JP5256245B2 - Method for producing propylene-based polymer having long chain branching - Google Patents

Description

  The present invention relates to a method for producing a propylene-based polymer, and more specifically, melt properties such as melt tension and melt viscoelasticity are good, and accordingly, blow molding is excellent in molding processability due to a high swell ratio, The present invention relates to 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 properties during extrusion foam molding.

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 poor melt properties such as melt tension and melt viscoelasticity, and has problems such as limitations 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 a pre-polymerization stage is known. Such components that increase the melt tension generally have low elastic modulus, strength, heat resistance, or poor fluidity, and thus have the disadvantage that the original characteristics of polypropylene are impaired when added.

  As another method for improving the melt physical properties, a method has been proposed in which the melt tension is increased by introducing a long-chain branch into a polypropylene molecular structure or a polypropylene molecular structure. 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 radically 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 of propylene and polyene, the effect of improving the melt tension is not always sufficient, and the formation 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 as another method for improving melt physical properties.
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. Metallocene catalysts themselves have been known for a long time. For example, ethylenebis (indenyl) zirconium dichloride and ethylenebis (4,5,6,7-tetrahydroindenyl) found as complexes capable of producing isotactic polyolefins. Zirconium dichloride (Japanese Patent Laid-Open No. 61-130314), dimethylsilylene bis-substituted cyclopentadienyl zirconium dichloride having a silylene group as a crosslinking group (Japanese Patent Laid-Open No. 1-301704), dimethylsilylene bis (indenyl) zirconium dichloride (special) No. 1-275609), dimethylsilylenebis (2-methylindenyl) zirconium whose degree of stereoregularity and molecular weight is improved to some extent by attaching a substituent next to the crosslinking group (2-position) of the cyclopentadienyl compound. Dicro (Japanese Patent Laid-Open No. 4-268307), and dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride in which an aryl group is further introduced at the 4-position to further improve the activity, stereoregularity and molecular weight (Japanese Patent Laid-Open No. 6-100579), dimethylsilylene bis (2-methyl-4-phenyl-4-hydroazurenyl) zirconium dichloride (Japanese Patent Laid-Open No. 10-226712), and more recently, the identification of the 4-position aryl group Dichloro (1,1′-dimethylsilylenebis (2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4H-azulenyl)) hafnium having a specific substituent introduced at the site (JP 2003-292518 A) No. 2002-194016, in which a bulky hetero substituent is introduced at the 2-position. 2002-535339, JP-2004-2259, JP-2004-352707 Patent Publication JP is disclosed.
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.

  The macromer copolymerization method using a metallocene catalyst is, for example, a multi-stage polymerization method, which is terminated at a terminal depending on a specific catalyst and specific polymerization conditions in the first stage of polymerization (hereinafter also referred to as a macromer synthesis step). Propylene macromer having a vinyl structure is produced, and then, in the second stage of polymerization (hereinafter also referred to as macromer copolymerization step), propylene and propylene macromer are copolymerized with a specific catalyst and specific polymerization conditions. It has been proposed (see Patent Documents 4 and 5). Polypropylene obtained by such a method has no high-order cross-linking, the original chemical stability as polypropylene is not impaired, it is excellent in recyclability, and there is no concern about the occurrence of gel for improving melt tension. There are advantages.

  However, in this method, it is necessary to polymerize at a relatively high temperature and low pressure in order to efficiently obtain the terminal vinyl structure required as a macromer in the first stage of polymerization. Also, in the second stage of polymerization, the macromer obtained in the first stage and propylene are copolymerized, but since the amount of macromer to be copolymerized is small relative to the charged amount of macromer, A macromer having a low molecular weight and low stereoregularity remains in an amount that cannot be ignored. 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.

A single-stage polymerization method (in situ macromer generation 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.
As another method for improving the melt properties, recently, two metallocene complexes, specifically rac-Me ₂ Si [2-Me-4-Ph-Ind] ₂ ZrCl ₂ and rac-Me ₂ Si, are used. Using a complex such as [2-Me-4-Ph-Ind] ₂ HfCl _{2 in} combination with silica supporting methylaluminoxane (MAO), the propylene polymer obtained by multistage polymerization is relatively It has been reported to show a high melt tension (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 have supported two kinds of complexes of a macromer production complex having a specific structure and a macromer copolymerization 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. In the future, in order to produce a molded product having a higher expansion ratio, a long-chain branched polymer is further used. It is desired to obtain a propylene-based polymer having an increased branching amount, 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

“Macromolecules”, 1993, 26, 14, p. 3467-3471

  In view of the above-mentioned problems of the prior art, the object of the present invention is excellent in melt physical properties such as melt tension and melt viscoelasticity. 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 foam molding.

  As a result of intensive studies to solve the above problems, the present inventors have carried out propylene polymerization, preferably by single-stage polymerization, in the presence of a catalyst containing two specific types of transition metal compounds. The inventors have found that a polymer having a long chain branching amount can be efficiently produced, and have completed the present invention.

According to the first aspect of the present invention, there is provided a method for producing a propylene polymer, characterized in that propylene polymerization is carried out in the presence of a catalyst containing at least the following components [A] to [C]. The
[A]: At least two transition metal compounds each selected from the following components [A-1] and [A-2], which are group 4 transition metal compounds of the periodic table. However, the ratio of the molar amount of [A-1] to the total molar amount of components [A-1] and [A-2] is 0.30 to 0.99.
[A-1] Transition metal compound represented by general formula (a1)

[In General Formula (a1), R ¹ and R ¹¹ may each independently have a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group having 1 to 18 carbon atoms, or a substituent. The sulfur-containing heterocyclic group which may have a good oxygen-containing heterocyclic group or a substituent is shown. However, at least one of R ¹ and R ¹¹ is an oxygen-containing heterocyclic group which may have a substituent or a sulfur-containing heterocyclic group which may have a substituent. R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon having 1 to 10 carbon atoms. Group, silyl group having a hydrocarbon group having 1 to 18 carbon atoms, halogenated hydrocarbon group having 1 to 18 carbon atoms, alkoxy group or aryloxy group having a substituent having 1 to 20 carbon atoms, oxygen-containing heterocyclic group Alternatively, it represents a sulfur-containing heterocyclic group, and adjacent Rs may form a 6-membered ring, which may contain an unsaturated bond. R ⁷ , R ⁸ , R ⁹ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a silyl group having a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms. Or it is a C1-C18 halogenated hydrocarbon group. Q 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, and X and Y react with [B]. Thus, a σ covalent bond auxiliary ligand that exhibits olefin polymerization ability is shown. ]
[A-2] Transition metal compound represented by formula (a2)

[In General Formula (a2), R ²¹ , R ²² , R ²³ and R ²⁴ each independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms. A silyl group or a halogenated hydrocarbon group having 1 to 18 carbon atoms. However, any two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are substituents other than a hydrogen atom, and any one or more of R ²¹ , R ²² , R ²³ and R ²⁴ are a hydrogen atom. is there. R ³¹ and R ³² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 18 carbon atoms, or a halogenated hydrocarbon group having 1 to 18 carbon atoms. Represents an alkoxy group having 1 to 20 carbon atoms, an aryloxy group or an oxygen-containing heterocyclic group. R ³³ is a hydrocarbon group having 6 to 20 carbon atoms, a halogenated hydrocarbon group having 6 to 20 carbon atoms, a hydrocarbon group having 6 to 20 carbon atoms having a substituted silyl group, an alkoxy group, an aryloxy group or an oxygen-containing group. A hydrocarbon group having 6 to 20 carbon atoms having a heterocyclic group, or a hydrocarbon group having 6 to 20 carbon atoms having an amino group, an alkylamino group, an (alkyl) (aryl) amino group or a nitrogen-containing heterocyclic group; . R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms. Is a halogenated hydrocarbon group. Q 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, and X and Y react with [B]. The σ covalent bond auxiliary ligand that expresses the olefin polymerization ability and M ² represents a transition metal of Group 4 of the periodic table. ]
[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].
[C]: Organoaluminum compound.

According to the second invention of the present invention, in the first invention, in the transition metal compound represented by [A-1] general formula (a1), both R ¹ and R ¹¹ are substituted. Provided is a method for producing a propylene-based polymer, which is an oxygen-containing heterocyclic group which may have or a sulfur-containing heterocyclic group which may have a substituent.
Furthermore, according to the third invention of the present invention, in the second invention, R ¹ and R ¹¹ in the general formula (a1) are each independently an alkyl group having 1 to 10 carbon atoms or 1 to 1 carbon atoms. A furyl group or a thienyl group optionally having 10 alkylsilyl groups, and Q is a divalent alkylene group having 1 or 2 carbon atoms that may have an alkyl group having 1 to 5 carbon atoms, Provided is a method for producing a propylene-based polymer, which is a silylene group or a germylene group which may have an alkyl group having 1 to 20 carbon atoms.

According to a fourth aspect of the present invention, in any one of the first to third aspects, the component [B] is an ion-exchange layered silicate [B-4]. A method for producing a coalescence is provided.
Furthermore, according to a fifth invention of the present invention, in any one of the first to fourth inventions, the ion-exchange layered silicate [B-4] is a smectite group. A manufacturing method is provided.

According to a sixth invention of the present invention, in any one of the first to fifth inventions, M ² in the component [A-2] general formula (a2) is hafnium. A method for producing a coalescence is provided.
Furthermore, according to the seventh aspect of the present invention, in any one of the first to sixth aspects, the components [A] and [B], or the components [A], [B] and [C] Propylene polymerization is carried out using a catalyst obtained by contacting an olefin in the presence and preliminarily polymerizing the olefin in a weight ratio of 0.01 to 100 with respect to the component [B]. A manufacturing method is provided.

According to an eighth invention of the present invention, in any one of the first to seventh inventions, the propylene polymerization is performed by bulk polymerization using liquefied propylene as a solvent or gas phase polymerization that keeps propylene in a gaseous state. A method for producing a propylene polymer is provided.
According to a ninth aspect of the present invention, there is provided a method for producing a propylene polymer according to any one of the first to eighth aspects, wherein the polymerization process is single-stage polymerization.
Furthermore, according to the tenth aspect of the present invention, in any one of the first to ninth aspects, the branching index (g ′) at a molecular weight (M) of 1 million (log M = 6) is 0.80 or less. Provided is a method for producing a propylene polymer, characterized by producing a polymer.

  According to 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. As the amount of long chain branching increases, the melt properties such as melt tension and melt viscoelasticity are good, and accordingly, the swell ratio is high at the time of blow molding, so it is excellent in moldability and strong strain hardening at the time of extrusion foam molding. In order to show the property, the closed cell ratio can be increased, and it can be suitably used for blow molding, extrusion foam molding and the like. For this reason, the industrial significance of the production method of the present invention is very large.

It is a figure explaining the analysis result [Branching index (g ') in molecular weight (M)] of the propylene polymer in the example / comparative example of the present invention by GPC-VIS. It is a figure of the description of the base line of a chromatogram in GPC, and an area.

The method for producing a propylene polymer of the present invention is characterized in that propylene polymerization is preferably carried out by single-stage polymerization in the presence of a catalyst containing at least the components [A] to [C] described later.
The polymer (polymer) obtained by this production method is a long-chain branched propylene polymer whose melt fluidity and melt tension are controlled by its characteristics and has an excellent balance between physical properties and processability. .
Hereinafter, the production method of the propylene polymer of the present invention will be described in detail for each item, such as the catalyst used in the production method, the polymerization step, and the characteristics of the propylene polymer.

1. Catalyst It is essential that the catalyst used in the production method of the present invention contains the following components [A] to [C].
(1) Component [A]
As the component [A], at least two kinds of transition metal compounds selected from the following components [A-1] and [A-2] are 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.

  In the present invention, when the above-mentioned two kinds of transition metal compounds are used in combination, the mixing ratio of both is that of [A-1] with respect to the total molar amount of the components [A-1] and [A-2]. The proportion of the molar amount is 0.30, preferably 0.40, more preferably 0.50 as the lower limit, and 0.99, preferably 0.95, more preferably 0.90 as the upper limit. is necessary.

(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 ¹ and R ¹¹ may each independently have a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group having 1 to 18 carbon atoms, or a substituent. The sulfur-containing heterocyclic group which may have a good oxygen-containing heterocyclic group or a substituent is shown. However, at least one of R ¹ and R ¹¹ is an oxygen-containing heterocyclic group which may have a substituent or a sulfur-containing heterocyclic group which may have a substituent. R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon having 1 to 10 carbon atoms. Group, silyl group having a hydrocarbon group having 1 to 18 carbon atoms, halogenated hydrocarbon group having 1 to 18 carbon atoms, alkoxy group or aryloxy group having a substituent having 1 to 20 carbon atoms, oxygen-containing heterocyclic group Alternatively, it represents a sulfur-containing heterocyclic group, and adjacent Rs may form a 6-membered ring, which may contain an unsaturated bond. R ⁷ , R ⁸ , R ⁹ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a silyl group having a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms. Or it is a C1-C18 halogenated hydrocarbon group. Q 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, and X and Y react with [B]. Thus, a σ covalent bond auxiliary ligand that exhibits olefin polymerization ability is shown. ]

Naturally, the transition metal compound according to the present invention is a compound (stereoisomer) in which the indenyl skeletons are symmetrical with respect to the plane containing Hf, X and Y in terms of relative positions via the bonding group Q. ), I.e. isomers (a; commonly referred to as racemic isomers or pseudo-racemic isomers) and isomers (b; usually referred to as meso-isomers or pseudo-meso isomers).
However, in order to produce a propylene polymer maintaining stereoregularity, from the viewpoint of the action of regulating the growth direction of the polymer chain and the coordination direction of the monomer, the above compound (a), that is, Hf It is preferable to use a compound in which two ligands facing each other across a plane including X and Y are not in a relationship between an entity and a mirror image with respect to the plane.

In general formula (a1), R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, halogen atom, carbon A hydrocarbon group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 18 carbon atoms, a halogenated hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having a substituent having 1 to 20 carbon atoms, or aryloxy Group, oxygen-containing heterocyclic group or sulfur-containing heterocyclic group.
Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine, and fluorine and chlorine are preferable because complex synthesis may be difficult due to reactivity.
Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n -Alkyl groups such as hexyl, cyclopropyl, cyclopentyl, cyclohexyl and the like, and alkenyl groups such as vinyl, propenyl, cyclohexenyl, etc., as well as phenyl groups, can be mentioned, more preferably, methyl, ethyl, i-propyl, t -A butyl group can be mentioned.

Specific examples of the silyl group having a hydrocarbon group having 1 to 18 carbon atoms include trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl.
In the halogenated hydrocarbon group having 1 to 18 carbon atoms, preferred examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. And as for said halogenated hydrocarbon group, when a halogen atom is a fluorine atom, the compound which the fluorine atom substituted to the arbitrary positions of the C1-C10 hydrocarbon group mentioned above is mentioned preferably.
Specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2,1 , 1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 2-, 3-, 4-substituted fluorophenyl, 2-, 3-, 4-substituted Each of chlorophenyl, 2-, 3-, 4-substituted bromophenyl, 2,4-, 2,5-, 2,6-, 3,5-substituted difluorophenyl, 2,4-, 2, 5-, 2,6-, 3,5-substituted dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl Cycloalkenyl, pentafluorophenyl and pentachlorophenyl and the like.

Specific examples of the alkoxy group having 1 to 20 carbon atoms and the aryloxy group include alkoxy groups such as methoxy, ethoxy, propoxy, cyclopropoxy, butoxy, phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy and the like. Aryloxy groups, arylalkoxy groups such as phenylmethoxy, naphthylmethoxy and the like can be mentioned.
The oxygen-containing heterocyclic group is preferably a furyl group or a furyl group having a substituent, and the sulfur-containing heterocyclic group is preferably a thienyl group or a thienyl group having a substituent. Specific examples include 2-furyl group, 2- (5-methylfuryl) group, 2- (5-ethylfuryl) group, 2- (5-n-propylfuryl) group, 2- (5-n-butylfuryl). ) Group, 2- (5-i-propylfuryl) group, 2- (5-i-butylfuryl) group, 2- (5-t-butylfuryl) group, 2- (5-cyclopentylfuryl) group, 2- ( Oxygen-containing heterocyclic groups such as 5-cyclohexylfuryl) group, 2- (5-trimethylsilylfuryl) group, 2- (5-phenylfuryl) group, 2- (4,5-dimethylfuryl) group, 2-benzofuryl group , 2-thienyl group, 2- (5-methyl Ruthienyl) group, 2- (5-ethylfuryl) group, 2- (5-n-propylfuryl) group, 2- (5-n-butylthienyl) group, 2- (5-i-propylthienyl) group, 2- (5-i-butylthienyl) group, 2- (5-t-butylthienyl) group, 2- (5-cyclopentylthienyl) group, 2- (5-cyclohexylthienyl) group, 2- (5-trimethylsilyl) Thienyl) group, 2- (5-phenylthienyl) group, 2- (4,5-dimethylthienyl) group, 2-benzothienyl group and the like.

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be adjacent to each other to form a 6-membered ring, It may contain an unsaturated bond. Specific examples of the substituent containing a phenyl group at the 4-position of the indenyl ring include a naphthyl group, an anthryl group, and a phenanthryl group.
Furthermore, R ² , R ⁶ , R ¹² and R ¹⁶ are preferably hydrogen atoms, and R ⁴ and R ¹⁴ are silyl groups having a hydrocarbon group having 1 to 10 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms. Is particularly preferred.

In general formula (a1), R ¹ and R ¹¹ may each independently have a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group having 1 to 18 carbon atoms, or a substituent. An oxygen-containing heterocyclic group or a sulfur-containing heterocyclic group which may have a substituent is shown. However, at least one of R ¹ and R ¹¹ is an oxygen-containing heterocyclic group which may have a substituent or a sulfur-containing heterocyclic group which may have a substituent. Further, preferably, both R ¹ and R ¹¹ are an oxygen-containing heterocyclic group which may have a substituent or a sulfur-containing heterocyclic group which may have a substituent. The oxygen-containing heterocyclic group is preferably a furyl group, and the sulfur-containing heterocyclic group is preferably a thienyl group.
Specific examples of the oxygen-containing heterocyclic group or sulfur-containing heterocyclic group which may have a substituent include a 2-furyl group, a 2- (5-methylfuryl) group, and 2- (5-ethylfuryl). Group, 2- (5-n-propylfuryl) group, 2- (5-n-butylfuryl) group, 2- (5-i-propylfuryl) group, 2- (5-i-butylfuryl) group, 2- (5-t-butylfuryl) group, 2- (5-cyclopentylfuryl) group, 2- (5-cyclohexylfuryl) group, 2- (5-trimethylsilylfuryl) group, 2- (5-phenylfuryl) group, 2 -(4,5-dimethylfuryl) group, oxygen-containing heterocyclic group such as 2-benzofuryl group, 2-thienyl group, 2- (5-methylthienyl) group, 2- (5-ethylfuryl) group, 2- (5-n-propylfuryl) group, 2- (5-n-butylthie Group), 2- (5-i-propylthienyl) group, 2- (5-i-butylthienyl) group, 2- (5-t-butylthienyl) group, 2- (5-cyclopentylthienyl) group, Sulfur such as 2- (5-cyclohexylthienyl) group, 2- (5-trimethylsilylthienyl) group, 2- (5-phenylthienyl) group, 2- (4,5-dimethylthienyl) group, 2-benzothienyl group A containing heterocyclic group.
Among them, particularly preferred is a furyl group or a thienyl group which may have an alkyl group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms, specifically 2- (5- Methylfuryl) group, 2- (5-ethylfuryl) group, 2- (5-n-propylfuryl) group, 2- (5-n-butylfuryl) group, 2- (5-i-propylfuryl) group, 2- (5-i-butylfuryl) group, 2- (5-t-butylfuryl) group, 2- (5-trimethylsilylfuryl) group, 2- (5-methylthienyl) group, 2- (5-ethylfuryl) Group, 2- (5-n-propylfuryl) group, 2- (5-n-butylthienyl) group, 2- (5-i-propylthienyl) group, 2- (5-i-butylthienyl) group, 2- (5-t-butylthienyl) group, 2- (5-trimethylsilyl) Thienyl) is a group.

In general formula (a1), R ⁷ , R ⁸ , R ⁹ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms. A silyl group having a hydrocarbon group or a halogenated hydrocarbon group having 1 to 18 carbon atoms. Among these substituents, a hydrogen atom and a hydrocarbon group having 1 to 5 carbon atoms are preferable, and hydrogen or a methyl group is more preferable.

In general formula (a1), Q is a divalent hydrocarbon group having 1 to 20 carbon atoms and a silylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms, which binds two five-membered rings. Or a germylene group 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. Preferably, it may have an alkyl group having 1 to 5 carbon atoms, a divalent alkylene group having 1 or 2 carbon atoms, a silylene group that may have an alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms It is a germylene group which may have 1 to 20 alkyl groups.
Specific examples of Q include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i -Propyl) silylene, di (cyclohexyl) silylene, and other alkylsilylene groups; germylene groups; and alkylgermylene groups in which silicon in the silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium. be able to.
In these, the silylene group which may have a C1-C20 alkyl group, or the germylene group which may have a C1-C20 alkyl group is still more preferable, a dimethylsilylene group, dimethyl gel Mylene groups are particularly preferred.

In general formula (a1), X and Y are σ covalent auxiliary ligands that react with [B] to develop olefin polymerization ability. Specifically, each independently represents hydrogen. Atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, hydrocarbon group having 1 to 20 carbon atoms having a substituted silyl group, alkylamino group having 1 to 20 carbon atoms Group, (alkyl) (aryl) amino group or nitrogen-containing heterocyclic group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As these X and Y, a hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, a C1-C20 alkylamino group is preferable, a halogen atom, a C1-C20 hydrocarbon group, or carbon number 1-20 alkylamino groups are more preferable, and a chlorine atom, methyl group, i-butyl group, phenyl group, benzyl group, dimethylamino group or diethylamino group is particularly preferable.

Of the compounds represented by the general formula (a1), preferred compounds are specifically exemplified below.
Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2 -(5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dic B [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium dichloride, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) ) -4-Phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2- (5-methyl-2-furyl) -4- Enyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furfuryl) -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- (4-fluoro Phenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1 , 1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-methylphenyl) -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-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl)- 4- (4-Trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1, 1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-free ) -4- (2-Phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1 , 1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -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- (2-phenanthryl)- Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium Dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-t-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] Hafnium, dichloro [1,1′-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro And b- [1,1′-dimethylsilylene (2-methyl-4-phenyl-indenyl) {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium.

  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 , R ²² , R ²³ and R ²⁴ each independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms. A silyl group or a halogenated hydrocarbon group having 1 to 18 carbon atoms. However, any two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are substituents other than a hydrogen atom, and any one or more of R ²¹ , R ²² , R ²³ and R ²⁴ are a hydrogen atom. is there. R ³¹ and R ³² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 18 carbon atoms, or a halogenated hydrocarbon group having 1 to 18 carbon atoms. Represents an alkoxy group having 1 to 20 carbon atoms, an aryloxy group or an oxygen-containing heterocyclic group. R ³³ is a hydrocarbon group having 6 to 20 carbon atoms, a halogenated hydrocarbon group having 6 to 20 carbon atoms, a hydrocarbon group having 6 to 20 carbon atoms having a substituted silyl group, an alkoxy group, an aryloxy group or an oxygen-containing group. A hydrocarbon group having 6 to 20 carbon atoms having a heterocyclic group, or a hydrocarbon group having 6 to 20 carbon atoms having an amino group, an alkylamino group, an (alkyl) (aryl) amino group or a nitrogen-containing heterocyclic group; . R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms. Is a halogenated hydrocarbon group. Q 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, and X and Y react with [B]. The σ covalent bond auxiliary ligand that expresses the olefin polymerization ability and M ² represents a transition metal of Group 4 of the periodic table. ]

Specific examples of the hydrocarbon group having 1 to 20 carbon atoms of R ²¹ , R ²² , R ²³ and R ²⁴ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s- In addition to alkyl groups such as butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl and cyclohexyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, phenyl, tolyl, dimethylphenyl, ethylphenyl and trimethylphenyl , Aryl groups such as t-butylphenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl and anthryl.
Specific examples of the silyl group having a hydrocarbon group having 1 to 10 carbon atoms include trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl.
Furthermore, in the halogenated hydrocarbon group having 1 to 18 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated hydrocarbon group is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group.
Specific examples of the halogenated hydrocarbon group include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trimethyl Fluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 2-, 3-, 4-substituted fluorophenyl, 2 -, 3-, 4-substituted chlorophenyl, 2-, 3-, 4-substituted bromophenyl, 2,4-, 2,5-, 2,6-, 3,5-substituted difluorophenyl 2,4-, 2,5-, 2,6-, 3,5-substituted dichlorophenyl, 2,4,6-trifluorophenyl, 4,6-trichlorophenyl, pentafluorophenyl and pentachlorophenyl and the like.

Among these, R ²¹ , R ²² , R ²³ and R ²⁴ are hydrogen, or methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, Alkyl groups having 1 to 6 carbon atoms such as n-pentyl, n-hexyl, cyclopropyl, cyclopentyl and cyclohexyl, or aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl groups, halogen-substituted phenyl groups, halogen-substituted C6-C12 halogenated aryl groups, such as a naphthyl group, are preferable.
However, any two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are substituents other than a hydrogen atom, and any one or more of R ²¹ , R ²² , R ²³ and R ²⁴ are hydrogen. Is an atom.

In addition, although two types of isomers exist depending on the arrangement of R ²¹ , R ²² , R ²³ and R ²⁴ , a mixture of isomers can also be used in the present invention. However, when either of the isomers produces atactic polypropylene with no regularity, it must be separated. Adjacent R ²¹ , R ²² , R ²³ and R ²⁴ are structures that do not form a ring.

In general formula (a2), R ³¹ and R ³² are preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R ³¹ is particularly preferably a methyl, ethyl, or i-propyl group, and R ³² is particularly preferably a hydrogen atom.

Specific examples of the hydrocarbon group having 6 to 20 carbon atoms of R ³³ include a phenyl group, a tolyl group, a dimethylphenyl group, a mesityl group, an ethylphenyl group, a diethylphenyl group, a triethylphenyl group, and i-propylphenyl. Group, di-i-propylphenyl group, tri-i-propylphenyl group, n-butylphenyl group, di-n-butylphenyl group, tri-n-butylphenyl group, t-butylphenyl group, di-t-butylphenyl group, tri Examples thereof include t-butylphenyl group, biphenylyl group, p-terphenyl group, m-terphenyl group, naphthyl group, anthryl group, and phenanthryl group aryl group.

In the halogenated hydrocarbon group having 6 to 20 carbon atoms of R ³³ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated hydrocarbon substituent is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group.
Specifically, fluorodimethylphenyl group, (fluoromethyl) methylphenyl group, ethylfluorophenyl group, diethylfluorophenyl group, triethylfluorophenyl group, fluoro i-propylphenyl group, fluorodi i-propylphenyl group, (fluoro i -Propyl) i-propylphenyl group, fluorotri-i-propylphenyl group, n-butylfluorophenyl group, di-n-butylfluorophenyl group, (fluorobutyl) butylphenyl group, tri-n-butylfluorophenyl group, t- Butylfluorophenyl group, di-t-butylfluorophenyl group, tri-t-butylfluorophenyl group, fluorobiphenylyl group, fluoro p-terphenyl group, fluoro m-terphenyl group, fluoronaphthyl group, fluoroanthryl group, fluoro And phenanthryl groups.

Further, specific examples of the hydrocarbon group having 6 to 20 carbon atoms having the substituted silyl group of R ³³ include trimethylsilylphenyl, triethylsilylphenyl, isopropyldimethylsilylphenyl, t-butyldimethylsilylphenyl, phenyldimethylsilylphenyl, and the like. And a silyl group-substituted aryl group.
Specific examples of the hydrocarbon group having 6 to 20 carbon atoms having an alkoxy group, an aryloxy group or an oxygen-containing heterocyclic group represented by R ³³ include 4-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxy group. -3-methylphenyl group, 4-methoxy-3,5-dimethylphenyl group, 4-ethoxyphenyl group, 6-methoxy-2-naphthyl group, 4-phenoxyphenyl group, 4- (2-furyl) phenyl group, 4- (5-methyl-2-furyl) phenyl group and the like can be mentioned.
Furthermore, specific examples of the hydrocarbon group having 6 to 20 carbon atoms having an amino group, an alkylamino group, an (alkyl) (aryl) amino group or a nitrogen-containing heterocyclic group represented by R ³³ include a 4-aminophenyl group, Examples include 4- (dimethylamino) phenyl group, 4- (diethylamino) phenyl group, 4- (methylphenylamino) phenyl group, indolyl group, and the like.

In the general formula (a2), specific examples of the hydrocarbon group having 1 to 10 carbon atoms of R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are methyl, ethyl, n-propyl, i-propyl, Examples thereof include alkyl groups such as n-butyl and alkenyl groups such as vinyl and propenyl.
The halogenated hydrocarbon group is a compound in which a halogen atom is substituted at an arbitrary position of the above hydrocarbon group. As the halogen, fluorine, chlorine or bromine is preferable, and fluorine or chlorine is particularly preferable.
Specific examples of the halogenated hydrocarbon having 1 to 18 carbon atoms include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl and the like.
Specific examples of the silyl group having a hydrocarbon group having 1 to 18 carbon atoms include trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl, and di (alkyl) such as dimethylphenylsilylmethyl and dimethyltolylsilylmethyl. ) (Aryl) silylmethyl group and the like.
Among these, R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are particularly preferably hydrogen atoms.

In general formula (a2), Q is a divalent hydrocarbon group having 1 to 20 carbon atoms and a silylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms, which binds two five-membered rings. Or a germylene group 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. Preferably, it may have an alkyl group having 1 to 5 carbon atoms, a divalent alkylene group having 1 or 2 carbon atoms, a silylene group or a germylene group optionally having an alkyl group having 1 to 20 carbon atoms. It is.
Specific examples of Q include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di ( alkylsilylene groups such as i-propyl) silylene and di (cyclohexyl) silylene, and germylene groups; alkylgermylene groups in which silicon in the silylene groups having a divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium. Can be mentioned.
In these, the silylene group or germylene group which may have a C1-C20 alkyl group is further more preferable, and a dimethylsilylene group and a dimethylgermylene group are especially preferable.

Further, in the general formula (a2), X and Y are σ covalent auxiliary ligands that react with [B] to develop olefin polymerization ability. Specifically, each independently represents hydrogen. Atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, hydrocarbon group having 1 to 20 carbon atoms having a substituted silyl group, alkylamino group having 1 to 20 carbon atoms Group, (alkyl) (aryl) amino group or nitrogen-containing heterocyclic group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As these X and Y, a hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, a C1-C20 alkylamino group is preferable, a halogen atom, a C1-C20 hydrocarbon group, or carbon number 1-20 alkylamino groups are more preferable, and a chlorine atom, methyl group, i-butyl group, phenyl group, benzyl group, dimethylamino group or diethylamino group is particularly preferable.
M represents a transition metal belonging to Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium or hafnium.

The following can be mentioned as a non-limiting example of the transition metal compound of the component (A-2) of the metallocene compound.
(1) Dichloro {1,1′-dimethylsilylene (2,3-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (2) dichloro {1,1′-dimethylsilylene (3,4-dimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (3) dichloro {1,1′-dimethylsilylene (2,5-dimethylcyclopentadienyl) ( 2-methyl-4-phenyl-4H-azurenyl)} hafnium (4) dichloro {1,1′-dimethylsilylene (2,3-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H) -Azulenyl)} hafnium (5) dichloro {1,1′-dimethylsilylene (3,4-di-t-butylcyclopentadienyl) (2-methyl-4-phen -4H-azurenyl)} hafnium (6) dichloro {1,1′-dimethylsilylene (2,5-di-t-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium ( 7) Dichloro {1,1′-dimethylsilylene (2,3-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (8) dichloro {1,1′-dimethylsilylene ( 3,4-diphenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (9) dichloro {1,1′-dimethylsilylene (2,5-diphenylcyclopentadienyl) (2 -Methyl-4-phenyl-4H-azulenyl)} hafnium (10) dichloro {1,1′-dimethylsilylene (2-methyl-4-ethyl) Clopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (11) dichloro {1,1′-dimethylsilylene (2-ethyl-4-methylcyclopentadienyl) (2-methyl- 4-phenyl-4H-azurenyl)} hafnium (12) dichloro {1,1′-dimethylsilylene (2-methyl-4-tert-butylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl) } Hafnium (13) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (14) dichloro {1,1 '-Dimethylsilylene (2,3,4-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} Hough Um (15) dichloro {1,1'-dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (16) dichloro {1,1 ' -Dimethylsilylene (2,3-dimethyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (17) dichloro {1,1'-dimethylsilylene (2,3- Dimethyl-5-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (18) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-Ethyl-4-phenyl-4H-azurenyl)} hafnium (19) dichloro {1,1′-dimethylsilylene (2,4,5- Trimethylcyclopentadienyl) (2-ethyl-4-phenyl-4H-azurenyl)} hafnium (20) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (4-phenyl) -2-i-propyl-4H-azulenyl)} hafnium

(21) Dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-i-propyl-4-t-phenyl-2-i-propyl-4H-azurenyl)} hafnium (22) Dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (4-chlorophenyl) -2-methyl-4H-azurenyl)} hafnium (23 ) Dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (4-chlorophenyl) -2-methyl-4H-azulenyl)} hafnium (24) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (3-methylphenyl) -4H-azule Nyl)} hafnium (25) dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (3-methylphenyl) -4H-azulenyl)} hafnium ( 26) Dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (4-t-butylphenyl) -2-methyl-4H-azurenyl)} hafnium (27) Dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (4-tert-butylphenyl) -2-methyl-4H-azurenyl)} Hafnium (28) dichloro {1,1'-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4- (2-naphthyl) -4H- Azulenyl)} hafnium (29) dichloro {1,1′-dimethylsilylene (2,4,5-trimethylcyclopentadienyl) (2-methyl-4- (2-naphthyl) -4H-azurenyl)} hafnium (30 ) Dichloro {1,1′-methylphenylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (31) dichloro {1,1′-sila Cyclobutenyl (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (32) dichloro {1,1′-silacyclopropenyl (2,4,5 -Trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (33) dichloro {1,1′-shirafu Olenyl (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (34) dichloro {1,1′-methylphenylgermylene (2-methyl-4- Phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (35) dichloro {1,1′-germacyclobutenyl (2,4,5-trimethylcyclopentadienyl) (2 -Methyl-4-phenyl-4H-azulenyl)} hafnium (36) dichloro {1,1′-germacyclopropenyl (2,4,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H— Azulenyl)} hafnium (37) dichloro {1,1′-germafluorenyl (2,4,5-trimethylcyclopentadienyl) ( -Methyl-4-phenyl-4H-azurenyl)} hafnium (38) dichloro [dimethylsilylene {2-methyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl) )] Hafnium (39) dichloro [dimethylsilylene {2-methyl-4- (cyclopropylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (40) dichloro [dimethylsilylene { 3- (2-methylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium

(41) Dichloro [dimethylsilylene {2-methyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (42) dichloro [dimethylsilylene { 2-methyl-4- (cyclohexylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (43) dichloro [dimethylsilylene {2-methyl-4- (1,2-dimethyl) Propyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (44) dichloro [dimethylsilylene {3- (1-cyclopropylethyl) -5-methylcyclopentadienyl} (2 -Methyl-4-phenyl-4H-azurenyl)] hafnium (45) dichloro [dimethylsilyl {3- (1,2-dimethylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (46) dichloro [dimethylsilylene {2-methyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (47) dichloro [dimethylsilylene {3- (1-cyclohexylethyl) -5-methyl Cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (48) dichloro [dimethylsilylene {2-methyl-4- (1-i-propylpropyl) cyclopentadienyl} (2- Methyl-4-phenyl-4H-azulenyl)] hafnium (49) dichloro [dimethylsilylene {2-methyl-4- 1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (50) dichloro [dimethylsilylene {3- (1-ethyl-2-methylbutyl) -5-methylcyclo Pentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (51) dichloro [dimethylsilylene {2-methyl-4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl -4-phenyl-4H-azurenyl)] hafnium (52) dichloro [dimethylsilylene {2-methyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] Hafnium (53) dichloro [dimethylsilylene {3- (1-i-propylbutyl) -5-methyl Tilcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (54) dichloro [dimethylsilylene {3- (1-cyclopropylbutyl) -5-methylcyclopentadienyl} (2- Methyl-4-phenyl-4H-azurenyl)] hafnium (55) dichloro [dimethylsilylene {3- (1-s-butylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azule) )] Hafnium (56) dichloro [dimethylsilylene {3- (1-t-butylbutyl) -5-methylcyclopentadienyl} (2-methyl-4-phenyl-4H-azulel)] hafnium (57) dichloro [dimethyl Silylene {3- (1-cyclohexylbutyl) -5-methylcyclopentadienyl} (2-methyl 4-phenyl-4H-azurenyl)] hafnium (58) dichloro [dimethylsilylene {2-ethyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (59) Dichloro [dimethylsilylene {2-ethyl-4- (cyclopropylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (60) dichloro [dimethylsilylene {3- ( 2-methylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium

(61) Dichloro [dimethylsilylene {2-ethyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (62) dichloro [dimethylsilylene { 2-ethyl-4- (cyclohexylmethyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (63) dichloro [dimethylsilylene {2-ethyl-4- (1,2-dimethyl) Propyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (64) dichloro [dimethylsilylene {2-ethyl-4- (1-cyclopropylethyl) -methyl) -cyclopentadi Enyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (65) dichloro [ Methylsilylene {3- (1,2-dimethylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (66) dichloro [dimethylsilylene {2-ethyl-4 -(1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (67) dichloro [dimethylsilylene {2-ethyl-4- (1-cyclohexylethyl) ) Cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (68) dichloro [dimethylsilylene {2-ethyl-4- (1-i-propylpropyl) cyclopentadienyl} (2 -Methyl-4-phenyl-4H-azurenyl)] hafnium (69) dichloro [dimethylsilylene {2- Tyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (70) dichloro [dimethylsilylene {3- (1-ethyl-2-methylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (71) dichloro [dimethylsilylene {2-ethyl-4- (1-t-butylpropyl) cyclopentadienyl } (2-Methyl-4-phenyl-4H-azurenyl)] hafnium (72) dichloro [dimethylsilylene {2-ethyl-4- (1-cyclohexylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-) 4H-azulenyl)] hafnium (73) dichloro [dimethylsilylene {3- (1-i-propylbutyrate) ) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (74) dichloro [dimethylsilylene {3- (1-cyclopropylbutyl) -5-ethylcyclopentadi Enyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (75) dichloro [dimethylsilylene {3- (1-s-butylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4- Phenyl-4H-azurenyl)] hafnium (76) dichloro [dimethylsilylene {3- (1-t-butylbutyl) -5-ethylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium ( 77) Dichloro [dimethylsilylene {3- (1-cyclohexylbutyl) -5-ethylcyclopentadieny } (2-methyl-4-phenyl-4H-azurenyl)] hafnium (78) dichloro [dimethylsilylene {2-n-propyl-4- (2-methylpropyl) cyclopentadienyl} (2-methyl-4- Phenyl-4H-azurenyl)] hafnium (79) dichloro [dimethylsilylene {3- (cyclopropylmethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium ( 80) Dichloro [dimethylsilylene {3- (2-methylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium

(81) Dichloro [dimethylsilylene {2-n-propyl-4- (2,2-dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (82) dichloro [dimethyl Silylene {3- (cyclohexylmethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (83) dichloro [dimethylsilylene {2-n-propyl-4- (1,2-Dimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (84) dichloro [dimethylsilylene {3- (1-cyclopropylethyl) -5-n- Propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (85 Dichloro [dimethylsilylene {3- (1,2-dimethylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (86) dichloro [dimethylsilylene {2 -N-propyl-4- (1,2,2-trimethylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (87) dichloro [dimethylsilylene {3- (1- (Cyclohexylethyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (88) dichloro [dimethylsilylene {2-n-propyl-4- (1-i-) Propylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (8 ) Dichloro [dimethylsilylene {2-n-propyl-4- (1-cyclopropylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (90) dichloro [dimethylsilylene {3 -(1-Ethyl-2-methylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (91) dichloro [dimethylsilylene {2-n-propyl- 4- (1-t-butylpropyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (92) dichloro [dimethylsilylene {2-n-propyl-4- (1-cyclohexyl) Propyl) cyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium ( 93) Dichloro [dimethylsilylene {3- (1-i-propylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (94) dichloro [dimethylsilylene {3- (1-cyclopropylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (95) dichloro [dimethylsilylene {3- (1-s -Butylbutyl) -5-n-propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azulenyl)] hafnium (96) dichloro [dimethylsilylene {3- (1-t-butylbutyl) -5-n -Propylcyclopentadienyl} (2-methyl-4-phenyl-4H-azurenyl)] hafnium (97) dichroic [Dimethylsilylene {3- (1-cyclohexyl-butyl) -5-n-propyl-cyclopentadienyl} (2-methyl-4-phenyl -4H- azulenyl)] hafnium

  The preferred compounds represented by the above general formulas (a1) and (a2) are described with only representative exemplary compounds, avoiding many complicated examples, and compounds with a central metal of hafnium. It goes without saying that zirconium compounds can also be used, and it is obvious that various ligands, cross-linking groups or auxiliary ligands can be arbitrarily used.

(2) Component [B]
Component [B] includes an aluminum oxy compound [B-1], an ionic compound or Lewis acid [B-2] that can be converted to a cation by reacting with the transition metal compound [A], and solid acid fine particles. At least one selected from the group consisting of [B-3] and an ion-exchange layered silicate [B-4] is used.

(2-1) Component [B-1]
Specific examples of the aluminum oxy compound [B-1] include compounds represented by the following general formula (3), (4) or (5).

In each of the above general formulas, R ^a and R ^b 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. Further, the plurality of R ^a and R ^b 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: 1 of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the following general formula (6). It can be obtained by a (molar ratio) reaction.
In the general formulas (5) and (6), R ^b and R ^c represent a hydrocarbon residue or a 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]
Component [B-2] is an ionic compound or Lewis acid that can be converted to a cation by reacting with the transition metal compound [A] described above.
Specifically, the ionic compound includes a cation such as a carbonium cation or an ammonium cation, and an organic boron compound such as triphenylboron, tris (3,5-difluorophenyl) boron, or tris (pentafluorophenyl) boron. And a complex with a cation.

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.
Component [B-2] can also be used by being supported on a particulate carrier. The fine particle carrier will be described later.

(2-3) Component [B-3]
Examples of the solid acid fine particles [B-3] include solid acids such as alumina and silica-alumina.
Here, the particulate carrier in [B-1] and [B-2] described above 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]
Component [B-4] is an ion-exchange layered silicate (hereinafter sometimes 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 a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable 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 silicate. 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 treatment conditions with salts and acids are not particularly limited, but 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 , 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 matter treatment Examples of the organic matter used for the organic matter 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].
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%.

In the present invention, as the component [B], an ion-exchange layered silicate having a water content of 3% by weight or less obtained by performing a salt treatment and / or an acid treatment is particularly preferable.
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.

The component [B] is preferably spherical particles having an average particle diameter 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 process. 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-4] ion-exchange layered silicate is particularly preferable.
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]
As the component [C], an organoaluminum compound is used. In the present invention, the following general formula:
AlR ^d _q Z _3-q (7)
An organoaluminum compound represented by the formula is suitable.
In the present invention, it goes without saying that the compounds represented by this formula can be used singly, mixed in plural or in combination.
In this formula, R ^d 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 ^d is preferably an alkyl group, and Z is chlorine when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and 1 carbon atom 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 with q = 3 and dialkylaluminum hydride with q = 2 are preferable. More preferably, R ^d is a trialkylaluminum having 1 to 8 carbon atoms.

2. Formation of catalyst / preliminary polymerization The catalyst according to the present invention is obtained by contacting the above component [A] and component [B] in a (preliminary) polymerization tank simultaneously or continuously, or once or several times. Can be formed.
In addition, when the component [A] and the component [B] are contacted, the component [C] may be contacted simultaneously or continuously, or at one time or a plurality of times. In particular, in [A-1] or [A-2] of component [A], when X and Y are other than a hydrocarbon group having 1 to 20 carbon atoms, for example, a halogen group, component [C] is used. It is preferable.
As the contact order, any desired combination can be used, but particularly preferable ones for each component are as follows.
When component [C] is used, before contacting component [A] with component [B], component [A], or component [B], or both component [A] and component [B] Contacting component [C], or contacting component [A] and component [B] at the same time as contacting component [C], or contacting component [A] and component [B] The component [C] can be brought into contact with the component [C] after this, but preferably, the component [C] is brought into contact with any of the components [C] before the component [A] and the component [B] are brought into contact with each other.
The contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC and 150 degreeC.
After contacting each component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of components [A], [B] and [C] used in the present invention is arbitrary. For example, the amount of component [A] 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].
The amount of component (C) relative to component (A) is preferably in the range of 0.01 to 5 × 10 ⁶ , particularly preferably 0.1 to 1 × 10 ⁴ in terms of the molar ratio of the transition metal. .

Component [A-1] and component [A-2] used in the present invention are related to the ratio of the molar amount of [A-1] to the total molar amount of each component [A-1] and [A-2]. 0.30 or more and 0.99 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 decreased g ′ by increasing the branching amount, 0.30 or more is required, preferably 0.50 or more, and more preferably 0.70 or more.
Further, 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, and more preferably 0.90 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 amount of hydrogen.

The catalyst according to the present invention is preferable because it can be subjected to prepolymerization consisting of being brought into contact with an olefin and polymerized in a small amount. By performing the prepolymerization, the melt properties can be improved when the main polymerization is performed.
The reason is considered to be that the branched component can be uniformly distributed among the polymer particles when the main polymerization is performed. On the other hand, when pre-polymerization is not performed, there is a concern that, depending on the conditions, the non-uniformity becomes prominent, so that a gel is generated and the quality is impaired.
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.
In addition to the components [A] to [C], the catalyst used in the present invention is not limited to the purpose of the present invention, but is usually a polymer such as polyethylene or polypropylene, or an inorganic material such as silica or titania. An oxide solid or the like may be added.

3. Use of Catalyst / Propylene Polymerization As the polymerization mode, any mode can be adopted as long as the olefin polymerization catalyst including the component [A], the component [B] and the component [C] is in efficient contact with the monomer.
Specifically, a slurry method using an inert solvent, a so-called bulk method using a liquefied propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or each monomer in a gaseous state without using substantially a liquid solvent. For example, a gas phase method can be used. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied. In addition to the single-stage polymerization, the polymerization process for propylene polymerization can also be performed in 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.
Also, by changing the amount of hydrogen used, in addition to the average molecular weight of the polymer to be produced, the molecular weight distribution, the deviation of the molecular weight distribution toward the high molecular weight side, very high molecular weight components, branching (amount, length, Distribution) can be controlled, whereby the melt physical properties such as strain hardening degree, melt tension, and melt spreadability can be controlled.

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.

[Consideration of polymerization mechanism]
The macromer is considered to be produced by a special chain transfer reaction generally called β-methyl elimination, and industrially effective bulk polymerization is achieved by using the component [A-1] having a specific structure of the present invention. It has been found that it can be produced by gas phase polymerization.
Further, it has been found that the use of the component [A-1] having a specific structure does not lower the macromer selectivity even in the presence of hydrogen.
On the other hand, long-chain branching on the high molecular weight side is achieved by combining with a component [A-2] having a specific structure, which has the ability to form higher molecular weight polymers and has a higher ability to copolymerize macromers with propylene. It is believed that it has become possible to produce a propylene-based polymer with a large amount of introduced.

4). Branched structure analysis of propylene-based polymer In the present invention, a macromer having a vinyl structure at the terminal is generated from a component [A-1] having a specific structure by a β-methyl elimination reaction, and further a component having a specific structure [A-2] is characterized in that 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.

Furthermore, in the present invention, the present inventors have found that the amount of long chain branching increases when a cyclopentadienyl-hydroazulenyl complex is used as [A-2].
Therefore, the propylene-based polymer that can be produced in the present invention is characterized in that it is a polymer into which many long chain branches are introduced. Moreover, it can be inferred that the introduction of a lot of long-chain branches further improves the melt physical properties and is advantageous for various moldings.

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

[Branch structure analysis by GPC-VIS]
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.

In FIG. 1, an example of the analysis result by the said GPC-VIS about the Example / comparative example in an Example was shown. FIG. 1 represents a branching index (g ′) in molecular weight (M) (vertical axis: g ′ is plotted against horizontal axis: LogM). Here, grade name: FY6 (manufactured by Nippon Polypro Co., Ltd.) was used as the linear polymer.
As can be seen from FIG. 1, in both Examples / Comparative Examples, the branching index (g ′) is 1 or less at 1 million (log M = 6) which is a molecular weight region mainly produced by the copolymer complex [A-2]. This demonstrates that long chain branching has been introduced into the molecular weight region. Among them, in Example 1, the branching index (g ′) is 0.79, and it can be seen that many long chain branches are introduced.

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.
Accordingly, the propylene-based polymer according to the present invention is characterized in that the branching index (g ′) is 0.80 or less at a molecular weight (M) of 1,000,000, and further 0.75 or less. And

5. Melt property of propylene polymer Since the propylene polymer of 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.

  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, analysis, etc. in a following example follow 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) Molecular weight and molecular weight distribution (Mw, Mn, Q value)
The value of the weight average molecular weight (Mw) is obtained by gel permeation chromatography (GPC), and the details of the measuring method and measuring instrument are as follows.
Equipment: GPC manufactured by Waters (ALC / GPC, 150C)
Detector: MIRAN, 1A, IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml

The sample is prepared by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolving it at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are performed as shown in FIG.
Further, the conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a standard curve prepared in advance by standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
Brand: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000

Inject 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL to create a calibration curve. The calibration curve uses a cubic equation obtained by approximation by the least square method.
Viscosity formula used for conversion to molecular weight: [η] = K × M ^α uses the following numerical values.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

(3) Branched structure analysis by GPC-VIS It was performed by the method described in the present specification.

[Example 1]
(1) Synthesis of Component [A-1]: Synthesis of rac-dichlorodimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4-trimethylsilylphenyl) -indenyl) hafnium:
Synthesis of (1-a) 4- (4-trimethylsilylphenyl) -indene:
To a 500 ml glass reaction vessel, add 25 g (0.13 mol) of 4-trimethylsilylphenylboronic acid and 200 ml of dimethoxyethane (DME), add a solution of 90 g (0.28 mol) of cesium carbonate and 150 ml of water, and add 4-bromoindene. 20 g (0.10 mmol) and tetrakistriphenylphosphinopalladium 10 g (8.6 mmol) were sequentially added, and the mixture was heated at 80 ° C. for 8 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 25.8 g (yield 95%) of 4- (4-trimethylsilylphenyl) -indene as a colorless liquid.

(1-b) Synthesis of 2-bromo-4- (4-trimethylsilylphenyl) -indene:
To a 500 ml glass reaction vessel, 25.8 g (0.097 mol) of 4- (4-trimethylsilylphenyl) -indene, 7 ml of distilled water and 250 ml of DMSO were added, and 23 g (0.13 mol) of N-bromosuccinimide was gradually added thereto. added. 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, 2.8 g (15 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 by a silica gel column to obtain 17.1 g (yield 51%) of 2-bromo-4- (4-trimethylsilylphenyl) -indene as a pale yellow liquid. .

Synthesis of (1-c) 2- (2- (5-methylfuryl))-4- (4-trimethylsilylphenyl) -indene:
To a 1000 ml glass reaction vessel, 8.6 g (0.11 mol) of 2-methylfuran and 300 ml of DME were added and cooled to −70 ° C. in a dry ice-methanol bath. To this, 63 ml (0.11 mol) of a 1.66 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred as it was for 5 hours. While cooling to -70 ° C, a solution of 26 ml (26 mmol) of triisopropyl borate and 30 ml of DME was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
The reaction solution was hydrolyzed by adding 100 ml of distilled water, and then a solution of 22 g of sodium carbonate and 100 ml of water and 17.1 g (50 mmol) of 2-bromo-4- (4-trimethylsilylphenyl) -indene were added in that order 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 give 12.8 g of 2- (2- (5-methylfuryl))-4- (4-trimethylsilylphenyl) -indene as a colorless solid ( Yield 62%) was obtained.

Synthesis of (1-d) dimethylbis (2- (2- (5-methylfuryl))-4- (4- (trimethylsilylphenyl) -indenyl) silane:
To a 500 ml glass reaction vessel, 11.4 g (33 mmol) of 2- (2- (5-methylfuryl))-4- (4-trimethylsilylphenyl) -indene and 100 ml of THF are added, and -70 in a dry ice-methanol bath. Cooled to ° C. 20 ml (33 mmol) of a 1.66 mol / L n-butyllithium-hexane solution was added dropwise thereto, and the mixture was stirred as it was for 3 hours. While cooling at −70 ° C., 0.13 ml (1.6 mmol) of 1-methylimidazole and 2.1 g (16 mmol) of dimethyldichlorosilane were sequentially added, and the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel and washed with brine until neutral, and sodium sulfate was added to dry the reaction solution. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column. 11.2 g (91% yield) of a yellow solid was obtained.

Synthesis of (1-e) rac-dichlorodimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4-trimethylsilylphenyl) -indenyl) hafnium:
To a 500 ml glass reaction vessel, 11.2 g (15 mmol) of dimethylbis (2- (2- (5-methylfuryl))-4- (4-trimethylsilylphenyl) -indenyl) silane and 100 ml of diethyl ether are added and dried. It cooled to -70 degreeC with the ice-methanol bath. To this, 19 ml (32 mmol) of a 1.66 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred for 3 hours. The solvent of the reaction solution was distilled off under reduced pressure, 300 ml of toluene and 15 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 4.8 g (15 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallized with dichloromethane-hexane, and racemic rac-dichlorodimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4- (trimethylsilylindenyl) hafnium. Was obtained as yellow crystals (4.9 g, yield 33%).

About the obtained racemic body, the identification value by a proton nuclear magnetic resonance method (< ¹ > H-NMR) is described below.
¹ H-NMR (CDCl ₃ ):
Racemate: δ 0.27 (s, 18H), δ 1.12 (s, 6H), δ 2.41 (s, 6H), δ 6.06 (d, 2H), δ 6.24 (d, 2H), δ6. 79 (dd, 2H), δ 6.97 (d, 2H), δ 6.99 (s, 2H), δ 7.29 (d, 2H), δ 7.56 to δ 7.62 (m, 8H).

(2) Synthesis of component [A-2]: dichloro {1,1′-dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium Synthesis The synthesis of dichloro {1,1′-dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium is described in JP-A-2007-308486. Performed according to the method described.

(3) Synthesis of Component [B-4]: Production and Preparation of Ion Exchangeable Layered Silicate (3-1) Chemical Treatment of Ion Exchangeable Layered Silicate 96% Sulfuric Acid (668 g) in 2264 g of distilled water in a separable flask ) And then 4 L of montmorillonite (Mizusawa Chemical Benclay SL: average particle size 19 μm) was added as a layered silicate. The slurry was heated at 90 ° C. for 210 minutes. The reaction slurry was filtered after adding 4000 g of distilled water to obtain 810 g of a cake-like solid.
Next, 432 g of lithium sulfate and 1924 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution, and the entire amount of the solid on the cake was charged. The slurry was reacted at room temperature for 120 minutes. 4 L of distilled water was added to this slurry, followed by filtration, further washing with distilled water to pH 5-6, and filtration. As a result, 760 g of a cake-like solid was obtained.
The obtained solid was preliminarily dried overnight at 100 ° C. under a nitrogen stream, and then coarse particles of 53 μm or more were removed, followed by drying under reduced pressure at 200 ° C. for 2 hours to obtain 220 g of chemically treated smectite.
Then, before using as a catalyst component, 200 degreeC vacuum drying was implemented for 5 hours, and it was used by the following catalyst preparation.

(4) Catalyst preparation In a three-necked flask (volume: 1 L), 10 g of the ion-exchanged layered silicate chemically treated as described above was added, and 66 mL of heptane was added to form a slurry. 34 mL of a heptane solution in mL) was added and stirred for 1 hour, and then washed with heptane (residual liquid ratio 1/100) to make the total volume 50 mL.
Thereafter, triisobutylaluminum (0.42 mmol: 0.60 mL of a 140 mg / mL concentration of heptane solution) was added, and then rac-dichloro [1,1′-dimethylsilylene prepared in another flask (volume 200 mL) was prepared. A toluene solution (21 mL) of bis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] hafnium (0.105 mmol) was added, and after another 5 minutes, triisobutylaluminum (0 18 mmol: dichloro {1,1′-dimethylsilylene (2,3,5-trimethylcyclopenta) prepared in another flask (volume 200 mL) after adding 140 mg / mL heptane solution (0.26 mL) Dienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium (0. What was slurry was added with toluene (9.0 mL) solution of 45 mmol), and allowed to stir to react at room temperature for 60 minutes. Thereafter, 220 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was stabilized at 40 ° C., propylene was fed at a rate of 5 g / hour, and prepolymerization was performed for 4 hours while maintaining 40 ° C. Thereafter, propylene feed was stopped, and residual polymerization was carried out at 40 ° C. for 1 hour. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (12 mmol: 8.5 mL of a 144 ml / mL heptane solution) was added to the portion remaining by the decantation and stirred for 10 minutes.
This solid was dried under reduced pressure for 2 hours to obtain a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.45.

(5) Polymerization of propylene After drying well by flowing nitrogen through a 3 L autoclave in advance, 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) and introducing 750 g of liquefied propylene, the temperature was raised to 70 ° C.
Thereafter, 200 mg of the prepolymerized catalyst synthesized above was fed into the polymerization tank with high-pressure argon in a weight excluding the prepolymerized polymer, and polymerization was started. After maintaining at 70 ° C. for 1 hour, unreacted propylene was quickly purged to terminate the polymerization.
As a result, 214 g of a polymer was obtained.
The analysis results of the obtained polymer are summarized in Table 1. Further, GPC-VIS measurement was performed, and the GPC-VIS measurement result is shown in FIG.

[Example 2]
(1) Synthesis of component [A-2]: dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium Synthesis The synthesis of dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} hafnium is described in JP-A-2007-308486. Performed according to the method described.

(2) Catalyst preparation Except for using the complex as component [A-2], the prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1 in the same manner as in Example 1 (4). A prepolymerization catalyst of .35 was prepared.

(3) Polymerization of propylene The same operation as in Example 1 (5) was performed except that the prepolymerized catalyst prepared in (2) above was used.
As a result, 70 g of a polymer was obtained. The analysis results are summarized in Table 1.

[Comparative Example 1]: (Example using bis-hydroazurenyl complex as component [A-2])
(1) Synthesis of component [A-1]: rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} ] Synthesis of hafnium:
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium is disclosed in JP 2009-299046. It implemented like the method as described in Example 8 of the gazette.

(2) Synthesis of component [A-2]: Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium:
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 1 of JP-A-11-240909. As well as.

(3) Catalyst preparation 10 g of the ion-exchange layered silicate synthesized in Example 1 was placed in a three-necked flask (volume: 1 L), and 66 mL of heptane was added to form a slurry, to which triisobutylaluminum (25 mmol: concentration 144 mg). / ML heptane solution (34 mL) was added and stirred for 1 hour, and then washed with heptane (residual liquid ratio up to 1/100) to make the total volume 50 mL.
Thereafter, triisobutylaluminum (0.42 mmol: 0.60 mL of a 140 mg / mL concentration of heptane solution) was added, and then rac-dichloro [1,1′-dimethylsilylenebis prepared in another flask (volume 200 mL) was prepared. Toluene solution (21 mL) of {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium (0.105 mmol) was added, and after another 5 minutes, triisobutylaluminum ( 0.18 mmol: rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4] prepared in another flask (volume 200 mL) after adding 140 mg / mL heptane solution (0.26 mL) -(4-Chlorophenyl) -4-hydroazulenyl}] hafnium (0.045 mmol) Added (3.0 mL) solution which was slurry addition was allowed to stir to react at room temperature for 60 minutes. 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 stabilized at 40 ° C., propylene was fed at a rate of 5 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 2 hours. Thereafter, propylene feed was stopped, and residual polymerization was carried out at 40 ° C. for 1 hour. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (12 mmol: 8.5 mL of a 144 ml / mL heptane solution) was added to the portion remaining by the decantation and stirred for 10 minutes.
This solid was dried under reduced pressure for 2 hours to obtain 28.7 g of a dry prepolymerized catalyst. The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.87.

(4) Polymerization of propylene After drying well by circulating nitrogen through a 3 L autoclave in advance, 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), 70 Nml of hydrogen and then 750 g of liquid propylene were introduced, and then the temperature was raised to 70 ° C.
Thereafter, 100 mg of the pre-polymerized catalyst synthesized above was fed into the polymerization tank with high-pressure argon in a weight excluding the pre-polymerized polymer, and polymerization was started. After maintaining at 70 ° C. for 1 hour, unreacted propylene was quickly purged to terminate the polymerization.
As a result, 339 g of a polymer was obtained. The analysis results are summarized in Table 1.

[Comparative Example 2]: (Example in which cyclopentadienyl-hydroazurenyl complex having all substituents on Cp is used as component [A-2])
(1) Synthesis of component [A-2]: dichloro {1,1′-dimethylsilylene (tetramethylcyclopentadienyl) (2-methyl-4- (4-trimethylsilyl-3,5-dichlorophenyl-4H-azurenyl) )} Synthesis of hafnium:
A mixed solution of 1-bromo-3,5-dichlorophenyl-4-trimethylsilylbenzene (2.98 g, 10 mmol) in hexane (50 mL) and diisopropyl ether (5 mL) at −10 ° C. in a hexane solution of n-butyllithium (6. 33 mL, 10 mmol, 1.58 M) was added dropwise and the mixture was stirred at −10 ° C. for 1 hour. To this was added 2-methylazulene (1.37 g, 9.7 mmol), and the mixture was warmed to room temperature and stirred for about 1 hour. Tetrahydrofuran (20 mL) and N-methylimidazole (40 μL) were added thereto and cooled to 0 ° C., followed by chlorodimethyl (2,3,4,5-trimethyl-2,4-cyclopentadienyl) silane (2. 14 mL, 9.7 mL), heated to room temperature and continued stirring for 30 minutes. After this, water was added and the layers were separated, and then the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain dimethyl (2,3,4,5-tetramethylcyclopentadienyl) (2-methyl- A crude product of 4- (4-trimethylsilyl-3,5-dichlorophenyl) -1,4-dihydroazurenyl} silane (5.64 g) was obtained.
Next, the crude ligand (2.6 g) obtained above was dissolved in diethyl ether (25 mL), and a hexane solution of n-butyllithium (5.7 mL, 8.93 mmol) was added dropwise at 0 ° C. The mixture was gradually warmed up to and stirred for another 2 hours. Further, toluene (200 mL) was added, and the mixture was cooled to −60 ° C., hafnium tetrachloride (599 mg, 1.87 mmol) was added, the temperature was raised to room temperature over about 1 hour, and the mixture was further stirred for 1 hour. Lithium chloride produced from the reaction solution was removed, and the filtrate was evaporated. This was washed once with 40 mL of n-hexane and twice with 20 mL to obtain almost pure dichloro {1,1′-dimethylsilylene (tetramethylcyclopentadienyl) (2-methyl-4- (4-trimethylsilyl- 3,5-dichlorophenyl-4H-azurenyl)} hafnium was obtained (1.61 g).

(2) Catalyst preparation Except for using the complex as component [A-2], the prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1 in the same manner as in Example 1 (4). A prepolymerized catalyst of .43 was prepared.

(3) Polymerization of propylene The same operation as in Example 1 (5) was performed except that the prepolymerized catalyst prepared in (2) above was used.
As a result, 33 g of a polymer was obtained. The analysis results are summarized in Table 1.

[Comparative Example 3]: (Example in which component [A-2] is not used and a catalyst consisting only of component [A-1] is used)
(1) Catalyst preparation Example 1 (4) except that the transition metal compound (0.150 mmol) of Example 1 (1) was used as component [A-1] and component [A-2] was not used. In the same manner, a prepolymerized catalyst having a prepolymerization ratio (a value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) of 0.50 was prepared.

(2) Polymerization of propylene The same operation as in Example 1 (5) except that the prepolymerization catalyst prepared in (1) above was used and the polymerization temperature was 75 ° C.
As a result, 233 g of a polymer was obtained. The analysis results are summarized in Table 1.

(Discussion):
Bulk using a polymer obtained by performing bulk polymerization using a catalyst combining two specific types of complexes shown in Examples 1 and 2 and a catalyst combining two types of complexes shown in Comparative Examples 1 and 2 When the results of GPC-VIS with the polymer subjected to polymerization are compared according to FIG. 1 and Table 1 above, in the case of the example, for example, the branching index (g ′) around MW 1 million (LOGM = 6). It can be seen that is a low value. This indicates that the amount of branching in the example is larger than that in the comparative example, and from this, it can be considered that the polymer of the example has improved melt properties.

In the method for producing a propylene-based polymer of the present invention, since a catalyst in which two specific types of complexes are combined is used, the resulting propylene-based polymer is introduced with a lot of long-chain branches. Improved melt properties, high swell ratio during blow molding, excellent molding processability, and strong extrusion hardening during extrusion foaming, high closed cell ratio, suitable for blow molding and extrusion foaming It can be used for industrial purposes and has high industrial applicability.

Claims (10)

A method for producing a propylene-based polymer, comprising propylene polymerization in the presence of a catalyst containing at least the components shown in the following [A] to [C].
[A]: At least two transition metal compounds each selected from the following components [A-1] and [A-2], which are group 4 transition metal compounds of the periodic table. However, the ratio of the molar amount of [A-1] to the total molar amount of components [A-1] and [A-2] is 0.30 to 0.99.
[A-1] Transition metal compound represented by general formula (a1)

[In General Formula (a1), R ¹ and R ¹¹ may each independently have a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group having 1 to 18 carbon atoms, or a substituent. The sulfur-containing heterocyclic group which may have a good oxygen-containing heterocyclic group or a substituent is shown. However, at least one of R ¹ and R ¹¹ is an oxygen-containing heterocyclic group which may have a substituent or a sulfur-containing heterocyclic group which may have a substituent. R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon having 1 to 10 carbon atoms. Group, silyl group having a hydrocarbon group having 1 to 18 carbon atoms, halogenated hydrocarbon group having 1 to 18 carbon atoms, alkoxy group or aryloxy group having a substituent having 1 to 20 carbon atoms, oxygen-containing heterocyclic group Alternatively, it represents a sulfur-containing heterocyclic group, and adjacent Rs may form a 6-membered ring, which may contain an unsaturated bond. R ⁷ , R ⁸ , R ⁹ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a silyl group having a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms. Or it is a C1-C18 halogenated hydrocarbon group. Q 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, and X and Y react with [B]. Thus, a σ covalent bond auxiliary ligand that exhibits olefin polymerization ability is shown. ]
[A-2] Transition metal compound represented by formula (a2)

[In General Formula (a2), R ²¹ , R ²² , R ²³ and R ²⁴ each independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 10 carbon atoms. A silyl group or a halogenated hydrocarbon group having 1 to 18 carbon atoms. However, any two or more of R ²¹ , R ²² , R ²³ and R ²⁴ are substituents other than a hydrogen atom, and any one or more of R ²¹ , R ²² , R ²³ and R ²⁴ are a hydrogen atom. is there. R ³¹ and R ³² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 18 carbon atoms, or a halogenated hydrocarbon group having 1 to 18 carbon atoms. Represents an alkoxy group having 1 to 20 carbon atoms, an aryloxy group or an oxygen-containing heterocyclic group. R ³³ is a hydrocarbon group having 6 to 20 carbon atoms, a halogenated hydrocarbon group having 6 to 20 carbon atoms, a hydrocarbon group having 6 to 20 carbon atoms having a substituted silyl group, an alkoxy group, an aryloxy group or an oxygen-containing group. A hydrocarbon group having 6 to 20 carbon atoms having a heterocyclic group, or a hydrocarbon group having 6 to 20 carbon atoms having an amino group, an alkylamino group, an (alkyl) (aryl) amino group or a nitrogen-containing heterocyclic group; . R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms. Is a halogenated hydrocarbon group. Q 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, and X and Y react with [B]. The σ covalent bond auxiliary ligand that expresses the olefin polymerization ability and M ² represents a transition metal of Group 4 of the periodic table. ]
[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].
[C]: Organoaluminum compound. [A-1] In the transition metal compound represented by the general formula (a1), both R ¹ and R ¹¹ have an oxygen-containing heterocyclic group or a substituent which may have a substituent. The method for producing a propylene-based polymer according to claim 1, which is a good sulfur-containing heterocyclic group. R ¹ and R ¹¹ in the general formula (a1) are independently a furyl group or a thienyl group optionally having an alkyl group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms. , Q is a divalent alkylene group having 1 or 2 carbon atoms which may have an alkyl group having 1 to 5 carbon atoms, a silylene group which may have an alkyl group having 1 to 20 carbon atoms, or germylene. The method for producing a propylene-based polymer according to claim 2, which is a group.   The method for producing a propylene-based polymer according to any one of claims 1 to 3, wherein the component [B] is an ion-exchange layered silicate [B-4].   The method for producing a propylene-based polymer according to any one of claims 1 to 4, wherein the ion-exchange layered silicate [B-4] is a smectite group. Component [A-2] production method for the propylene-based polymer according to any one of claims 1 to 5, wherein the M ² of the general formula (a2) is hafnium.   In the presence of the component [A] and the component [B], or the component [A], the component [B] and the component [C], the olefin is brought into contact with the component [B] to a weight ratio of 0.01 to The method for producing a propylene polymer according to any one of claims 1 to 6, wherein propylene polymerization is performed using a catalyst preliminarily polymerized in a range of 100.   The method for producing a propylene-based polymer according to any one of claims 1 to 7, wherein the propylene polymerization is performed by bulk polymerization using liquefied propylene as a solvent, or gas phase polymerization which keeps propylene in a gaseous state. .   The method for producing a propylene-based polymer according to any one of claims 1 to 8, wherein the polymerization process is single-stage polymerization.   Propylene according to any one of claims 1 to 9, wherein a polymer having a molecular weight (M) of 1 million (log M = 6) and a branching index (g ') of 0.80 or less is produced. A method for producing a polymer.

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