JP2014181314A - Catalyst for polymerizing propylene and method for manufacturing propylene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing, efficiently based on a simple methodology, a propylene polymer suitable for blow molding and extrusion foam molding, etc., exhibiting favorable fluid characteristics such as melt tension, melt viscoelasticity, etc. and accordingly an excellent molding workability on a blow molding occasion owing to a high swell ratio, and capable, on an extrusion foam molding occasion, of enhancing the isolated foam ratio owing to a potent strain curability.SOLUTION: The provided catalyst for polymerizing propylene, etc. includes at least the following components [A] through [D]: component [A]: at least two types of transition metal compounds selected respectively from between components [A-1] and [A-2] comprising compounds of group 4 transition metals of the periodic table; component [B]: at least one type selected from the compound group consisting of [B-1] aluminum oxy compounds supported on solid particulates, [B-2] ionic compounds or Lewis acids supported on solid particulates and convertible into cations as a result of reactions thereof with the transition metal compound [A], and [B-3] ion-exchangeable laminar silicates; component [C]: an organoaluminum compound; and component [D]: a cyclopentadiene derivative.

Description

  The present invention relates to a catalyst for propylene polymerization and a method for producing a propylene-based polymer. More specifically, the flow characteristics such as melt tension and melt viscoelasticity are good, and accordingly, the molding process is performed because the swell ratio is high at the time of blow molding. Propylene polymerization catalyst capable of producing a propylene polymer suitable for blow molding, extrusion foam molding and the like, and a propylene-based polymer using the same The present invention relates to a method for manufacturing coalescence.

Conventionally, polypropylene has high mechanical strength such as rigidity, excellent balance of physical properties, chemically stable, excellent weather resistance, hardly affected by chemicals, etc., and has a high melting point, excellent heat resistance, and light weight. Since it has features such as being inexpensive, it is widely used in many fields.
However, ordinary polypropylene has low melt tension and melt viscoelasticity, and has problems such as restrictions on use in thermoforming, foam molding, blow molding and the like.

  In order to solve them, as a method of adding a component that increases the melt tension, a method of mixing high-density polyethylene with a high melt tension produced by a chromium catalyst, a method of mixing low-density polyethylene by a high-pressure radical polymerization method, propylene A method of polymerizing high molecular weight polyethylene in the pre-polymerization stage is known, but the original characteristics of polypropylene are impaired, such as lack of elasticity, strength, heat resistance, or fluidity of components that increase melt tension. There is a disadvantage that it ends up.

  In view of this, methods have been proposed in which melt tension can be increased by introducing cross-linking or long-chain branching of polypropylene itself, and various attempts have been made. As a method for crosslinking, a method of irradiating an electron beam after polymerization (see Patent Document 1), a method using a peroxide, a peroxide and a crosslinking aid (see Patent Document 2), or a long chain. Examples of the method for introducing a branch include a method of grafting a radical polymerizable monomer onto polypropylene (see Non-Patent Document 1), a method of copolymerizing propylene and polyene (see Patent Document 3), and the like.

  However, in the method of cross-linking after polymerization, it is difficult to control the side reaction of high-order cross-linking, the appearance defects and the mechanical properties are adversely affected by the generation of gel, and the moldability is arbitrarily controlled. However, there is a problem that the control range is narrow. On the other hand, in the method of grafting a radically polymerizable monomer, the chemical stability of polypropylene is impaired, and there is a problem in recyclability. Furthermore, in the method based on copolymerization with polyene, the effect of improving the melt tension is not always sufficient, and the occurrence of gel is also a concern, so it is difficult to control the physical properties. In addition, a process for separating and recovering the polyene is essential after the completion of the copolymerization, and there remains a problem in terms of production cost.

Recently, a macromer copolymerization method mainly using a metallocene catalyst has been proposed.
The metallocene catalyst is a transition metal compound having at least one conjugated five-membered ring ligand in a broad sense, and a ligand having a crosslinked structure is generally used for propylene polymerization. Initially found as complexes capable of producing isotactic polyolefin, ethylene bis (indenyl) zirconium dichloride and ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride (Japanese Patent Laid-Open No. 61-130314) ), Dimethylsilylene bis-substituted cyclopentadienylzirconium dichloride having a silylene group as a bridging group (JP-A-1-301704), dimethylsilylenebis (indenyl) zirconium dichloride (JP-A-1-275609), cyclopentadiene Dimethylsilylenebis (2-methylindenyl) zirconium dichloride (Japanese Patent Laid-Open No. 4-268307) whose stereoregularity and molecular weight are improved to some extent by attaching a substituent next to the bridging group of the enyl compound (2-position). further Dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride (Japanese Patent Laid-Open No. 6-1005209) and dimethylsilylene bis, which are further improved in activity, stereoregularity and molecular weight by introducing an aryl group at the position (2-Methyl-4-phenyl-4-hydroazurenyl) zirconium dichloride (Japanese Patent Laid-Open No. 10-226712), and more recently, dichloro (1,1) having a specific substituent introduced into a specific position of the 4-position aryl group 1'-dimethylsilylenebis (2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4H-azulenyl)) hafnium (Japanese Patent Laid-Open No. 2003-292518), bulky hetero substitution at position 2 JP-A 2002-194016, JP-T 2002-535339, JP-A 2004 2259, JP-2004-352707 Patent Publication discloses JP.
These are mainly for the purpose of improving the catalytic activity and the melting point and molecular weight of the resulting polypropylene, and there is no suggestion of the suitability for producing macromers or polypropylene having long chain branches.

  As a macromer copolymerization method using a metallocene catalyst, for example, in the first stage of polymerization (hereinafter also referred to as a macromer synthesis step), a propylene macromer having a vinyl structure at the terminal is produced using a specific catalyst and specific polymerization conditions. Then, in the second stage of polymerization (hereinafter also referred to as a macromer copolymerization process), copolymerization with propylene under a specific catalyst and specific polymerization conditions eliminates high-order crosslinking, and inherently as polypropylene. Has been proposed (hereinafter also referred to as a macromer copolymerization method), which is excellent in recyclability and free from concern about gel formation for improving melt tension (Patent Document). 4 and 5).

  However, in this method, it is necessary to perform polymerization at a relatively high temperature and low pressure in order to efficiently obtain the terminal vinyl structure required as a macromer in the previous stage. In the latter stage, copolymerization of the macromer and propylene obtained in the previous stage is carried out, but since the amount of macromer to be copolymerized is small relative to the charged amount of macromer, the amount of macromer copolymer to be produced is a non-negligible amount. Macromers with low molecular weight and stereoregularity remain. Furthermore, a component having a low molecular weight and low regularity other than vinyl, for example, a saturated terminal component, which is by-produced in the macromer synthesis process, is contained without being copolymerized, and as a result, the product As a result, mechanical properties such as rigidity and impact strength are lowered, stickiness problems occur, and control of fluidity and moldability becomes difficult.

In contrast to the above-described multistage polymerization method, a homopolymerization method in which a macromer synthesis step and a macromer copolymerization step are simultaneously performed has been proposed (for example, see Patent Document 6).
However, with this known technique, the amount of macromer produced and the amount of macromer copolymerization are not necessarily sufficient, and the effect of improving the melt properties is insufficient.

On the other hand, a method for producing a propylene polymer having a wide molecular weight distribution and a wide stereoregularity distribution using two types of complexes is also known, for example, ethylene bisindenyl hafnium dichloride and a small amount of ethylene bisindenyl zirconium dichloride. Polypropylene having a molecular weight distribution (Q value) of 4.8 to 6.3 has been reported to be obtained by a catalyst composed of a complex mixed with methylaluminoxane (see Patent Document 7), but it is simply bimodal. Only the molecular weight distribution is obtained, and the effect of improving the melt physical properties is not great.
Recently, two metallocene complexes, specifically rac-SiMe ₂ [2-Me-4-Ph-Ind] ₂ ZrCl ₂ and rac-SiMe ₂ [2-Me-4-Ph-Ind] ₂ It has been reported that a propylene-based polymer obtained by multistage polymerization exhibits a relatively high melt tension in a catalyst combined with silica supporting methylaluminoxane (MAO) using a complex such as HfCl ₂ ( (See Patent Document 8).
However, none of these methods has been put into practical use, and development of a method for producing a propylene-based polymer capable of improving the melt properties by a simpler technique industrially is desired.

Further, in view of the situation as described above, the present inventors supported two kinds of complexes of a macromer production complex having a specific structure and a macromer copolymer complex having a specific structure on the same carrier, The present inventors have found a method for producing a propylene polymer having improved melt properties in which long chain branching has been introduced (see Patent Documents 9, 10, and 11).
However, the propylene-based polymer having improved melt properties can be suitably used, for example, for foam molding, but in the future, in order to produce a molded article having a higher expansion ratio, the amount of branching is further increased. It is desired to obtain a propylene-based polymer, and it is strongly desired to find a method for efficiently producing such a polymer.

US Pat. No. 5,541,236 WO99 / 27007 International Publication Pamphlet Japanese Patent Laid-Open No. 05-194778 JP-T-2001-525460 JP 10-338717 A Special table 2002-523575 gazette Japanese Patent Laid-Open No. 02-255812 JP 2001-064314 A JP 2009-108247 A JP 2009-057542 A JP 2009-040959 A

T. T. et al. C. Chung et al, Synthesis of Polypropylene-graft-poly (methyl methacrylate) Polymers by Borane Approach, Macromolecules, (1993), volume 26. 14, page 3467-3471

  The object of the present invention is to provide excellent flow characteristics such as melt tension and melt viscoelasticity in view of the above-mentioned problems of the prior art. An object of the present invention is to provide a method for efficiently producing a propylene-based polymer suitable for blow molding, extrusion foam molding and the like, which can increase the closed cell ratio because it exhibits strong strain hardening at the time of molding.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research, and as a result, carried out propylene polymerization by single-stage polymerization in the presence of a catalyst comprising two specific transition metal compound components and a cyclopentadiene derivative. However, the inventors have found that a polymer having a large amount of long-chain branching can be efficiently produced, and have completed the present invention.

That is, according to the first aspect of the present invention, there is provided a propylene polymerization catalyst comprising at least the following components [A] to [D].
Component [A]: At least two kinds of transition metal compounds each selected from the following components [A-1] and [A-2], which are Group 4 transition metal compounds. However, the ratio of the molar amount of [A-1] to the total molar amount of components [A-1] and [A-2] {[A-1] / ([A-1] + [A-2]) } Is 0.20 to 0.99.
[A-1]: A compound represented by the general formula (a1).

[In General Formula (a1), R ¹¹ and R ¹² independently represent a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen, or sulfur. R ¹³ and R ¹⁴ are each independently an aryl group having 6 to 16 carbon atoms which may contain a halogen atom, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these, Alternatively, it represents a heterocyclic group having 6 to 16 carbon atoms containing nitrogen, oxygen or sulfur. M ¹¹ represents zirconium or hafnium, and X ¹¹ and Y ¹¹ each independently represent a silyl having a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Group, a C1-C20 halogenated hydrocarbon group, an amino group, or a C1-C20 alkylamino group. Q ¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]
[A-2]: A compound represented by the general formula (a2).

[In General Formula (a2), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms. R ²³ and R ²⁴ are each independently a halogen atom, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. Q ²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. M ²¹ represents zirconium or hafnium, and X ²¹ and Y ²¹ each independently represent a silyl having a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Group, a C1-C20 halogenated hydrocarbon group, an amino group, or a C1-C20 alkylamino group. ]
Component [B]: an aluminum oxy compound [B-1], an ionic compound or Lewis acid [B-2] that can be converted into a cation by reacting with the transition metal compound [A], solid acid fine particles [B -3], and at least one selected from the group of compounds consisting of ion-exchangeable layered silicate [B-4].
Component [C]: an organoaluminum compound.
Component [D]: cyclopentadiene derivative.

  According to a second aspect of the present invention, there is provided a propylene polymerization catalyst characterized in that, in the first aspect, the component [D] is a cyclopentadiene derivative represented by the following general formula (2): Provided.

[In General Formula (2), E ^a1 and E ^a2 are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. Q ^a1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

According to a third aspect of the present invention, there is provided a catalyst for propylene polymerization according to the first or second aspect, wherein the component [B] is an ion-exchange layered silicate [B-4]. Is done.
Furthermore, according to the fourth invention of the present invention, there is provided a propylene polymerization catalyst characterized in that, in the third invention, the ion-exchange layered silicate [B-4] is a smectite group.

  Moreover, according to 5th invention of this invention, the manufacturing method of the propylene polymer characterized by using the catalyst for propylene polymerization which concerns on any 1st-4th invention is provided.

  According to the propylene polymerization catalyst and the method for producing a propylene polymer of the present invention, a propylene polymer having a large amount of long-chain branching can be efficiently produced by a simple technique. Increased long chain branching provides good flow properties such as melt tension and melt viscoelasticity, and is accompanied by high swell ratio during blow molding, and excellent processability, and strong strain hardening during extrusion foam molding. Therefore, it can be used suitably for blow molding, extrusion foam molding and the like, which can increase the closed cell ratio. For this reason, the industrial significance of the present invention is very large.

It is a figure which shows the evaluation result of the branching index (g ') in 3D-GPC of the propylene-type polymer of Example 1 and Comparative Example 1.

The propylene polymerization catalyst of the present invention is characterized by containing at least the components [A] to [D] described later. The polymer (polymer) obtained by this catalyst is a long-chain branched propylene polymer that is controlled in its melt fluidity and melt tension depending on its properties and has an excellent balance between physical properties and processability.
Hereinafter, the propylene polymerization catalyst of the present invention and the method for producing a propylene polymer using the same will be described in detail for each item.

1. Propylene Polymerization Catalyst The propylene polymerization catalyst used in the method for producing a propylene polymer of the present invention must contain the following components [A] to [D].

1-1. Propylene Polymerization Catalyst Component (1) Component [A]: Transition Metal Compound As component [A], there are at least two transition metal compounds selected from the following components [A-1] and [A-2], respectively. Used.
That is, in this case, it means that two or more transition metal compounds selected from at least one from [A-1] and at least one from [A-2] are used. It is preferable to use one from each of A-2]. In addition to one or more of each, a transition metal compound other than the components [A-1] and [A-2] can be used in combination.

(1-1) Component [A-1]
Component [A-1] is a transition metal compound represented by the following structural formula (general formula) (a1).

[In General Formula (a1), R ¹¹ and R ¹² independently represent a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen, or sulfur. R ¹³ and R ¹⁴ are each independently an aryl group having 6 to 16 carbon atoms which may contain a halogen atom, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these, Alternatively, it represents a heterocyclic group having 6 to 16 carbon atoms containing nitrogen, oxygen or sulfur. M ¹¹ represents zirconium or hafnium, and X ¹¹ and Y ¹¹ each independently represent a silyl having a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Group, a C1-C20 halogenated hydrocarbon group, an amino group, or a C1-C20 alkylamino group. Q ¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

The heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms of R ¹¹ and R ¹² is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, a substituted group. 2-furfuryl group, more preferably a substituted 2-furyl group.
Moreover, as a substituted 2-furyl group, a substituted 2-thienyl group, and a substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group, Examples thereof include halogen atoms such as fluorine atom and chlorine atom, alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, and trialkylsilyl groups. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
Further, R ¹¹ and R ¹² are particularly preferably a 2- (5-methyl) -furyl group. R ¹¹ and R ¹² are preferably the same as each other.

R ¹³ and R ¹⁴ are aryl groups having 6 to 16 carbon atoms, which may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these, In addition, as the aryl group, in the range of 6 to 16 carbon atoms, on the aryl cyclic skeleton, one or more hydrocarbon groups having 1 to 6 carbon atoms, trialkylsilyl groups having 1 to 6 carbon atoms, carbon The halogen-containing hydrocarbon group of Formula 1-6 may have as a substituent.
R ¹³ and R ¹⁴ may be a heterocyclic group having 6 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Such a heterocyclic group is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, or a substituted 2-furfuryl group, and more preferably a substituted 2 furyl group. -Furyl group. Examples of these substituents include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl and propyl groups, halogen atoms such as fluorine and chlorine atoms, alkoxy having 1 to 6 carbon atoms such as methoxy and ethoxy groups. Group, a trialkylsilyl group. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
R ¹³ and R ¹⁴ are preferably at least one of a phenyl group, a 4-t-butylphenyl group, a 2,3-dimethylphenyl group, a 3,5-di-t-butylphenyl group, and a 4-phenyl-phenyl group. , A chlorophenyl group, a naphthyl group, or a phenanthryl group, and more preferably a phenyl group, a 4-t-butylphenyl group, and a 4-chlorophenyl group. R ¹³ and R ¹⁴ are preferably the same as each other.

In the general formula (a1), M ¹¹ is zirconium or hafnium, preferably hafnium.
Further, the X ¹¹ and Y ¹¹ are auxiliary ligands, it reacts with the cocatalyst component (B), to form an active metallocene having olefin polymerizability. Therefore, as long as this object is achieved, X ¹ and Y ¹ are not limited to the type of ligand, and are independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. Represents a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, or an alkylamino group having 1 to 20 carbon atoms.
Here, the silyl group having a hydrocarbon group having 1 to 20 carbon atoms is a trialkylsilyl group, dialkylarylsilyl group, alkyldiarylsilyl group, or triarylsilyl group having 1 to 20 carbon atoms.

In general formula (a1), Q ¹¹ is a divalent valence having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings. Or a silylene 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 or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

Of the compounds represented by the general formula (a1), preferred compounds are specifically exemplified below.
(1) dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium,
(2) dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl-indenyl}] hafnium,
(3) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(4) dichloro [1,1′-diphenylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(5) Dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(6) dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium,
(7) dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(8) dichloro [1,1′-dimethylsilylenebis {2- (5-trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(9) Dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium,
(10) Dichloro [1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium dichloride,
(11) Dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) -4-phenyl-indenyl}] hafnium,
(12) dichloro [1,1′-dimethylsilylenebis {2- (2-furfuryl) -4-phenyl-indenyl}] hafnium,
(13) Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium,
(14) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] hafnium,
(15) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium,
(16) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium,
(17) Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] hafnium,
(18) dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium,
(19) Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium,
(20) dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium,

(21) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium,
(22) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium,
(23) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium,
(24) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium,
(25) dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium,
(26) dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium,
(27) Dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium,
(28) Dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium,
And so on.

  Of these, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethyl gel are more preferable. Mylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( 4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1, 1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-tert-butylphenyl) -indenyl}] hafnium, dichloro [1,1′- Methylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl- 2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-biphenylyl-indenyl}] hafnium It is.

  Particularly preferred is dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl }] Hafnium.

(1-2) Component [A-2]
Component [A-2] is a transition metal compound represented by the following structural formula (general formula) (a2).

[In General Formula (a2), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms. R ²³ and R ²⁴ are each independently a halogen atom, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. Q ²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. M ²¹ represents zirconium or hafnium, and X ²¹ and Y ²¹ each independently represent a silyl having a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Group, a C1-C20 halogenated hydrocarbon group, an amino group, or a C1-C20 alkylamino group. ]

R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.

R ²³ and R ²⁴ each independently contain a halogen atom, silicon, or a plurality of heteroelements selected from these, having 6 to 30 carbon atoms, preferably 6 to 6 carbon atoms. 24 aryl groups. Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

X ²¹ and Y ²¹ are auxiliary ligands, which react with the component [B] as a cocatalyst to generate an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ²¹ and Y ²¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms. Show.

Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that connects two five-membered rings and bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms. It shows either a silylene group or a germylene group which may have 1 to 20 hydrocarbon groups. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ²¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.
Further, M ²¹ is zirconium or hafnium, preferably hafnium.

Non-limiting examples of the transition metal compound represented by the general formula (a2) include the following.
However, only representative exemplary compounds are described avoiding many complicated examples. Moreover, although the compound in which the central metal is hafnium has been described, it is obvious that the same zirconium compound can also be used, and various ligands, cross-linking groups, or auxiliary ligands can be arbitrarily used.
(1) dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazurenyl)} hafnium,
(2) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium,
(3) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(4) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(5) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(6) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(7) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(8) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(9) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (1-naphthyl) -4-hydroazurenyl}] hafnium,
(10) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4-hydroazurenyl}] hafnium,
(11) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium,
(12) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(13) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(14) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (9-phenanthryl) -4-hydroazurenyl}] hafnium,
(15) Dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium,
(16) dichloro [1,1′-dimethylsilylenebis {2-n-propyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(17) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,
(18) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
(19) Dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(20) Dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (4-tert-butylphenyl) -4-hydroazurenyl}] hafnium,

(21) Dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium,
(22) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium,
(23) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium,
(24) dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium,
Etc.

  Of these, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- Methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4 -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] ha Dichloro, [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, is there.

  Particularly preferably, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl -4- (2-Fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4- Hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] Hafnium.

(2) Component [B]
As the component [B], an aluminum oxy compound [B-1], an ionic compound that can be converted into a cation by reacting with the transition metal compounds [A-1] and [A-2], or a Lewis acid [ B-2], solid acid fine particles [B-3], and ion-exchanged layered silicate [B-4] are used.

(2-1) Component [B-1]: Aluminum Oxy Compound As the aluminum oxy compound [B-1], specifically, a compound represented by the following general formula (3), (4) or (5) Is mentioned.

In each of the above general formulas, R ³¹ , R ⁴¹ and R ⁵¹ represent a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. A plurality of R ³¹ , R ⁴¹ and R ⁵¹ may be the same or different. P represents an integer of 0 to 40, preferably 2 to 30.
The compounds represented by the general formulas (3) and (4) are also called alumoxanes. Among these, methylalumoxane or methylisobutylalumoxane is preferable.
The above-mentioned alumoxane can be used in combination within a group and between groups. And said alumoxane can be prepared on well-known various conditions.
The compound represented by the general formula (5) is 10: 1 to 1 of one type of trialkylaluminum or two or more types of trialkylaluminum and the alkylboronic acid represented by the following general formula (6). : 1 (molar ratio) reaction.
In general formulas (5) and (6), R ⁵² and R ⁵¹ represent a hydrocarbon residue or halogenated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

  Component [B-1] can also be used by being supported on a particulate carrier. The fine particle carrier will be described later.

(2-2) Component [B-2]: An ionic compound or Lewis acid component [B-2] that can be converted into a cation by reacting with the transition metal compound [A] is the transition metal compound described above. An ionic compound or a Lewis acid that can be converted to a cation by reacting with [A].
Specifically, examples of the ionic compound include a cation such as a carbonium cation and an ammonium cation, and an organic boron compound such as tetraphenylboron, tetrakis (3,5-difluorophenyl) boron, and tetrakis (pentafluorophenyl) boron. And a complex with an anion.
Examples of the Lewis acid that can convert the component [A] into a cation include various organoboron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halogen 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 component [A] and can convert component [A] into a cation. Therefore, the compounds belonging to both the Lewis acid and the ionic compound belong to either one. The fine particle carrier will be described later.

(2-3) Component [B-3]: Solid acid fine particles As solid acid fine particles [B-3], solid acids such as alumina and silica-alumina, and the components [B-1] and [B-2] described above are used. And a solid acid or the like supported on a particulate carrier.
Here, a solid acid having components [B-1] and [B-2] supported on a particulate carrier will be described.
In the present invention, the elemental composition and the compound composition of the particulate carrier are not particularly limited. For example, a particulate carrier made of an inorganic or organic compound can be exemplified. Examples of the inorganic carrier include silica, alumina, silica / alumina magnesium chloride, activated carbon, inorganic silicate, and the like. Alternatively, a mixture thereof may be used.
Examples of the organic carrier include polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturated carbonization such as styrene and divinylbenzene. Examples thereof include a porous polymer fine particle carrier made of a polymer of hydrogen. Alternatively, a mixture thereof may be used.
These fine particle carriers usually have an average particle diameter of 1 μm to 5 mm, preferably 5 μm to 1 mm, more preferably 10 μm to 200 μm.

(2-4) Component [B-4]: Ion Exchange Layered Silicate Component [B-4] is an ion exchange layered silicate (hereinafter simply referred to as silicate).
In the present invention, the silicate used as a raw material is a silicate compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with each other and having exchangeable ions. Say. Most silicates are naturally produced mainly as the main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. But you can. Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
That is, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stemite and other smectites, vermiculite and other vermiculites, mica, illite, sericite and sea chlorite and other mica, attapulgite, sepiolite and palygorskite , Bentonite, pyrophyllite, talc, chlorite group, etc.

The silicate used as a raw material in the present invention is preferably a silicate in which the main component silicate has a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The type of interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easy and inexpensive to obtain as an industrial raw material.
Although the silicate used by this invention can be used as it is, without performing a process especially, it is preferable to give a chemical process. Here, the chemical treatment may be any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the structure of the clay. Specific examples of the chemical treatment in the present invention include (a) acid treatment, (b) salt treatment, (c) alkali treatment, (d) organic matter treatment, and the like described below.

(A) Acid treatment In addition to removing impurities on the surface, the acid treatment can elute some or all of cations such as Al, Fe, Mg, etc. having a crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid. Two or more salts and acids may be used in the treatment. The conditions for treatment with salts and acids are not particularly limited. Usually, the salt and acid concentrations are selected from 0.1 to 50% by weight, the treatment temperature is from room temperature to boiling point, and the treatment time is from 5 minutes to 24 hours. Then, it is preferable to carry out under the condition that at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchanged layered silicate is eluted. In addition, salts and acids are generally used in an aqueous solution.

(B) Salt treatment In the present invention, 40% or more, preferably 60% or more, of the exchangeable Group 1 metal cation contained in the ion-exchangeable layered silicate before treatment with salts is described below. It is preferable to exchange ions with cations dissociated from the salts shown.

The salt used in the salt treatment for the purpose of ion exchange is a group consisting of a cation containing at least one atom selected from the group consisting of group 1 to 14 atoms, a halogen atom, an inorganic acid, and an organic acid. A compound comprising at least one anion selected from the group consisting of at least one anion selected from the group consisting of 2 to 14 atoms, and Cl, Br, I, F, PO. ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), At least one anion selected from the group consisting of OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₅ H ₅ O ₇ Is a compound consisting of

_{Specifically, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O 4, LiClO 4, Li ₃ PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg (PO ₄ ) ₂ , _{mg (ClO 4) 2, MgC} 2 O 4, mg (NO 3) 2, mg (OOCCH 3) 2, MgC 4 H 4 O 4 and the like _{and, Ti (OOCCH 3) 4,} Ti (CO 3) 2, Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , Zr F ₄ , ZrCl ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), HF (OOCCH ₃ ) ₄ , HF (CO ₃ ) ₂ , HF (NO ₃ ) ₄ , _{HF (SO 4) 2, HFOCl} 2, HFF 4, HFCl 4, V (CH 3 COCHCOCH 3) 3, VOSO 4, VOCl 3, VCl 3, VCl 4, VBr 3 , etc. _{and, Cr (CH 3 COCHCOCH 3)} 3 Cr (OOCCH ₃ ) ₂ OH, Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₂ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI _{3 , Mn (OOCCH 3) 2,} Mn (CH 3 COCHCOCH 3) 2, MnCO 3, Mn (NO 3) 2, MnO, Mn _{ClO 4) 2, MnF 2,} MnCl 2, Fe (OOCCH 3) 2, Fe (CH 3 COCHCOCH 3) 3, FeCO 3, Fe (NO 3) 3, Fe (ClO 4) 3, FePO 4, FeSO 4, Fe ₂ (SO ₄ ) ₃ , FeF ₃ , FeCl ₃ , FeC ₆ H ₅ O ₇ , Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _2, etc., Zn (OOCCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Z n (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.

(C) Alkali treatment Examples of the treating agent used in the alkali treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (OH) ₂ .

(D) Organic substance treatment Examples of the organic substance used for the organic substance treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
Further, examples of the anion constituting the organic treatment agent include hexafluorophosphate, tetrafluoroborate, and tetraphenylborate other than the anion exemplified as the anion constituting the salt treatment agent. However, it is not limited to these.

These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water and use them as component [B-4].
The heat treatment method of the ion-exchange layered silicate adsorbed water and interlayer water is not particularly limited, but it is necessary to select conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the water content of the component b after removal is 3% by weight or less, preferably 1 when the water content is 0% by weight when dehydrated for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. It is preferable that it is below wt%.

As described above, in the present invention, as the component [B-4], a particularly preferable one is an ion-exchange layered material obtained by performing a salt treatment and / or an acid treatment and having a water content of 3% by weight or less. Silicate.
The ion-exchange layered silicate can be treated with the component [C] described later before being used as a catalyst or as a catalyst, which is preferable. Although there is no restriction | limiting in the usage-amount of component [C] with respect to 1g of ion-exchange layered silicate, Usually, 20 mmol or less, Preferably it is 0.5 mmol or more and 10 mmol or less. There is no limitation on the treatment temperature and time, the treatment temperature is usually 0 ° C. or more and 70 ° C. or less, and the treatment time is 10 minutes or more and 3 hours or less. It is also possible and preferable to wash after the treatment. As the solvent, the same hydrocarbon solvent as that used in the preliminary polymerization and slurry polymerization described later is used.

Component [B-4] is preferably spherical particles having an average particle size of 5 μm or more. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation or the like may be used.
Examples of the granulation method used here include agitation granulation method and spray granulation method, but commercially available products can also be used.
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation.

  The spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization step. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited especially when prepolymerization is performed.

Among the above-mentioned component [B], [B-3] solid acid fine particles and [B-4] ion-exchange layered silicate are preferable, and [B-4] ion-exchange layered silicate is particularly preferable. It is.
In the propylene polymerization catalyst according to the present invention, [B-1] an aluminum oxy compound, [B-2] an ionic compound capable of reacting with component [A] to convert component [A] into a cation, or Lewis The acid, [B-3] solid acid fine particles, or [B-4] ion-exchange layered silicate fine particles are each used alone as the component [B], and these four components can be combined as appropriate, Can be used.

(3) Component [C]: Organoaluminum Compound An organoaluminum compound is used as the component [C]. In the present invention, an organoaluminum compound represented by the following general formula (7) is suitable.

In the present invention, it goes without saying that the compounds represented by this formula can be used singly or in combination of two or more. In the formula (7), R ⁷¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, hydrogen, an alkoxy group, or an amino group. q is a number greater than 0 and up to 3. R ⁷¹ is preferably an alkyl group, and Z is a chlorine atom when it is a halogen atom, a C 1-8 alkoxy group when it is an alkoxy group, or a carbon atom number 1 when it is an amino group. An amino group of ˜8 is preferred.

Specific examples of preferred organoaluminum compounds include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethyl Examples include aluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like.
Of these, trialkylaluminum and dialkylaluminum hydrides with q = 3 are preferred. More ^preferably trialkylaluminum ^{R 71} is 1 to 8 carbon atoms.

(4) Component [D]: Cyclopentadiene derivative In the propylene polymerization catalyst of the present invention, a cyclopentadiene derivative is used as the component [D]. The cyclopentadiene derivative does not contain a metal complex.

The cyclopentadiene derivative is cyclopentadiene, indene, fluorene, or azulene, and each may have a substituent. Examples of the substituent include an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur, halogen, silicon, or a plurality of hetero elements selected from these The aryl group may contain 6 to 30 carbon atoms, and the aryl group may have one or more carbon atoms of 1 to 6 on the aryl cyclic skeleton within the range of 6 to 16 carbon atoms. A hydrocarbon group of 1 to 6 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms, and a halogen-containing hydrocarbon group having 1 to 6 carbon atoms as a substituent.
Specific examples of the substituent include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, furyl, 2- Methylfuryl, phenyl group, 4-i-propylphenyl group, 4-trimethylsilylphenyl group, 4-t-butylphenyl group, 2,3-dimethylphenyl group, 3,5-di-t-butylphenyl group, 4-phenyl -Phenyl group, chlorophenyl group, naphthyl group, phenanthryl group, etc. are mentioned, preferably methyl, ethyl, furyl, 2-methylfuryl, phenyl group, 4-i-propylphenyl group, 4-trimethylsilylphenyl group, 4- t-Butylphenyl group.

Specific examples of cyclopentadiene derivatives include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, isobutylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octyl Cyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, methylethylcyclopentadiene, methylpropylcyclopentadiene, methylbutylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3, 4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, methylindene, ethylindene, propyl 7 carbon atoms such as Ndene, Butylindene, 4-Methyl-1-indene, 4,7-Dimethylindene, 4,5,6,7-Tetrahydroindene, Azulene, Methylazulene, Ethylazulene, Fluorene, Methylfluorene -24 cyclopolyenes or substituted cyclopolyenes.
The cyclopentadiene derivative may have two or more cyclopentadienyl rings cross-linked by a cross-linking group, and examples thereof include compounds having the following structure.

[In general formula (d1), E ^d1 and E ^d2 each independently represent a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. Q ^d1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

E ^d1 and E ^d2 are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent.
Of these, a substituted cyclopentadienyl group and a substituted indenyl group are preferable, and a substituted indenyl group is particularly preferable.

  Moreover, the said cyclopentadiene derivative may be bridge | crosslinked, and the following structure 8 can be illustrated.

[In the structure 8, R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or It is a C4-C16 heterocyclic group containing nitrogen, oxygen or sulfur. Q ⁸¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. In addition, the existence of isomers that differ only in the position of the double bond in the cyclopentadienyl group can be considered, and only one of them is illustrated, but only the position of the double bond in the cyclopentadienyl group May be other isomers different from each other or a mixture thereof. ]

In the structure 8, R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or nitrogen , A heterocyclic group having 4 to 16 carbon atoms containing oxygen or sulfur.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, furyl, 2-methylfuryl and the like. And preferably a methyl group.

Q ⁸¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms that bonds two conjugated five-membered ring ligands through carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, It shows either a silylene 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 or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ⁸¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups.

Non-limiting examples of the compound represented by the structure 8 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) Dimethyl [bis (2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl)] silane,
(2) Dimethyl [bis (2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl)] methane,
(3) [Bis (2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl)] methane,
(4) [Bis (2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl)] ethane,
(5) Dimethyl [bis (2,4-cyclopentadien-1-yl)] silane,
(6) Dimethyl [bis (2,4-cyclopentadien-1-yl)] methane,
(7) [Bis (2,4-cyclopentadien-1-yl)] methane,
(8) [2,4-cyclopentadien-1-yl)] ethane,
(9) Dimethyl [bis (2,3,5-trimethyl-2,4-cyclopentadien-1-yl)] silane,
(10) Dimethyl [bis (2,3,5-trimethyl-2,4-cyclopentadien-1-yl)] methane,
(11) [Bis (2,3,5-trimethyl-2,4-cyclopentadien-1-yl)] methane,
(12) [Bis (2,3,5-trimethyl-2,4-cyclopentadien-1-yl)] ethane,
(13) Dimethyl [bis (2,5-dimethyl-3-phenyl-2,4-cyclopentadien-1-yl)] silane,
(14) Dimethyl [bis (2,5-dimethyl-3-phenyl-2,4-cyclopentadien-1-yl)] methane,
(15) [Bis (2,5-dimethyl-3-phenyl-2,4-cyclopentadien-1-yl)] methane,
(16) [Bis (2,5-dimethyl-3-phenyl-2,4-cyclopentadien-1-yl)] ethane,
(17) Dimethyl [bis (2-ethyl-3-phenyl-5-methyl-2,4-cyclopentadien-1-yl)] silane,
(18) Dimethyl [bis (2-ethyl-3-phenyl-5-methyl-2,4-cyclopentadien-1-yl)] methane,
(19) [Bis (2-ethyl-3-phenyl-5-methyl-2,4-cyclopentadien-1-yl)] methane,
(20) [Bis (2-ethyl-3-phenyl-5-methyl-2,4-cyclopentadien-1-yl)] ethane,

(21) Dimethyl [bis (2,3,5-triethyl-2,4-cyclopentadien-1-yl)] silane,
(22) Dimethyl [bis (2,3,5-triethyl-2,4-cyclopentadien-1-yl)] methane,
(23) [Bis (2,3,5-triethyl-2,4-cyclopentadien-1-yl)] methane,
(24) [Bis (2,3,5-triethyl-2,4-cyclopentadien-1-yl)] ethane,
(25) Dimethyl [bis (2,5-dimethyl-3-ethyl-2,4-cyclopentadien-1-yl)] silane,
(26) Dimethyl [bis (2,5-dimethyl-3-ethyl-2,4-cyclopentadien-1-yl)] methane,
(27) [Bis (2,5-dimethyl-3-ethyl-2,4-cyclopentadien-1-yl)] methane,
(28) [Bis (2,5-dimethyl-3-ethyl-2,4-cyclopentadien-1-yl)] ethane,
(29) Dimethyl [bis (2,3-dimethyl-5-ethyl-2,4-cyclopentadien-1-yl)] silane,
(30) Dimethyl [bis (2,3-dimethyl-5-ethyl-2,4-cyclopentadien-1-yl)] methane,
(31) [Bis (2,3-dimethyl-5-ethyl-2,4-cyclopentadien-1-yl)] methane,
(32) [Bis (2,3-dimethyl-5-ethyl-2,4-cyclopentadien-1-yl)] ethane,
(33) Dimethyl [bis (2,5-dimethyl-3-i-propyl-2,4-cyclopentadien-1-yl)] silane,
(34) Dimethyl [bis (2,5-dimethyl-3-i-propyl-2,4-cyclopentadien-1-yl)] methane,
(35) [Bis (2,5-dimethyl-3-i-propyl-2,4-cyclopentadien-1-yl)] methane,
(36) [Bis (2,5-dimethyl-3-i-propyl-2,4-cyclopentadien-1-yl)] ethane,
Etc.

  Moreover, the following structure 9 can be illustrated.

[In the structure 9, R ⁹¹ and R ⁹³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a heterocyclic ring having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Indicates a group. R ⁹² and R ⁹⁴ are each independently a hydrogen atom, a halogen atom, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. Q ⁹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. In addition, the existence of isomers that differ only in the position of the double bond in the 5-membered ring in the indenyl group can be considered, and only one of them is illustrated, but the double in the 5-membered ring in the indenyl group is exemplified. Other isomers that differ only in the position of the bond may be used, or a mixture thereof. ]

R ⁹¹ and R ⁹³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, furyl, 2-methylfuryl and the like. Preferably methyl, ethyl, furyl, 2-methylfuryl.
R ⁹² and R ⁹⁴ are a hydrogen atom, halogen, silicon, or an aryl group having 6 to 30 carbon atoms that may contain a plurality of hetero elements selected from these. As the group, in the range of 6 to 16 carbon atoms, one or more hydrocarbon groups having 1 to 6 carbon atoms, trialkylsilyl groups having 1 to 6 carbon atoms, 1 to 1 carbon atoms on the aryl cyclic skeleton. 6 halogen-containing hydrocarbon groups may be substituted.
Specific examples include a phenyl group, 4-i-propylphenyl group, 4-trimethylsilylphenyl group, 4-t-butylphenyl group, 2,3-dimethylphenyl group, 3,5-dit-butylphenyl group, 4 -Phenyl-phenyl group, chlorophenyl group, naphthyl group, phenanthryl group and the like can be mentioned, preferably. A phenyl group, a 4-i-propylphenyl group, a 4-trimethylsilylphenyl group, and a 4-t-butylphenyl group.

Q ⁹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bonds two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, It shows either a silylene 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 or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ^91, methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, alkylene group and the like; arylalkylene group such as diphenylmethylene; silylene group; methylsilylene, dimethylsilylene, diethyl silylene, di Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermylene Examples include groups.

Non-limiting examples of the compound represented by the structure 9 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) Dimethyl [bis {2- (2-furyl) -4-phenyl-indenyl}] silane,
(2) Dimethyl [bis {2- (2-thienyl) -4-phenyl-indenyl}] silane,
(3) Dimethyl [bis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] silane,
(4) diphenyl [bis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] silane,
(5) Dimethyl [bis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] germanium,
(6) Dimethyl [bis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] germanium,
(7) Dimethyl [bis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] silane,
(8) Dimethyl [bis {2- (5-trimethylsilyl-2-furyl) -4-phenyl-indenyl}] silane,
(9) Dimethyl [bis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] silane,
(10) Dimethyl [bis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] silane,
(11) Dimethyl [bis {2- (2-benzofuryl) -4-phenyl-indenyl}] silane,
(12) Dimethyl [bis {2- (2-furfuryl) -4-phenyl-indenyl}] silane,
(13) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] silane,
(14) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] silane,
(15) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] silane,
(16) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] silane,
(17) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl}] silane,
(18) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] silane,
(19) Dimethyl [bis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] silane,
(20) Dimethyl [bis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] silane,

(21) Dimethyl [bis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] silane,
(22) Dimethyl [bis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] silane,
(23) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] silane,
(24) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] silane,
(25) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] silane,
(26) Dimethyl [bis {2- (5-methyl-2-furyl) -4- (9-phenanthryl) -indenyl}] silane,
(27) Dimethyl [bis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] silane,
(28dimethyl [bis {2- (5-t-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] silane,
(29) Dimethyl [bis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] silane,
(30) Dimethyl [bis {2- (5-t-butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] silane,
(31) Dimethyl {bis (2-methyl-4-phenylindenyl)} silane,
(32) Dimethyl [bis {2-methyl-4- (4-chlorophenyl) indenyl}] silane,
(33) Dimethyl [bis {2-methyl-4- (4-t-butylphenyl) indenyl}] silane,
(34) Dimethyl [bis {2-methyl-4- (4-trimethylsilylphenyl) indenyl}] silane,
(35) Dimethyl [bis {2-methyl-4- (3-chloro-4-t-butylphenyl) indenyl}] silane,
(36) Dimethyl [bis {2-methyl-4- (3-methyl-4-t-butylphenyl) indenyl}] silane,
(37) Dimethyl [bis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) indenyl}] silane,
(38) Dimethyl [bis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) indenyl}] silane,
(39) Dimethyl [bis {2-methyl-4- (1-naphthyl) indenyl}] silane,
(40) Dimethyl [bis {2-methyl-4- (2-naphthyl) indenyl}] silane,

(41) Dimethyl [bis {2-methyl-4- (2-fluoro-4-biphenyl) indenyl}] silane,
(42) Dimethyl [bis {2-methyl-4- (2-chloro-4-biphenyl) indenyl}] silane,
(43) Dimethyl [bis {2-methyl-4- (9-phenanthryl) indenyl}] silane,
(44) Dimethyl [bis {2-methyl-4- (4-chloro-2-naphthyl) indenyl}] silane,
(45) Dimethyl [bis {2-ethyl-4- (3-chloro-4-t-butylphenyl) indenyl}] silane,
(46) Dimethyl [bis {2-methyl-4- (2-fluoro-4-biphenyl) indenyl}] germanium,
(47) Dimethyl [bis {2-methyl-4- (4-t-butylphenyl) indenyl}] germanium,
It is.

  Moreover, the following structure 10 can be illustrated.

[In the structure 10, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a carbon atom. Represents a silicon-containing hydrocarbon group having a number of 1 to 20, which may be the same or different, and adjacent substituents R ^{101 to} R ¹⁰⁴ and R ^{105 to} R ¹⁰⁸ are bonded to each other to form a ring. Also good. Q ¹⁰¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

Q ¹⁰¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which bonds two conjugated five-membered ring ligands via carbon having 1 or 2 carbons, which bonds two five-membered rings, carbon Either a silylene group or a germylene group which may have a hydrocarbon group of 1 to 20 is shown. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹⁰¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 10 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) 1,2-di (9H-fluoren-9-yl) ethane,
(2) Di (9H-fluoren-9-yl) (dimethyl) silane,
(3) di (9H-fluoren-9-yl) (diphenyl) silane,
(4) 1- {2,7-di-t-butyl (9H-fluoren-9-yl)}-2- (9H-fluoren-9-yl) ethane,
(5) {2,7-di-t-butyl (9H-fluoren-9-yl)} (9H-fluoren-9-yl) (dimethyl) silane,
(6) {2,7-di-t-butyl (9H-fluoren-9-yl)} (9H-fluoren-9-yl) (diphenyl) silane,
(7) 1- {3,6-di-t-butyl (9H-fluoren-9-yl)}-2- (9H-fluoren-9-yl) ethane,
(8) {3,6-di-t-butyl (9H-fluoren-9-yl)} (9H-fluoren-9-yl) (dimethyl) silane,
(9) {3,6-di-t-butyl (9H-fluoren-9-yl)} (9H-fluoren-9-yl) (diphenyl) silane,
(10) 1- {2,7-diphenyl (9H-fluoren-9-yl)}-2- (9H-fluoren-9-yl) ethane,
(11) {2,7-diphenyl (9H-fluoren-9-yl)} (9H-fluoren-9-yl) (dimethyl) silane,
(12) {2,7-diphenyl (9H-fluoren-9-yl)} (9H-fluoren-9-yl) (diphenyl) silane,
(13) 1-((12H-1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzo [b, h Fluoren-12-yl) -2- (9H-fluoren-9-yl) ethane,
(14) (12H-1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzo [b, h] fluorene- 12-yl) (9H-fluoren-9-yl) (dimethyl) silane,
(15) (12H-1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzo [b, h] fluorene- 12-yl) (9H-fluoren-9-yl) (diphenyl) silane,
Etc.

  Moreover, the following structure 11 can be illustrated.

[In the structure 11, R ¹¹¹ and R ¹¹² are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ¹¹³ and R ¹¹⁴ are each independently a halogen atom, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. Q ¹¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. Further, the existence of isomers that differ only in the position of the double bond in the 5-membered ring in the azulenyl group can be considered, and only one of them is illustrated, but the double in the 5-membered ring in the azulenyl group is exemplified. Other isomers that differ only in the position of the bond may be used, or a mixture thereof. ]

R ¹¹¹ and R ¹¹² are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
Specific examples include methyl, ethyl, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl and the like. Preferably, methyl, ethyl and n-propyl are used.

R ¹¹³ and R ¹¹⁴ are each independently an aryl group having 6 to 30 carbon atoms, which may contain halogen, silicon, or a plurality of hetero elements selected from these.
Specific examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

Q ¹¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bonds two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, It shows either a silylene 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 or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ¹⁵¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 11 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) Dimethyl {bis (2-methyl-4-phenyl-4-hydroazurenyl)} silane,
(2) Dimethyl [bis {2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] silane,
(3) Dimethyl [bis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] silane,
(4) Dimethyl [bis {2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazurenyl}] silane,
(5) Dimethyl [bis {2-methyl-4- (3-chloro-4-t-butylphenyl) -4-hydroazurenyl}] silane,
(6) Dimethyl [bis {2-methyl-4- (3-methyl-4-t-butylphenyl) -4-hydroazurenyl}] silane,
(7) Dimethyl [bis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] silane,
(8) Dimethyl [bis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] silane,
(9) Dimethyl [bis {2-methyl-4- (1-naphthyl) -4-hydroazulenyl}] silane,
(10) Dimethyl [bis {2-methyl-4- (2-naphthyl) -4-hydroazulenyl}] silane,
(11) Dimethyl [bis {2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] silane,
(12) Dimethyl [bis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] silane,
(13) Dimethyl [bis {2-methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] silane,
(14) Dimethyl [bis {2-methyl-4- (9-phenanthryl) -4-hydroazurenyl}] silane,
(15) Dimethyl [bis-2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] silane,
(16-dimethyl [bis {2-n-propyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazulenyl}] silane,
(17) Dimethyl [bis {2-ethyl-4- (3-chloro-4-t-butylphenyl) -4-hydroazurenyl}] silane,
(18) Dimethyl [bis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] silane,
(19) Dimethyl [bis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] germanium,
(20) Dimethyl [bis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] germanium,

(21) 9,9-bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}]-9-silafluorene,
(22) Dimethyl [bis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] silane,
(23) Dimethyl [bis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] silane,
(24) 9,9-bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}]-9-silafluorene,
Etc.

  Moreover, the following structure 12 can be illustrated.

[In the structure 12, R ¹²¹ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ¹⁶² is an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, or a plurality of hetero elements selected from these. R ¹²³ , R ¹²⁴ , R ¹²⁵ and R ¹²⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Q ¹²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. In addition, it is possible to consider the existence of isomers that differ only in the position of the double bond in the 5-membered ring in the cyclopentadienyl group and the azulenyl group, and only one of them is exemplified, but cyclopentadienyl Other isomers that differ only in the position of the double bond in the 5-membered ring in the group and the azulenyl group may be used, or a mixture thereof. ]

In the structure 12, R ¹²¹ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably Methyl, ethyl, n-propyl.
R ¹²² is halogen, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. Specific examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl. 4- (2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3,5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl and the like can be mentioned.
R ¹²³ , R ¹²⁴ , R ¹²⁵ and R ¹²⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, n- Examples include propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, and phenyl, and a methyl group is preferable.

Q ¹²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. Q ¹⁶¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via 1 or 2 carbon atoms, which bonds two five-membered rings; It shows either a silylene 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 or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹²¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 12 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) Dimethyl {(2,3-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(2) Dimethyl {(3,4-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(3) Dimethyl {(2,5-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(4) Dimethyl {(2,3-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(5) Dimethyl {(3,4-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(6) Dimethyl {(2,5-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(7) Dimethyl {(2,3-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(8) Dimethyl {(3,4-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(9) Dimethyl {(2,5-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(10) Dimethyl {(2-methyl-4-ethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(11) Dimethyl {(2-ethyl-4-methylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(12) Dimethyl {(2-methyl-4-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(13) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(14) Dimethyl {(2,3,4-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(15) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(16) Dimethyl {(2,3-dimethyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(17) Dimethyl {(2,3-dimethyl-5-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(18) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azurenyl)} silane,
(19) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azurenyl)} silane,
(20) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (4-phenyl-2-i-propyl-4H-azurenyl)} silane,

(21) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-i-propyl-4-t-phenyl-2-i-propyl-4H-azurenyl)} silane,
(22) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (4-chlorophenyl) -2-methyl-4H-azulenyl)} silane,
(23) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (4-chlorophenyl) -2-methyl-4H-azurenyl)} silane,
(24) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (3-methylphenyl) -4H-azulenyl)} silane,
(25) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (3-methylphenyl) -4H-azurenyl)} silane,
(26) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (4-tert-butylphenyl) -2-methyl-4H-azurenyl)} silane,
(27) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (4-tert-butylphenyl) -2-methyl-4H-azurenyl)} silane,
(28) Dimethyl {(2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (2-naphthyl) -4H-azurenyl)} silane,
(29) Dimethyl {(2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (2-naphthyl) -4H-azurenyl)} silane,
(30) methylphenyl {(2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} silane,
(31) 1- (2,4,5-trimethylcyclopentadienyl) -1- (2-methyl-4-phenyl-4H-azurenyl)} silacyclobutane,
(32) 1- (2,4,5-trimethylcyclopentadienyl) -1- (2-methyl-4-phenyl-4H-azurenyl)} silacyclopentane,
(33) 9- (2,4,5-trimethylcyclopentadienyl) -9- (2-methyl-4-phenyl-4H-azurenyl)} silafluorene,
(34) methylphenyl (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} germanium,
(35) 1- (2,4,5-trimethylcyclopentadienyl) -1- (2-methyl-4-phenyl-4H-azurenyl)} germacyclobutane,
(36) 1- (2,4,5-trimethylcyclopentadienyl) -1- (2-methyl-4-phenyl-4H-azurenyl)} germacyclopentane,
(37) 9- (2,4,5-trimethylcyclopentadienyl) -9- (2-methyl-4-phenyl-4H-azurenyl)} germafluorene,
(38) Dimethyl [{2-methyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(39) Dimethyl [{2-methyl-4- (cyclopropylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(40) Dimethyl [{3- (2-methylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,

(41) Dimethyl [{2-methyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(42) Dimethyl [{2-methyl-4- (cyclohexylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(43) Dimethyl [{2-methyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(44) Dimethyl [{3- (1-cyclopropylethyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(45) Dimethyl [{3- (1,2-dimethylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(46) Dimethyl [{2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(47) Dimethyl [{3- (1-cyclohexylethyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(48) Dimethyl [{2-methyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(49) Dimethyl [{2-methyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(50) Dimethyl [{3- (1-ethyl-2-methylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(51) Dimethyl [{2-methyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(52) Dimethyl [{2-methyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(53) Dimethyl [{3- (1-i-propylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(54) Dimethyl [{3- (1-cyclopropylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(55) Dimethyl [{3- (1-s-butylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azuler)] silane,
(56) Dimethyl [{3- (1-t-butylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azuler)] silane,
(57) Dimethyl [{3- (1-cyclohexylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(58) Dimethyl [{2-ethyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(59) Dimethyl [{2-ethyl-4- (cyclopropylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(60) Dimethyl [{3- (2-methylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,

(61) Dimethyl [{2-ethyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(62) Dimethyl [{2-ethyl-4- (cyclohexylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(63) Dimethyl [{2-ethyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(64) Dimethyl [{2-ethyl-4- (1-cyclopropylethyl) -methyl) -cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(65) Dimethyl [{3- (1,2-dimethylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(66) Dimethyl [{2-ethyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(67) Dimethyl [{2-ethyl-4- (1-cyclohexylethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(68) Dimethyl [{2-ethyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(69) Dimethyl [{2-ethyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(70) Dimethyl [{3- (1-ethyl-2-methylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(71) Dimethyl [{2-ethyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(72) Dimethyl [{2-ethyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(73) Dimethyl [{3- (1-i-propylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(74) Dimethyl [{3- (1-cyclopropylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(75) Dimethyl [{3- (1-s-butylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(76) Dimethyl [{3- (1-t-butylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(77) Dimethyl [{3- (1-cyclohexylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(78) Dimethyl [{2-n-propyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(79) Dimethyl [{3- (cyclopropylmethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(80) Dimethyl [{3- (2-methylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,

(81) Dimethyl [{2-n-propyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(82) Dimethyl [{3- (cyclohexylmethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(83) Dimethyl [{2-n-propyl-4- (1,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(84) Dimethyl [{3- (1-cyclopropylethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(85) Dimethyl [{3- (1,2-dimethylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(86) Dimethyl [{2-n-propyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(87) Dimethyl [{3- (1-cyclohexylethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(88) Dimethyl [{2-n-propyl-4- (1-i-propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(89) Dimethyl [{2-n-propyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(90) Dimethyl [{3- (1-ethyl-2-methylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(91) Dimethyl [{2-n-propyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(92) Dimethyl [{2-n-propyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(93) Dimethyl [{3- (1-i-propylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(94) Dimethyl [{3- (1-cyclopropylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(95) Dimethyl [{3- (1-s-butylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(96) Dimethyl [{3- (1-t-butylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
(97) Dimethyl [{3- (1-cyclohexylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] silane,
Etc.

  Moreover, the following structure 13 can be illustrated.

[In the structure 13, R ¹³¹ , R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁵ , R ¹³⁶ , R ¹³⁷ and R ¹³⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a carbon number. 1 to 20 silicon-containing hydrocarbon groups, which may be the same or different, and adjacent substituents from R ^{135 to} R ¹³⁸ may be bonded to each other to form a ring. Q ¹³¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. In addition, the existence of isomers that differ only in the position of the double bond in the cyclopentadienyl group can be considered, and only one of them is illustrated, but only the position of the double bond in the cyclopentadienyl group May be other isomers different from each other or a mixture thereof. ]

In the structure 13, Q ¹³¹ is a divalent carbon atom having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings. It represents either a hydrogen group, a silylene 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 or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹³¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 13 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) 2- (3-i-propylcyclopentadienyl) -2′-fluorenylpropane,
(2) 2- (3-tert-butylcyclopentadienyl) -2′-fluorenylpropane,
(3) 2- (3-trimethylsilylcyclopentadienyl) -2′-fluorenylpropane,
(4) 2- {3- (t-butyldimethylsilyl) cyclopentadienyl} -2′-fluorenylpropane,
(5) 2- (3-i-propyl-5-methylcyclopentadienyl) -2'-fluorenylpropane,
(6) 2- (3-tert-butyl-5-methylcyclopentadienyl) -2′-fluorenylpropane,
(7) 2- (3-trimethylsilyl-5-methylcyclopentadienyl) -2′-fluorenylpropane,
(8) 2- {3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl} -2′-fluorenylpropane,
(9) 2- (3-i-propyl-5-ethylcyclopentadienyl) -2'-fluorenylpropane,
(10) 2- (3-tert-butyl-5-ethylcyclopentadienyl) -2′-fluorenylpropane,
(11) 2- (3-trimethylsilyl-5-ethylcyclopentadienyl) -2′-fluorenylpropane,
(12) 2- {3- (t-butyldimethylsilyl) -5-ethylcyclopentadienyl} -2′-fluorenylpropane,
(13) 2- (3-i-propyl-5-methylcyclopentadienyl) -2 '-(3,6-di-t-butylfluorenyl) propane,
(14) 2- (3-tert-butyl-5-methylcyclopentadienyl) -2 ′-(3,6-ditert-butylfluorenyl) propane,
(15) 2- (3-trimethylsilyl-5-methylcyclopentadienyl) -2 '-(3,6-di-t-butylfluorenyl) propane,
(16) 2- {3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl} -2 ′-(3,6-di-t-butylfluorenyl) propane,
(17) 2- (3-i-propyl-5-methylcyclopentadienyl) -2 '-(2,7-di-t-butylfluorenyl) propane,
(18) 2- (3-t-butyl-5-methylcyclopentadienyl) -2 ′-(2,7-di-t-butylfluorenyl) propane,
(19) 2- (3-trimethylsilyl-5-methylcyclopentadienyl) -2 '-(2,7-di-t-butylfluorenyl) propane,
(20) 2- {3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl} -2 ′-(2,7-di-t-butylfluorenyl) propane,

(21) 2- (3-tert-butyl-5-methylcyclopentadienyl) -2 '-(dibenzo [b, e] fluorenyl) propane,
(22) 2- (3-trimethylsilyl-5-methylcyclopentadienyl) -2 ′-(dibenzo [b, e] fluorenyl) propane,
(23) 2- (3-tert-butyl-5-methylcyclopentadienyl) -2 '-(2,2,5,5,8,8,11,11-octamethyl-2,3,4,5 , 8,9,10,11-octahydrodibenzo [b, e] fluorenyl) propane,
(24) 2- (3-Trimethylsilyl-5-methylcyclopentadienyl) -2 '-(2,2,5,5,8,8,11,11-octamethyl-2,3,4,5,8 , 9,10,11-octahydrodibenzo [b, e] fluorenyl) propane,
(25) Diphenyl (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) propane,
(26) Diphenyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) methane,
(27) Diphenyl (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) methane,
(28) Diphenyl {3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl} (3,6-di-t-butylfluorenyl) methane,
(29) Dimethyl (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(30) Dimethyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(31) Dimethyl (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(32) methyl (3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(33) diphenyl (3-i-propyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(34) diphenyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(35) diphenyl (3-trimethylsilyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) silane,
(36) Diphenyl {3- (t-butyldimethylsilyl) -5-methylcyclopentadienyl} (3,6-di-t-butylfluorenyl) silane,
Etc.

  Moreover, the following structure 14 can be illustrated.

[In the structure 14, each of R ¹⁴¹ and R ¹⁴² is independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur. Each of R ¹⁴³ and R ¹⁴⁴ is independently a hydrogen atom, a halogen atom, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. Q ¹⁴¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. In addition, the existence of isomers that differ only in the position of the double bond in the 5-membered ring in the indenyl group and the azulenyl group can be considered, and only one of them is illustrated, It may be another isomer that differs only in the position of the double bond in the 5-membered ring, or a mixture thereof. ]

R ¹⁴¹ and R ¹⁴² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen or sulfur.
Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, furyl, 2-methylfuryl and the like. Of these, methyl, ethyl, furyl, and 2-methylfuryl are preferable.
R ¹⁴³ and R ¹⁴⁴ are each independently a hydrogen atom or an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, or a plurality of hetero elements selected from these. In addition, as the aryl group, in the range of 6 to 16 carbon atoms, one or more hydrocarbon groups having 1 to 6 carbon atoms and trialkylsilyl groups having 1 to 6 carbon atoms on the aryl cyclic skeleton The halogen-containing hydrocarbon group having 1 to 6 carbon atoms may be substituted.
Specific examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

Q ¹⁴¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, It shows either a silylene 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 or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹⁴¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 14 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)] silane,
(2) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4-phenyl-4H-1-azurenyl)] silane,
(3) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-chlorophenyl) -4H-1-azurenyl)] silane,
(4) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-chlorophenyl) -4H-1-azulenyl)] silane,
(5) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-fluorophenyl) -4H-1-azurenyl)] silane,
(6) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-fluorophenyl) -4H-1-azurenyl)] silane,
(7) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-tert-butylphenyl) -4H-1-azurenyl)] silane,
(8) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-tert-butylphenyl) -4H-1-azulenyl)] silane,
(9) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (4-trimethylsilylphenyl) -4H-1-azurenyl)] silane,
(10) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (4-trimethylsilylphenyl) -4H-1-azurenyl)] silane,
(11) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (1-naphthyl) -4H-1-azurenyl)] silane,
(12) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (1-naphthyl) -4H-1-azurenyl)] silane,
(13) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4- (2-naphthyl) -4H-1-azurenyl)] silane,
(14) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-methyl-4- (2-naphthyl) -4H-1-azurenyl)] silane,
(15) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] silane,
(16) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] silane,
(17) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-ethyl-4- (4-chlorophenyl) -4H-1-azulenyl)] silane,
(18) Dimethyl [(2-ethyl-4-phenyl-1-indenyl) (2-ethyl-4- (4-chlorophenyl) -4H-1-azurenyl)] silane,
(19) Dimethyl [(2-methyl-4-phenyl-1-indenyl) (2-methyl-4-phenyl-4H-5,6,7,8-tetrahydro-1-azurenyl)] silane,
(20) Dimethyl [(2-ethyl-1-indenyl) (2-methyl-4-phenyl-4H-5,6,7,8-tetrahydro-1-azurenyl)] silane,
Etc.

  Moreover, the following structure 15 can be illustrated.

[In the structure 15, R ¹⁵¹ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen, or sulfur. R ¹⁵² is halogen, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ and R ¹⁵⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Q ¹⁵¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. In addition, the existence of isomers that differ only in the position of the double bond in the 5-membered ring in the cyclopentadienyl group and the indenyl group can be considered, and only one of them is exemplified, but cyclopentadienyl It may be another isomer that differs only in the position of the double bond in the 5-membered ring in the group and the indenyl group, or a mixture thereof. ]

R ¹⁵¹ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen, or sulfur. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, furyl, 2-methylfuryl and the like. Of these, methyl, ethyl, furyl, and 2-methylfuryl are preferable.
R ¹⁵² is an aryl group having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, which may contain halogen, silicon, or a plurality of hetero elements selected from these.
Specific examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl. 4- (2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3,5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl and the like can be mentioned.

R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ and R ¹⁵⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, n-propyl, Examples include i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, phenyl and the like, preferably methyl, ethyl and n-propyl. .

Q ¹⁵¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. Q ¹⁵¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms that bridges two conjugated five-membered ring ligands via carbon having 1 or 2 carbon atoms, which bonds two five-membered rings, It shows either a silylene 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 or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of the above Q ¹⁵¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, diethylene Alkylsilylene groups such as (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilene; germylene groups; alkylgermylene groups in which silicon in the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; arylgermille And the like.

Non-limiting examples of the compound represented by the structure 15 include the following.
However, only representative exemplary compounds are described avoiding many complicated examples.
(1) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2-methyl-4-phenyl-indenyl} ethane,
(2) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2-methyl-4- (4-tert-butylphenyl) -indenyl} ethane,
(3) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2-methyl-4- (4-i-propylphenyl) -indenyl} ethane,
(4) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2-methyl-4- (4-trimethylsilyl) -indenyl} ethane,
(5) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (2-furyl) -4-phenyl-indenyl} ethane,
(6) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} ethane,
(7) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} ethane,
(8) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} ethane,
(9) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ethane,
(10) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} ethane,
(11) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} ethane,
(12) 1- (2,4,5-trimethylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} ethane,
(13) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4-phenyl-indenyl} (dimethyl) silane,
(14) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(15) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(16) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(17) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4-phenyl-indenyl} (dimethyl) silane,
(18) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(19) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(20) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,

(21) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl} (dimethyl) silane,
(22) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(23) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(24) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(25) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4-phenyl-indenyl} (diphenyl) silane,
(26) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(27) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(28) (2,4,5-trimethylcyclopentadienyl) {2-methyl-4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(29) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4-phenyl-indenyl} (diphenyl) silane,
(30) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(31) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(32) (2,4,5-trimethylcyclopentadienyl) {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(33) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl} (diphenyl) silane,
(34) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(35) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(36) (2,4,5-trimethylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(37) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2-methyl-4-phenyl-indenyl} ethane;
(38) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2-methyl-4- (4-tert-butylphenyl) -indenyl} ethane;
(39) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2-methyl-4- (4-i-propylphenyl) -indenyl} ethane,
(40) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2-methyl-4- (4-trimethylsilyl) -indenyl} ethane,

(41) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2- (2-furyl) -4-phenyl-indenyl} ethane,
(42) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-tert-butylphenyl) -indenyl} ethane,
(43) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} ethane,
(44) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} ethane,
(45) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ethane,
(46) 1- (2-Methyl-4-t-butylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} ethane ,
(47) 1- (2-Methyl-4-tert-butylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} ethane ,
(48) 1- (2-methyl-4-tert-butylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} ethane,
(49) (2-methyl-4-tert-butylcyclopentadienyl) {2-methyl-4-phenyl-indenyl} (dimethyl) silane,
(50) (2-methyl-4-tert-butylcyclopentadienyl) {2-methyl-4- (4-tert-butylphenyl) -indenyl} (dimethyl) silane,
(51) (2-methyl-4-tert-butylcyclopentadienyl) {2-methyl-4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(52) (2-methyl-4-t-butylcyclopentadienyl) {2-methyl-4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(53) (2-Methyl-4-tert-butylcyclopentadienyl) {2- (2-furyl) -4-phenyl-indenyl} (dimethyl) silane,
(54) (2-Methyl-4-t-butylcyclopentadienyl) {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(55) (2-Methyl-4-tert-butylcyclopentadienyl) {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(56) (2-methyl-4-tert-butylcyclopentadienyl) {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(57) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl} (dimethyl) silane,
(58) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(59) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(60) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,

(61) (2-Methyl-4-t-butylcyclopentadienyl) {2-methyl-4-phenyl-indenyl} (diphenyl) silane,
(62) (2-Methyl-4-t-butylcyclopentadienyl) {2-methyl-4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(63) (2-Methyl-4-t-butylcyclopentadienyl) {2-methyl-4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(64) (2-Methyl-4-t-butylcyclopentadienyl) {2-methyl-4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(65) (2-Methyl-4-t-butylcyclopentadienyl) {2- (2-furyl) -4-phenyl-indenyl} (diphenyl) silane,
(66) (2-Methyl-4-t-butylcyclopentadienyl) {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(67) (2-Methyl-4-t-butylcyclopentadienyl) {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(68) (2-Methyl-4-t-butylcyclopentadienyl) {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(69) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl} (diphenyl) silane,
(70) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(71) (2-Methyl-4-tert-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(72) (2-Methyl-4-t-butylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(73) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2-methyl-4-phenyl-indenyl} ethane,
(74) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2-methyl-4- (4-t-butylphenyl) -indenyl} ethane,
(75) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2-methyl-4- (4-i-propylphenyl) -indenyl} ethane,
(76) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2-methyl-4- (4-trimethylsilyl) -indenyl} ethane,
(77) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (2-furyl) -4-phenyl-indenyl} ethane;
(78) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} ethane,
(79) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} ethane,
(80) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} ethane,

(81) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ethane;
(82) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} ethane,
(83) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} ethane,
(84) 1- (2-methyl-4-phenylcyclopentadienyl) -2- {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} ethane,
(85) (2-methyl-4-phenylcyclopentadienyl) {2-methyl-4-phenyl-indenyl} (dimethyl) silane,
(86) (2-methyl-4-phenylcyclopentadienyl) {2-methyl-4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(87) (2-methyl-4-phenylcyclopentadienyl) {2-methyl-4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(88) (2-Methyl-4-phenylcyclopentadienyl) {2-methyl-4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(89) (2-methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4-phenyl-indenyl} (dimethyl) silane,
(90) (2-Methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(91) (2-Methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(92) (2-Methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(93) (2-Methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl} (dimethyl) silane,
(94) (2-Methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} (dimethyl) silane,
(95) (2-Methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} (dimethyl) silane,
(96) (2-Methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} (dimethyl) silane,
(97) (2-methyl-4-phenylcyclopentadienyl) {2-methyl-4-phenyl-indenyl} (diphenyl) silane,
(98) (2-Methyl-4-phenylcyclopentadienyl) {2-methyl-4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(99) (2-Methyl-4-phenylcyclopentadienyl) {2-methyl-4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(100) (2-methyl-4-phenylcyclopentadienyl) {2-methyl-4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,

(101) (2-Methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4-phenyl-indenyl} (diphenyl) silane,
(102) (2-Methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(103) (2-methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(104) (2-Methyl-4-phenylcyclopentadienyl) {2- (2-furyl) -4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
(105) (2-Methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl} (diphenyl) silane,
(106) (2-methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} (diphenyl) silane,
(107) (2-methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl} (diphenyl) silane,
(108) (2-methyl-4-phenylcyclopentadienyl) {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl) -indenyl} (diphenyl) silane,
Etc.

Among these, a preferred form of the component [D] is preferably one in which two or more substituents are attached to the cyclopentadienyl ring, and more preferably, the substituents are bonded to each other to form a bicyclic ring. A structure is preferred. Specifically, an indenyl ring and an azulenyl ring are preferable. Of these, those having a substituent on the indenyl ring, the azulenyl ring, and the like are particularly preferable.
As a more preferable form, a structure in which two cyclic compounds such as an indenyl ring and an azulenyl ring are cross-linked is preferable, and the cross-linking group is preferably a cross-linked one-position of the ring structure. Particularly preferred are those containing silicon. Among these, the most preferable is a structure in which a substituted indenyl ring is crosslinked with silicon.

1-2. Propylene polymerization catalyst production method (preparation method)
(1) Contacting method The catalyst according to the present invention comprises the above component [A-1], component [A-2], component [B], component [C] and component [D] simultaneously or continuously or once. It can be formed by contacting with a plurality of times.
As the contact order, any desired combination can be used, but the following are the preferable ones for each component.
(A) After contacting component [A-1] with component [B] previously contacted with component [C], contacting component [D], and further contacting component [C], A method of contacting [A-2].
(B) Component [A-1] was contacted with component [B] that had been previously contacted with component [C], then component [C] was further contacted, and component [A-2] was contacted Thereafter, the method of contacting the component [D].
(C) After contacting the component [A-1] previously contacted with the component [C] with the contact product obtained by contacting the component [B] with the component [D] previously contacted with the component [C] The method of contacting component [A-2].
(D) The component [A-1] previously contacted with the component [C] is contacted with the component [B], the component [A-2] previously contacted with the component [C] is contacted, D] is contacted.
(E) The component [A-1] is brought into contact with the contact product obtained by bringing the component [D] into contact with the component [B] previously brought into contact with the component [C], and then the component [A-2] is brought into contact with the component [B]. How to contact.
(F) Method in which component [A-1] is contacted with component [B] that has been previously contacted with component [C], then component [A-2] is contacted, and then component [D] is contacted .
(G) A method in which the component [A-1], the component [A-2], and the component [D] are simultaneously brought into contact with the component [B] that has been contacted with the component [C] in advance.
The above examples can be shown, and among these, the component [A-1] is preferably brought into contact with the component [B] previously brought into contact with the component [C], and then the component [A-1] [D] is a method in which the component [C] is further contacted, and then the component [A-2] is contacted.

The reaction mechanism that exhibits the effects of the present invention is not always clear at present, but the present inventors consider as follows.
That is, when the component [D] is added to the catalyst component, the component [D] is located between the cationized complex in which the transition metal complex is activated and the anion of the cocatalyst. It is thought to change the intensity of action. In particular, by interacting with the cation complex of component “A-2”, which is a complex used for copolymerization, the coordination space in which the macromer can be copolymerized is expanded, and the macromer can be inserted up to the high molecular weight side. I think.
Therefore, the present inventors, based on the consideration of the reaction mechanism as described above, have identified the specific component [D] and the two transitions as a method that most exhibits such a reaction mechanism, that is, a method that has the most effect. To find a method for efficiently producing a preferable polymer in which a branch is introduced to an ultrahigh molecular weight component by ingeniously combining a combination with the metal complex component [A], particularly the component “A-2”. It came.

  The contacting of each component is usually performed in an aliphatic hydrocarbon or an aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It carries out between -20 degreeC-150 degreeC, Preferably it carries out between 0 degreeC-60 degreeC, More preferably, it is between 10 degreeC-30 degreeC.

(2) Usage amount The usage amounts of Component [A-1], Component [A-2], Component [B], [C] and [D] used in the present invention are arbitrary. For example, the amount of the component [A-1] and the component [A-2] used with respect to the component [B] is preferably 0.1 μmol to 100 μmol, particularly preferably 0.5 μmol to 50 μmol, relative to 1 g of the component [B]. It is a range. In addition, the amount of component [D] used relative to component [B] is preferably in the range of 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of component [B]. However, the molar ratio of component [D] to component [A-2] ([D] / [A-2]) is 0.1 to 99.0, preferably 1.0 to 10.0. .
The amount of the component [C-1] relative to the component [A-1], the component [A-2], or the component [D] is preferably 0.01 to 5 × 10 ⁶ , particularly preferably 0. 1 to 1 × 10 ^4, preferably in the range of.

Component [A-1] and component [A-2] used in the present invention are the ratio of the molar amount of component [A-1] to the total molar amount of each component [A-1] and [A-2] { [A-1] / ([A-1] + [A-2])} is 0.20 or more and 0.99 or less, preferably 0.3 or more and 0.95 or less, particularly Preferably they are 0.4 or more and 0.9 or less. By changing this ratio, it is possible to adjust the balance between melt physical properties and catalyst activity.
That is, from the component [A-1], a low molecular weight terminal vinyl macromer is produced, and from the component [A-2], a high molecular weight body obtained by copolymerizing a part of the macromer is produced.
Therefore, the macromer concentration can be changed by changing the ratio of the component [A-1], and thereby the branching amount can be changed.
In order to produce a polymer having a reduced branching index (g ′) by increasing the branching amount, the molar amount of [A-1] relative to the total molar amount of components [A-1] and [A-2] The ratio is required to be 0.20 or more, preferably 0.30 or more, more preferably 0.40 or more, still more preferably 0.50 or more, and particularly preferably 0.70 or more. The upper limit is 0.99 or less, and in order to efficiently obtain the polymer of the present invention with high catalytic activity, it is preferably 0.95 or less, more preferably 0.93 or less, and still more preferably It is 0.90 or less, particularly preferably 0.85 or less.
In addition, by using component [A-1] within the above range, it is possible to adjust the balance between the average molecular weight and the catalytic activity with respect to the hydrogen amount.

(3) Prepolymerization The catalyst of the present invention can be subjected to prepolymerization consisting of a small amount of polymerization by bringing an olefin into contact therewith.
Therefore, the amount of the polymer to be prepolymerized is preferably 0.01 or more, more preferably 0.1 or more by weight ratio with respect to the component [B], and the upper limit is 100 or less for economy and handling. Preferably it is 50 or less. Here, the weight ratio of the polymer to the component [B] may be expressed as the prepolymerization magnification.

The olefin used for the prepolymerization is not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcyclohexane. Examples include alkane and styrene, and propylene is preferable.
The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant rate or a constant pressure in the reaction tank, a combination thereof, or a stepwise change. The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. Moreover, component [C] can also be added or added at the time of prepolymerization. It is also possible to wash after the prepolymerization.
The catalyst used in the present invention includes components [A-1], [A-2], component [B], component [C] and component [D], as long as the object of the present invention is not impaired. Ordinarily used polymers such as polyethylene and polypropylene, and solids of inorganic oxides such as silica and titania may be added.

2. Use of Catalyst / Propylene Polymerization The polymerization mode is such that the catalyst for propylene polymerization including the components [A-1], [A-2], the component [B], the component [C] and the component [D] and the monomer efficiently contact each other. If you do, you can adopt any style.
Specifically, a slurry method using an inert solvent, a so-called bulk method using a propylene as a solvent without using an inert solvent as a solvent, a solution polymerization method, or a monomer without using a liquid solvent substantially. A gas phase method can be used. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied. In addition to single-stage polymerization, it is possible to carry out multistage polymerization of two or more stages.

In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent.
The polymerization temperature is 0 ° C. or higher and 150 ° C. or lower. In particular, when bulk polymerization is used, the temperature is preferably 40 ° C or higher, more preferably 50 ° C or higher. The upper limit is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.
Furthermore, when using vapor phase polymerization, 40 degreeC or more is preferable, More preferably, it is 50 degreeC or more. The upper limit is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.

The polymerization pressure is 1.0 MPa or more and 5.0 MPa or less. In particular, when bulk polymerization is used, the pressure is preferably 1.5 MPa or more, more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.
Furthermore, when using vapor phase polymerization, 1.0 MPa or more is preferable, and 1.5 MPa or more is more preferable. The upper limit is preferably 3.0 MPa or less, more preferably 2.5 MPa or less.

Furthermore, as a molecular weight regulator and for activity improvement effect, hydrogen is supplementarily used in a molar ratio of 1.0 × 10 ⁻⁶ or more and 1.0 × 10 ⁻² or less with respect to propylene. be able to.

In addition to the propylene monomer, copolymerization using an α-olefin having about 2 to 20 carbon atoms (excluding those used as a monomer) as a comonomer may be performed. The (total) comonomer content in the propylene-based polymer is in the range of 0 mol% or more and 20 mol% or less, and a plurality of the above-mentioned comonomers can be used. Specifically, they are ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene.
Among these, in order to obtain the propylene polymer according to the present invention in a good balance between melt properties and catalytic activity, it is preferable to use ethylene at 5 mol% or less. In particular, in order to obtain a polymer having high rigidity, it is preferable to use ethylene so that ethylene contained in the polymer is 1 mol% or less, and propylene homopolymerization is more preferable.

3. Analysis of Propylene-Based Polymer In the present invention, a component [A-1] having a specific structure generates a macromer having a vinyl structure at the terminal by β-methyl elimination reaction. -2], the macromer is copolymerized to produce a polymer having a long-chain branched structure.
Regarding the components [A-1] and [A-2] having such a specific structure, as described above, the present inventors have disclosed JP-A 2009-108247 (Patent Document 9) and As shown in Japanese Unexamined Patent Publication No. 2009-057542 (Patent Document 10), as [A-2], a method of using a complex having a bisindene structure and a complex having a bisazulene structure has been found.

  The propylene-based polymer that can be produced in the present invention is a polymer in which many long-chain branches are introduced into the ultrahigh molecular weight region (MW = 3 million or more) by introducing the catalyst component “D”. And Moreover, it can be inferred that the introduction of many long-chain branches further improves the melt tension (MT), which is advantageous for various moldings.

Examples of the method for quantifying the amount of long chain branching include measurement methods using ¹³ C-NMR and 3D-GPC shown below.
In the present invention, the amount of long chain branching was evaluated using the branching index (g ′) calculated from the 3D-GPC measurement shown below.

[Branch structure analysis by 3D-GPC]
In this specification, 3D-GPC refers to a GPC device to which three detectors are connected. Three such detectors are a differential refractometer (RI), a viscosity detector (Viscometer) and a multi-angle laser light scattering detector (MALLS).
Waters Alliance GPCV2000 was used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer).
In addition, as a light scattering detector, a DAWN-E manufactured by Wyatt Technology, a multi-angle laser light scattering detector (MALLS) was used.
The detectors were connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (antioxidant Irganox 1076 added at a concentration of 0.5 mg / mL). The flow rate is 1 mL / min. As a column, two Tosoh Corporation GMHHR-H (S) HT were connected and used. The temperature of the column, sample injection section, and each detector is 140 ° C. The sample concentration was 1 mg / mL. The injection volume (sample loop volume) is 0.2175 mL.
In order to obtain the absolute molecular weight (M) obtained from MALLS, the radius of inertia (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer, data processing software ASTRA (version 4.73.04) attached to MALLS was used. The calculation was performed with reference to the following documents.

References:
1. Developments in polymer characterization, vol. 4). Essex: Applied Science; 1984. Chapter 1.
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000)
4). Macromolecules, 33, 6945-6952 (2000)

[Calculation of branching index (g ′)]
The branching index (g ′) is a ratio (ηbranch / ηlin) between the intrinsic viscosity (ηbranch) obtained by measuring the sample with the above Viscometer and the intrinsic viscosity (ηlin) obtained separately by measuring a linear polymer. ,calculate.
When long chain branching is introduced into a polymer molecule, the radius of inertia is reduced compared to a linear polymer molecule having the same molecular weight. Since the intrinsic viscosity becomes smaller when the radius of inertia becomes smaller, the ratio of the intrinsic viscosity (ηbranch) of the branched polymer to the intrinsic viscosity (ηbrin) of the linear polymer having the same molecular weight (ηbranch / ηlin) as long chain branching is introduced Is getting smaller.
Therefore, when the branching index (g ′ = ηbranch / ηlin) is smaller than 1, it means that a branch is introduced, and as the value decreases, the introduced long chain branch increases. Means to do.

The propylene-based polymer that can be produced according to the present invention is characterized in that a lot of long-chain branches are introduced, thereby having an effect of improving melt properties.
Therefore, the propylene-based polymer according to the present invention is characterized in that the branching index (g ′) is 0.82 or less at a molecular weight (M) of 3 million, and further 0.80 or less. It is characterized by being 0.75 or less especially.

4). Melt property of propylene polymer Since the propylene polymer according to the present invention has an increased branching amount, the melt property is remarkably improved. That is, it has the characteristic of having a high melt tension. As an index of melt tension, it can be expressed by melt tension (MT) measured by the following measurement method.

[Measurement of melt tension (MT)]
A method for measuring the melt tension (MT) will be described.
Using a Capillograph 1B manufactured by Toyo Seiki Co., Ltd., the tension detected by the pulley when the resin is extruded in a string shape under the following conditions and wound on a roller is defined as a melt tension (MT).
Capillary: 2.1mm in diameter
Cylinder diameter: 9.6mm
Cylinder extrusion speed: 10 mm / min Winding speed: 4.0 m / min Temperature: 190 ° C
Here, a larger MT value means a higher melt tension.
The propylene-based polymer of the present invention has improved melt tension by broadening the molecular weight distribution and introducing branches, and therefore, MT is preferably 60 g or more.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In addition, the physical-property measurement, an analysis, etc. in a following example follow the analysis of said propylene polymer, and the following method.

(1) Melt flow rate (MFR)
It was measured according to the melt flow rate (test condition: 230 ° C., load 2.16 kgf) of the polypropylene test method of JIS K6758. The unit is g / 10 minutes.
(2) Branched structure analysis by 3D-GPC The analysis was performed by the method described in the present specification.
(3) Measurement of melt tension (MT) The measurement was performed by the method described in the present specification.

[Example 1]
1. Synthesis of catalyst component [Synthesis Example 1 of catalyst component [A-1]]
(1) Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl-phenyl) -indenyl}] hafnium (component [A-1 ]):
Synthesis of dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilyl-phenyl) -indenyl}] hafnium was carried out according to the method described in JP2009-299046. Performed similarly to the method described in Example 11.

[Synthesis Example 2 of catalyst component [A-2]]:
(1) Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (synthesis of component [A-2] (complex 2)) :
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is carried out according to the method described in Example 7 of JP-A-11-240909. As well as.

[Synthesis Example 3 of catalyst component [D]]:
(1) Synthesis of dimethyl [bis {2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl}] silane:
(1-1) Synthesis of 4- (4-i-propylphenyl) indene:
To a 500 ml glass reaction vessel, 15 g (91 mmol) of 4-i-propylphenylboronic acid and 200 ml of dimethoxyethane (DME) are added, a solution of 90 g (0.28 mol) of cesium carbonate and 100 ml of water is added, and 4-bromoindene is added. 13 g (67 mmol) and tetrakistriphenylphosphinopalladium 5 g (4 mmol) were sequentially added, and the mixture was heated at 80 ° C. for 6 hours.
After allowing to cool, the reaction solution was poured into 500 ml of distilled water, transferred to a separatory funnel, and extracted with diisopropyl ether. The ether layer was 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 by a silica gel column to obtain 15.4 g (yield 99%) of 4- (4-i-propylphenyl) indene as a colorless liquid.

(1-2) Synthesis of 2-bromo-4- (4-i-propylphenyl) indene:
To a 500 ml glass reaction vessel, 15.4 g (67 mmol) of 4- (4-i-propylphenyl) indene, 7.2 ml of distilled water and 200 ml of DMSO were added, and 17 g (93 mmol) of N-bromosuccinimide was gradually added thereto. . The mixture was stirred at room temperature for 2 hours, poured into 500 ml of ice water, and extracted three times with 100 ml of toluene. The toluene layer was washed with saturated brine, 2 g (11 mmol) of p-toluenesulfonic acid was added, and the mixture was heated to reflux for 3 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 19.8 g (yield 96%) of 2-bromo-4- (4-i-propylphenyl) indene as a yellow liquid. .

(1-3) Synthesis of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene:
To a 500 ml glass reaction vessel, 6.7 g (82 ml 1 mol) of 2-methylfuran and 100 ml of DME were added and cooled to -70 ° C. in a dry ice-methanol bath. To this was added dropwise 51 ml (81 mmol) of a 1.59 mol / L n-butyllithium-n-hexane solution, and the mixture was stirred for 3 hours. The solution was cooled to −70 ° C., and a solution of 20 ml (87 mmol) of triisopropyl borate and 50 ml of DME was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After the reaction solution was hydrolyzed with 50 ml of distilled water, a solution of 223 g of potassium carbonate and 100 ml of water and 19.8 mg (63 mmol) of 2-bromo-4- (4-i-propylphenyl) indene were added in this order, and the mixture was heated at 80 ° C. The mixture was heated and reacted for 3 hours while removing low-boiling components. After allowing to cool, the reaction solution was poured into 300 ml of distilled water, transferred to a separatory funnel and extracted three times with diisopropyl ether. The ether layer was 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 obtain 19.6 g of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene as a colorless liquid ( Yield 99%).

(1-4) Synthesis of dimethyl [bis {2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl}] silane:
To a 500 ml glass reaction vessel, 9.1 g (29 mmol) of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene and 200 ml of THF are added, and -70 in a dry ice-methanol bath. Cooled to ° C. To this, 17 ml (28 mmol) of a 1.66 mol / L n-butyllithium-hexane solution was dropped, and the mixture was stirred as it was for 3 hours. The mixture was cooled to −70 ° C., 0.1 ml (2 mmol) of 1-methylimidazole and 1.8 g (14 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. Dimethyl [bis {2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl}] silane 8.6 g (88% yield) of a pale yellow solid was obtained.

[Synthesis Example of Catalyst Component (B)]
Chemical treatment of ion-exchange layered silicate:
In a separable flask, 96% sulfuric acid (1044 g) was added to 3456 g of distilled water, and then 600 g of montmorillonite (Mizusawa Chemical Benclay SL: average particle size 19 μm) was added as a layered silicate. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, added with 2400 g of distilled water and then filtered to obtain 1230 g of a cake-like solid.
Next, 648 g of lithium sulfate and 1800 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution, and the entire amount of the above solid on the cake was added, and 522 g of distilled water was further added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, filtered after adding 1980 g of distilled water, further washed with distilled water to pH 3, and filtered to obtain 1150 g of cake-like solid.
The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, and further, rotary kiln drying was performed under a condition of 215 ° C. under a nitrogen stream for a residence time of 10 minutes. 340 g was obtained.
The composition of this chemically treated smectite is Al: 7.81 wt%, Si: 36.63 wt%, Mg: 1.27 wt%, Fe: 1.82 wt%, Li: 0.20 wt%, Al / Si = 0.222 [mol / mol].

2. Preparation of catalyst In a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite obtained above was added, and heptane (66 mL) was added to form a slurry. The solution was added with 34.0 mL) and stirred for 1 hour, and then washed with heptane until the residual liquid ratio became 1/100 to make the total volume 50 mL.
In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) prepared in Synthesis Example 1 of the catalyst component [A-1] was prepared. ) -4- (4-Trimethylsilyl-phenyl) -indenyl}] hafnium (75 μmol) was dissolved in toluene (15 mL) (solution 1),
In another flask (volume: 200 mL), the dimethyl [bis {2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) prepared in Synthesis Example 1 of the catalyst component [D] was prepared. ) Indenyl}] silane (75 μmol) in toluene (15 mL) (solution 2)
Furthermore, in another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) prepared in Synthesis Example 2 of the catalyst component [A-2] was prepared. ) -4-Hydroazulenyl}] hafnium (75 μmol) was dissolved in toluene (15 mL) (solution 3).
Triisobutylaluminum (0.42 mmol: 0.6 mL of a heptane solution with a concentration of 143 mg / mL) was added to the 1 L flask containing the chemically treated smectite, and then the above solution 1 (15 mL) was added and stirred at room temperature for 20 minutes. did.
Then, after adding the above solution 2 (15 mL) and stirring at room temperature for 20 minutes, triisobutylaluminum (0.18 mmol: 0.25 mL of a heptane solution having a concentration of 143 mg / mL) was added, and then the above solution 3 (15 mL) In addition, the mixture was stirred for 1 hour at room temperature.
Thereafter, 170 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 5 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 4 hours. Thereafter, propylene feed was stopped and residual polymerization was carried out for 1 hour. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (6 mmol: 8.5 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 1 hour to obtain 28.6 g of a dry prepolymerized catalyst (Catalyst A). The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.86 (Catalyst A).

3. Polymerization of Propylene After passing nitrogen through a 3 L autoclave while heating, it was thoroughly dried in advance, and then the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (144 mg / mL), 57 Nml of hydrogen was introduced, 750 g of liquid propylene was introduced, and the temperature was raised to 70 ° C.
Thereafter, 100 mg of the catalyst A synthesized as described above in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 70 ° C. for 1 hour, ethanol was added to terminate the polymerization.
As a result, 354 g of a polymer was obtained. The MFR was 0.7 g / 10 min, and the activity was 3540 gPP / g catalyst · hour. The results are summarized in Table 1. Moreover, the result of 3D-GPC is shown in FIG.

[Example 2]
In Example 1, the same polymerization was carried out except that 80 mg of the catalyst to be introduced was introduced and 81 Nml of hydrogen was introduced.
As a result, 304 g of polymer was obtained. The MFR was 1.3 g / 10 min, and the activity was 3800 g PP / g catalyst · hour. The results are summarized in Table 1.

[Comparative Example 1]
1. Preparation of catalyst In a three-necked flask (volume: 1 L), 10 g of the chemically treated smectite obtained above was added, and heptane (66 mL) was added to form a slurry. The solution was added with 34.0 mL) and stirred for 1 hour, and then washed with heptane until the residual liquid ratio became 1/100 to make the total volume 50 mL.
In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) prepared in Synthesis Example 1 of the catalyst component [A-1] was prepared. ) -4- (4-Trimethylsilyl-phenyl) -indenyl}] hafnium (75 μmol) was dissolved in toluene (15 mL) (solution 1),
Furthermore, in another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) prepared in Synthesis Example 2 of the catalyst component [A-2] was prepared. ) -4-Hydroazulenyl}] hafnium (75 μmol) was dissolved in toluene (15 mL) (solution 2).
Triisobutylaluminum (0.42 mmol: 0.6 mL of a heptane solution with a concentration of 143 mg / mL) was added to the 1 L flask containing the chemically treated smectite, and then the above solution 1 (15 mL) was added and stirred at room temperature for 20 minutes. did.
Further, triisobutylaluminum (0.18 mmol: 0.25 mL of a heptane solution having a concentration of 143 mg / mL) was added, then the above solution 2 (15 mL) was added, and the mixture was stirred at room temperature for 1 hour.
Thereafter, 170 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 5 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 4 hours. Thereafter, propylene feed was stopped and residual polymerization was carried out for 1 hour. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (6 mmol: 8.5 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 1 hour to obtain 29.9 g of a dried prepolymerized catalyst (Catalyst B). The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.99 (catalyst B).

2. Polymerization of Propylene After thoroughly drying in advance by flowing nitrogen through a 3 L autoclave, the inside of the tank was replaced with propylene and cooled to room temperature. After adding 2.86 mL of a heptane solution of triisobutylaluminum (144 mg / mL), 57 Nml of hydrogen was introduced, 750 g of liquid propylene was introduced, and the temperature was raised to 70 ° C.
Thereafter, 100 mg of the catalyst B synthesized as described above in a weight excluding the prepolymerized polymer was pumped to the polymerization tank with high-pressure argon to initiate polymerization. After maintaining at 70 ° C. for 1 hour, ethanol was added to terminate the polymerization.
As a result, 368 g of a polymer was obtained. The MFR was 0.6 g / 10 min, and the activity was 3680 gPP / g catalyst · hour. The results are summarized in Table 1. Moreover, the result of 3D-GPC is shown in FIG.

[Comparative Example 2]
In Comparative Example 1, the same polymerization was carried out except that 81 Nml of hydrogen to be introduced was introduced.
As a result, 390 g of a polymer was obtained. The MFR was 1.6 g / 10 min, and the activity was 3900 gPP / g catalyst · hour. The results are summarized in Table 1.

  As is clear from Table 1 and FIG. 1, Examples 1 and 2 polymerized using the propylene polymerization catalyst A of the present invention were compared with the catalyst B of the conventional method not containing the component (D) of the conventional method. Compared to Examples 1 and 2, for example, in Example 1, the branching index (g ′) is 0.80, which is smaller than 0.83 of Comparative Example 1, and many long chain branches are introduced. Moreover, it turns out that a propylene-type polymer with high melt tension (MT) can be manufactured efficiently.

  The propylene polymerization catalyst of the present invention can efficiently produce a propylene-based polymer with improved melt properties into which long chain branches have been introduced by a simple technique, and is highly industrially applicable. In addition, the propylene polymer polymerized using the propylene polymerization catalyst of the present invention has good flow characteristics such as melt tension and melt viscoelasticity due to an increase in the amount of long-chain branching, and accordingly, blow molding Sometimes it has excellent molding processability due to its high swell ratio, and it can be used suitably for blow molding and extrusion foam molding, etc. because it exhibits a high strain hardening property during extrusion foam molding and can be used for blow molding and extrusion foam molding. The possibility is high.

Claims (5)

A propylene polymerization catalyst comprising at least the following components [A] to [D].
Component [A]: At least two kinds of transition metal compounds each selected from the following components [A-1] and [A-2], which are Group 4 transition metal compounds. However, the ratio of the molar amount of [A-1] to the total molar amount of components [A-1] and [A-2] {[A-1] / ([A-1] + [A-2]) } Is 0.20 to 0.99.
[A-1]: A compound represented by the general formula (a1).

[In General Formula (a1), R ¹¹ and R ¹² independently represent a heterocyclic group having 4 to 16 carbon atoms containing nitrogen, oxygen, or sulfur. R ¹³ and R ¹⁴ are each independently an aryl group having 6 to 16 carbon atoms which may contain a halogen atom, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these, Alternatively, it represents a heterocyclic group having 6 to 16 carbon atoms containing nitrogen, oxygen or sulfur. M ¹¹ represents zirconium or hafnium, and X ¹¹ and Y ¹¹ each independently represent a silyl having a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Group, a C1-C20 halogenated hydrocarbon group, an amino group, or a C1-C20 alkylamino group. Q ¹¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]
[A-2]: A compound represented by the general formula (a2).

[In General Formula (a2), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms. R ²³ and R ²⁴ are each independently a halogen atom, silicon, or an aryl group having 6 to 30 carbon atoms which may contain a plurality of hetero elements selected from these. Q ²¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. M ²¹ represents zirconium or hafnium, and X ²¹ and Y ²¹ each independently represent a silyl having a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Group, a C1-C20 halogenated hydrocarbon group, an amino group, or a C1-C20 alkylamino group. ]
Component [B]: an aluminum oxy compound [B-1], an ionic compound or Lewis acid [B-2] that can be converted into a cation by reacting with the transition metal compound [A], solid acid fine particles [B -3], and at least one selected from the group of compounds consisting of ion-exchangeable layered silicate [B-4].
Component [C]: an organoaluminum compound.
Component [D]: cyclopentadiene derivative. Component [D] is the cyclopentadiene derivative represented by following General formula (2), The catalyst for propylene polymerization of Claim 1 characterized by the above-mentioned.

[In General Formula (2), E ^a1 and E ^a2 are each independently a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, and each may have a substituent. Q ^a1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]   The catalyst for propylene polymerization according to claim 1 or 2, wherein the component [B] is an ion-exchange layered silicate [B-4].   The catalyst for propylene polymerization according to claim 3, wherein the ion-exchange layered silicate [B-4] is a smectite group.   A method for producing a propylene-based polymer, wherein the propylene polymerization catalyst according to any one of claims 1 to 4 is used.

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