It is.

  When a solid acid is used as component (B), or when an ion-exchange layered compound is used as component (D), 0.001 to 10 mmol of metallocene compound per 1 g of component (B) or component (D), preferably The range is 0.001 to 1 mmol. These use ratios are examples of normal ratios, and the present invention is limited by the range of use ratios described above as long as the catalyst meets the purpose of the invention. It is natural that it must not be.

  An olefin polymerization catalyst comprising a metallocene compound and a co-catalyst is supported on a carrier as needed before being used as a catalyst for the main polymerization, and then ethylene, propylene, 1-butene, 1-hexene, 1-octene. , 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and other olefins may be preliminarily polymerized in a small amount. A known method can be used as the prepolymerization method.

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

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

4). Analysis of characteristic values of 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, in CP The α-olefin polymerization ratio is determined by the following method. In addition, although the following examples are the cases where ethylene is used as the α-olefin in CP, α-olefins other than ethylene are obtained using a method according to the following example.

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

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

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

(4) Post-processing and analysis of measurement results The elution amount and molecular weight distribution of the components eluted at each temperature are determined 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 × Mα) used at that time.
(I) Calibration curve using standard polystyrene K = 0.000138, α = 0.70
(Ii) Sample measurement of propylene-based block copolymer K = 0.000103, α = 0.78
Ethylene content distribution of each eluted component (ethylene content distribution along the molecular weight axis), using the ratio between the absorbance of the absorbance and 2927cm ^-1 of 2956Cm ^-1 obtained by GPC-IR, polyethylene and polypropylene, and ¹³ Converted to ethylene polymerization rate (mol%) using a calibration curve prepared in advance using ethylene-propylene-rubber (EPR) and mixtures thereof whose ethylene content is known by C-NMR measurement, etc. And ask.

(5) CP content The CP content of the propylene-based block copolymer in the present invention is defined by the following formula (I), and is determined by the following procedure.

CP content (% by weight) = W ₄₀ × A ₄₀ / B ₄₀ + W ₁₀₀ × A ₁₀₀ / B ₁₀₀ (I)
In the formula (I), W ₄₀ and W ₁₀₀ are elution ratios (unit: weight%) in the above-mentioned fractions, and A ₄₀ and A ₁₀₀ are actual values in the respective fractions corresponding to W ₄₀ and W _100. It is the average ethylene content (unit: wt%) of measurement, and B ₄₀ and B ₁₀₀ are the ethylene content (unit: wt%) of CP contained in each fraction. A method for _obtaining A ₄₀ , A ₁₀₀ , B ₄₀ , and B ₁₀₀ 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 does not contain PP, W ₄₀ contributes to the content of CP derived from fraction 1 as a whole, but fraction 1 contains a small amount of components in addition to CP-derived components. Since components derived from PP (extremely low molecular weight components and atactic polypropylene) are also included, it is necessary to correct the portion. Therefore, by multiplying W ₄₀ by A ₄₀ / B ₄₀ , the amount derived from the CP component in fraction 1 is calculated. For example, when the average ethylene content (A ₄₀ ) of fraction 1 is 30% by weight and the ethylene content (B ₄₀ ) of CP contained in fraction 1 is 40% by weight, 30/40 = 3 of fraction 1 / 4 (that is, 75% by weight) is derived from CP, and 1/4 is derived from PP. Thus, the operation of multiplying A ₄₀ / B ₄₀ in the first term on the right side means that the contribution of CP is calculated from the weight% (W ₄₀ ) 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 A _40, A _100, A ₁₄₀ of fractions 1-3, the ethylene content of the weight ratio and each data point for each data point in the chromatogram absorbance 2945cm ^-1 (absorbance at 2956cm ^-1 And the product of the absorbance at 2927 cm ⁻¹ ).

The ethylene content corresponding to the peak position in the differential molecular weight distribution curve of fraction 1 is defined as B ₄₀ (unit is% by weight). Fraction 2 is considered to be completely eluted at 40 ° C. and cannot be defined with the same definition, so in the present invention, it is defined as B ₁₀₀ = 100. B ₄₀ and B ₁₀₀ are the ethylene content 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 investigations using various model samples, B ₄₀ can explain the improvement effect of material properties well when ethylene content corresponding to the peak position of the differential molecular weight distribution curve of fraction 1 is used. all right. B ₁₀₀ 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 there is almost no error in calculation. Therefore, analysis is performed with B ₁₀₀ = 100. Therefore, the CP content can be determined according to the following formula (II).

CP content _{(wt%) = W 40 × A 40} / B 40 + W 100 × A 100/100 ··· (II)
_{That, W 40 × A 40 / B} 40 is a first term of the formula (II) the right-hand side shows the CP content having no crystallinity _{(wt%), W 100 × A 100} /100 is a paragraph The CP content (% by weight) having crystallinity is shown.

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

  From the value of the ethylene content (% by weight) in the CP obtained here, the molecular weight of ethylene and propylene is finally used to convert to mol%.

Hereinafter, in order to explain the present invention more specifically and clearly, the present invention will be described in contrast to Examples and Comparative Examples, and the rationality and significance of the constituent elements of the present invention will be demonstrated. Unless it exceeds the gist, it is not limited to the following examples. In the following examples, the catalyst synthesis step and the polymerization step were all carried out in a purified nitrogen atmosphere, and the solvent was dehydrated with MS-4A (molecular sieve) and then degassed by bubbling with purified nitrogen. . The measurement and evaluation methods in the present invention are as follows.
(1) MFR measurement:
To 6 g of polymer, 6 g of an acetone solution (0.6 wt%) of a heat stabilizer (BHT) was added. Subsequently, after drying said polymer, it filled with the melt indexer (230 degreeC), and was left to stand on the conditions of a 2.16kg load for 5 minutes. Thereafter, the extrusion amount of the polymer was measured, converted into an amount per 10 minutes, and used as the MFR value (unit: g / 10 minutes).
(2) Cross separation (abbreviated as CFC)
According to the method detailed above.

[Example 1]
(1) Synthesis of metallocene compound dichloro {dimethylsilylene (2-indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium in tetrahydrofuran solution of 2-bromoindene (4.0 g, 20.6 mmol) ( 4 mL) was added dropwise to a mixture of magnesium (0.75 g, 30.9 mmol) and dichlorodimethylsilane (5.0 mL, 41.2 mmol) in tetrahydrofuran (4 mL) such that the reaction temperature was maintained at 50 ° C. After stirring at room temperature for 3 hours, the solvent was removed under reduced pressure, and the resulting solid component was extracted with hexane (30 mL × 2). Removal of the solvent under reduced pressure gave chloro (2-indenyl) dimethylsilane (3.5 g, 81%).

  2-Methylazulene (3.46 g, 16.6 mmol) was dissolved in hexane (30 mL), and a solution of phenyllithium in cyclohexane / diethyl ether (12.6 mL, 13.3 mmol) was added dropwise at 0 ° C. After dropping, the mixture was warmed to room temperature and stirred for 1 hour. After the suspension was settled down, the supernatant was removed, tetrahydrofuran (10 mL) and N-methylimidazole (0.025 mL) were added, and the chloro (2-indenyl) dimethylsilane (3.46 g, A hexane solution (10 mL) of 16.6 mmol) was added dropwise at 0 ° C. After dropping, the mixture was stirred at room temperature for 2 hours, and distilled water was added to the reaction solution, followed by extraction with diethyl ether. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (solvent: hexane) to give (2-indenyl) dimethyl (2-methyl-4-phenyl-1,4-dihydroazurenyl) silane (3.91 g). was gotten.

The obtained ligand (3.91 g) was dissolved in diethyl ether (25 mL), and a hexane solution of n-butyllithium (12.5 mL, 19.8 mmol) was added dropwise at 0 ° C. After stirring at room temperature for 3 hours, toluene (125 mL) was added, cooled to −10 ° C., and hafnium tetrachloride (2.85 g, 8.9 mmol) was added. The temperature was raised slowly and the mixture was stirred at room temperature for 3 hours. The resulting reaction solution was concentrated once and washed with diisopropyl ether (30 mL, 20 mL, 60 mL). Subsequently, the mixture was washed with a mixed solvent of diisopropyl ether (20 mL) and toluene (6 mL) and toluene (30 mL, 20 mL). When extracted from the obtained solid component with a mixed solvent of dichloromethane (10 mL) and toluene (10 mL), the target metallocene compound is dichloro {dimethylsilylene (2-indenyl) (2-methyl-4- Phenyl-4H-1-azulenyl)} hafnium (2.89 g, 51%) was obtained.
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.91 (s, 3H, Si (CH ₃ ) ₂ ), 0.96 (s, 3H, Si (CH ₃ ) ₂ ), 2.22 (s, 3H, 2 _{-CH 3), 5.00 (brd,} 1H, Azu-4-H), 5.58 (s, 1H, Azu-3-H), 5.85-6.30 (m, 5H), 6. 83 (d, J = 12 Hz, 1H, Azu-8-H), 7.2-7.7 (m, 9H, arom)

(2) Catalyst preparation Pure water (1,698 g) was put into a 5 L separable flask equipped with a stirring blade and a reflux device, and 98% sulfuric acid (501 g) was added dropwise. Further, 300 g of commercially available granulated montmorillonite (Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 19.5 μm) was added and stirred. Thereafter, the mixture was reacted at 90 ° C. for 2 hours. This slurry was washed with an apparatus in which an aspirator was connected to Nutsche and a suction bottle. An aqueous solution (900 mL) of lithium sulfate monohydrate (324 g) was added to the recovered cake and reacted at 90 ° C. for 2 hours. This slurry was washed to pH> 4 with an apparatus in which an aspirator was connected to Nutsche and a suction bottle. The collected cake was dried at 120 ° C. overnight. As a result, 275 g of a chemically treated product was obtained.
10.0 g of the chemically treated montmorillonite obtained above was weighed in a flask having an internal volume of 1 L, heptane (65 mL) and a heptane solution of triisobutylaluminum (35.4 mL, 25 mmol) were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the remaining liquid was washed to 1/100 with heptane, and finally the amount of slurry was adjusted to 100 mL.

(3) Prepolymerization with propylene A heptane solution of triisobutylaluminum (0.85 mL) was added to the montmorillonite heptane slurry prepared above and treated with triisobutylaluminum, and the mixture was stirred for 10 minutes at room temperature. In addition, a toluene (60 mL) solution of dichloro {dimethylsilylene (2-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium (300 μmol) synthesized in (1) was added to the above 1 L flask. In addition, the mixture was stirred at room temperature for 60 minutes.

Next, heptane (340 mL) was further added to the montmorillonite heptane slurry, and the mixture was introduced into a stirring autoclave having an internal volume of 1 L. At 40 ° C., propylene was added at a constant rate of 238.1 mmol / hr (10 g / hr). Feed in minutes. After completion of the propylene supply, the temperature was raised to 50 ° C. and maintained for 2 hours, after which the remaining gas was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand, and the supernatant liquid was extracted. A heptane solution of triisobutylaluminum (8.5 mL, 6.0 mmol) was added to the remaining solid at room temperature, stirred at room temperature for 10 minutes, and then dried under reduced pressure to recover 25.5 g of a solid catalyst.
The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.49.

(4) Block polymerization After the inside of the stirred autoclave with an internal volume of 3 L was sufficiently substituted with propylene, triisobutylaluminum / n-heptane solution (2.76 ml, 2.02 mmol) was added, hydrogen (90 mL), Subsequently, liquid propylene (750 g) was introduced, and the temperature was raised to 65 ° C. to maintain the temperature. The prepolymerized catalyst prepared in the above (3) was slurried in normal heptane, and 50 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. The temperature in the tank was maintained at 65 ° C., and the remaining monomer was purged after 1 hour from the introduction of the catalyst.

Thereafter, 0.9 MPa of propylene and then 1.1 MPa of ethylene were introduced, and the internal temperature was raised to 80 ° C. Thereafter, a mixed gas of propylene and ethylene prepared in advance was introduced, and the polymerization reaction was controlled for 30 minutes while adjusting the internal pressure to be 2.0 MPa so that the monomer composition ratio did not change during the polymerization. As a result, 37 g of a propylene block polymer having good particle properties was obtained.
From the result of CFC-IR, the propylene block copolymer obtained above has a rubber content (CP content) of 14% by weight, an ethylene content in rubber (CP) of 51 mol%, and MFR Was 52 (g / 10 min).

[Example 2]
(1) Synthesis of metallocene compound dichloro {dimethylsilylene (4,7-dimethyl-2-indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium 2-bromo-4,7-dimethylindene ( 4.0 g, 18.0 mmol) in tetrahydrofuran (8 mL) was added to a mixture of magnesium (0.66 g, 27 mmol) and dichlorodimethylsilane (4.4 mL, 36 mmol) in tetrahydrofuran (4 ml) at a reaction temperature of 55 ° C. Dropped to keep. After stirring at room temperature for 2 hours, the solvent was removed under reduced pressure, and the resulting solid component was extracted with hexane (30 mL × 2). Removal of the solvent under reduced pressure gave chlorodimethyl (4,7-dimethyl-2-indenyl) silane (3.25 g, 77%).
2-Methylazulene (1.56 g, 11.0 mmol) was dissolved in hexane (30 mL), and a solution of phenyllithium in cyclohexane / diethyl ether (11.2 mL, 11.7 mmol) was added dropwise at 0 ° C. After dropping, the mixture was warmed to room temperature and stirred for 1 hour. After the suspension was settled down, the supernatant was removed, tetrahydrofuran (10 mL) and N-methylimidazole (0.025 mL) were added, and chlorodimethyl (4,7-dimethyl-2) obtained above at 0 ° C. -Indenyl) silane (3.25 g, 13.8 mmol) in hexane (10 mL) was added dropwise. After dropping, the mixture was stirred at room temperature for 2 hours, and distilled water was added to the reaction solution, followed by extraction with diethyl ether. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting crude product is purified by silica gel column chromatography (solvent: hexane) to obtain dimethyl (4,7-dimethyl-2-indenyl) (2-methyl-4-phenyl-1,4-dihydroazurenyl). Silane (3.46 g) was obtained.

The obtained ligand (3.46 g) was dissolved in diethyl ether (25 mL), and a hexane solution of n-butyllithium (10.5 mL, 16.5 mmol) was added dropwise at 0 ° C. After stirring at room temperature for 2 hours, toluene (125 mL) was added, cooled to −10 ° C., and hafnium tetrachloride (2.63 g, 8.3 mmol) was added. The temperature was raised slowly and the mixture was stirred overnight at room temperature. The resulting reaction solution was concentrated to about ½ and washed with hexane (10 mL).
Subsequently, it was washed with ethanol (10 mL) and subsequently with hexane (5 mL). When the obtained solid component was dried under reduced pressure, dichloro {dimethylsilylene (4,7-dimethyl-2-indenyl) (2-methyl-4-phenyl-4H-1- Azulenyl)} hafnium (2.76 g, 50%) was obtained.
¹ H NMR (400 MHz, CDCl ₃ ) δ 0.91 (s, 3H, Si (CH ₃ ) ₂ ), 0.97 (s, 3H, Si (CH ₃ ) ₂ ), 2.21 (s, 3H, 2 _{-CH 3), 2.45 (s,} 3H, CH 3), 2.47 (s, 3H, CH 3), 5.00 (brd, 1H, Azu-4-H), 5.60 (s, 1H, Azu-3-H), 5.85-6.25 (m, 5H), 6.83 (d, J = 12 Hz, 1H, Azu-8-H), 6.65-6.97 (m , 2H, arom), 7.20-7.35 (m, 5H, arom)

(2) Preliminary polymerization and block polymerization Implemented except that the dichloro {dimethylsilylene (4,7-dimethyl-2-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)} hafnium synthesized above was used. A prepolymerized catalyst was prepared in the same manner as in Example 1, (2) and (3). The prepolymerization ratio (value obtained by dividing the prepolymerized polymer amount by the solid catalyst amount) was 0.82.
Subsequently, after the inside of the stirred autoclave having an internal volume of 3 L was sufficiently substituted with propylene, triisobutylaluminum / n-heptane solution (2.76 mL, 2.02 mmol) was added, followed by liquid propylene (750 g). The temperature was raised to 65 ° C. and maintained at that temperature. The prepolymerized catalyst prepared in the above (2) was slurried in normal heptane, and 200 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. The temperature inside the tank was maintained at 75 ° C., and after 1 hour from the catalyst addition, the remaining monomer was purged, and the inside of the tank was replaced five times with argon. Stirring was stopped, a Teflon tube was inserted into the tank, and a small amount of polypropylene was extracted. As a result of measurement after drying for 30 minutes under a nitrogen stream at 90 ° C., the extraction amount was 2 g. Thereafter, 0.8 MPa of propylene and then 1.2 MPa of ethylene were introduced, and the internal temperature was raised to 80 ° C. Thereafter, a mixed gas of propylene and ethylene prepared in advance was introduced, and the polymerization reaction was controlled for 30 minutes while adjusting the internal pressure to be 2.0 MPa so that the monomer composition ratio did not change during the polymerization. As a result, 45 g of a propylene-based block polymer having good particle properties was obtained.
From the result of CFC-IR, the propylene-based block copolymer obtained above has a rubber content (CP content) of 40% by weight, an ethylene content in rubber (CP) of 42.5 mol%, MFR Was 1600 g / 10 min.

[Comparative Example 1]
(1) Metallocene compound Dichloro {1,1'-dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenylyl)-having the following structural formula by the method described in JP-A 2000-95791 4H-azulenyl)} hafnium was synthesized. This metallocene compound has a structure in which two hydroazurenyl groups are bonded at the 1-position via a dimethylsilylene group which is a bridging group, and is a comparative example not included in the claims of this application.
(2) Prepolymerization and block polymerization Example 1 of Example 1 except that dichloro {1,1'-dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl)} hafnium is used. A prepolymerized catalyst was prepared in the same manner as (2) and (3). The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 2.22.

  Subsequently, polymerization was carried out in the same manner as in Example 4 (4). As a result, 28.3 g and 433 g of a propylene-based block polymer were obtained at the end of the first stage polymerization. From the result of CFC-IR, the obtained propylene block copolymer has a rubber content (CP content) of 58.6% by weight, an ethylene content in rubber (CP) of 25.8 mol%, and MFR. Was 24 g / 10 min.

[Comparative Example 2]
(1) Metallocene compound Dichloro {dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4-phenyl-4H-) having the following structural formula by the method described in JP-A-2005-2158 1-azurenyl)} hafnium was synthesized. This metallocene compound has a structure in which a hydroazurenyl group and an indenyl group are bonded to each other via a dimethylsilylene group as a bridging group at the 1-position, and is a comparative example not included in the claims of the present application.
(2) Prepolymerization and block polymerization Example 1 except that dichloro {dimethylsilylene (2-methyl-1-benzo [e] indenyl) (2-methyl-4-phenyl-4H-1-azulenyl)} hafnium is used. A prepolymerized catalyst was prepared in the same manner as in (2) and (3). The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.12.

  Subsequently, polymerization was carried out in the same manner as in Example 2 (2). As a result, 17 g and 137 g of a propylene-based block polymer were obtained at the end of the first stage polymerization. From the result of CFC-IR, the resulting propylene-based block copolymer has a rubber content (CP content) of 20% by weight, an ethylene content in rubber (CP) of 24 mol%, and an MFR of 13 ( g / 10 minutes).

[Consideration of results of Examples and Comparative Examples]
By comparing each of the above Examples and Comparative Examples, it can be seen that in the present invention, a copolymer having a higher ethylene content is obtained with the same gas composition than in the Comparative Example. Therefore, in the present invention, when a novel metallocene compound having a specific structure represented by the general formula (I) or (II) and a catalyst comprising the same are used, ethylene or an α- having 4 to 20 carbon atoms is used. It has been shown that a catalyst exhibiting a balanced reactivity of olefin and propylene can be provided.

In each of the comparative examples in which the metallocene compound of the present invention is not used as a catalyst, a copolymer having a desired ethylene content is not obtained in both comparative examples 1 and 2. Although the ethylene content can be increased by increasing the ethylene partial pressure, such operations are industrially limited and there is also a limitation on increasing the ethylene content.

Claims (12)

Metallocene compounds represented by the following general formula (I).

(Wherein, R ^1, R ^2, R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group, any of R ^1, R ² One of them is a hydrogen atom, R ³ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 6 carbon atoms, and R ⁴ represents a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing group. represents a hydrocarbon group, n is 0 or an 2 times or less an integer number of carbon atoms in R ^3, when n is 2 or more, R ⁴ to each other to form a ring structure at an arbitrary position R ⁷ represents a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing hydrocarbon group having 6 or more carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen Represents an atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group, Q represents a bridging group, and X and Y are Each independently represents a ligand that forms a σ bond with M, and M represents a transition metal of Groups 4 to 6 of the periodic table.) A metallocene compound represented by the following general formula (II).

(Wherein, R ^1, R ^2, R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group, any of R ^1, R ² One of them is a hydrogen atom, R ³ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 6 carbon atoms, and R ⁴ represents a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing group. represents a hydrocarbon group, m represents an integer of 0 to 4, when m is 2 or more, may be R ⁴ to each other to form a ring structure at an arbitrary position .R ^7, the carbon Represents a hydrocarbon group, a halogenated hydrocarbon group or a silicon-containing hydrocarbon group having a number of 6 or more, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a hydrocarbon group or a silicon-containing group. Represents a hydrocarbon group or a halogenated hydrocarbon group, Q represents a bridging group, and X and Y each independently represent M It represents a ligand forming a σ bond, M represents a 4-6 transition metals of the periodic table.) R ¹ , R ² , R ⁵ and R ⁶ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group. Metallocene compounds described in 1. The metallocene compound according to any one of claims 1 to 3, wherein R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, a silicon-containing hydrocarbon group, or a halogenated hydrocarbon group. R < ⁷ > is a C6-C12 hydrocarbon group, a halogenated hydrocarbon group, or a silicon-containing hydrocarbon group, The metallocene compound of any one of Claims 1-4. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a silicon-containing hydrocarbon group or a halogenated hydrocarbon group. The metallocene compound of any one of these.   The metallocene compound according to any one of claims 1 to 6, wherein the transition metal M is titanium, zirconium or hafnium.   A catalyst component for olefin polymerization, comprising the metallocene compound according to any one of claims 1 to 7. An olefin polymerization catalyst comprising the following components (A) and (B) and optionally a component (C).
Component (A): Metallocene compound described in any one of claims 1 to 7 Component (B): An organoaluminum oxy compound, which reacts with component (A) to convert component (A) into a cation Compound component (C) selected from the group consisting of possible ionic compounds or Lewis acids: particulate carrier An olefin polymerization catalyst comprising the following components (A) and (D) and optionally a component (E).
Component (A): Metallocene compound described in any one of claims 1 to 7 Component (D): Compound component selected from the group consisting of an ion-exchange layered compound or inorganic silicate (E): Organoaluminum compound   An α-olefin polymerization method using the olefin polymerization catalyst according to claim 9 or 10, wherein the α-olefin is polymerized. A method for polymerizing an α-olefin, characterized in that propylene is copolymerized with ethylene or an α-olefin having 4 to 20 carbon atoms using the olefin polymerization catalyst according to claim 9 or 10.