JP6264808B2 - Metallocene compound and method for producing olefin polymer using polymerization catalyst using the same - Google Patents

Description

  The present invention relates to a novel metallocene complex and a method for producing an olefin polymer using a polymerization catalyst using the same, and more specifically, in the copolymerization of propylene and ethylene, the ethylene incorporation efficiency is high and the ethylene-propylene copolymer having a high molecular weight is high. The present invention relates to a novel metallocene complex in which a substituent is introduced at a specific position so that a polymerized rubber component can be produced, and a method for producing an olefin polymer using a polymerization catalyst using the same.

Crystalline polypropylene is widely used in various molding fields because of its excellent mechanical properties and chemical resistance. However, a propylene homopolymer or a random copolymer with a small amount of an α-olefin has high rigidity but may have insufficient impact resistance.
Therefore, a method of adding a rubber component such as an ethylene-propylene copolymer (EPR) to a propylene homopolymer, or a copolymerization of propylene and ethylene or an α-olefin after the homopolymerization of propylene and containing a rubber component Thus, the impact resistance has been improved by producing so-called impact copolymers. Furthermore, by increasing the amount of the rubber component of the impact copolymer, flexibility and impact resistance can be improved.

On the other hand, it is known that isotactic polypropylene can be obtained by polymerizing propylene using a metallocene catalyst different from the conventional Ziegler type catalyst system. It is also known to produce an impact copolymer by homopolymerizing propylene and subsequently copolymerizing ethylene and propylene using the same catalyst (see, for example, Patent Documents 1 and 2). Furthermore, an impact copolymer having good rigidity and impact properties is also disclosed (for example, see Patent Document 3).
In particular, in the impact copolymer, in order to exhibit high impact resistance, for example, it is necessary to exhibit a lower glass transition temperature, and in order to satisfy this, co-use of propylene and ethylene or α-olefin is required. It is said that it is preferable to carry out the polymerization so that each content satisfies a certain range (for example, see Non-Patent Document 1).
Many examples of the transition metal compound constituting the metallocene catalyst have already been known. In particular, in order to improve the rigidity of the impact copolymer, a transition metal compound that gives a homopolypropylene having a high melting point is already known (see, for example, Patent Document 4).

However, when such a propylene-based impact copolymer is produced with a metallocene-based catalyst, the following technical problems have arisen due to the difference in reactivity between propylene and other comonomers.
That is, when a copolymer of propylene and ethylene or α-olefin is copolymerized after propylene homopolymerization by a conventional production method using a metallocene catalyst, the gas composition of propylene / (ethylene or α-olefin) in the polymerization atmosphere Ratio and the amount of propylene polymerized in the atmosphere / the amount of polymerization of (ethylene amount or α-olefin amount) greatly differ, and the amount of polymer (ethylene or α-olefin) polymerized may decrease. . In other words, in order to obtain a copolymer having the desired ethylene or α-olefin content, it is necessary to polymerize by supplying a gas having a monomer ratio greatly different from the content in the copolymer. there were. Furthermore, in extreme cases, a copolymer having a desired content may not be produced due to limitations of the polymerization apparatus.

Thus, a catalyst using a metallocene complex is preferably a metallocene complex having a high ethylene / α-olefin uptake efficiency that has a large difference in ethylene content between the ethylene / propylene mixed gas and the polymer.
In addition, when a metallocene catalyst known so far is used, when copolymerization of propylene and ethylene or α-olefin is carried out in the gas phase, there is a problem that the molecular weight of the resulting copolymer is low. In order to express high impact resistance in the propylene-ethylene block copolymer, it is necessary that the copolymer molecular weight has a certain value or more, and a metallocene complex that can produce a high molecular weight copolymer. Is desired.

Already, Patent Document 5 discloses a metallocene complex having a substituent at the 5-position of the indenyl ring and a furyl group or a thienyl group which may have a substituent at the 2-position of the indenyl ring, Disclosed are metallocene complexes that can provide high ethylene incorporation efficiency and high molecular weight copolymers.
Patent Document 6 discloses a metallocene complex having a cyclic structure between the 5-position and 6-position of the indenyl ring and having a substituent such as an alkyl group at the 2-position of the indenyl ring, which has high activity. Discloses metallocene complexes that can provide high molecular weight copolymers.
However, the creation of a high-performance metallocene complex that has a high incorporation efficiency of ethylene and α-olefin and can provide a copolymer having a higher molecular weight is desired.
In Patent Document 7, a metallocene complex having a cyclic structure between the 5-position and the 6-position of an indenyl ring and further having a substituent on a 5-membered ring is synthesized.

JP-A-4-337308 JP-A-6-287257 JP 2003-206325 A Japanese Patent Laid-Open No. 11-240909 JP 2010-163423 A Special table 2008-535799 gazette JP-T-2006-509059

Polymer, 2001, 42, 9611

  In view of the above-mentioned problems of the prior art, the object of the present invention is to improve the incorporation efficiency of comonomer ethylene and α-olefin in the copolymerization of olefins containing propylene as a monomer, as compared with conventional metallocene catalysts. It is another object of the present invention to provide a metallocene complex capable of polymerizing the rubber component of the present invention and a method for producing an olefin polymer using a polymerization catalyst using the metallocene complex.

As a result of various studies to solve the above-mentioned problems, the present inventors have found that the ligand structure of the transition metal compound as the metallocene complex in the metallocene-based polymerization catalyst is symmetrical due to its basic skeleton, catalytic activity. (I) Efficient uptake of ethylene and α-olefins, taking into account empirical rules from the viewpoint of the mechanism of polymer formation at the point and the effects of steric and electronic effects of substituents on coordination monomers and growing polymers And (ii) seeking a method for improving the molecular weight, conducting a multifaceted examination and conducting an experimental search, in the process, forming a transition metal compound having a specific three-dimensional structure, The present inventors have found that a catalytic function that exhibits the above-described catalytic performance in a well-balanced manner is manifested, and have completed the present invention.
That is, in order to solve the above-mentioned problems, the present inventors have a metallocene complex having a specific substituent, particularly a cyclic structure between the 5-position and the 6-position of the indenyl ring, and arrange the substituent on the ring. A metallocene complex characterized by a structure and further having a furyl group which may have an alkyl group or a substituent or a thienyl group which may have a substituent at the 2-position of the indenyl ring I found. And based on these knowledge, it came to complete this invention.

  That is, according to 1st invention of this invention, the metallocene complex represented with the following general formula [I] formula is provided.

（式中、Ｍは、Ｔｉ、Ｚｒ又はＨｆであり、Ｑは、炭素、珪素又はゲルマニウムである。Ｘ^１とＸ^２は、それぞれ独立して、ハロゲン原子、炭素数１〜６のアルキル基、炭素数６〜１８のアリール基、炭素数１〜６のアルキル基で置換されたアミノ基、炭素数１〜６のアルコキシ基、炭素数１〜６のハロゲン含有アルキル基又は炭素数６〜１８のハロゲン含有アリール基である。
Ｒ^１とＲ^１１は、互いに同じでも異なっていてもよく、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数６〜１８のアリール基、置換基を有していてもよいフリル基又は置換基を有していてもよいチエニル基である。
Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^９、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１９は、互いに同じでも異なっていてもよく、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数１〜６のアルケニル基、炭素数１〜６のハロゲン含有アルキル基、炭素数１〜６の炭化水素基を有するシリル基、炭素数６〜１８のアリール基、炭素数６〜１８のハロゲン含有アリール基、又は置換基を有していてもよい５員環若しくは６員環を構成する複素環基であり、また、隣接するＲ双方で６〜７員環を構成してもよく、６〜７員環が不飽和結合を含んでいてもよい。
各Ｒ^７とＲ^１７は、互いに同じでも異なっていてもよく、水素原子、炭素数１〜６のアルキル基又は炭素数１〜６のアルコキシ基であって、各Ｒ^７と各Ｒ^１７のいずれかひとつは、水素原子以外の置換基である。
各Ｒ^８とＲ^１８は、互いに同じでも異なっていてもよく、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数６〜１８のアリール基のいずれかである。
Ｒ^１０とＲ^２０は、互いに同じでも異なっていてもよく、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルケニル基、炭素数１〜６のハロゲン含有アルキル基、炭素数１〜６の珪素含有アルキル基、炭素数６〜１８のアリール基、炭素数６〜１８のハロゲン含有アリール基、又は置換基を有していてもよい５員環若しくは６員環を構成する複素環基であり、Ｒ^１０とＲ^２０で４〜７員環を構成していてもよい。）

(In the formula, M is Ti, Zr or Hf, Q is carbon, silicon or germanium. X ¹ and X ² are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, An aryl group having 6 to 18 carbon atoms, an amino group substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or an alkyl group having 6 to 18 carbon atoms It is a halogen-containing aryl group.
R ¹ and R ¹¹ may be the same or different from each other and have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a substituent. And a thienyl group which may have a furyl group or a substituent.
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁹ may be the same as or different from each other, and may be a hydrogen atom, halogen, An atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, and a hydrocarbon group having 1 to 6 carbon atoms. A silyl group, an aryl group having 6 to 18 carbon atoms, a halogen-containing aryl group having 6 to 18 carbon atoms, or a heterocyclic group constituting a 5-membered ring or 6-membered ring which may have a substituent, Moreover, 6-7 membered ring may be comprised by both adjacent R, and the 6-7 membered ring may contain the unsaturated bond.
Each R ⁷ and R ¹⁷ may be the same or different from each other, and are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and each of R ⁷ and R ¹⁷ One is a substituent other than a hydrogen atom.
Each R ⁸ and R ¹⁸ may be the same as or different from each other, and may be any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group having 6 to 18 carbon atoms. is there.
R ¹⁰ and R ²⁰ may be the same as or different from each other, and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or a carbon number. 1 to 6 silicon-containing alkyl group, 6 to 18 carbon aryl group, 6 to 18 halogen-containing aryl group, or a heterocycle constituting a 5-membered or 6-membered ring which may have a substituent It is a cyclic group, and R ¹⁰ and R ²⁰ may constitute a 4- to 7-membered ring. )

According to the second invention of the present invention, in the first invention, one or both of R ¹ and R ¹¹ may have a furyl group or a substituent which may have a substituent. Metallocene complexes are provided that are any of the good thienyl groups.
Furthermore, according to the third invention of the present invention, in the first or second invention, each R ⁷ and each R ^{17 in the} general formula [I] is an alkyl group having 1 to 6 carbon atoms. A metallocene complex is provided.

According to a fourth aspect of the present invention, there is provided an olefin polymerization catalyst comprising the metallocene complex according to any one of the first to third aspects.
According to a fifth aspect of the present invention, there is provided an olefin polymerization catalyst comprising the following components (A), (B) and (C) in the fourth aspect: .
Component (A): Metallocene complex according to any one of the first to third inventions Component (B): Compound or ion-exchange layered silicate that reacts with component (A) to form an ion pair Component (C): Organic Aluminum Compound Furthermore, according to the sixth aspect of the present invention, there is provided an olefin polymerization catalyst according to the fifth aspect, wherein the component (B) is an ion-exchange layered silicate.

According to a seventh invention of the present invention, a method for producing an olefin polymer, wherein the olefin polymerization or copolymerization is carried out using the olefin polymerization catalyst according to any one of the fourth to sixth inventions. Is provided.
According to the eighth aspect of the present invention, (i) a step of polymerizing 90 to 100% by weight of propylene and 0 to 10% by weight of ethylene or α-olefin with respect to all monomer components, and (ii) ) A method for producing an olefin polymer comprising a step of polymerizing propylene in an amount of 10 to 90% by weight and ethylene or an α-olefin having 4 or more carbon atoms in an amount of 10 to 90% by weight with respect to all monomer components. Provided.

  Furthermore, according to the ninth invention of the present invention, in the eighth invention, (i) 90 to 100% by weight of propylene and 0 to 10% by weight of ethylene or α-olefin with respect to all monomer components, A process that is bulk polymerization using propylene as a solvent or gas phase polymerization that keeps the monomer in a gaseous state, and (ii) 10 to 90% by weight of propylene and 10 to 90% by weight of ethylene or α-olefin with respect to all monomer components %, A method for producing an olefin polymer is provided.

By using the metallocene complex of the present invention as a polymerization catalyst, it is possible to obtain a high-molecular-weight rubber component, particularly an ethylene / propylene copolymer component, which has higher ethylene or α-olefin uptake efficiency than conventional metallocene compounds. it can.
As a result, a propylene polymer excellent in flexibility and impact resistance can be efficiently produced, and the novel metallocene complex of the present invention and the method for producing an olefin polymer using a polymerization catalyst using the same are industrially used. From the point of view, it is very useful. For example, in a propylene / α-olefin block copolymer produced by multi-stage polymerization of a polypropylene component and a propylene / α-olefin copolymer component, the α-olefin uptake efficiency is high, and a high molecular weight propylene / α- Since the olefin copolymer component can be polymerized, a propylene / α-olefin block copolymer having a good balance between rigidity and impact resistance can be obtained.

The fact that the metallocene complex of the present invention exhibits the effects of the present invention will be discussed below.
That is, the metallocene complex constituting the basic constitution of the present invention is a novel transition metal compound, and is characterized by the electronic and steric structure of the ligand, thereby incorporating ethylene and α-olefin. A catalytic function capable of polymerizing a rubber component having high efficiency and high molecular weight is manifested.
The metallocene complex is composed of a transition metal compound represented by the above general formula [I], and is used as a catalyst component of an olefin polymerization catalyst in the present invention. -Forming an olefin polymerization catalyst;

By using the transition metal compound of the present invention as a catalyst component for olefin polymerization, as demonstrated by the comparison of Examples and Comparative Examples described later, ethylene and α-olefin uptake efficiency is good, and a high molecular weight rubber component is used. A metallocene catalyst for α-olefin polymerization that can be polymerized can be realized.
The reason is not necessarily clear, but the transition metal compound represented by the general formula [I] in the present invention has a 5-membered ring structure between the 5-position and the 6-position of the indenyl ring, and further the 5-membered ring The basic feature is that the structure is a sterically unique structure in which a substituent is arranged on the surface. As a more preferred embodiment, an alkyl group or a substituent may be present at the 2-position of the indenyl ring. It has a thienyl group or the like which may have a furyl group or a substituent, and it can be inferred that these characteristics bring about the specificity of the present invention.
In particular, with such a structure, the dihedral angle between the substituted phenyl group located at the 4-position of the indenyl ring and the indenyl ring containing a 5-membered ring structure is moderately adjusted, and the 2-position angle of the indenyl ring is adjusted. The angle of the substituent is also adjusted, and it is considered that an optimum steric effect on the coordination field can be expressed by the synergistic effect. As a result, it is considered that the steric effect of the 4-position substituent of the indenyl ring functions to increase the molecular weight of the polymer produced by suppressing the polymer elimination reaction, and has an excellent effect.

  Hereinafter, the metallocene complex of the present invention and a method for producing a propylene-based polymer using the metallocene complex (or metallocene compound) will be described in detail for each item.

1. Metallocene Complex The metallocene complex of the present invention is a metallocene complex having a specific substituent represented by the general formula [I].

(In the formula, M is Ti, Zr or Hf, Q is carbon, silicon or germanium. X ¹ and X ² are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, An aryl group having 6 to 18 carbon atoms, an amino group substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or an alkyl group having 6 to 18 carbon atoms It is a halogen-containing aryl group.
R ¹ and R ¹¹ may be the same or different from each other and have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a substituent. Or a thienyl group which may have a substituent.
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁹ may be the same as or different from each other, and may be a hydrogen atom, halogen, An atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, and a hydrocarbon group having 1 to 6 carbon atoms. A silyl group, an aryl group having 6 to 18 carbon atoms, a halogen-containing aryl group having 6 to 18 carbon atoms, or a heterocyclic group constituting a 5-membered ring or 6-membered ring which may have a substituent, Moreover, 6-7 membered ring may be comprised by both adjacent R, and the 6-7 membered ring may contain the unsaturated bond.
Each R ⁷ and R ¹⁷ may be the same as or different from each other, and are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and each of R ⁷ and R ¹⁷ One is a substituent other than a hydrogen atom.
Each R ⁸ and R ¹⁸ may be the same as or different from each other, and may be any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group having 6 to 18 carbon atoms. is there.
R ¹⁰ and R ²⁰ may be the same as or different from each other, and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or a carbon number. 1 to 6 silicon-containing alkyl group, 6 to 18 carbon aryl group, 6 to 18 halogen-containing aryl group, or a heterocycle constituting a 5-membered or 6-membered ring which may have a substituent It is a cyclic group, and R ¹⁰ and R ²⁰ may constitute a 4- to 7-membered ring. )

In the general formula [I], specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n -Pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl and the like can be mentioned.
Specific examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, tert-butoxy, phenoxy and the like.

  In the general formula [I], specific examples of the furyl group, thienyl group, substituted furyl group or substituted thienyl group include 2-furyl, 2- (5-methylfuryl), 2- (5- Ethylfuryl), 2- (5-n-propylfuryl), 2- (5-i-propylfuryl), 2- (5-t-butylfuryl), 2- (5-trimethylsilylfuryl), 2- (5- Triethylsilylfuryl), 2- (5-phenylfuryl), 2- (5-tolylfuryl), 2- (5-fluorophenylfuryl), 2- (5-chlorophenylfuryl), 2- (4,5-dimethylfuryl) ), 2- (3,5-dimethylfuryl), 2-benzofuryl, 3-furyl, 3- (5-methylfuryl), 3- (5-ethylfuryl), 3- (5-n-propylfuryl), 3- (5-i-propy Furyl), 3- (5-t-butylfuryl), 3- (5-trimethylsilylfuryl), 3- (5-triethylsilylfuryl), 3- (5-phenylfuryl), 3- (5-tolylfuryl), 3 -(5-fluorophenylfuryl), 3- (5-chlorophenylfuryl), 3- (4,5-dimethylfuryl), 3-benzofuryl, 2-thienyl, 2- (5-methylthienyl), 2- (5 -Ethylthienyl), 2- (5-n-propylthienyl), 2- (5-i-propylthienyl), 2- (5-t-butylthienyl), 2- (5-trimethylsilylthienyl), 2- ( 5-triethylsilylthienyl), 2- (5-phenylthienyl), 2- (5-tolylthienyl), 2- (5-fluorophenylthienyl), 2- (5-chlorophenylthienyl), -(4,5-dimethylthienyl), 2- (3,5-dimethylthienyl), 2-benzothienyl, 3-thienyl, 3- (5-methylthienyl), 3- (5-ethylthienyl), 3- (5-n-propylthienyl), 3- (5-i-propylthienyl), 3- (5-t-butylthienyl), 3- (5-trimethylsilylthienyl), 3- (5-triethylsilylthienyl), 3- (5-phenylthienyl), 3- (5-tolylthienyl), 3- (5-fluorophenylthienyl), 3- (5-chlorophenylthienyl), 3- (4,5-dimethylthienyl), 3- And benzothienyl.

In the general formula [I], examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Specific examples of the alkenyl group having 1 to 6 carbon atoms include vinyl, propenyl, and allyl. , Butenyl, cyclohexenyl and the like.
Moreover, as a halogen atom of a C1-C6 halogen-containing alkyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, A C1-C6 halogen-containing alkyl group is C1-C6. The hydrogen on the skeleton of the alkyl group is substituted with a halogen. 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, 5-chloropentyl, 5,5,5-trichloropentyl, 5-fluoropentyl, 5,5,5-trifluoro Mention may be made of pentyl, 6-chlorohexyl, 6,6,6-trichlorohexyl, 6-fluorohexyl and 6,6,6-trifluorohexyl.

  The silyl group having a hydrocarbon group having 1 to 6 carbon atoms is a substituent in which three different hydrocarbon groups having 1 to 6 carbon atoms which may be different are substituted on silicon, and 1 to 6 carbon atoms. The hydrocarbon of general formula [I] includes an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and a phenyl group. Specific examples include trimethylsilyl, triethylsilyl, tri-n-butylsilyl, t-butyldimethylsilyl, trivinylsilyl, triallylsilyl, and triphenylsilyl.

In the general formula [I], the aryl group having 6 to 18 carbon atoms may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. Specific examples thereof include phenyl, tolyl, dimethylphenyl, ethylphenyl, Examples thereof include trimethylphenyl, t-butylphenyl, biphenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl and anthryl.
Further, specific examples of the halogen-containing aryl group having 6 to 18 carbon atoms are those in which the hydrogen atom of the aryl group having 6 to 18 carbon atoms is substituted with halogen, specifically, 2-, 3- , 4-substituted fluorophenyls, 2-, 3-, 4-substituted chlorophenyls, 2-, 3-, 4-substituted bromophenyls, 2,4-, 2,5-, 2,6- 3,5-substituted difluorophenyl, 2,4-, 2,5-, 2,6-, 3,5-substituted dichlorophenyl, 2,4,6-, 2,3,4, -2 , 4,5-, 3,4,5-substituted trifluorophenyl, 2,4,6-, 2,3,4-, 2,4,5-, 3,4,5-substituted tri Chlorophenyl, pentafluorophenyl, pentachlorophenyl, 3,5-dimethyl-4-chlorophenyl, 3,5-dichloro-4 Biphenyl and the like.
In the general formula [I], examples of the amino group substituted with an alkyl group having 1 to 6 carbon atoms include dimethylamino, diethylamino, dinormalpropylamino, diisopropylamino, methylisopropylamino, dicyclohexylamino, and methylcyclohexylamino. Preferably, it is dimethylamino.
In the general formula [I], examples of the silicon-containing alkyl group having 1 to 6 carbon atoms include trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylpropyl, and the like, preferably trimethylsilylmethyl.

  In the general formula [I], the heterocyclic group constituting a 5-membered ring or 6-membered ring which may have a substituent is a heteroatom which is not directly bonded to an alkadienyl group. Specific examples of pyrrolidyl, pyridyl, pyrimidyl, quinolyl, isoquinolyl, carbazolyl, furyl, thienyl, thianofuryl, imidazolyl, pyrazolyl, pyrrolyl, oxazolyl, thiazolyl, isothiazolyl, isoxazolyl, and these heterocyclic rings have 1 to 6 carbon atoms. Alkyl group, alkenyl group having 1 to 6 carbon atoms, halogen-containing alkyl group having 1 to 6 carbon atoms, silyl group having a hydrocarbon group having 1 to 6 carbon atoms, aryl group having 6 to 18 carbon atoms, or carbon number It may have a substituent of 6-18 halogen-containing aryl groups, and forms a 5- to 7-membered ring with both adjacent atoms Even well, it may have an unsaturated bond therein, a 5- to 7-membered ring which may contain a hetero atom. This includes the above-mentioned furyl group, thienyl group, furyl group having a substituent or thienyl group having a substituent.

In the general formula [I], M is Ti, Zr or Hf, preferably Zr or Hf, particularly preferably Zr. Q is carbon, silicon or germanium, preferably silicon or germanium.
The substituents R ¹⁰ and R ²⁰ on Q are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 7 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms, and more preferably Is an alkyl group having 1 to 6 carbon atoms. A 4- to 7-membered ring may be formed, and specific examples include silacyclobutane, silacyclopentane, 2,5-dimethylsilacyclopentane, silacyclohexane, and silafluorene.

X ¹ and X ² are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, an amino group substituted with an alkyl group having 1 to 6 carbon atoms, or the number of carbon atoms An alkoxy group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms, and X ¹ and X ² may have a crosslinked structure. Specific examples include a chlorine atom, bromine atom, iodine atom, fluorine atom, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, phenyl group, dimethylamino group or diethylamino group. it can.
Among these, a halogen atom and a C1-C6 alkyl group are preferable. Specifically, a chlorine atom, a methyl group, an i-butyl group, and a phenyl group are particularly preferable.

Each R ⁷ and each R ¹⁷ may be the same as or different from each other, and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and each R ⁷ and each R ¹⁷ Any one is a substituent other than a hydrogen atom. Preferred substituents include an alkyl group having 1 to 6 carbon atoms, more preferably methyl group, particularly preferably all of the R ⁷ and each R ¹⁷ is a methyl group.
Each R ⁸ and each R ¹⁸ is any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group having 6 to 18 carbon atoms, preferably a hydrogen atom , An alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group.

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may constitute a 6-7 membered ring in both adjacent Rs, The 7-membered ring may contain an unsaturated bond. Specifically, as a substituent at the 4-position of the indenyl ring, 1-naphthyl, 2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, 5,6,7,8-tetrahydro-2-naphthyl , Phenanthryl, anthryl and the like.

R ¹ and R ¹¹ may be the same or different from each other and have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a substituent. Or a thienyl group which may have a substituent.
The substituent for R ¹ and R ¹¹ is preferably an alkyl group having 1 to 6 carbon atoms, a furyl group which may have a substituent, or a thienyl group which may have a substituent. Among the 1 to 6 alkyl groups, methyl, ethyl, n-propyl, n-butyl, i-propyl and i-butyl are preferable, and a methyl group is particularly preferable. Further, as a furyl group, a thienyl group, a furyl group having a substituent, or a thienyl group having a substituent, which are substituents for R ¹ and R ¹¹ , those particularly preferable can be represented by the following formula [II].

(In the formula, Z is an oxygen atom or a sulfur atom, and R ³¹ and R ³² may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 1 carbon atoms. An alkoxy group having 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms having a trialkylsilyl group, and a hydrocarbon group having 1 to 6 carbon atoms. A silyl group, an aryl group having 6 to 18 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms, and both adjacent Rs may form a 6-membered ring, and the 6-membered ring is an unsaturated bond. May be included.)

In the formula [II], R ³¹ and R ³² are preferably a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms, preferably an alkyl having 1 to 6 carbon atoms. Group, an aryl group having 6 to 18 carbon atoms.

In the general formula [I], one or both of R ¹ and R ¹¹ is preferably a furyl group which may have a substituent or a thienyl group which may have a substituent.
R ¹ and R ¹¹ are preferably both a furyl group, a thienyl group, a furyl group having a substituent, or a thienyl group having a substituent, and more preferably a substituent in view of high ethylene incorporation efficiency. Or a thienyl group having a substituent, more preferably a furyl group having a substituent.

Substituents on the phenyl group at the 4-position of the indenyl ring (R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ ) include R ³ , R ⁴ , R ⁵ , R ¹³ , R ¹⁴ , R ¹⁵ are preferably substituted, more preferably any one or more of R ³ , R ⁴ , R ⁵ , and It is preferable that any one or more of R ¹³ , R ¹⁴ , and R ¹⁵ have a substituent.
Preferred substituents are silyl having a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms. Group, an aryl group having 6 to 18 carbon atoms, and a halogen-containing aryl group having 6 to 18 carbon atoms, more preferably a silyl group having an alkyl group having 1 to 6 carbon atoms and a hydrocarbon group having 1 to 6 carbon atoms. , An aryl group having 6 to 18 carbon atoms.

In addition, it is preferable that R ⁴ and R ¹⁴ have a substituent in terms of high rubber activity. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, and an alkyl having 1 to 6 carbon atoms having a trialkylsilyl group. Group, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a halogen-containing aryl group having 6 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. , A halogen-containing alkyl group having 1 to 6 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and an aryl group having 6 to 18 carbon atoms.

Specific examples of metallocene compounds:
Specific examples of the metallocene complex of the present invention are shown below.

(1) Dichlorodimethylsilylenebis [2- (2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium, 4-position substitution Changes in group:
(2) Dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (3) Dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (2-methylphenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl- s-indacenyl] zirconium (4) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (2-ethylphenyl) -1,5,6,7-tetrahydro-5,5,7, 7-tetramethyl-s-indacenyl] zirconium (5) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (2-methoxyphenyl) -1,5,6,7-tetrahi B-5,5,7,7-tetramethyl-s-indacenyl] zirconium (6) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (2-chlorophenyl) -1,5 6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (7) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (3-methylphenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (8) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- ( 3-methoxyphenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (9) dichlorodimethylsilylenebis [2- 5-methyl-2-furyl) -4- (3-chlorophenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (10) dichlorodimethylsilylene bis [2- (5-Methyl-2-furyl) -4- (4-methylphenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (11 ) Dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (4-ethylphenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s- Indacenyl] zirconium (12) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -1,5,6,7-tetrahydro-5,5,7, 7-tetramethyl-s-indacenyl] zirconium (13) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -1,5,6,7-tetrahydro -5,5,7,7-tetramethyl-s-indacenyl] zirconium (14) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (4-biphenylyl) -1,5,6 , 7-Tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (15) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -1 , 5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (16) dichlorodimethylsilylenebis [2- (5-methyl) -2-furyl) -4- (4-methoxyphenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (17) dichlorodimethylsilylenebis [2 -(5-Methyl-2-furyl) -4- (4-trifluoromethylphenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (18 ) Dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s- Indacenyl] zirconium (19) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydride -5,5,7,7-tetramethyl-s-indacenyl] zirconium (20) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (3,5-diethylphenyl) -1, 5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium

(21) Dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (3,5-di-i-propylphenyl) -1,5,6,7-tetrahydro-5,5,7 , 7-Tetramethyl-s-indacenyl] zirconium (22) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (3,5-di-t-butylphenyl) -1,5, 6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (23) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (3,5-di -Methoxyphenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (24) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (3,5-bis (trifluoromethyl) phenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (25) dichlorodimethylsilylene bis [2- (5-Methyl-2-furyl) -4- (3,4,5-trimethylphenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl Zirconium (26) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (3,5-dimethyl-4-trimethylsilylphenyl) -1,5,6,7-tetrahydro-5,5 , 7,7-Tetramethyl-s-indacenyl] zirconium (27) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (3,5-dichloro-4-trime Rusilylphenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (28) dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (1-naphthyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (29) dichlorodimethylsilylenebis [2- (5-methyl- 2-furyl) -4- (2-naphthyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (30) dichlorodimethylsilylenebis [2- ( 5-methyl-2-furyl) -4- (9-phenanthryl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (3 1) Dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4- (2-phenanthryl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s- Indacenyl] zirconium

-Changes in substituents on the 2-position furyl group:
(32) Dichlorodimethylsilylenebis [2- (5-trimethylsilyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (33) Dichlorodimethylsilylenebis [2- (5-phenyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (34) Dichlorodimethylsilylenebis [2- (4,5-dimethyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl Zirconium (35) dichlorodimethylsilylene bis [2- (4,5-benzofuryl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5 5,7,7-tetramethyl-s-indacenyl] zirconium (36) dichlorodimethylsilylenebis [2- (5-methyl-2-thienyl) -4-phenyl-1,5,6,7-tetrahydro-5 5,7,7-tetramethyl-s-indacenyl] zirconium (37) dichlorodimethylsilylenebis [2- (5-trimethylsilyl-2-furyl) -4- (3,5-dimethylphenyl) -1,5,6 , 7-Tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (38) dichlorodimethylsilylenebis [2- (5-phenyl-2-furyl) -4- (3,5-dimethylphenyl) ) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (39) dichlorodimethylsilylene [2- (4,5-dimethyl-2-furyl) -4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s- Indacenyl] zirconium (40) dichlorodimethylsilylenebis [2- (4,5-benzofuryl-2-furyl) -4- (3,5-dimethylphenyl) -1,5,6,7-tetrahydro-5,5 7,7-tetramethyl-s-indacenyl] zirconium (41) dichlorodimethylsilylenebis [2- (5-methyl-2-thienyl) -4- (3,5-dimethylphenyl) -1,5,6,7 -Tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium

-Asymmetric substituent at the 2-position:
(42) Dichlorodimethylsilylene [4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] [2- (5-methyl-2-furyl) -4 -Phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (43) dichlorodimethylsilylene [2-methyl-4-phenyl-1,5,6 7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] [2- (5-methyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5 7,7-tetramethyl-s-indacenyl] zirconium (44) dichlorodimethylsilylene [2-ethyl-4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s- B [Dacenyl] [2- (5-methyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (45) dichlorodimethyl Silylene [2- (5-methyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] [2- (5-ethyl -2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (46) dichlorodimethylsilylene [2- (5-methyl- 2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] [2- (5-trimethylsilyl-2-furyl) -4-phenyl -1, , 6,7-Tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] zirconium (47) dichlorodimethylsilylene [2- (5-methyl-2-furyl) -4-phenyl-1,5 6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl] [2- (5-methyl-2-thienyl) -4-phenyl-1,5,6,7-tetrahydro-5, 5,7,7-tetramethyl-s-indacenyl] zirconium

In addition, instead of dimethylsilylene, the bridge portion of the exemplified compound is a compound of diethylsilylene, diphenylsilylene, dimethylgermylene, diethylgermylene, diphenylgermylene, and X ¹ and X ² Alternatively, compounds in which one or both are replaced with a bromine atom, an iodine atom, a methyl group, a phenyl group, a dimethylamino group, a diethylamino group, or the like can also be exemplified.

Method for synthesizing metallocene compounds:
The metallocene complex (compound) of the present invention can be synthesized by an arbitrary method depending on the substituent or bonding mode. An example of a typical synthesis route is shown below.

In the above synthesis route, Compound 1 can be synthesized with reference to JP-T 2006-509059 and the like. Then, 2 is obtained by performing a coupling reaction between 1 and phenylboronic acid in the presence of a palladium catalyst. The bromination of 2 to 3 can be carried out by the method described in the literature (J. Org. Chem. 1982, 47, 705-709), etc., and N-bromosuccinimide is reacted with 2 in the presence of water, p- It can be obtained by dehydration with an acid such as toluenesulfonic acid. 4 is obtained by conducting a coupling reaction of 3 and 5-methylfuryl-2-boronic acid in the presence of a palladium catalyst. 5 is obtained by anionization of 4 with butyllithium or the like and then reaction with dimethyldichlorosilane. After 5 is dianionized with 2 equivalents of alkyllithium or the like, the metallocene compound 6 is obtained by reaction with zirconium tetrachloride.
The synthesis of a metallocene compound into which a substituent is introduced can be synthesized by using a corresponding substitution raw material, and instead of 5-methylfuryl-2-boronic acid, a corresponding boronic acid such as 4,5-dimethyl is synthesized. By using furyl-2-boronic acid, 2-thienylboronic acid, etc., the corresponding 2-position substituent (R ¹ , R ¹¹ ) can be introduced, and the 2-position substituent (R ¹ , R ¹¹ ) can be introduced. When introducing an alkyl group, it can be introduced by reacting 3 with a Grignard reagent under a Ni catalyst as in the literature (J. Org. Chem. 1984, 49, 4226).
The synthesis of metallocene compounds with different substituents on the two indenyl rings can be bridged by sequentially reacting different substituted indenes with Me ₂ QCl ₂ . Further, a crosslinking aid such as an amine compound (for example, methylimidazole) may be present during crosslinking.

2. Olefin Polymerization Catalyst The metallocene complex of the present invention forms a catalyst component for olefin polymerization, and the catalyst component can be used as a catalyst for olefin polymerization. For example, the metallocene complex is preferably used as an olefin polymerization catalyst described below, which includes the component (A).

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

(2) Component (A) for each component:
As the metallocene complex represented by the general formula [I] of component (A), two or more compounds represented by the same or different general formula [I] may be used.

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

  In aluminum oxy compounds, it is well known that aluminum oxy compounds can activate metallocene complexes. Specific examples of such compounds include compounds represented by the following general formulas.

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

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

An ion-exchange layered silicate (hereinafter, sometimes simply referred to as “silicate”) has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other and have a binding force. Refers to a silicate compound in which the ions to be exchanged are exchangeable. Various known silicates are known, and are specifically described in Shiramizu Haruo "Clay Mineralogy" Asakura Shoten (1995).
In the present invention, those preferably used as the component (B) belong to the smectite group, and specific examples include montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, and stevensite. Of these, montmorillonite is preferable because of its high polymerization activity.
Since most silicates are naturally produced mainly as the main component of clay minerals, they often contain impurities (such as quartz and cristobalite) other than ion-exchanged layered silicates. Hybrids may be contained in the smectite silicate.

Granulation of ion-exchange layered silicate:
Silicates may be used in a dry state or in a slurry state in a liquid. In addition, the shape of the ion-exchange layered silicate is not particularly limited, and may be a naturally produced shape, a shape when artificially synthesized, or a shape by operations such as pulverization, granulation, and classification. You may use the processed ion exchange layered silicate. Of these, the use of granulated silicate is particularly preferred because it gives good polymer particle properties.
The shape processing of the ion-exchange layered silicate such as granulation, pulverization, and classification may be performed before the acid treatment, or the shape may be processed after the acid treatment.

  Examples of the granulation method used here include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation method, emulsion granulation method. , Submerged granulation method, compression molding granulation method, and the like, but are not particularly limited. Preferred examples include agitation granulation method, spray granulation method, rolling granulation method, and fluidization granulation method, and particularly preferred are agitation granulation method and spray granulation method.

  When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene is used as a dispersion medium for the raw slurry. Preferably, water is used as a dispersion medium. The concentration of the component (B) in the raw slurry liquid for spray granulation from which spherical particles are obtained is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight. . Although the inlet temperature of the hot air of spray granulation from which spherical particles are obtained varies depending on the dispersion medium, taking water as an example, the temperature is 80 to 260 ° C, preferably 100 to 220 ° C.

  In granulation, in order to obtain a carrier having high particle strength and to improve propylene polymerization activity, the silicate is refined as necessary. The silicate may be refined by any method. As a method for miniaturization, either dry pulverization or wet pulverization is possible. Preferably, wet pulverization using water as a dispersion medium and utilizing the swellability of silicate, for example, a forced stirring method using polytron or the like, a dyno mill, a pearl mill, or the like. The average particle size before granulation is 0.01 to 3 μm, preferably 0.05 to 1 μm.

  Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation. Examples of the binder used include magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycols and the like.

  The spherical particles obtained as described above preferably have a compressive fracture strength of 0.2 MPa or more in order to suppress crushing and fine powder generation in the polymerization step. The particle size of the granulated ion-exchange layered silicate is in the range of 0.1 to 1000 μm, preferably 1 to 500 μm. There is no particular limitation on the pulverization method, and either dry pulverization or wet pulverization may be used.

Acid treatment:
The silicate used in the present invention is used after being subjected to an acid treatment, but may be treated by combining other chemical treatments. Other chemical treatments include alkali treatment, salt treatment, organic matter treatment, and the like.
The acid treatment of the silicate can change the acid strength of the solid. In addition to the effect of ion exchange and removal of surface impurities, the acid treatment also has an effect of eluting part of cations such as Al, Fe, Mg, Li having a crystal structure.
Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid, and phthalic acid. Two or more of these may be used simultaneously. Of these, inorganic acids are preferable, sulfuric acid, hydrochloric acid, and nitric acid are preferable, and sulfuric acid is more preferable.
In addition, a method in which acid treatment and salt treatment are combined is particularly preferable, a method in which acid treatment is performed after salt treatment, a method in which salt treatment is performed after acid treatment, a method in which salt treatment and acid treatment are performed simultaneously, salt treatment There is a method of performing salt treatment and acid treatment at the same time after the treatment.

The treatment conditions with the acid are usually selected from the conditions where the acid concentration is 0.1 to 30% by weight, the treatment temperature is the temperature range from room temperature to the boiling point of the solvent used, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the conditions under which at least a part is eluted. The acid is generally used as an aqueous solution. For example, when sulfuric acid is used, the treatment temperature is preferably 80 ° C. to 100 ° C., and the treatment time is preferably 0.5 hours or more and less than 5 hours.
By performing the salt treatment at the same time, the surface area and interlayer distance can be changed by forming an ion complex, a molecular complex, an organic derivative, or the like. For example, a layered substance in a state where the layers are expanded can be obtained by replacing the exchangeable ions between the layers with other large and bulky ions using ion exchange.
When the acid treatment is performed, shape control may be performed by pulverization or granulation before, during, or after the treatment. Further, other chemical treatments such as alkali treatment, organic compound treatment, and organometallic treatment may be used in combination.

The salt used for the ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of 1 to 14 atoms, and preferably selected from the group consisting of 1 to 14 atoms. And a compound comprising a cation containing at least one atom and an anion derived from at least one atom or atomic group selected from the group consisting of a halogen atom, an inorganic acid and an organic acid. Is a cation containing at least one atom selected from the group consisting of group 2 to 14 atoms, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₃ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), OH, O ₂ Cl ₂ , OCl ₃ , OOC It is a compound comprising at least one anion selected from the group consisting of H, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₆ H ₅ O ₇ . Two or more of these salts may be used simultaneously.

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

Composition of silicate after acid treatment:
The acid-treated silicate that is the component (B) according to the present invention has an Al / Si atomic ratio of 0.01 to 0.29, preferably 0.03 to 0.25, and more preferably. Is preferably in the range of 0.05 to 0.23 in view of the activity of the polymerization catalyst and the molecular weight of the rubber component.
The Al / Si atomic ratio is an index of the acid treatment strength of the clay portion, and the method for controlling the Al / Si atomic ratio is controlled by adjusting the acid species for acid treatment, the acid concentration, the acid treatment time and the temperature. can do.
Aluminum and silicon in the silicate are measured by a method in which a calibration curve is prepared by a chemical analysis method by JIS method and quantified by fluorescent X-rays.

Component (C):
An example of the organoaluminum compound is represented by the following general formula.
AlR _a X _3-a
In the general formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a hydrogen atom, a halogen, an alkoxy group, or a siloxy group, and a represents a number greater than 0 and 3 or less.
Specific examples of the organoaluminum compound represented by the general formula include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, halogen or alkoxy such as diethylaluminum monochloride, diethylaluminum monomethoxide An alkyl aluminum is mentioned. Of these, trialkylaluminum is preferred. Two or more of the above organoaluminum compounds may be used in combination.

(3) Catalyst Preparation Method In the method for preparing an olefin polymerization catalyst according to the present invention, the contact method of component (A), component (B) and component (C) is not particularly limited, but the following method is used. Can be illustrated. (I) Method of adding component (C) after contacting component (A) and component (B) (ii) After contacting component (A) and component (C), component (B) (Iii) Method of adding component (A) after contacting component (B) and component (C) (iv) Contacting each component (A), (B), (C) simultaneously Let

Further, different components may be used as a mixture in each component, or the components may be contacted in different orders. This contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin.
Alternatively, the component (B) and the component (C) may be contacted and then the mixture of the component (A) and the component (C) may be added, and the components may be divided and brought into contact with each component.
The contact of each of the components (A), (B), and (C) is preferably performed in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, and xylene in an inert gas such as nitrogen. The contact can be performed at a temperature between −20 ° C. and the boiling point of the solvent, and is preferably performed at a temperature between room temperature and the boiling point of the solvent.

  In the polymerization catalyst according to the present invention, when the component (B) is a silicate, the preferred amounts of the component (A), the component (B) and the component (C) are used as the component (A) with respect to 1 g of the component (B). The metallocene compound is in the range of 0.001 to 10 mmol, more preferably 0.001 to 1 mmol. The amount of the component (C) used is an Al / metallocene compound molar ratio of 0.1 to 100,000, preferably 1 to 10,000. These use ratios show examples of normal ratios, and the present invention is limited by the range of use ratios described above as long as the catalyst meets the purpose of the present invention. Must not.

  Before using the catalyst containing the components (A), (B) and (C) as a catalyst for olefin polymerization (main polymerization), ethylene, propylene, 1-butene, 1-hexene, 1 -Prepolymerization treatment for preliminarily polymerizing a small amount of an olefin such as octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene or the like may be performed. As the prepolymerization method, a known method can be used.

(4) Olefin The catalyst for olefin polymerization of the present invention can be used for homopolymerization of one kind of polymerization monomer selected from ethylene and α-olefin, and copolymerization between two or more kinds of polymerization monomers.
The α-olefin refers to, for example, an olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1 -Dodecene, 1-hexadecene, 4-methyl-1-pentene, styrene, vinylcyclohexane, diene, triene, cyclic olefin and the like.

3. Polymerization method In the present invention, the polymerization form may be any mode as long as the polymerization catalyst containing the metallocene complex represented by the above general formula [I] can be efficiently contacted with the monomer to polymerize or copolymerize the olefin. Can be adopted.
Specifically, a slurry method using an inert solvent, a bulk polymerization method using propylene as a solvent without substantially using an inert solvent, or a gas phase polymerization method for maintaining each monomer in a gaseous state without using a liquid solvent. Etc. can be adopted.
As the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied.
The combination of polymerization types is not particularly limited, and can be a bulk polymerization two-stage, a gas phase polymerization after bulk polymerization, or a two-stage gas phase polymerization, and can be produced with more polymerization stages. Is possible.
In order to obtain a polymer having a particularly good particle shape, the first step is performed by bulk polymerization and the second step is performed by gas phase polymerization, or both the first step and the second step are performed by gas phase polymerization. Is preferred.

  By using the catalyst of the present invention, a high molecular weight copolymer can be produced, and a propylene-based polymer having rigidity and impact resistance can be produced. As a production method, the following step 1 and A polymerization method including the step 2 is preferable, and a polymerization method in which the polymerization in the step 2 is performed following the step 1 is particularly preferable. In addition, multistage polymerization produced in three or more stages in combination with other polymerization conditions is also possible.

[Step 1]:
Step 1 is a step of polymerizing propylene in an amount of 90 to 100% by weight and ethylene or α-olefin in an amount of 0 to 10% by weight with respect to all monomer components.
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 to 150 ° C., and hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure is suitably from 0 to 3 MPaG, preferably from 0 to 2 MPaG.
In the case of the bulk polymerization method, the polymerization temperature is 0 to 90 ° C, preferably 60 to 80 ° C. The polymerization pressure is 0 to 5 MPaG, preferably 0 to 4 MPaG.
In the case of gas phase polymerization, the polymerization temperature is 0 to 200 ° C, preferably 50 to 120 ° C, more preferably 60 to 100 ° C. The polymerization pressure is suitably from 0 to 4 MPaG, preferably from 0 to 3 MPaG.
Further, ethylene or α-olefin can coexist in the range of 0 to 10% without deteriorating the polymer shape with respect to all monomer components, and the molecular weight, activity, and melting point can be adjusted. Moreover, you may use hydrogen as a molecular weight modifier.

[Step 2]:
Step 2 is a step of polymerizing propylene in an amount of 10 to 90% by weight and ethylene or α-olefin in an amount of 10 to 90% by weight with respect to all monomer components, and manufacturing a rubber component exhibiting suitable impact resistance. Can do. The amount of propylene with respect to the monomer component is preferably 20 to 80% by weight in terms of giving a propylene polymer having high impact resistance.
As polymerization conditions in the second step, slurry polymerization and bulk polymerization are the same as those in the first step, but in the case of gas phase polymerization, the monomer composition is different from that in the first step, so the polymerization temperature is 0 to 200 ° C. Preferably, it is 20-90 degreeC, More preferably, it is 30-80 degreeC. The polymerization pressure is suitably from 0 to 4 MPaG, preferably from 1 to 3 MPaG. Moreover, you may use hydrogen as a molecular weight regulator.

  In step 2, when ethylene is used as a monomer, the propylene-based polymer obtained by the polymerization method of the present invention has a portion containing ethylene in a 100 ° C. soluble component in CFC-IR. Improvements in impact resistance and transparency are expected due to the site containing ethylene.

[Polymerization monomer]
In the present invention, the “α-olefin” means an olefin having 3 to 20 carbon atoms as described above, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, Examples include 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene, styrene, vinylcyclohexane, diene, triene, and cyclic olefin.
The monomer used together with propylene is preferably ethylene or 1-butene, and more preferably ethylene. Further, these monomers may be used in combination.

[Analysis of characteristic values of polymerized olefin polymer]
Content of copolymer component (rubber component, hereinafter referred to as “CP”) obtained in the second step in the propylene polymer obtained using the catalyst according to the present invention, ethylene in CP Alternatively, the α-olefin polymerization ratio is determined by the following method.
In addition, although the following examples are when ethylene in CP is used, α-olefins other than ethylene are obtained using a method according to the following examples.

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

(2) CFC measurement conditions (i) Solvent: orthodichlorobenzene (ODCB)
(Ii) Sample concentration: 4 mg / mL
(Iii) Injection volume: 0.4 mL
(Iv) Crystallization: The temperature is lowered from 140 ° C. to 40 ° C. over about 40 minutes.
(V) Sorting method:
The fractionation temperature at the time of temperature-raising elution fractionation is 40, 100, and 140 ° C., and fractionation is performed in three fractions.
In addition, the elution ratio (unit:% by weight) of the component eluting at 40 ° C. or lower (fraction 1), the component eluting at 40 to 100 ° C. (fraction 2), and the component eluting at 100 to 140 ° C. (fraction 3), respectively It is defined as W40, W100, and W140. W40 + W100 + W140 = 100. Moreover, each fractionated fraction is automatically transported to the FT-IR analyzer as it is.
(Vi) Solvent flow rate during elution: 1 mL / min

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

(4) Post-treatment and analysis of measurement results The elution amount and molecular weight distribution of the components eluted at each temperature are obtained using the absorbance at 2945 cm ⁻¹ obtained by FT-IR as a chromatogram. The elution amount is normalized so that the total elution amount of each elution component is 100%. Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
(F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000)

A calibration curve is created by injecting 0.4 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. Conversion to molecular weight uses a general-purpose calibration curve with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical values are used for the viscosity equation ([η] = K × M ^α ) used at that time.
(I) When creating a calibration curve using standard polystyrene:
K = 0.000138, α = 0.70
(Ii) When measuring a sample of a propylene-based block copolymer:
K = 0.000103, α = 0.78
The ethylene content distribution (distribution of ethylene content along the molecular weight axis) of each eluted component is the ratio of the absorbance of 2956 cm ⁻¹ and the absorbance of 2927 cm ⁻¹ obtained by GPC-IR, and is obtained by using polyethylene, polypropylene, or ¹³ Ethylene polymerization ratio (mol%) by a calibration curve prepared in advance using ethylene-propylene-copolymer (EPR) having a known ethylene content by C-NMR measurement or a mixture thereof. Calculate by converting to

(5) CP content The CP content of the propylene-based block copolymer in the present invention is defined by the following formula (I), and is determined by the following procedure.
CP content (% by weight) = W40 × A40 / B40 + W100 × A100 / B100 (I)

In formula (I), W40 and W100 are the elution ratios (unit: weight%) in each of the above-mentioned fractions, and A40 and A100 are the average ethylene content of actual measurement in each fraction corresponding to W40 and W100. (Unit: wt%), and B40 and B100 are the ethylene content (unit: wt%) of CP contained in each fraction. A method for obtaining A40, A100, B40, and B100 will be described later.
Further, the meaning of the formula (I) is as follows.
That is, the first term on the right side of the formula (I) is a term for calculating the amount of CP contained in fraction 1 (portion soluble at 40 ° C.). When fraction 1 contains only CP and does not contain PP, W40 contributes to the CP content derived from fraction 1 as a whole, but fraction 1 contains a small amount of components in addition to CP-derived components. Since components derived from PP (extremely low molecular weight components and atactic polypropylene) are also included, it is necessary to correct the portion. Therefore, by multiplying W40 by A40 / B40, the amount derived from the CP component in fraction 1 is calculated. For example, when the average ethylene content (A40) of fraction 1 is 30% by weight and the ethylene content (B40) of CP contained in fraction 1 is 40% by weight, 30/40 = 3/4 of fraction 1 (Ie, 75% by weight) is derived from CP, and 1/4 is derived from PP. Thus, the operation of multiplying A40 / B40 in the first term on the right side means that the contribution of CP is calculated from the weight% (W40) of fraction 1. The same applies to the second term on the right side, and for each fraction, the CP content is calculated by adding and calculating the contribution of CP.

The average ethylene content A40 of fractions 1 to 3, A100, A140, the ethylene content of the weight ratio and each data point for each data point in the chromatogram absorbance 2945cm ^-1 (absorbance 2956Cm ^-1 and 2927cm ^{- (} Obtained from the ratio to the absorbance of ¹ ).
The ethylene content corresponding to the peak position in the differential molecular weight distribution curve of fraction 1 is defined as B40 (unit is% by weight).
Fraction 2 is considered to be completely eluted at 40 ° C. and cannot be defined with the same definition. Therefore, in the present invention, it is defined as B100 = 100. B40 and B100 are ethylene contents of CP contained in each fraction, but it is practically impossible to obtain this value analytically. The reason is that there is no means for completely separating and separating PP and CP mixed in the fraction.
As a result of studies using various model samples, B40 can rationally explain the effect of improving material properties when the ethylene content corresponding to the peak position of the differential molecular weight distribution curve of fraction 1 is used. I found that I can do it. Moreover, B100 has crystallinity derived from ethylene chain, and for two reasons that the amount of CP contained in these fractions is relatively smaller than the amount of CP contained in fraction 1, Approximation with 100 is closer to the actual situation, and there is almost no error in calculation. Therefore, the analysis is performed with B100 = 100.
Therefore, the CP content can be determined according to the following formula (II).
CP content (% by weight) = W40 × A40 / B40 + W100 × A100 / 100 (II)

That is, W40 × A40 / B40, which is the first term on the right side of the formula (II), indicates the CP content (% by weight) having no crystallinity, and W100 × A100 / 100, which is the second term, represents the crystallinity. The CP content (wt%) is shown.
The ethylene content in the copolymer component is determined by the following formula (III) using the content of the copolymer component determined by the formula (II).
Ethylene content (% by weight) in copolymer component = (W40 × A40 + W100 × A100 + W140 × A140) / [content of copolymer component (% by weight)] (III)

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

(6) Ethylene polymerization ratio The ethylene content in CP is determined by the following formula.
Ethylene content (% by weight) in CP = (W40 × A40 + W100 × A100) / [CP]
However, [CP] is the CP content (% by weight) obtained previously.
From the value of the ethylene content (% by weight) in the CP obtained here, the molecular weight of ethylene and propylene is finally used to convert to mol%.

Hereinafter, in order to describe the present invention more specifically and clearly, the present invention will be described in contrast to Examples and Comparative Examples, and the rationality and significance of the constituent elements of the present invention and the superiority over the prior art will be demonstrated. To do.
In the following examples, the complex synthesis step, the catalyst synthesis step, and the polymerization step were all performed under a purified nitrogen atmosphere, and the solvent was dehydrated and then bubbled with purified nitrogen and used after deaeration.
In addition, physical property measurement, analysis, and the like in the examples are according to the above-described method and the following method.

(1) MFR measurement:
To 6 g of polymer, 6 g of an acetone solution (0.6 wt%) of a heat stabilizer (BHT) was added.
Subsequently, after drying said polymer, it filled with the melt indexer (230 degreeC), and was left to stand for 5 minutes on the conditions of a 2.16 kg load. Thereafter, the extrusion amount of the polymer was measured, converted into an amount per 10 minutes, and used as the MFR value (unit: g / 10 minutes).

(2) Measurement of melting point (Tm):
Using DSC (TA2000 model manufactured by DuPont or DSC6200 model manufactured by Seiko Instruments Inc.), the temperature is raised and lowered once from 20 to 200 ° C. at 10 ° C./min, and then the second time at 10 ° C./min. It was determined from the measured value at the time of temperature rise.

(3) CFC measurement:
According to the method detailed in the above specification.

[Example 1]
Synthesis of metallocene complex A: dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s- Synthesis of indacenyl] zirconium

(1-1) Synthesis of 5,5,7,7-tetramethyl-3,5,6,7-tetrahydro-2H-s-indasen-1-one To a solution of aluminum chloride (32 g) in nitromethane (150 mL) A mixture of 1,1,3,3-tetramethylindane (34.3 g) and 3-chloropropionyl chloride (25 g) was added dropwise on an ice bath. After warming to room temperature and stirring for 5 hours, the reaction solution was poured into 1N hydrochloric acid-ice water and stirred. The organic layer was separated, washed with 1N hydrochloric acid, water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Sulfuric acid (150 mL) was added thereto, and the mixture was heated and stirred at 80 ° C. for 3 hours. After completion of the reaction, the reaction solution was poured into ice water and extracted with diethyl ether. The organic layer was washed with water and saturated brine, and then dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 27.5 g of a crude product of 5,5,7,7-tetramethyl-3,5,6,7-tetrahydro-2H-s-indasen-1-one.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.33 (s, 6H), 1.35 (s, 6H), 1.97 (s, 2H), 2.69 (t, 2H), 3.10 (T, 2H), 7.19 (s, 1H), 7.53 (s, 1H).

(1-2) Synthesis of 1,1,3,3-tetramethyl-4-bromo-1,2,3,5-tetrahydro-s-indacene 5,5,7,7-tetramethyl-3,5 The crude product (27.5 g) of 6,7-tetrahydro-2H-s-indasen-1-one was added to a suspension of aluminum chloride (37 g) and chloroform (150 mL), stirred for 0.5 hours, and then ice bath. Under cooling, a chloroform solution (20 mL) of bromine (6.2 mL) was added dropwise and reacted at room temperature for 4 hours. After completion of the reaction, the mixture was poured into 1N hydrochloric acid-ice water and stirred. The organic layer was separated, washed with 1N hydrochloric acid, water and saturated brine, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and recrystallization purification was performed with diethyl ether and hexane to obtain a yellow solid (18 g). Subsequently, the obtained solid was suspended in methanol (120 mL), sodium borohydride (2.2 g) was added under ice bath cooling, and the mixture was stirred at room temperature for 2 hours. After the reaction, about half of the solvent was distilled off under reduced pressure, and 1N hydrochloric acid was added to quench the reaction, followed by extraction with diethyl ether. The organic layer was washed successively with 1N hydrochloric acid, water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Further, a toluene (150 mL) solution of the obtained yellow solid (18 g) and p-toluenesulfonic acid (0.1 g) was heated to reflux. After 1 hour, water was added to separate the organic layer, washed with saturated brine, and dried over magnesium sulfate. The solvent was distilled off, and the resulting crude product was purified by silica gel column chromatography to obtain 1,1,3,3-tetramethyl-4-bromo-1,2,3,5-tetrahydro-s- Indacene (15 g) was obtained.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.31 (s, 6H), 1.52 (s, 6H), 1.99 (s, 2H), 3.36 (s, 2H), 6.54 (D, 1H), 6.86 (d, 1H), 7.10 (s, 1H).

(1-3) Synthesis of 1,1,3,3-tetramethyl-4-phenyl-1,2,3,5-tetrahydro-s-indacene Phenylboronic acid (3.2 g, 26 mmol) was added to dimethoxyethane (80 mL). ), An aqueous solution (30 mL) of cesium carbonate (11.3 g), 1,1,3,3-tetramethyl-4-bromo-1,2,3,5-tetrahydro-s-indacene (5.06 g) , 17.4 mmol) and tetrakis (triphenylphosphine) palladium (0.8 g) were sequentially added. After reacting for 13 hours under heating and refluxing, the reaction solution was poured into 1N hydrochloric acid-ice water, stirred and extracted with diethyl ether. The organic layer was washed with saturated brine and dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. This was purified by silica gel column chromatography to obtain the desired 1,1,3,3-tetramethyl-4-phenyl-1,2,3,5-tetrahydro-s-indacene (3.8 g, yield 77). %).

(1-4) Synthesis of 1,1,3,3-tetramethyl-4-phenyl-6- (5-methyl-2-furyl) -1,2,3,5-tetrahydro-s-indacene 1,1,3,3-Tetramethyl-4-phenyl-1,2,3,5-tetrahydro-s-indacene (3.8 g, 13.2 mmol) was dissolved in dimethyl sulfoxide (100 mL) and water (4 mL ) Was added. N-bromosuccinimide (3 g) was added at 0 ° C., and the mixture was stirred at room temperature day and night. The reaction was quenched by adding water on an ice bath, and toluene was added to extract the organic layer. After adding p-toluenesulfonic acid monohydrate (0.1 g) to the organic layer and reacting for 1 hour under heating and refluxing, water was added to the reaction solution to separate the organic layer. The organic layer was washed with saturated brine and dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product.

  On the other hand, 2-methylfuran (1.8 mL, 19.8 mmol) was dissolved in dimethoxyethane (50 mL), and n-butyllithium in n-hexane (1.64 M, 12.1 mL) was added dropwise in an ice bath. After stirring for 1 hour, trimethoxyborane (2.5 mL, 22 mmol) was added dropwise with cooling in an ice bath, and the mixture was stirred at room temperature for 16 hours. Water (10 mL) was added and stirred for 1 hour, and then the solvent was distilled off under reduced pressure. Thereto, an aqueous solution (30 mL) of sodium carbonate (2.8 g, 26.4 mmol), a dimethoxyethane (25 mL) solution of the above synthesized crude product, tetrakis (triphenylphosphine) palladium (0.38 g) were added in this order. The reaction was carried out for 3 hours under heating to reflux. Water was added to the reaction solution, and the organic layer was separated, washed with saturated brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain the desired 1,1,3,3-tetramethyl-4-phenyl-6- (5-methyl-2-furyl) -1,2, 3,5-Tetrahydro-s-indacene (2.25 g) was obtained.

(1-5) Dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s-indacenyl Synthesis of zirconium 1,1,3,3-tetramethyl-4-phenyl-6- (5-methyl-2-furyl) -1,2,3,5-tetrahydro-s-indacene (2.25 g, 6 0.1 mmol) was dissolved in diethyl ether (40 mL), and n-butyllithium in n-hexane (1.64 M, 3.7 mL) was added dropwise at −20 ° C. After stirring at room temperature for 2 hours, N-methylimidazole (0.02 mL) and dichlorodimethylsilane (0.37 mL, 3.1 mmol) were added dropwise at −20 ° C., and the mixture was stirred at room temperature for 1.5 hours. Water was added to separate the organic layer, and after drying over magnesium sulfate, the solvent was distilled off under reduced pressure. Dimethylbis [2- (5-methyl-2-furyl) -4-phenyl-5,5,7 , 7-Tetramethyl-1,5,6,7-tetrahydro-s-indacenyl] silane (2.6 g) was obtained. It was dissolved in diethyl ether (40 mL) and n-butyllithium in n-hexane (1.64 M, 3.7 mL) was added dropwise on an ice bath. After stirring at room temperature for 2 hours, the solvent was distilled off under reduced pressure.

Diethyl ether (4 mL) and toluene (80 mL) were added, and the mixture was cooled to −72 ° C., zirconium tetrachloride (0.76 g, 3.3 mmol) was added, and the mixture was stirred at room temperature for 2 hr. The obtained reaction solution was concentrated once, extracted with n-hexane and concentrated again to dryness. After washing with n-hexane and washing with diethyl ether repeatedly, toluene extraction was performed to remove impurities with low solubility. Thereby, the desired dichlorodimethylsilylenebis [2- (5-methyl-2-furyl)}-4-phenyl-1,5,6,7-tetrahydro-5,5,7,7-tetramethyl-s- 0.2 g of racemic form of indazenil] zirconium was obtained.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.98 (s, 6H), 1.09 (s, 12H), 1.16 (s, 6H), 1.20 (s, 6H), 1.76 (S, 4H), 2.36 (s, 6H), 5.94 (s, 2H), 6.16 (s, 2H), 6.26 (s, 2H), 6.7-7.7 ( 12H).

(1-6) Acid treatment and salt treatment acid treatment of smectite group ion-exchange layered silicate:
Distilled water (1130 g) and 96% sulfuric acid (750 g) were added to a separable flask, the internal temperature was kept at 90 ° C., and granulated montmorillonite Benclay SL (average particle size 19 μm, 300 g) as a granulated montmorillonite was added thereto. Added and allowed to react for 2 hours. The suspension was cooled to room temperature in 1 hour and washed with distilled water to pH = 4. The washing magnification at this time was 1/10000 or less.

Salt treatment:
Lithium sulfate monohydrate (210 g) was dissolved in distilled water (520 g) using a separable flask, and filtered acid-treated clay was added thereto, followed by stirring at room temperature for 120 minutes. The slurry was filtered, distilled water (3000 mL) was added to the obtained solid, and the mixture was stirred at room temperature for 5 minutes. The slurry was filtered. Distilled water (2500 mL) was added to the obtained solid, stirred for 5 minutes, and then filtered again. This operation was repeated four more times. The obtained solid was pre-dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, followed by drying under reduced pressure at 200 ° C. for 2 hours to obtain chemically treated montmorillonite. Obtained.

(1-7) Catalyst Preparation Using Metallocene Complex A (Catalyst A)
The chemically treated montmorillonite (5.0 g) obtained above was weighed into a flask having an internal volume of 1 L, 32 ml of heptane and a heptane solution of triisobutylaluminum (17 mL, 12.5 mmol) were added, and the mixture was stirred at room temperature for 1 hour. Then, the remaining liquid rate was washed to 1/100 with heptane, and finally the slurry amount was adjusted to 50 mL. A heptane solution of triisobutylaluminum (1.0 mL) was added thereto, and the mixture was stirred for 10 minutes at room temperature. Furthermore, a solution of metallocene complex A (100 mg, 105 μmol) in toluene (30 mL) was added and stirred at room temperature for 60 minutes.
Next, heptane (240 mL) was added to the slurry, introduced into a stirred autoclave having an internal volume of 1 L, and propylene was supplied at 40 ° C. at a constant rate of 5 g / hour for 120 minutes.
After completion of the propylene supply, the temperature was raised to 50 ° C. and maintained for 3 hours. Thereafter, the residual gas was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand, and the supernatant liquid was extracted. A heptane solution of triisobutylaluminum (4.3 mL, 3.0 mmol) was added to the remaining solid at room temperature, stirred at room temperature for 5 minutes, and then dried under reduced pressure to recover 7.8 g of a solid catalyst (catalyst A). The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 0.52.

(1-8) Propylene-propylene / ethylene block copolymer first step with catalyst A:
After the inside of the stirring autoclave having an internal volume of 3 L was sufficiently substituted with propylene, an n-heptane solution of triisobutylaluminum (2.76 mL, 2.02 mmol) was added, followed by hydrogen (540 mL), followed by liquid propylene ( 750 g) was introduced and the temperature was raised to 65 ° C. and maintained at that temperature. Thereto, 40 mg (excluding the weight of the prepolymerized polymer) of catalyst A slurried with n-heptane was injected to initiate polymerization. The temperature inside the tank was maintained at 65 ° C., and after 1 hour from the addition of the catalyst, the remaining monomer was purged, and the inside of the tank was replaced with argon. Stirring was stopped, and while flowing argon, a Teflon (registered trademark) tube was inserted into the tank, and a small amount of polypropylene was extracted.

Second step:
Thereafter, propylene and ethylene were introduced at an internal temperature of 60 ° C. to 1.8 MPa so that propylene / ethylene = 50/50 in a gas mol composition, and the internal temperature was raised to 80 ° C. Thereafter, while introducing a mixed gas of propylene and ethylene prepared in advance, the polymerization reaction was controlled for 1 hour while adjusting the internal pressure to 2.0 MPa.
As a result, 69 g of propylene-propylene • ethylene block copolymer having good particle properties was obtained. The average gas mol composition in the tank during the polymerization of propylene and ethylene was propylene / ethylene = 52/48.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 46 wt%, an ethylene content in rubber (CP) of 35 mol%, and a weight average of CP parts. The molecular weight (Mw) was 1,07,000. The rubber polymerization activity (CP activity) was 1,000 (g-CP / g-Cat / hr). The Tm of the propylene homopolymer separately collected in the first step was 157 ° C.
The results are summarized in Table 1.

[Example 2] Propylene-propylene / ethylene block copolymerization with catalyst A The catalyst used was 70 mg, and the average gas mol composition in the tank during propylene / ethylene polymerization was adjusted to be propylene / ethylene = 42/58. The operation was performed in the same manner as in [Example 1] [1-8] except that the polymerization time in the second step was 25 minutes. As a result, 174 g of a propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 51 wt%, an ethylene content in rubber (CP) of 55 mol%, and a weight average of CP parts. The molecular weight (Mw) was 656,000. The rubber polymerization activity (CP activity) was 4,000 (g-CP / g-Cat / hr). The Tm of the propylene homopolymer separately collected in the first step was 157 ° C.
The results are summarized in Table 1.

[Comparative Example 1]
(Ratio 1-1) Synthesis of metallocene complex X: synthesis of dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-s-indacenyl] zirconium The metallocene complex X was synthesized with reference to the method described in JP 2012-121882 A and Example 1 to obtain a racemate.

(Ratio 1-2) Catalyst preparation using metallocene complex X (catalyst X)
Instead of the metallocene complex A, 7.3 g of a solid catalyst (catalyst X) was obtained by the same operation as in Example 1, except that 63 mg (75 μmol) of the metallocene complex X was used.
The pre-polymerization magnification (the value obtained by dividing the pre-polymerized polymer amount by the solid catalyst amount) was 0.44.

(Ratio 1-3) Propylene-Propylene / Ethylene Block Copolymerization with Catalyst X Except that the average gas mol composition in the tank during propylene / ethylene polymerization was adjusted to be propylene / ethylene = 57/43 [Examples] The same operation as in 1] was performed. As a result, 156 g of a propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 8 wt%, an ethylene content in rubber (CP) of 32 mol%, and a weight average of CP parts. The molecular weight (Mw) was 321,000. The rubber polymerization activity (CP activity) was 3000 (g-CP / g-Cat / hr). The Tm of the propylene homopolymer separately collected in the first step was 160 ° C.
The results are summarized in Table 1.

[Comparative Example 2]
Propylene-propylene / ethylene block copolymerization with catalyst X The same operation as in Example 1 except that the average gas molar composition in the tank during propylene / ethylene polymerization was adjusted to be propylene / ethylene = 41/59. did. As a result, 105 g of propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 17 wt%, an ethylene content in rubber (CP) of 52 mol%, and a weight average of CP parts. The molecular weight (Mw) was 513,000. The rubber polymerization activity (CP activity) was 2100 (g-CP / g-Cat / hr).
The results are summarized in Table 1.

[Comparative Example 3]
(Ratio 3-1) Synthesis of metallocene complex Y: dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4-phenylindenyl] zirconium

  The synthesis of the metallocene complex Y was synthesized with reference to the method described in JP-A No. 2002-128832 and Example 1 to obtain a racemate.

(Ratio 3-2) Catalyst Preparation Using Metallocene Complex Y (Catalyst Y)
Instead of the metallocene complex A, 14.3 g of a solid catalyst (catalyst D) was obtained by the same operation as the catalyst preparation described in [Example 1] (1-7) except that 111 mg (147 μmol) of the metallocene complex Y was used. It was.
The prepolymerization magnification at that time (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.80.

(Ratio 3-3) Instead of the propylene-propylene / ethylene block copolymerization catalyst A by catalyst Y, 30 mg of catalyst Y was used, and the average gas mol composition in the tank during propylene / ethylene polymerization was propylene / ethylene = 43 / The same operation as in [Example 1] except that the adjustment was made to be 57. As a result, 173 g of propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 9 wt%, an ethylene content in rubber (CP) of 51 mol%, and a weight average of CP parts. The molecular weight (Mw) was 121,000. The rubber polymerization activity (CP activity) was 1,200 (g-CP / g-Cat / hr). Separately collected propylene homopolymer had a Tm of 154 ° C. and an MFR of 162 (dg / min).
The results are summarized in Table 1.

Metallocene complex A: dichlorodimethylsilylene bis [2- (5-methyl-2-furyl) -4-phenyl-5,5,7,7-tetramethyl-1,5,6,7-tetrahydro-s-indacenyl Zirconium / metallocene complex X: dichlorodimethylsilylenebis [2- (5-methyl-2-furyl) -4-phenyl-1,5,6,7-tetrahydro-s-indacenyl] zirconium / metallocene complex Y: dichlorodimethyl Silylenebis [2- (5-methyl-2-furyl) -4-phenylindenyl] zirconium

  From the polymerization results in Table 1, it is clear that the metallocene complex of the present invention and the catalyst containing it can polymerize a high molecular weight rubber component while maintaining higher ethylene uptake efficiency than conventional metallocene catalysts. is there.

  The metallocene complex of the present invention, the catalyst containing it and the olefin polymerization method can produce a high molecular weight rubber component, and can efficiently produce a block copolymer having a high ethylene or α-olefin content in the rubber part. It is very useful industrially.

Claims (6)

Using an olefin polymerization catalyst containing a metallocene complex represented by the following general formula [I], (i) 90 to 100% by weight of propylene and 0 to 10 of ethylene or α-olefin with respect to all monomer components Polymerizing at weight percent, and
(Ii) A method for producing a propylene polymer comprising a step of polymerizing propylene in an amount of 10 to 90% by weight and ethylene or an α-olefin having 4 or more carbon atoms in an amount of 10 to 90% by weight with respect to all monomer components .

(In the formula, M is Ti, Zr or Hf, Q is carbon, silicon or germanium. X ¹ and X ² are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, An aryl group having 6 to 18 carbon atoms, an amino group substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or an alkyl group having 6 to 18 carbon atoms It is a halogen-containing aryl group.
R ¹ and R ¹¹ may be the same or different from each other and have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a substituent. And a thienyl group which may have a furyl group or a substituent.
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁹ may be the same as or different from each other, and may be a hydrogen atom, halogen, An atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, and a hydrocarbon group having 1 to 6 carbon atoms. A silyl group, an aryl group having 6 to 18 carbon atoms, a halogen-containing aryl group having 6 to 18 carbon atoms, or a heterocyclic group constituting a 5-membered ring or 6-membered ring which may have a substituent, Moreover, 6-7 membered ring may be comprised by both adjacent R, and the 6-7 membered ring may contain the unsaturated bond.
Each R ⁷ and R ¹⁷ may be the same or different from each other, and are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and each of R ⁷ and R ¹⁷ One is a substituent other than a hydrogen atom.
Each R ⁸ and R ¹⁸ may be the same as or different from each other, and may be any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group having 6 to 18 carbon atoms. is there.
R ¹⁰ and R ²⁰ may be the same as or different from each other, and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or a carbon number. 1 to 6 silicon-containing alkyl group, 6 to 18 carbon aryl group, 6 to 18 halogen-containing aryl group, or a heterocycle constituting a 5-membered or 6-membered ring which may have a substituent It is a cyclic group, and R ¹⁰ and R ²⁰ may constitute a 4- to 7-membered ring. ) (I) 90 to 100% by weight of propylene, 0 to 10% by weight of ethylene or α-olefin, and bulk polymerization using propylene as a solvent or gas phase polymerization to keep the monomer in a gaseous state with respect to all monomer components Process, and
The propylene according to claim 1, comprising a step of vapor phase polymerization of (ii) 10 to 90% by weight of propylene and 10 to 90% by weight of ethylene or α-olefin with respect to all monomer components. A method for producing a polymer. In the general formula [I], one or both of R ¹ and R ¹¹ is a metallocene complex which is either a furyl group which may have a substituent or a thienyl group which may have a substituent. The method for producing a propylene-based polymer according to claim 1 or 2 , wherein an olefin polymerization catalyst is used . In general formula [I], in any one of claims 1 to 3 in which each R ⁷ and R ¹⁷ is characterized by the use of olefin polymerization catalyst containing the metallocene complex is an alkyl group having 1 to 6 carbon atoms The manufacturing method of the propylene-type polymer of description. The method for producing a propylene-based polymer according to any one of claims 1 to 4 , wherein an olefin polymerization catalyst containing the following components (A), (B) and (C) is used .
Component (A): Metallocene complex of general formula [I] Component (B): Compound or ion-exchange layered silicate that reacts with component (A) to form an ion pair Component (C): Organoaluminum compound The method for producing a propylene-based polymer according to claim 5, wherein the component (B) is an ion-exchange layered silicate.