JP2017145209A - Transition metal compound, catalyst for olefin polymerization and method for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel transition metal compound to serve as an active ingredient of an olefin polymerization catalyst that can produce a polyethylene having excellent olefin polymerization activity and copolymerizability as well as a controlled high comonomer content with high efficiency and productivity.SOLUTION: The present invention provides a transition metal compound represented by Si-crosslinked zirconocene shown by formula (1) (M is Ti, Zr or Hf).SELECTED DRAWING: None

Description

  The present invention relates to a transition metal compound having a specific structure useful as a catalyst or catalyst component for olefin polymerization (also referred to as a metallocene compound in the present invention), an olefin polymerization catalyst containing the transition metal compound, and the presence of the catalyst. In particular, the present invention relates to a method for producing an olefin polymer, in particular, homopolymerization of ethylene or copolymerization with one or more monomers selected from ethylene and α-olefin. More specifically, the present invention relates to a method for producing an olefin polymer having a high comonomer content.

  A metallocene catalyst is composed of a transition metal atom and an organic compound called a ligand. It can be obtained by a polymerization reaction by changing the position of the ligand structure and the steric electronic effect of the substituent. Widely controls the physical properties of polymers. In order to synthesize characteristic polymers, many bridged metallocene compounds having a specific structure have been synthesized.

  For example, Non-Patent Document 1 reports propylene polymerization of a complex in which various alkyl groups are introduced among complexes in which a cyclopentadienyl group and an indenyl group are silicon-bridged, but the effect when applied to ethylene polymerization is reported. There is no mention of.

Non-Patent Documents 2 and 3 describe polyethylene polymerization of complexes having substituents that can be supported on SiO ₂ carrier and Mg carrier, but there is no mention of copolymerizability.
Patent Document 1 discloses a catalyst in which a plurality of alkyl groups are introduced at a specific position of an indenyl group as a catalyst for producing a polyolefin that can be used as a macromonomer. Not mentioned.

  Patent Document 2 discloses a catalyst in which an aryl group having a specific substituent at the 3-position of an indenyl group is introduced as a catalyst capable of producing LLDPE having a large number of branches, but there is no polymerization example.

Patent Document 3 describes that the processability of polyethylene produced by making the cross-linked part into a cyclic structure can be improved, but there is no description regarding copolymerizability.
Patent Document 4 or 5 describes that long chain branching can be introduced into polyethylene produced by a catalyst in which a substituent is introduced at a specific position of indene, but there is no mention of copolymerizability.

  Patent Document 6 discloses a catalyst in which an aryl group having a specific substituent at the 4-position of an indenyl group is introduced as a catalyst capable of introducing a long chain branch into polyethylene to be produced. However, as far as the density of the polymers obtained in the examples is concerned, there is no significant difference between the examples and the comparative examples.

JP 2008-50278 A WO2014-099303 Japanese Patent No. 3607615 Japanese Patent Laid-Open No. 2014-070029 Japanese Patent Laying-Open No. 2015-063515 JP 2013-227271 A

Organometallics 2003, 22, 2790. Eur. J. et al. Inorg. Chem. 2005, 2924. Eur. J. et al. Inorg. Chem. 2008, 330.

  Although the development described above has been performed as an olefin polymerization catalyst, it cannot be said that an attempt to control the comonomer content of polyethylene to be produced is sufficient. On the other hand, olefin copolymers represented by linear low-density polyethylene have a wide range of applications in various applications. There has been a strong demand for a method for producing an olefin polymer using a catalyst.

  The present invention has been made in view of the above problems. The object is to provide a method for efficiently producing an ethylene polymer in which the comonomer content in the polymer is particularly controlled, and a transition metal compound and a catalyst suitably used for obtaining the ethylene polymer. is there.

As a result of diligent research in view of such circumstances, the inventor of the present invention has introduced a metallocene compound into which a specific group of substituents has been introduced, that is, a heteroatom-containing electron-donating substituent has been introduced, and the heteroatom-containing electron-donating substituent has When a metallocene compound having a substituent introduced at a close position is used as a catalyst for olefin polymerization, the catalyst is highly active. When an ethylene copolymer is produced, a comonomer in the ethylene copolymer is used. The present inventors have found that the content can be dramatically increased and have completed the present invention.
The transition metal compound [A] of the present invention is represented by the following general formula (A-1).

一般式（Ａ−１）中、Ｍはチタン原子、ジルコニウム原子、またはハフニウム原子を示し、ｎはＸの数を表し、その数は１〜４のＭの価数を満たす値であり、Ｘはそれぞれ独立に水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基、リン含有基、ホウ素含有基、アルミニウム含有基、または共役ジエン系二価誘導体基を示し、ｎが２以上の場合は、互いに結合して環を形成してもよく、Ｑは２価の炭化水素基、２価のケイ素含有基、または２価のゲルマニウム含有基を示し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子、炭素数１〜２０の炭化水素基、ハロゲン原子、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基、イオウ含有基、またはリン含有基を示し、これらは同一でも異なっていてもよく、これらのうち隣接する置換基は互いに結合して飽和の環を形成してもよく、Ｒ^a1〜Ｒ^a4は、水素原子、炭素数１〜４０の炭化水素基、ハロゲン原子、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基、イオウ含有基、またはリン含有基を示し（但し、Ｒ^a2およびＲ^a3は水素原子ではない）、これらは同一でも異なっていてもよく、隣接する置換基は互いに結合して環を形成してもよく、Ｒ^a5は下記一般式（Ａ−１ａ）で示される置換基、または窒素、酸素、イオウから選ばれる元素を少なくとも１つ含む母骨格を５員環とする置換基を有していてもよい複素環を示し、Ｚは結合する炭素原子に対してＲ¹〜Ｒ⁶と同様の置換基を有していてもよい縮合環を形成する炭素数３または４の飽和または不飽和の２価または３価の炭化水素基を示し、その置換基はＲ^a1、Ｒ^a4と互いに結合して環を形成してもよい。）

In general formula (A-1), M represents a titanium atom, a zirconium atom, or a hafnium atom, n represents the number of X, and the number is a value satisfying the valence of M of 1 to 4, and X is Each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene group. When n is 2 or more, they may be bonded to each other to form a ring, and Q represents a divalent hydrocarbon group, a divalent silicon-containing group, or a divalent germanium-containing group. R ^{1 to} R ⁶ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group. Group, these are the same May be different, substituents adjacent of these may be bonded to form a saturated ring together, R ^a1 to R ^a4 represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen atom , A halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group (provided that R ^a2 and R ^a3 are not hydrogen atoms), which may be the same or different The adjacent substituents may be bonded to each other to form a ring, and R ^a5 represents at least one of the substituents represented by the following general formula (A-1a) or an element selected from nitrogen, oxygen and sulfur A heterocyclic ring optionally having a substituent having a 5-membered mother skeleton as a ring is shown, and Z is a condensed optionally having the same substituent as R ^{1 to} R ⁶ with respect to the carbon atom to which it is bonded. C 3 or 4 carbon atoms forming a ring are saturated or unsaturated divalent Alternatively, it represents a trivalent hydrocarbon group, and the substituents may be bonded to R ^a1 and R ^a4 to form a ring. )

一般式（Ａ−１ａ）中、Ｙは酸素、窒素、イオウから選ばれる元素を示し、ｍはＹの価数を満たす１〜２の整数であり、Ｒ^bは水素原子、炭素数１〜４０の炭化水素基、ケイ素含有基、エーテル結合含有炭化水素基、または３級アミノ基含有炭化水素基であり、Ｒ^a2、Ｒ^a3と互いに結合して置換基を有していてもよい環を形成してもよく、ｍが２の場合、それぞれ同一でも異なっていてもよく、Ｒ^b同士互いに結合して置換基を有していてもよい環を形成してもよい。
遷移金属化合物［Ａ］が下記一般式（Ａ−２）で示されることが好ましい。

In General Formula (A-1a), Y represents an element selected from oxygen, nitrogen, and sulfur, m is an integer of 1 to 2 that satisfies the valence of Y, and R ^b is a hydrogen atom and has 1 to 40 carbon atoms. A hydrocarbon group, a silicon-containing group, an ether bond-containing hydrocarbon group, or a tertiary amino group-containing hydrocarbon group, which is bonded to R ^a2 and R ^a3 to form an optionally substituted ring. Alternatively, when m is 2, they may be the same or different, and R ^b may be bonded to each other to form a ring that may have a substituent.
It is preferable that the transition metal compound [A] is represented by the following general formula (A-2).

一般式（Ａ−２）中、Ｍ、Ｘ、ｎ、Ｑ、Ｒ¹〜Ｒ⁶、Ｒ^a1〜Ｒ^a5はそれぞれ、一般式（Ａ−１）におけるＭ、Ｘ、ｎ、Ｑ、Ｒ¹〜Ｒ⁶、Ｒ^a1〜Ｒ^a5と同じ意味を示し、Ｒ⁷〜Ｒ⁹はそれぞれ独立に水素原子、炭素数１〜２０の炭化水素基、ハロゲン原子、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基、イオウ含有基、またはリン含有基を示し、これらは同一でも異なっていてもよく、これらのうち隣接する置換基は互いに結合して環を形成してもよく、Ｒ⁷はＲ^a1、Ｒ^a4と互いに結合して環を形成してもよい。

In general formula (A-2), M, X, n, Q, R ^{1 to} R ⁶ , and R ^{a1 to} R ^a5 are M, X, n, Q, R ¹ to R in general formula (A-1), respectively. R ⁶ and R ^{a1 to} R ^a5 have the same meaning, and R ^{7 to} R ⁹ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, or an oxygen-containing group. , A nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, which may be the same or different, and adjacent substituents may be bonded to each other to form a ring, and R ⁷ is R ^a1 and R ^a4 may be bonded to each other to form a ring.

In the general formula (A-2), R ^a5 is preferably a substituent represented by the general formula (A-1a).
In the general formula (A-2), M is a zirconium atom or a hafnium atom, X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group, and Q is It is preferably a divalent hydrocarbon group or a divalent silicon-containing group.

In the general formula (A-2), R ^{1 to} R ⁶ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group, which may be the same or different. In 1a), Y is preferably an element selected from oxygen and nitrogen.

In the general formula (A-2), Q is a divalent silicon-containing group, R ^{1 to} R ⁴ are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and these may be the same or different. Well, however, not all are simultaneously hydrogen, R ⁵ and R ⁶ are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, and R ^{7 to} R ⁹ are each independently hydrogen atoms and carbon atoms having 1 to 20 carbon atoms. A hydrogen group, a silicon-containing group, or an oxygen-containing group, R ^a1 and R ^a4 are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group, and R ^a2 and R ^a3 are each a group having 1 to 1 carbon atoms A hydrocarbon group of 40 or a silicon-containing group, and in general formula (A-1a), R ^b is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and at least selected from R ^a2 and R ^a3 One may be bonded to each other to form a saturated ring, and m is 2 When R ^b is bonded to each other to form a ring, it is preferably a saturated ring.

In the general formula (A-2), R ^{1 to} R ⁵ , R ^a2 and R ^a3 are hydrocarbon groups having 1 to 10 carbon atoms, R ⁶ , R ^a1 and R ^a4 are hydrogen atoms, R ^a5 Is preferably an alkoxy group, a dialkylamino group or a pyrrolidinyl group.

The catalyst for olefin polymerization of the present invention comprises the transition metal compound [A] of the present invention.
Moreover, the manufacturing method of the olefin polymer of this invention is characterized by including the process of superposing | polymerizing an olefin in presence of the catalyst for olefin polymerization of this invention.

  In this specification, the term “polymerization” is used to mean not only homopolymerization but also copolymerization, and the term “polymer” includes not only a homopolymer but also a copolymer. Used in the inclusive sense.

  The catalyst for olefin polymerization containing the transition metal compound [A] according to the present invention produces an ethylene-based polymer having good polymerization activity and high comonomer content, especially when copolymerizing ethylene and α-olefin. can do.

Next, the present invention will be specifically described.
<Olefin polymerization catalyst>
Hereinafter, the olefin polymerization catalyst in the present invention will be specifically described.
The catalyst for olefin polymerization according to the present invention includes a novel transition metal compound [A] represented by the general formula (A-1) (preferably the general formula (A-2)), and [B]. At least one selected from the group consisting of a compound (B-3) that reacts with an organometallic compound (B-1), an organoaluminum oxy compound (B-2), and a transition metal compound [A] to form an ion pair. It is preferable to include a compound. The transition metal compound [A] is also provided by the present invention. In the present specification, the olefin refers to any compound having a polymerizable double bond. Hereinafter, the transition metal compound [A] and the compound [B] ((B-1) to (B-3)) will be described in detail in this order.

[[A] transition metal compound]
The transition metal compound [A] constituting the olefin polymerization catalyst of the present invention is a compound represented by the general formula (A-1).

  In general formula (A-1), M represents a titanium atom, a zirconium atom, or a hafnium atom, preferably a zirconium atom or a hafnium atom, and particularly preferably a zirconium atom.

  X is a hydrogen atom, halogen atom (X1), hydrocarbon group (G1), halogen-containing group (H1), silicon-containing group (Si1), oxygen-containing group (O1), sulfur-containing group (S1), nitrogen-containing group ( N1), a phosphorus-containing group (P1), a boron-containing group (B1), an aluminum-containing group (Al1), or a conjugated diene-based divalent derivative group. X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group.

  n represents the number of X, and the number is a value satisfying the valence of M of 1 to 4, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other , May be bonded to each other to form a ring, but preferably 1 or 2. Further, when a plurality of the rings are present, they may be the same as or different from each other.

Specific examples of the halogen atom (X1) include fluorine, chlorine, bromine and iodine, with chlorine or bromine being preferred.
The hydrocarbon group (G1) is not particularly limited as long as the effects of the present invention are exhibited. 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) ) Group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl (3-methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, thiamil (1,2-dimethylpropyl) group, iso-hexyl (4-methylpentyl) group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl (2,3-dimethylbutane - yl) group, a linear or branched alkyl group, such as 4,4-dimethylpentyl group;
Vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl (prop-1,2-dien-1- Yl group), but-3-en-1-yl group, crotyl (but-2-en-1-yl) group, but-3-en-2-yl group, methallyl (2-methylallyl) group, erythrenyl (Buta-1,3-dienyl) group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl (3- Methylbut-3-en-1-yl) group, 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl (3-methylbut-2-en-1-yl) Linear or branched alkenyl groups or unsaturated double bonds such as Yumoto;
Linear or branched alkynyl group or unsaturated triple bond-containing group such as ethynyl group, prop-2-yn-1-yl group, propargyl (prop-1-yn-1-yl) group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl (4-iso-propylbenzyl) group, 2,4,6- Aromatic-containing linear or branched such as tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl (diphenylmethyl) group An alkyl group and an unsaturated double bond-containing group;
Cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group;
Phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, duryl (2,3,5,6-tetra) Methylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group And aromatic substituted (aryl) groups such as naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, and the like.

  Among the hydrocarbon groups, a methyl group, iso-butyl (2-methylpropyl) group, neopentyl (2,2-dimethylpropyl) group, thiamil (1,2-dimethylpropyl) group, benzyl group, phenyl group are preferable. Group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group.

  The halogen-containing group (H1) is not particularly limited as long as the effects of the present invention are exhibited. For example, a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, 2,2,2-trifluoro Examples thereof include an ethyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, and a hexachloroantimonate anion.

Of the halogen-containing groups (H1), a pentafluorophenyl group is preferable.
The silicon-containing group (Si1) is not particularly limited as long as the effects of the present invention are exhibited. For example, a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group Tert-butyldiphenylsilyl group, triphenylsilyl group, tris (trimethylsilyl) silyl group, trimethylsilylmethyl group and the like.

Among the silicon-containing groups (Si1), a trimethylsilylmethyl group is preferable.
The oxygen-containing group (O1) is not particularly limited as long as the effect of the present invention is exhibited. For example, a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec- Butoxy group, iso-butoxy group, tert-butoxy group, benzyloxy group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di- tert-butylphenoxy group, 2,4,6-trimethylphenoxy group, 2,4,6-tri-iso-propylphenoxy group, acetoxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetoxy group, perchlorate anion, Periodate anion, diethyl ether, tetrahydrofuran, dioxane, 1, - it can be exemplified ethers such as dimethoxyethane.

Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferable.
The sulfur-containing group (S1) is not particularly limited as long as the effects of the present invention can be obtained. Examples thereof include a mesyl (methanesulfonyl) group, a phenylsulfonyl group, a tosyl (p-toluenesulfonyl) group, and a trifuryl (trifluoromethanesulfonyl). Group, nonafryl (nonafluorobutanesulfonyl) group, mesylate (methanesulfonate) group, tosylate (p-toluenesulfonate) group, triflate (trifluoromethanesulfonate) group, nonaflate (nonafluorobutanesulfonate) group, thiazole, Examples include thiophene.

Among the sulfur-containing groups (S1), a triflate (trifluoromethanesulfonate) group is preferable.
The nitrogen-containing group (N1) is not particularly limited as long as the effects of the present invention can be obtained. Group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, pyrrolyl group, bistrifurylimide group, amines such as triethylamine, diethylamine, pyridine, picoline, lutidine, imidazole, oxazoline, oxazole, etc. Can be mentioned.

Among the nitrogen-containing groups (N1), a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistrifurylimide group are preferable.
The phosphorus-containing group (P1) is not particularly limited as long as the effects of the present invention can be obtained. For example, organic phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, and hexafluorophosphate anions And so on.

The boron-containing group (B1) is not particularly limited as long as the effects of the present invention can be obtained. For example, tetrafluoroborate anion, tetrakis (pentafluorophenyl) borate anion, (methyl) (tris (pentafluorophenyl) ) Borate anion, (benzyl) (tris (pentafluorophenyl)) borate anion, tetrakis ((3,5-bistrifluoromethyl) phenyl) borate anion, BR ₄ (R is hydrogen, alkyl group, substituent An aryl group which may have a halogen atom or the like).

The aluminum-containing group (Al1) is not particularly limited as long as the effects of the present invention can be achieved. (Atom-hydrocarbon group) AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent or a halogen atom, etc.) capable of forming a four-membered ring can be mentioned.

  The conjugated diene-based divalent derivative group is not particularly limited as long as the effects of the present invention can be achieved. For example, a 1,3-butadienyl group, an isoprenyl (2-methyl-1,3-butadienyl) group, a piperenyl (1, (3-pentadienyl) group, 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group, cyclopentadienyl group, and the like.

  Q is a divalent group for bonding two ligands, specifically, a divalent hydrocarbon group, a divalent silicon-containing group, or a divalent germanium-containing group. As a bivalent hydrocarbon group, a C1-C20 hydrocarbon group is mentioned. Q is preferably a divalent hydrocarbon group or a divalent silicon-containing group, and more preferably a divalent silicon-containing group.

  Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include methylene, ethylene, propylene, butylene, isopropylidene, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methyl Butylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditolylmethylene, methylnaphthylmethylene, dinaphthylmethylene, benzylphenylmethylene, dibenzylmethylene, 1-methyl Ethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, ethylene Isopropylidene, propylidene, and the like butylidene.

  Examples of divalent silicon-containing groups include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, and ditolyl. Examples include silylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene group, and the like.

Examples of the divalent germanium-containing group include a group obtained by converting silicon into germanium in the divalent silicon-containing group.
Preferred groups for Q are dimethylsilylene, dibutylsilylene, diphenylsilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, and dimethylsilylene is particularly preferred.

R ^{1 to} R ⁶ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (G2), a halogen atom (X1), a halogen-containing group (H2), a silicon-containing group (Si2), or an oxygen-containing group. (O2), a nitrogen-containing group (N2), a sulfur-containing group (S2), or a phosphorus-containing group (P2), which may be the same or different, and adjacent substituents are bonded to each other. A saturated ring may be formed. Further, when a plurality of the saturated rings are present, they may be the same as or different from each other. R ^{1 to} R ⁶ are each independently preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group. R ^{1 to} R ⁴ are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, but they are not all hydrogen at the same time, and R ⁵ and R ⁶ are hydrogen atoms or It is more preferably a hydrocarbon group having 1 to 20 carbon atoms.

The halogen atom (X1) is the same as described above, preferably fluorine or chlorine.
The hydrocarbon group (G2) is not particularly limited as long as the effects of the present invention can be achieved. 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group, 1-dodecanyl group, 1-eicosanyl, iso-propyl group, sec-butyl (butan-2-yl) group Tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl (3-methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, thiamil (1,2-dimethylpropyl) group, pentane-3-i Group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl (4-methylpentyl) group, 1,1-dimethylbutyl (2-methylpentan-2-yl) group, 3-methylpentane-2- Yl group, 4-methylpentan-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl (2,3-dimethylbut-2-yl) Group, 3-methylpentan-3-yl group, 3,3-dimethylbut-2-yl group, hexane-3-yl group, 2-methylpentan-3-yl group, heptane-4-yl group, 2, 4-dimethylpentan-3-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2, 3,3-trimethyl Tan-2-yl group, a linear or branched alkyl group having 1 to 20 carbon atoms, such as 2,3,4-trimethylpentane-3-yl group;
Vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl (prop-1,2-dien-1- Yl group), but-3-en-1-yl group, crotyl (but-2-en-1-yl) group, but-3-en-2-yl group, methallyl (2-methylallyl) group, erythrenyl (Buta-1,3-dienyl) group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl (3- Methylbut-3-en-1-yl) group, 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl (3-methyl-but-2-en-1- Yl) group, 2-methyl-but-2-en-1-yl group, penta-3-ene 2-yl group, 2-methyl-but-3-en-2-yl group, penta-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3- Dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl (2-methyl-buta-1,3-dien-1-yl) group, penta-2,4-diene- 2-yl group, hexa-5-en-1-yl group, hexa-4-en-1-yl group, hexa-3-en-1-yl group, hexa-2-en-1-yl group, 4 -Methyl-pent-4-en-1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-pent-4-en-1-yl group, hexa-5-ene- 2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl Ru-but-2-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethylpent-1-en-3-yl group, hexa-3,5-dien-1-yl Group, hexa-2,4-dien-1-yl group, 4-methylpenta-1,3-dien-1-yl group, 2,3-dimethyl-buta-1,3-dien-1-yl group, hexa A straight chain having 2 to 20 carbon atoms, such as -1,3,5-trien-1-yl group, 2- (cyclopentadienyl) propan-2-yl group, 2- (cyclopentadienyl) ethyl group, etc. A chain or branched alkenyl group or an unsaturated double bond-containing group;
Ethynyl group, prop-2-yn-1-yl group, propargyl (prop-1-in-1-yl) group, but-1-in-1-yl group, but-2-yn-1-yl group, But-3-yn-1-yl group, penta-1-in-1-yl group, penta-2-in-1-yl group, penta-3-in-1-yl group, penta-4-in- 1-yl group, 3-methyl-but-1-in-1-yl group, penta-3-in-2-yl group, 2-methyl-but-3-in-1-yl group, penta-4- In-2-yl group, hexa-1-in-1-yl group, 3,3-dimethyl-but-1-in-1-yl group, 2-methyl-pent-3-in-2-yl group, Carbon sources such as 2,2-dimethyl-but-3-yn-1-yl group, hexa-4-in-1-yl group, and hexa-5-in-1-yl group Linear or branched alkynyl group or unsaturated triple bond-containing group having from 2 to 20;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl (4-iso-propylbenzyl) group, 2,4,6- Tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropane-2-phenyl) Yl) group, 2- (4-methylphenyl) propan-2-yl group, 2- (3,5-dimethylphenyl) propan-2-yl group, 2- (4-tert-butylphenyl) propan-2- Yl group, 2- (3,5-di-tert-butylphenyl) propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1 6-dien-4-yl group, 1,2,3-triphenylpropan-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-3- En-1-yl group, 1,1,2-triphenylethyl group, trityl (triphenylmethyl) group, tri- (4-methylphenyl) methyl group, 2-phenylethyl group, styryl (2-phenylvinyl) Group, 2- (2-methylphenyl) ethyl group, 2- (4-methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group, 2- (3,5-dimethylphenyl) ethyl Group, 2- (2,4,6-tri-iso-propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3,5-di-tert-butylphenyl) ethyl group , 2- Til-1-phenylpropan-2-yl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, neophyll (2-methyl-2-phenylpropyl) group, 3-methyl-3-phenylbutyl Group, 2-methyl-4-phenylbutan-2-yl group, cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- ( 1-indenyl) ethyl group, 2- (tetrahydro-1-indacenyl) propan-2-yl group, (tetrahydro-1-indacenyl) diphenylmethyl group, 2- (tetrahydro-1-indacenyl) ethyl group, 2- (1 -Benzoindenyl) propan-2-yl group, (1-benzoindenyl) diphenylmethyl group, 2- (1-benzoindenyl) L) ethyl group, 2- (9-fluorenyl) propan-2-yl group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, 2- (1-azurenyl) propan-2-yl Group, an aromatic-containing linear or branched alkyl group having 7 to 20 carbon atoms and an unsaturated double bond-containing group, such as (1-azurenyl) diphenylmethyl group and 2- (1-azurenyl) ethyl group ;
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclo Pentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzyl Cyclohexyl, cycloheptyl, cycloheptenyl, cycloheptatrienyl, 1-methylcycloheptyl, 1-allylcycloheptyl, 1-benzylcycloheptyl, cyclooctyl, cyclooctenyl, cycl Octadienyl group, cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group 2-methylbicyclo [2.2.1] heptan-2-yl group, 7-methylbicyclo [2.2.1] heptan-7-yl group, bicyclo [2.2.2] octan-1-yl Group, bicyclo [2.2.2] octan-2-yl group, 1-adamantyl group, 2-adamantyl group, 1- (2-methyladamantyl), 1- (3-methyladamantyl), 1- (4- Methyl adamantyl), 1- (2-phenyladamantyl), 1- (3-phenyladamantyl), 1- (4-phenyladamantyl), 1- 3,5-dimethyladamantyl), 1- (3,5,7-trimethyladamantyl), 1- (3,5,7-triphenyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindace Cyclic saturated and unsaturated hydrocarbon groups having 3 to 20 carbon atoms, such as an nyl group, a benzoindenyl group, an azulenyl group;
Phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, duryl (2,3,5,6-tetra) Methylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group Allylphenyl group, (but-3-en-1-yl) phenyl group, (but-2-en-1-yl) phenyl group, methallylphenyl group, prenylphenyl group, 4-adamantylphenyl group, 3, 5-di-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group Anthracenyl group, pyrenyl group, carbon atoms, such as ferrocenyl group aromatic substitution (aryl) groups having 6 to 20; and the like.

  Among the linear or branched alkyl groups having 1 to 20 carbon atoms, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) ) Group, iso-pentyl (3-methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, pentan-3-yl group, iso-hexyl (4- Methylpentyl) group, 1,1-dimethylbutyl (2-methylpentan-2-yl) group, 3,3-dimethylbutyl group, texyl (2,3-dimethylbut-2-yl) group, -Methylpentan-3-yl group, heptane-4-yl group, 2,4-dimethylpentan-3-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptane -4-yl group, 4-propylheptan-4-yl group, and the like. Among them, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl are more preferable. Group, iso-propyl group, tert-butyl (2-methylpropan-2-yl) group.

  Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 20 carbon atoms, vinyl, allyl, but-3-en-1-yl, crotyl are preferable. (But-2-en-1-yl) group, methallyl (2-methylallyl) group, penta-4-en-1-yl group, prenyl (3-methyl-but-2-en-1-yl) group, Penta-1,4-dien-3-yl group, hexa-5-en-1-yl group, 2-methylpent-4-en-2-yl group, 2- (cyclopentadienyl) propan-2-yl Group, 2- (cyclopentadienyl) ethyl group, etc., among which, vinyl group, allyl group, but-3-en-1-yl group, penta-4-en-1-yl group are more preferable. , Prenyl (3-methyl-but-2-en-1-yl) A hex-5-en-1-yl group.

  Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 20 carbon atoms, ethynyl group, prop-2-yn-1-yl group, propargyl (prop-1 -In-1-yl) group, but-2-yn-1-yl group, but-3-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1- Yl group, 3-methyl-but-1-in-1-yl group, 3,3-dimethyl-but-1-in-1-yl group, hexa-4-in-1-yl group, hexa-5- In-1-yl group and the like can be mentioned, and among them, prop-2-yn-1-yl group, propargyl (prop-1-in-1-yl) group, but-2-yne-1- are more preferable. An yl group and a but-3-yn-1-yl group.

  Among the aromatic-containing linear or branched alkyl group and unsaturated double bond-containing group having 7 to 20 carbon atoms, preferably a benzyl group, a 2-methylbenzyl group, a 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl (4-iso-propylbenzyl) group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group 3,5-di-tert-butylbenzyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropan-2-yl) group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2 -Phenylethyl group, 2- (4-methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group, 2- (3,5-dimethylphenol L) ethyl group, 2- (2,4,6-tri-iso-propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3,5-di-tert-butylphenyl) ) Ethyl group, styryl (2-phenylvinyl) group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, neophyll (2-methyl-) 2-phenylpropyl) group, cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (9-fluorenyl) propan-2-yl group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, etc. More preferably, benzyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropan-2-yl) group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2-phenylethyl group, 3 -A phenylpropyl group and a 2-cinnamyl (3-phenylallyl) group.

  Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 20 carbon atoms, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a 1-methylcyclopentyl group, 1 -Allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1 -Methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo 2.2.1] heptan-2-yl group, bicyclo [2.2.2] octan-1-yl group, 1-adamantyl group, 2-adamantyl group, pentarenyl group, indenyl group, fluorenyl group and the like. Among them, more preferred are a cyclopentyl group, a cyclopentenyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group.

  Among the aromatic substituted (aryl) groups having 6 to 20 carbon atoms, phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) are preferable. Group, cumenyl (iso-propylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di -Tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group, etc. More preferably, phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) ) Group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, phenanthryl group, and anthracenyl group.

  The halogen-containing group (H2) is not particularly limited as long as the effects of the present invention are exhibited. For example, a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, 2,2,2-trifluoro Ethyl group, heptafluoropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group Chlorophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, Fluoromethoxyphenyl group, vist Fluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert-butyl-fluorobiphenyl group, Trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group, difluorophenoxy group, tri Fluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenol Xyl group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoromethylenedioxyphenyl group, trifluoroacetyl group, pentafluorobenzoyl group, fluorophenyliminomethyl group, pentafluorophenyliminomethyl group , Trifluoromethylphenyliminomethyl group, bistrifluoromethylphenyliminomethyl group, trifluoromethylthio group, trifuryl (trifluoromethanesulfonyl) group, nonafryl (nonafluorobutanesulfonyl) group, triflate (trifluoromethanesulfonate) group, nonaflate ( Nonafluorobutanesulfonate) group, bistrifurylimide group, trifluoromethylfuryl group, trifluoromethylbenzofuryl group , Trifluoromethyldibenzofuryl group, trifluoromethylpyrrolyl group, pentafluorophenylpyrrolyl group, fluoropyridyl group, tetrafluoropyridyl group, fluoroquinolyl group, fluoro-iso-quinolyl group, fluoroindolyl group, trifluoro Methylindolyl group, bistrifluoromethylcarbazolyl group, trifluoromethylimidazolyl group, trifluoromethyloxazolyl group, trifluoromethylthienyl group, trifluoromethylbenzothienyl group, trifluoromethyldibenzothienyl group, trifluoromethyl A thiazolyl group, a trifluoromethylbenzothiazolyl group, etc. can be mentioned.

  Among the halogen-containing groups, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, 4,4,4 are preferable. -Trifluorobutyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, pentafluorobiphenyl Group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxy group, pentafluorophenoxy group, bistrifluoromethylphenoxy group, bistrifluoromethylphenoxy group, difluoromethylenedioxy Enyl group, trifluoroacetyl group, pentafluorobenzoyl group, fluorophenyliminomethyl group, pentafluorophenyliminomethyl group, trifluoromethylphenyliminomethyl group, trifluoromethylthio group, trifuryl (trifluoromethanesulfonyl) group, triflate (trifluoro) Lomethanesulfonate) group, nonaflate (nonafluorobutanesulfonate) group, bistrifurylimide group, trifluoromethylfuryl group, trifluoromethylbenzofuryl group, trifluoromethyldibenzofuryl group, trifluoromethylpyrrolyl group, pentafluoro Phenylpyrrolyl group, fluoropyridyl group, tetrafluoropyridyl group, trifluoromethylindolyl group, bistrifluoromethylcarbazolyl group, trifluoromethyl A thienyl group, a trifluoromethylbenzothienyl group, a trifluoromethylthiazolyl group and the like can be mentioned. Among them, a trifluoromethyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoro group are more preferable. A methylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, and a pentafluorophenoxy group;

  The silicon-containing group (Si2) is not particularly limited as long as the effects of the present invention are exhibited. For example, a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group , Tert-butyldiphenylsilyl group, triphenylsilyl group, tris (trimethylsilyl) silyl group, cyclopentadienyldimethylsilyl group, di-n-butyl (cyclopentadienyl) silyl group, cyclopentadienyldiphenylsilyl group, Indenyldimethylsilyl group, di-n-butyl (indenyl) silyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, di-n-butyl (fluorenyl) silyl group, fluorenyldiphenylsilyl group, 4- Trimethylsilylphenyl 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-tert-butyldiphenylsilylphenyl group, 4-triphenylsilylphenyl group, 4-tris (trimethylsilyl) silylphenyl group, etc. Can do.

  Among the silicon-containing groups, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl are preferable. Group, indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl Group, 4-triphenylsilylphenyl group, etc. Among them, more preferred are trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilyl group. Butylphenyl group, a 4-tri -iso- propyl silyl phenyl group.

  The oxygen-containing group (O2) is not particularly limited as long as the effect of the present invention is exhibited. For example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, sec- Butoxy, iso-butoxy, tert-butoxy, methallyloxy, prenyloxy, benzyloxy, methoxymethoxy, methoxyethoxy, phenoxy, naphthoxy, toluyloxy, iso-propylphenoxy, allylphenoxy Group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, Toxiethyl group, allyloxyethyl group, benzyloxyethyl group, phenoxyethyl group, methoxypropyl group, allyloxypropyl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, phenoxy Vinyl group, methoxyallyl group, allyloxyallyl group, benzyloxyallyl group, phenoxyallyl group, formyl group, acetyl group, iso-butyryl group, pivaloyl group, benzoyl group, naphthoyl group, adamantanecarbonyl group, acetoxy group, pivaloyloxy group Benzoyloxy group, dimethoxymethyl group, di-iso-propoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, methyl carbonate group, phenyl carbonate Group, dimethyldioxanyl group, methyl carboxylate group, ethyl carboxylate group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, furyl group, methylfuryl group, A tetrahydrofuryl group, a pyranyl group, a tetrahydropyranyl group, a furfuryl group, a benzofuryl group, a dibenzofuryl group, and the like can be given.

  Among the oxygen-containing groups, methoxy group, ethoxy group, iso-propoxy group, allyloxy group, n-butoxy group, tert-butoxy group, prenyloxy group, benzyloxy group, phenoxy group, naphthoxy group, toluyloxy group are preferable. , Iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group Benzyloxyallyl group, phenoxyallyl group, formyl group, acetyl group, iso-butyryl group, pivaloyl group, benzoyl group, naphthoyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxa Group, dimethyldioxanyl group, methylcarboxylate group, ethylcarboxylate group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, furyl group, methylfuryl group , Tetrahydropyranyl group, furfuryl group, benzofuryl group, dibenzofuryl group, etc., among which, more preferably, methoxy group, iso-propoxy group, allyloxy group, phenoxy group, formyl group, acetyl group, benzoyl group, Dimethoxymethyl, dioxolanyl, methylcarboxylate, methoxyphenyl, iso-propoxyphenyl, allyloxyphenyl, phenoxyphenyl, furyl, methylfuryl, benzofuryl, dibenzofuryl It is.

  The nitrogen-containing group (N2) is not particularly limited as long as the effects of the present invention can be achieved. For example, a cyano group, an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a didecylamino group, and a benzylamino group. , Dibenzylamino group, pyrrolidinyl group, piperidinyl group, morphophoryl group, azepinyl group, formamide group, acetamide group, pivalamide group, benzamide group, naphthamide group, adamantanecarboxamide group, iminomethyl group, iminoethyl group, phenyliminomethyl group, phenyl Iminoethyl, dimethylhydrazonomethyl, pyrrolidinyliminomethyl, imide, uryl, methyluryl, dimethyluryl, guanidinyl, dimethylguanidinyl, methylformimidamide, phenyl Rumimidamide group, carbamoyl group, N-methylcarbamoyl group, N-benzylcarbamoyl group, N, N-dimethylcarbamoyl group, pyrrolidinylcarbamoyl group, N-phenylcarbamoyl group, carbamoyloxy group, N-methylcarbamoyloxy group, N- Benzylcarbamoyloxy group, N, N-dimethylcarbamoyloxy group, pyrrolidinylcarbamoyloxy group, N-phenylcarbamoyloxy group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzyl Aminomethyl, benzylaminoethyl, pyrrolidinylethyl, dimethylaminovinyl, benzylaminovinyl, pyrrolidinylvinyl, dimethylaminopropyl, benzylaminopropyl, pyrrole Nylpropyl, dimethylaminoallyl, benzylaminoallyl, pyrrolidinylallyl, nitrophenyl, dinitrophenyl, aminophenyl, cyanophenyl, dimethylaminophenyl, pyrrolidinylphenyl, pyrrolylphenyl , Pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenyl Pyrrolyl, pyridyl, quinolyl, tetrahydroquinolyl, iso-quinolyl, tetrahydro-iso-quinolyl, indolyl, indolinyl, carbazolyl, di-tert-butylcarbazolyl, imidazolyl, dimethyl Examples include imidazolidinyl group, benzoimidazolyl group, oxazolyl group, oxazolidinyl group, benzooxazolyl group and the like.

  Among the nitrogen-containing groups, cyano group, amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, formamide group, acetamide group, benzamide Group, iminomethyl group, iminoethyl group, phenyliminomethyl group, phenyliminoethyl group, dimethylhydrazonomethyl group, pyrrolidinyliminomethyl group, carbamoyl group, N-methylcarbamoyl group, N-benzylcarbamoyl group, N, N- Dimethylcarbamoyl group, pyrrolidinylcarbamoyl group, N-phenylcarbamoyl group, carbamoyloxy group, N-methylcarbamoyloxy group, N, N-dimethylcarbamoyloxy group, dimethylaminomethyl group, benzylaminomethyl Group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, nitrophenyl group, dinitrophenyl group, amino group Phenyl group, cyanophenyl group, dimethylaminophenyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydro Quinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, Oxazolyl group, oxa Examples include lysinyl group, benzoxazolyl group, and more preferably amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl. Group, an imidazolyl group.

  The sulfur-containing group (S2) is not particularly limited as long as the effect of the present invention is exhibited. For example, a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a naphthylthio group, a methylthiomethyl group, a benzylthiomethyl group, a phenylthio Methyl group, naphthylthiomethyl group, methylthioethyl group, benzylthioethyl group, phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, Benzylthiopropyl, phenylthiopropyl, naphthylthiopropyl, methylthioallyl, benzylthioallyl, phenylthioallyl, naphthylthioallyl, mercaptophenyl, methylthiophenyl, thienylphenyl, Ruthienylphenyl group, benzothienylphenyl group, dibenzothienylphenyl group, benzodithienylphenyl group, methylsulfinyl group, tert-butylsulfinyl group, phenylsulfinyl group, mesyl (methylsulfonyl) group, benzenesulfonyl group, tosyl (4- Methylbenzenesulfonyl) group, methanesulfonate group, 4-methylbenzenesulfonate group, thiouryl group, methylthiouryl group, bis (methylthio) methyl group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofuryl group, thienothienyl group, Benzothienyl, dibenzothienyl, thienobenzofuryl, benzodithienyl, dithiolanyl, dithianyl, oxathiolanyl, oxathianyl, thiazolyl, benzothiazolyl Group, and the like thiazolidinyl group.

  Among the sulfur-containing groups, a thienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group, thiazolyl group, and benzothiazolyl group are preferable.

  The phosphorus-containing group (P2) is not particularly limited as long as the effect of the present invention is exhibited. Group, diphenylphosphino group, di-o-tolylphosphino group, di-m-tolylphosphino group, di-p-tolylphosphino group, bis (3,5-dimethylphenyl) phosphino group, bis (2,4,6-trimethylphenyl) ) Phosphino group, bis (4-methoxyphenyl) phosphino group, bis (4-dimethylaminophenyl) phosphino group, 4- (dimethylphosphino) phenyl group, 4- (diethylphosphino) phenyl group, 4- (diisopropylphos Phino) phenyl group, 4- (di-tert-butylphosphine) B) phenyl group, 4- (dicyclohexylphosphino) phenyl group, 4- (diphenylphosphino) phenyl group, 4- (di-o-tolylphosphino) phenyl group, 4- (di-m-tolylphosphino) phenyl group, 4 -(Di-p-tolylphosphino) phenyl group, 4- (bis (3 ', 5'-dimethylphenyl) phosphino) phenyl group, 4- (bis (2', 4 ', 6'-trimethylphenyl) phosphino) phenyl A 4- (bis (4′-methoxyphenyl) phosphino) phenyl group, a 4- (bis (4′-dimethylaminophenyl) phosphino) phenyl group, and the like.

  Among the phosphorus-containing groups, dimethylphosphino group, diethylphosphino group, diisopropylphosphino group, di-tert-butylphosphino group, dicyclohexylphosphino group, diphenylphosphino group, di-o-tolylphosphino group, di -M-tolylphosphino group, di-p-tolylphosphino group, bis (4-methoxyphenyl) phosphino group, bis (4-dimethylaminophenyl) phosphino group, 4- (bis (4'-methoxyphenyl) phosphino) phenyl group, 4- (Bis (4′-dimethylaminophenyl) phosphino) phenyl group.

Of the R ^{1 to} R ⁶ , when adjacent substituents are bonded to each other to form a saturated ring, examples of the ring include a 5- to 8-membered ring condensed to a cyclopentadienyl ring portion. A saturated hydrocarbon group may be formed, preferably a 5-, 6- or 7-membered ring. In this case, the structure together with the cyclopentadienyl part of the mother nucleus is 4,5,6,7-tetrahydro Indene, 2-methyl-1,5,6,7-tetrahydro-s-indacene, 6,7-dihydro-5H-s-indacene, 6,7-dihydro-8H-as-indacene, 5,6,7, 8-tetrahydro-1H-benz [f] indene, 3H-benz [e] indene, 6,7,8,9-tetrahydro-3H-benz [e] indene, 5,7-dihydro-4H-cyclopenta [e] Acenaphthylene, azulene, , 4,5,6,7,8- such hexahydrophthalate azulene.

R ^{a1 to} R ^a4 are a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms (G3), a halogen atom (X1), a halogen-containing group (H3), a silicon-containing group (Si3), an oxygen-containing group (O3), nitrogen A containing group (N3), a sulfur containing group (S3), or a phosphorus containing group (P3) (provided that R ^a2 and R ^a3 are not hydrogen atoms), which may be the same or different, and are adjacent substituents The groups may be bonded to each other to form a ring. Further, when a plurality of the rings are present, they may be the same as or different from each other. R ^a1 and R ^a4 are preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group, and R ^a2 and R ^a3 are each a hydrocarbon group having 1 to 40 carbon atoms or a silicon-containing group. Preferably there is.

Although it does not specifically limit as said C1-C40 hydrocarbon group (G3) as long as there exists an effect of this invention, For example, a methyl group, an ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group, 1-dodecanyl group, 1-eicosanyl, iso-propyl group, sec-butyl (butane -2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl (3 -Methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, thiamil (1,2-dimethylpropyl) group, Ntan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl (4-methylpentyl) group, 1,1-dimethylbutyl (2-methylpentan-2-yl) group, 3- Methylpentan-2-yl group, 4-methylpentan-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl (2,3-dimethylbutane -2-yl) group, 3-methylpentan-3-yl group, 3,3-dimethylbut-2-yl group, hexane-3-yl group, 2-methylpentan-3-yl group, heptane-4- Yl group, 2,4-dimethylpentan-3-yl group, 3-ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptane-4- Ile group, 2, 3 3- trimethyl-2-yl group, a linear or branched alkyl groups such as 2,3,4-trimethylpentane-3-yl group;
Vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl (prop-1,2-dien-1- Yl group), but-3-en-1-yl group, crotyl (but-2-en-1-yl) group, but-3-en-2-yl group, methallyl (2-methylallyl) group, erythrenyl (Buta-1,3-dienyl) group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl (3- Methylbut-3-en-1-yl) group, 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl (3-methyl-but-2-en-1- Yl) group, 2-methyl-but-2-en-1-yl group, penta-3-ene 2-yl group, 2-methyl-but-3-en-2-yl group, penta-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3- Dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl (2-methyl-buta-1,3-dien-1-yl) group, penta-2,4-diene- 2-yl group, hexa-5-en-1-yl group, hexa-4-en-1-yl group, hexa-3-en-1-yl group, hexa-2-en-1-yl group, 4 -Methyl-pent-4-en-1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-pent-4-en-1-yl group, hexa-5-ene- 2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl Ru-but-2-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethylpent-1-en-3-yl group, hexa-3,5-dien-1-yl Group, hexa-2,4-dien-1-yl group, 4-methylpenta-1,3-dien-1-yl group, 2,3-dimethyl-buta-1,3-dien-1-yl group, hexa Linear or branched alkenyl groups such as -1,3,5-trien-1-yl group, 2- (cyclopentadienyl) propan-2-yl group, 2- (cyclopentadienyl) ethyl group Or an unsaturated double bond-containing group;
Ethynyl group, prop-2-yn-1-yl group, propargyl (prop-1-in-1-yl) group, but-1-in-1-yl group, but-2-yn-1-yl group, But-3-yn-1-yl group, penta-1-in-1-yl group, penta-2-in-1-yl group, penta-3-in-1-yl group, penta-4-in- 1-yl group, 3-methyl-but-1-in-1-yl group, penta-3-in-2-yl group, 2-methyl-but-3-in-1-yl group, penta-4- In-2-yl group, hexa-1-in-1-yl group, 3,3-dimethyl-but-1-in-1-yl group, 2-methyl-pent-3-in-2-yl group, Straight chain such as 2,2-dimethyl-but-3-in-1-yl group, hexa-4-in-1-yl group, hexa-5-in-1-yl group Other branched alkynyl group or unsaturated triple bond-containing group;
Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl (4-iso-propylbenzyl) group, 2,4,6- Tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropane-2-phenyl) Yl) group, 2- (4-methylphenyl) propan-2-yl group, 2- (3,5-dimethylphenyl) propan-2-yl group, 2- (4-tert-butylphenyl) propan-2- Yl group, 2- (3,5-di-tert-butylphenyl) propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1 6-dien-4-yl group, 1,2,3-triphenylpropan-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-3- En-1-yl group, 1,1,2-triphenylethyl group, trityl (triphenylmethyl) group, tri- (4-methylphenyl) methyl group, 2-phenylethyl group, styryl (2-phenylvinyl) Group, 2- (2-methylphenyl) ethyl group, 2- (4-methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group, 2- (3,5-dimethylphenyl) ethyl Group, 2- (2,4,6-tri-iso-propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3,5-di-tert-butylphenyl) ethyl group , 2- Til-1-phenylpropan-2-yl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, neophyll (2-methyl-2-phenylpropyl) group, 3-methyl-3-phenylbutyl Group, 2-methyl-4-phenylbutan-2-yl group, cyclopentadienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- ( 1-indenyl) ethyl group, 2- (tetrahydro-1-indacenyl) propan-2-yl group, (tetrahydro-1-indacenyl) diphenylmethyl group, 2- (tetrahydro-1-indacenyl) ethyl group, 2- (1 -Benzoindenyl) propan-2-yl group, (1-benzoindenyl) diphenylmethyl group, 2- (1-benzoindenyl) L) ethyl group, 2- (9-fluorenyl) propan-2-yl group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, 2- (1-azurenyl) propan-2-yl An aromatic-containing linear or branched alkyl group and an unsaturated double bond-containing group such as a group, (1-azurenyl) diphenylmethyl group, 2- (1-azurenyl) ethyl group;
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclo Pentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzyl Cyclohexyl, cycloheptyl, cycloheptenyl, cycloheptatrienyl, 1-methylcycloheptyl, 1-allylcycloheptyl, 1-benzylcycloheptyl, cyclooctyl, cyclooctenyl, cycl Octadienyl group, cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group 2-methylbicyclo [2.2.1] heptan-2-yl group, 7-methylbicyclo [2.2.1] heptan-7-yl group, bicyclo [2.2.2] octan-1-yl Group, bicyclo [2.2.2] octan-2-yl group, 1-adamantyl group, 2-adamantyl group, 1- (2-methyladamantyl), 1- (3-methyladamantyl), 1- (4- Methyl adamantyl), 1- (2-phenyladamantyl), 1- (3-phenyladamantyl), 1- (4-phenyladamantyl), 1- 3,5-dimethyladamantyl), 1- (3,5,7-trimethyladamantyl), 1- (3,5,7-triphenyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindace Cyclic saturated and unsaturated hydrocarbon groups such as nyl, benzoindenyl, and azulenyl;
Phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, duryl (2,3,5,6-tetra) Methylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group Allylphenyl group, (but-3-en-1-yl) phenyl group, (but-2-en-1-yl) phenyl group, methallylphenyl group, prenylphenyl group, 4-adamantylphenyl group, 3, 5-di-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group And the like; anthracenyl group, pyrenyl group, aromatic substitution (aryl) groups such as ferrocenyl groups.

  Among the linear or branched alkyl groups, a methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group are preferable. Group, iso-propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, iso-pentyl (3 -Methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, pentan-3-yl group, iso-hexyl (4-methylpentyl) group, 1,1 -Dimethylbutyl (2-methylpentan-2-yl) group, 3,3-dimethylbutyl group, texyl (2,3-dimethylbut-2-yl) group, 3-methylpentane-3 Yl group, heptane-4-yl group, 2,4-dimethylpentan-3-yl group, 3-ethylpentane-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group and the like can be mentioned, and among them, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, iso-propyl group are more preferable. , Tert-butyl (2-methylpropan-2-yl) group.

  Among the linear or branched alkenyl groups or unsaturated double bond-containing groups, a vinyl group, an allyl group, a but-3-en-1-yl group, a crotyl (but-2-ene-1) is preferable. -Yl) group, methallyl (2-methylallyl) group, penta-4-en-1-yl group, prenyl (3-methyl-but-2-en-1-yl) group, penta-1,4-diene- 3-yl group, hexa-5-en-1-yl group, 2-methylpent-4-en-2-yl group, 2- (cyclopentadienyl) propan-2-yl group, 2- (cyclopentadiyl) Enyl) ethyl group and the like, among which, more preferably, vinyl group, allyl group, but-3-en-1-yl group, penta-4-en-1-yl group, prenyl (3-methyl-buta -2-en-1-yl) group, hexa-5-ene- --yl group.

  Among the linear or branched alkynyl group or unsaturated triple bond-containing group, ethynyl group, prop-2-yn-1-yl group, propargyl (prop-1-yn-1-yl) group is preferable. But-2-yn-1-yl group, but-3-yn-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methyl-buta -1-in-1-yl group, 3,3-dimethyl-but-1-in-1-yl group, hexa-4-in-1-yl group, hexa-5-in-1-yl group and the like Among them, more preferred are prop-2-yn-1-yl group, propargyl (prop-1-in-1-yl) group, but-2-yn-1-yl group, but-3-yne It is a -1-yl group.

  Among the aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl are preferable. Group, 3,5-dimethylbenzyl group, cuminyl (4-iso-propylbenzyl) group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert -Butylbenzyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropan-2-yl) group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2-phenylethyl group, 2- ( 4-methylphenyl) ethyl group, 2- (2,4,6-trimethylphenyl) ethyl group, 2- (3,5-dimethylphenyl) ethyl group, 2- ( , 4,6-Tri-iso-propylphenyl) ethyl group, 2- (4-tert-butylphenyl) ethyl group, 2- (3,5-di-tert-butylphenyl) ethyl group, styryl (2-phenyl) Vinyl) group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, neophyll (2-methyl-2-phenylpropyl) group, cyclopenta Dienyldiphenylmethyl group, 2- (1-indenyl) propan-2-yl group, (1-indenyl) diphenylmethyl group, 2- (1-indenyl) ethyl group, 2- (9-fluorenyl) propan-2- Yl group, (9-fluorenyl) diphenylmethyl group, 2- (9-fluorenyl) ethyl group, and the like. Group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropan-2-yl) group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2-phenylethyl group, 3-phenylpropyl group , 2-cinnamyl (3-phenylallyl) group.

  Among the cyclic saturated and unsaturated hydrocarbon groups, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a 1-methylcyclopentyl group, a 1-allylcyclopentyl group, and a 1-benzyl group are preferable. Cyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1- Allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo [2.2.1] heptane Examples include 2-yl group, bicyclo [2.2.2] octane-1-yl group, 1-adamantyl group, 2-adamantyl group, pentarenyl group, indenyl group, fluorenyl group, and the like, more preferably cyclopentyl. Group, cyclopentenyl group, 1-methylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-adamantyl group.

  Among the aromatic substituted (aryl) groups, a phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propylphenyl) is preferable. ) Group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allyl Examples thereof include phenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group, and among them, phenyl group, tolyl are more preferable. (Methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2, , 6-trimethylphenyl) group, cumenyl (iso-propylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, phenanthryl group, and anthracenyl group.

The halogen atom (X1) is the same as described above, and is preferably chlorine or fluorine.
The halogen-containing group (H3) is not particularly limited as long as the effects of the present invention are exhibited. For example, a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, 2,2,2-trifluoro Ethyl group, heptafluoropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group Chlorophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, Fluoromethoxyphenyl group, vist Fluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert-butyl-fluorobiphenyl group, Trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group, difluorophenoxy group, tri Fluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenol Xyl group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoromethylenedioxyphenyl group, trifluoroacetyl group, pentafluorobenzoyl group, fluorophenyliminomethyl group, pentafluorophenyliminomethyl group , Trifluoromethylphenyliminomethyl group, bistrifluoromethylphenyliminomethyl group, trifluoromethylthio group, trifuryl (trifluoromethanesulfonyl) group, nonafryl (nonafluorobutanesulfonyl) group, triflate (trifluoromethanesulfonate) group, nonaflate ( Nonafluorobutanesulfonate) group, bistrifurylimide group, trifluoromethylfuryl group, trifluoromethylbenzofuryl group , Trifluoromethyldibenzofuryl group, trifluoromethylpyrrolyl group, pentafluorophenylpyrrolyl group, fluoropyridyl group, tetrafluoropyridyl group, fluoroquinolyl group, fluoro-iso-quinolyl group, fluoroindolyl group, trifluoro Methylindolyl group, bistrifluoromethylcarbazolyl group, trifluoromethylimidazolyl group, trifluoromethyloxazolyl group, trifluoromethylthienyl group, trifluoromethylbenzothienyl group, trifluoromethyldibenzothienyl group, trifluoromethyl A thiazolyl group, a trifluoromethylbenzothiazolyl group, etc. can be mentioned.

  Among the halogen-containing groups, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, 4,4,4 are preferable. -Trifluorobutyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, pentafluorobiphenyl Group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxy group, pentafluorophenoxy group, bistrifluoromethylphenoxy group, bistrifluoromethylphenoxy group, difluoromethylenedioxy Enyl group, trifluoroacetyl group, pentafluorobenzoyl group, fluorophenyliminomethyl group, pentafluorophenyliminomethyl group, trifluoromethylphenyliminomethyl group, trifluoromethylthio group, trifuryl (trifluoromethanesulfonyl) group, triflate (trifluoro) Lomethanesulfonate) group, nonaflate (nonafluorobutanesulfonate) group, bistrifurylimide group, trifluoromethylfuryl group, trifluoromethylbenzofuryl group, trifluoromethyldibenzofuryl group, trifluoromethylpyrrolyl group, pentafluoro Phenylpyrrolyl group, fluoropyridyl group, tetrafluoropyridyl group, trifluoromethylindolyl group, bistrifluoromethylcarbazolyl group, trifluoromethyl A thienyl group, a trifluoromethylbenzothienyl group, a trifluoromethylthiazolyl group and the like can be mentioned. Among them, a trifluoromethyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoro group are more preferable. A methylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, and a pentafluorophenoxy group;

  The silicon-containing group (Si3) is not particularly limited as long as the effects of the present invention can be obtained. , Tert-butyldiphenylsilyl group, triphenylsilyl group, tris (trimethylsilyl) silyl group, cyclopentadienyldimethylsilyl group, di-n-butyl (cyclopentadienyl) silyl group, cyclopentadienyldiphenylsilyl group, Indenyldimethylsilyl group, di-n-butyl (indenyl) silyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, di-n-butyl (fluorenyl) silyl group, fluorenyldiphenylsilyl group, 4- Trimethylsilylphenyl 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-tert-butyldiphenylsilylphenyl group, 4-triphenylsilylphenyl group, 4-tris (trimethylsilyl) silylphenyl group, etc. Can do.

  Among the silicon-containing groups, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl are preferable. Group, indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl Group, 4-triphenylsilylphenyl group, etc. Among them, more preferred are trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilyl group. Butylphenyl group, a 4-tri -iso- propyl silyl phenyl group.

  The oxygen-containing group (O3) is not particularly limited as long as the effect of the present invention is exhibited. For example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, sec- Butoxy, iso-butoxy, tert-butoxy, methallyloxy, prenyloxy, benzyloxy, methoxymethoxy, methoxyethoxy, phenoxy, naphthoxy, toluyloxy, iso-propylphenoxy, allylphenoxy Group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, Toxiethyl group, allyloxyethyl group, benzyloxyethyl group, phenoxyethyl group, methoxypropyl group, allyloxypropyl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, phenoxy Vinyl group, methoxyallyl group, allyloxyallyl group, benzyloxyallyl group, phenoxyallyl group, formyl group, acetyl group, iso-butyryl group, pivaloyl group, benzoyl group, naphthoyl group, adamantanecarbonyl group, acetoxy group, pivaloyloxy group Benzoyloxy group, dimethoxymethyl group, di-iso-propoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, methyl carbonate group, phenyl carbonate Group, dimethyldioxanyl group, methyl carboxylate group, ethyl carboxylate group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, furyl group, methylfuryl group, A tetrahydrofuryl group, a pyranyl group, a tetrahydropyranyl group, a furfuryl group, a benzofuryl group, a dibenzofuryl group, and the like can be given.

  Among the oxygen-containing groups, methoxy group, ethoxy group, iso-propoxy group, allyloxy group, n-butoxy group, tert-butoxy group, prenyloxy group, benzyloxy group, phenoxy group, naphthoxy group, toluyloxy group are preferable. , Iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group Benzyloxyallyl group, phenoxyallyl group, formyl group, acetyl group, iso-butyryl group, pivaloyl group, benzoyl group, naphthoyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxa Group, dimethyldioxanyl group, methylcarboxylate group, ethylcarboxylate group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, furyl group, methylfuryl group , Tetrahydropyranyl group, furfuryl group, benzofuryl group, dibenzofuryl group, etc., among which, more preferably, methoxy group, iso-propoxy group, allyloxy group, phenoxy group, formyl group, acetyl group, benzoyl group, Dimethoxymethyl, dioxolanyl, methylcarboxylate, methoxyphenyl, iso-propoxyphenyl, allyloxyphenyl, phenoxyphenyl, furyl, methylfuryl, benzofuryl, dibenzofuryl It is.

  The nitrogen-containing group (N3) is not particularly limited as long as the effect of the present invention is exhibited. , Dibenzylamino group, pyrrolidinyl group, piperidinyl group, morphophoryl group, azepinyl group, formamide group, acetamide group, pivalamide group, benzamide group, naphthamide group, adamantanecarboxamide group, iminomethyl group, iminoethyl group, phenyliminomethyl group, phenyl Iminoethyl, dimethylhydrazonomethyl, pyrrolidinyliminomethyl, imide, uryl, methyluryl, dimethyluryl, guanidinyl, dimethylguanidinyl, methylformimidamide, phenyl Rumimidamide group, carbamoyl group, N-methylcarbamoyl group, N-benzylcarbamoyl group, N, N-dimethylcarbamoyl group, pyrrolidinylcarbamoyl group, N-phenylcarbamoyl group, carbamoyloxy group, N-methylcarbamoyloxy group, N- Benzylcarbamoyloxy group, N, N-dimethylcarbamoyloxy group, pyrrolidinylcarbamoyloxy group, N-phenylcarbamoyloxy group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzyl Aminomethyl, benzylaminoethyl, pyrrolidinylethyl, dimethylaminovinyl, benzylaminovinyl, pyrrolidinylvinyl, dimethylaminopropyl, benzylaminopropyl, pyrrole Nylpropyl, dimethylaminoallyl, benzylaminoallyl, pyrrolidinylallyl, nitrophenyl, dinitrophenyl, aminophenyl, cyanophenyl, dimethylaminophenyl, pyrrolidinylphenyl, pyrrolylphenyl , Pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenyl Pyrrolyl, pyridyl, quinolyl, tetrahydroquinolyl, iso-quinolyl, tetrahydro-iso-quinolyl, indolyl, indolinyl, carbazolyl, di-tert-butylcarbazolyl, imidazolyl, dimethyl Examples include imidazolidinyl group, benzoimidazolyl group, oxazolyl group, oxazolidinyl group, benzooxazolyl group and the like.

  Among the nitrogen-containing groups, cyano group, amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, formamide group, acetamide group, benzamide Group, iminomethyl group, iminoethyl group, phenyliminomethyl group, phenyliminoethyl group, dimethylhydrazonomethyl group, pyrrolidinyliminomethyl group, carbamoyl group, N-methylcarbamoyl group, N-benzylcarbamoyl group, N, N- Dimethylcarbamoyl group, pyrrolidinylcarbamoyl group, N-phenylcarbamoyl group, carbamoyloxy group, N-methylcarbamoyloxy group, N, N-dimethylcarbamoyloxy group, dimethylaminomethyl group, benzylaminomethyl Group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, nitrophenyl group, dinitrophenyl group, amino group Phenyl group, cyanophenyl group, dimethylaminophenyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydro Quinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, Oxazolyl group, oxa Examples include lysinyl group, benzoxazolyl group, and more preferably amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl. Group, an imidazolyl group.

  The sulfur-containing group (S3) is not particularly limited as long as the effect of the present invention is achieved. For example, a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a naphthylthio group, a methylthiomethyl group, a benzylthiomethyl group, a phenylthio group. Methyl group, naphthylthiomethyl group, methylthioethyl group, benzylthioethyl group, phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, Benzylthiopropyl, phenylthiopropyl, naphthylthiopropyl, methylthioallyl, benzylthioallyl, phenylthioallyl, naphthylthioallyl, mercaptophenyl, methylthiophenyl, thienylphenyl, Ruthienylphenyl group, benzothienylphenyl group, dibenzothienylphenyl group, benzodithienylphenyl group, methylsulfinyl group, tert-butylsulfinyl group, phenylsulfinyl group, mesyl (methylsulfonyl) group, benzenesulfonyl group, tosyl (4- Methylbenzenesulfonyl) group, methanesulfonate group, 4-methylbenzenesulfonate group, thiouryl group, methylthiouryl group, bis (methylthio) methyl group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofuryl group, thienothienyl group, Benzothienyl, dibenzothienyl, thienobenzofuryl, benzodithienyl, dithiolanyl, dithianyl, oxathiolanyl, oxathianyl, thiazolyl, benzothiazolyl Group, and the like thiazolidinyl group.

  Among the sulfur-containing groups, a thienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group, thiazolyl group, and benzothiazolyl group are preferable.

  The phosphorus-containing group (P3) is not particularly limited as long as the effects of the present invention are exhibited. For example, dimethylphosphino group, diethylphosphino group, diisopropylphosphino group, di-tert-butylphosphino group, dicyclohexylphosphino Group, diphenylphosphino group, di-o-tolylphosphino group, di-m-tolylphosphino group, di-p-tolylphosphino group, bis (3,5-dimethylphenyl) phosphino group, bis (2,4,6-trimethylphenyl) ) Phosphino group, bis (4-methoxyphenyl) phosphino group, bis (4-dimethylaminophenyl) phosphino group, 4- (dimethylphosphino) phenyl group, 4- (diethylphosphino) phenyl group, 4- (diisopropylphos Phino) phenyl group, 4- (di-tert-butylphosphine) B) phenyl group, 4- (dicyclohexylphosphino) phenyl group, 4- (diphenylphosphino) phenyl group, 4- (di-o-tolylphosphino) phenyl group, 4- (di-m-tolylphosphino) phenyl group, 4 -(Di-p-tolylphosphino) phenyl group, 4- (bis (3 ', 5'-dimethylphenyl) phosphino) phenyl group, 4- (bis (2', 4 ', 6'-trimethylphenyl) phosphino) phenyl A 4- (bis (4′-methoxyphenyl) phosphino) phenyl group, a 4- (bis (4′-dimethylaminophenyl) phosphino) phenyl group, and the like.

  Among the phosphorus-containing groups, dimethylphosphino group, diethylphosphino group, diisopropylphosphino group, di-tert-butylphosphino group, dicyclohexylphosphino group, diphenylphosphino group, di-o-tolylphosphino group, di -M-tolylphosphino group, di-p-tolylphosphino group, bis (4-methoxyphenyl) phosphino group, bis (4-dimethylaminophenyl) phosphino group, 4- (bis (4'-methoxyphenyl) phosphino) phenyl group, 4- (Bis (4′-dimethylaminophenyl) phosphino) phenyl group.

R ^a5 is a substituent represented by the general formula (A-1a), or a heterocycle that may have a substituent having a 5-membered mother skeleton containing at least one element selected from nitrogen, oxygen, and sulfur. It is a ring.

In the general formula (A-1a), Y represents an element selected from oxygen, nitrogen and sulfur, preferably oxygen or nitrogen.
m is an integer of 1 to 2 satisfying the valence of Y. When m is 2, R ^b may be the same or different.

R ^b is hydrogen, a hydrocarbon group having 1 to 40 carbon atoms (G4), a silicon-containing group (Si4), an ether bond-containing hydrocarbon group, or a tertiary amino group-containing hydrocarbon group. 40 hydrocarbons are preferred. R ^b is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In this case, R ^b is bonded to at least one selected from R ^a2 and R ^a3 to form a saturated ring. Also good. When m is 2 and R ^b is bonded to each other to form a ring, it is preferably a saturated ring.

  Among the hydrocarbon groups having 1 to 40 carbon atoms (G4), a methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group are preferable. 1-octyl group, iso-propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, iso -Pentyl (3-methylbutyl) group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, allyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclo Heptyl group, cyclooctyl group, cyclooctenyl group, norbornyl group, bicyclo [2.2.2] octan-1-yl group, 1-adamanti Group, 2-adamantyl group, benzyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropan-2-yl) group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2-phenylethyl Group, 3-phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (Iso-propylphenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert- Butylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl Group, phenanthryl group, anthracenyl group, ferrocenyl group, more preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, allyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, benzyl group, phenyl group, tolyl (methylphenyl) ) Group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, naphthyl group, biphenyl group, ter-phenyl group.

  Among the silicon-containing groups (Si4), trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopenta Dienyldiphenylsilyl group, indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso -Propylsilylphenyl group, 4-triphenylsilylphenyl group, and the like. Among them, trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triphenylsilyl group are more preferable. Chill silyl phenyl group, a 4-tri -iso- propyl silyl phenyl group.

  The ether bond-containing hydrocarbon group is not particularly limited as long as the effects of the present invention are exhibited, and examples thereof include a methoxymethyl group, a methoxyethyl group, a tetrahydrofuryl group, a tetrahydropyranyl group, and a methoxyphenyl group.

  The tertiary amino group-containing hydrocarbon group is not particularly limited as long as the effects of the present invention are exerted. For example, N-dimethylamino group, N-diethylamino group, N-diallylamino group, N-dibenzylamino group, N-methylethylamino group, N-pyrrolidinyl group, N-piperidinyl group, N-morpholyl group, N-methyl-N-piperazinyl group, N-pyrrolyl group, N-indolinyl group, N-indolyl group, N-carbazolyl group N-di-tert-butylcarbazolyl group, N-imidazolyl group, N-dimethylimidazolidinyl group, N-benzoimidazolyl group, N-oxazolyl group, N-oxazolidinyl group, N-benzoxazolyl group Group and the like.

R ^b may be bonded to R ^a2 and R ^a3 to form an ^optionally substituted ring. For example, R ^b is bonded to R ^a2 and R ^a3 to be condensed into an aromatic ring moiety. It may be a 5- to 8-membered saturated or unsaturated hydrocarbon group which may have a ring substituent. As long as the effects of the present invention are exhibited, the ring is not particularly limited, but is preferably a 5- or 6-membered ring. In this case, the structure combined with the aromatic ring portion of the mother nucleus is, for example, 2,7-dimethylbenzofuran. -5-yl group, 2,2,7-trimethyl-2,3-dihydrobenzofuran-5-yl group, 4-methyldibenzo [b, d] furan-2-yl group, 2,7-dimethylbenzo [b ] Thiophen-5-yl group, 4-methyldibenzo [b, d] thiophen-2-yl group, 1,7-dimethylindol-5-yl group, 1,7-dimethylindoline-5-yl group, 1, And a 9-dimethylcarbazol-3-yl group and a 9-julolidinyl (2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizin-9-yl) group. -Dimethyl Indolin-5-yl group, 9-julolidinyl (2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-yl) group.

^Rb , when Y is a nitrogen atom and m is 2, ^Rb may be bonded to each other to form a ring which may have a substituent, for example, a 5- to 8-membered saturated or unsaturated hydrocarbon group. May be. Although it is not particularly limited as long as the effect of the present invention is exhibited, it is preferably a 5- or 6-membered ring. In this case, examples of the structure combined with the nitrogen atom portion of the mother nucleus include, for example, N-pyrrolidinyl group, N-piperidinyl group, N -Morpholyl group, N-methyl-N-piperazinyl group, N-pyrrolyl group, N-indolinyl group, N-indolyl group, N-carbazolyl group, N-di-tert-butylcarbazolyl group, N-imidazolyl group, N-dimethylimidazolidinyl group, N-benzimidazolyl group, N-oxazolyl group, N-oxazolidinyl group, N-benzoxazolyl group and the like are preferable, preferably N-pyrrolidinyl group, N-piperidinyl group , N-morpholyl group, N-methyl-N-piperazinyl group.

  Examples of the heterocyclic ring which may have a substituent having a mother skeleton containing at least one element selected from nitrogen, oxygen and sulfur as a 5-membered ring are represented by the following general formulas [2a] to [2h]. Group to be used.

前記一般式［２ａ］〜［２ｈ］中、Ｃｈは酸素原子あるいはイオウ原子であり、Ｒ^dはそれぞれ独立に、水素原子または前記炭化水素基（Ｇ２）であり、それぞれ同一でも異なっていてもよい。

In the general formulas [2a] to [2h], Ch is an oxygen atom or a sulfur atom, R ^d is independently a hydrogen atom or the hydrocarbon group (G2), and may be the same or different. .

  Among the hydrocarbon groups (G2), a methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso -Propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, iso-pentyl (3-methylbutyl) Group, neopentyl (2,2-dimethylpropyl) group, tert-pentyl (1,1-dimethylpropyl) group, allyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, Cyclooctenyl group, norbornyl group, bicyclo [2.2.2] octan-1-yl group, 1-adamantyl group, 2-adaman Group, benzyl group, benzhydryl (diphenylmethyl) group, cumyl (2-phenylpropan-2-yl) group, 1,1-diphenylethyl group, trityl (triphenylmethyl) group, 2-phenylethyl group, 3- Phenylpropyl group, 2-cinnamyl (3-phenylallyl) group, phenyl group, tolyl (methylphenyl) group, xylyl (dimethylphenyl) group, mesityl (2,4,6-trimethylphenyl) group, cumenyl (iso-propyl) Phenyl) group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, ter-phenyl group, binaphthyl group, phenanthri Group, anthracenyl group, ferrocenyl group, more preferably methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, sec-butyl (butan-2-yl) group, tert-butyl (2-methylpropan-2-yl) group, iso-butyl (2-methylpropyl) group, allyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, benzyl group, phenyl group, tolyl (methylphenyl) group, A xylyl (dimethylphenyl) group, a mesityl (2,4,6-trimethylphenyl) group, a naphthyl group, a biphenyl group, and a ter-phenyl group.

R ^d is a 5- to 8-membered saturated or unsaturated hydrocarbon group which may have a substituent, wherein R ^d adjacent to each other are bonded to each other and independently fused to a 5-membered heterocyclic moiety. Although it is not particularly limited as long as the effect of the present invention is exerted, it is preferably a 5- or 6-membered ring. In this case, examples of the structure combined with the aromatic ring portion of the mother nucleus include, for example, benzofuran ring, benzo Examples include a thiophene ring, an indole ring, a carbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, and a benzopyrazole ring.

Of the heterocyclic rings [2a] to [2h], [2a] is preferred.
In the heterocyclic ring [2a], a 2-furyl group, a 5-methyl-2-furyl group, a 2-thienyl group, a 5-methyl-2-thienyl group, and an N-pyrrolyl group are preferable.

R ^a5 is particularly preferably an alkoxy group, a dialkylamino group or a pyrrolidinyl group.
Among the alkoxy groups, methoxy group, ethoxy group, 1-propoxy group, 1-butoxy group, iso-propoxy group, sec-butoxy group, tert-butoxy group, iso-butoxy group, allyloxy group, cyclopentyloxy Group, cyclohexyloxy group, 1-adamantyloxy group and benzyloxy group, and methoxy group, ethoxy group, 1-propoxy group, iso-propoxy group and tert-butoxy group are most preferable.

  Among the dialkylamino groups, dimethylamino group, diethylamino group, diallylamino group, dibenzylamino group, di-n-butylamino group, di-iso-butylamino group, di-tert-butylamino group, Examples thereof include an ethylmethylamino group, and among them, a dimethylamino group, a diethylamino group, a dibenzylamino group, and a di-tert-butylamino group are more preferable.

Z is a saturated or unsaturated divalent or trivalent hydrocarbon having 3 or 4 carbon atoms which forms a condensed ring which may have the same substituent as R ^{1 to} R ⁶ with respect to the carbon atom to which it is bonded. Indicates a group. In this case, the structure combined with the cyclopentadienyl part of the mother nucleus is a substituted cyclopentathiophene ring, substituted indene ring, substituted tetrahydroindene ring, substituted azulene ring, substituted dihydroazulene ring, substituted tetrahydroazulene ring, substituted hexahydroazulene A ring etc. are mentioned, Preferably it is a substituted indene ring.

The substituents on Z may be bonded to R ^a1 and R ^a4 to form a ring. In this case, examples of the structure combined with the cyclopentadienyl portion and the aromatic ring portion of the mother nucleus include 3,6-dihydrocyclopentafluorene ring, cyclopentaphenanthrene ring, and 6,7-dihydrocyclopentaphenanthrene ring. .

The transition metal compound [A] constituting the olefin polymerization catalyst of the present invention is preferably a compound represented by the general formula (A-2).
In general formula (A-2), M, X, n, Q, R ^{1 to} R ⁶ , and R ^{a1 to} R ^a5 are M, X, n, Q, R ¹ to R in general formula (A-1), respectively. R ⁶ and R ^{a1 to} R ^a5 have the same meaning.

R ^{7 to} R ⁹ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (G2), a halogen atom (X1), a halogen-containing group (H2), a silicon-containing group (Si2), an oxygen-containing group (O2 ), A nitrogen-containing group (N2), a sulfur-containing group (S2), or a phosphorus-containing group (P2), which may be the same or different.

Examples and preferred examples of the hydrocarbon group having 1 to 20 carbon atoms (G2) include the same groups as those described above for R ^{1 to} R ⁶ .
Examples and preferred examples of the halogen atom (X1) include the same as those described above for R ^{1 to} R ⁶ .

Examples and preferred examples of the halogen-containing group (H2) include the same groups as those described above for R ^{1 to} R ⁶ .
Examples and preferred examples of the silicon-containing group (Si2) include the same groups as those described above for R ^{1 to} R ⁶ .

Examples and preferred examples of the oxygen-containing group (O2) include the same groups as those described above for R ^{1 to} R ⁶ .
Examples and preferred examples of the nitrogen-containing group (N2) include the same groups as those described above for R ^{1 to} R ⁶ .

Examples and preferred examples of the sulfur-containing group (S2) include the same as those described above for R ^{1 to} R ⁶ .
Examples and preferred examples of the phosphorus-containing group (P2) include the same groups as those described above for R ^{1 to} R ⁶ .

The adjacent substituents from R ^{7 to} R ⁹ may be bonded to each other to form a ring, and may have, for example, a substituent that is bonded to each other and condensed to an aromatic ring portion. A membered ring saturated or unsaturated hydrocarbon group may be formed. Although it is not particularly limited as long as the effect of the present invention is exerted, it is preferably a 5- or 6-membered ring. In this case, as a structure combined with a cyclopentadienyl part and an aromatic ring part of the mother nucleus, for example, a substituted tetrahydroindacene ring And substituted cyclopentatetrahydronaphthalene, and examples of the condensed ring structure of the R ^{1 to} R ⁴ moieties include a substituted fluorene ring, which is preferably a substituted tetrahydroindacene ring.

R ⁷ and R ^a1 or R ^a4 may be bonded to each other to form a ring. Saturated or unsaturated hydrocarbon groups may be formed. Although it is not particularly limited as long as the effects of the present invention are exhibited, it is preferably a 5- or 6-membered ring. In this case, the structure combined with the cyclopentadienyl part and the aromatic ring part of the mother nucleus is, for example, 3,6-dihydro Examples include a cyclopentafluorene ring, a cyclopentaphenanthrene ring, and a 6,7-dihydrocyclopentaphenanthrene ring.

R ^{7 to} R ⁹ are preferably each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (G2), or an oxygen-containing group (O2).
Preferred examples of the hydrocarbon group (G2) include the same groups as those described for R ^{a1 to} R ^a4 .

Among the oxygen-containing group (О2), preferred examples, the same alkoxy group mentioned in the R ^a5 and the like.
R ^{7 to} R ⁹ are more preferably each independently a hydrogen atom or the hydrocarbon group having 1 to 20 carbon atoms.

Among the hydrocarbon groups having 1 to 20 carbon atoms, particularly preferred examples include a methyl group, an iso-propyl group, and a tert-butyl (2-methylpropan-2-yl) group.
R ^{7 to} R ⁹ are particularly preferably all hydrogen atoms.

In the general formula (A-2), R ^{1 to} R ⁵ , R ^a2 and R ^a3 are hydrocarbon groups having 1 to 10 carbon atoms, R ⁶ , R ^a1 and R ^a4 are hydrogen atoms, R ^a5 Is particularly preferably an alkoxy group, a dialkylamino group or a pyrrolidinyl group.

[Production Method of Transition Metal Compound [A]]
The transition metal compound [A] of the present invention can be produced by a known method, and an example of a typical synthesis route is shown below, but the production method is not particularly limited.

  First, a 3,4,5-substituted aromatic compound having a heteroatom-containing electron-donating substituent at the 4-position and having a substituent introduced at the 3, 5-position in the vicinity is a known method. The manufacturing method is not particularly limited. Known production methods include, for example, “J. Am. Chem. Soc. 2006, 128, 16486.”, “Eur. J. Org. Chem. 2008, 1767.”, “Angew. Chem. Int. Ed. 52, 4239. "," Org. Process. Res. Dev. 2011, 15, 1178. "," Eur. J. Org. Chem. 2006, 2727. ", WO 2007/034975," J. Am. Chem. " Soc. 2014, 136, 10166. ”,“ Eur. J. Org. Chem. 2011, 6100. ”, WO 2013/011956, and the like.

  The aromatic substituted cyclopentadiene compound can be produced by a known method such as a cross-coupling reaction using the 3,4,5-substituted aromatic compound as a raw material, and the production method is particularly limited. is not. Known production methods include, for example, “Organometallics 2004, 23, 3267.”, WO 1998/040331, WO 1998/046547, JP-A 2004-2259, “Organometallics 2006, 25, 1217.”, US Pat. 7910783, Special Table 2011-500800, “Organometallics 2011, 30, 5744.”, “Chem. Eur. J. 2012, 18, 4174.”, “Organometallics 2012, 31, 4962.”, JP-A-2014-14. Japanese Patent Laid-Open No. 201519, Japanese Patent Application Laid-Open No. 7-286005, WO 2001/027124, WO 2004/029062, WO 2006/126608, etc. by the present applicant, etc. And the like.

  On the other hand, various cyclopentadiene compounds can be produced by known methods, and the production method is not particularly limited. Known production methods include, for example, Japanese Patent Application Laid-Open No. 2000-136195, Japanese Patent Application Laid-Open No. 2009-24019, Japanese Patent No. 3675509, WO 1998/015510, WO 2000/049029, “J. Organomet. Chem. 1999,”. 577, 211. ”,“ J. Organomet. Chem. 2003, 677, 133. ”,“ Organometallics 1988, 7, 1828. ”,“ Organometallics 1996, 15, 4857. ”,“ Organometallics 250. 1997 ”. "Organometallics 2004, 23, 4963.", "J. Am. Chem. Soc. 2004, 126, 2089.", "Macromol. Chem. Phy." 2004, 205, 2275. "," Org. Lett. 2008, 10, 2545. "," Chem. Rev. 1992, 92, 965. "," Science 2012, 338, 504. "

  Moreover, the precursor compound (ligand) of the transition metal compound [A] can be produced by a known method using the aromatic-substituted cyclopentadiene compound and the cyclopentadiene compound as raw materials. It is not limited. Examples of known production methods include, for example, JP-A-2013-227271, JP-A-2014-70029, JP-A-2015-63515 in addition to the above-mentioned aromatic-substituted cyclopentadiene compounds and the above-mentioned production methods of cyclopentadiene compounds. No. 3,607,615, No. 5,205,726, No. 5,387,325, No. 5,633,991, “Organometallics 2003, 22, 2790.”, “Eur. J. Inorg. Chem. 2005, 2924.”, “Eur. J. Inorg. Chem. 2008, 330. ”,“ Eur. J. Inorg. Chem. 2013, 1184. ”,“ New J. Chem. 1990, 14, 499 ”,“ Ange. Chem. Int. Ed. 1 95,34,2273. "," J.Оrganomet.Chem. 1997,530,75. "," J.Оrganomet.Chem. 2001,619,280. ", And the like.

  The target transition metal compound [A] can be produced by a known method using the precursor compound (ligand), and the production method is not particularly limited. As known production methods, for example, in addition to those mentioned as the production method of the precursor compound (ligand), JP-A-10-109996, JP-A-2002-88092, JP-A-2003-048893, JP2011-246373, JP2015-83631, JP4128306, JP4214792, JP4834964, JP4834965, JP52271465, JP5393098, U.S. Pat. “J. Organomet. Chem. 1997, 527, 297.”, “Organometrics 2012, 31, 4340.”, WO 2004/029062 by the present applicant, and the like.

  In addition, the transition metal compound [A] obtained by the production method of the present invention has two directions of the surface of the cyclopentadienyl ring portion that binds to the central metal across the cross-linked portion (front surface and back surface). Therefore, there are two types of structural isomers, pseudo-racemic and pseudo-meso, depending on the relative relationship between the two cyclopentadienyl ring moieties bound to the central metal across the bridging moiety. . In the general formula (A-1) or (A-2), the case where the cyclic substituent bonded to the cyclopentadienyl ring moiety is on the right side of the paper is a pseudo racemic body, and the case where it is on the left side is a pseudo meso body. The pseudo meso form of the general formula (A-1) has a structure represented by the following general formula (A-3).

これら構造異性体混合物の精製、疑似ラセミ体の分取、あるいは疑似ラセミ体の選択的な製造は、公知の方法によって可能であり、特に製造法が限定されるわけではない。公知の製造方法としては、前記遷移金属化合物［Ａ］の製造方法として挙げたものである。

Purification of these structural isomer mixtures, fractionation of pseudo racemates, or selective production of pseudo racemates can be performed by known methods, and the production method is not particularly limited. As the known production method, those mentioned as the production method of the transition metal compound [A] are listed.

  Specific examples of the transition metal compound [A] obtained by the production method of the present invention are shown below, but the scope of the present invention is not particularly limited by this. In the present invention, the transition metal compound [A] may be used singly or in combination of two or more, a pseudo racemate or a pseudo meso isomer, and a mixture of structural isomers. You may use, and you may use in combination of these above.

  For convenience, the ligand structure of the transition metal compound [A] of the present invention, excluding MXn (metal part), has a cyclopentadienyl ring (1) part, a bridging part, a cyclopentadienyl ring (2) part, cyclopentadiene. Enyl ring (2) partial aromatic substituent (Ar), cyclopentadienyl ring (2) partial aromatic substituents at positions 3 and 5 (T), cyclopentadienyl ring (2) partial aromatic Substituent in position 4 (U), cyclopentadienyl ring (2) substituent adjacent to partial bridge (R), cyclopentadienyl ring (2) partial oxygen atom-bonded alkyl substituent (Alk) It is divided into eight. The abbreviation of the cyclopentadienyl ring (1) moiety is α, the abbreviation of the bridging part is β, the cyclopentadienyl ring (2) part is γ, and the cyclopentadienyl ring (2) part of the aromatic substituent (Ar) The abbreviation δ, the abbreviation of the substituent (T) at the 3,5-position in the cyclopentadienyl ring (2) partial aromatic substituent is ε, and the 4-position in the cyclopentadienyl ring (2) partial aromatic substituent The abbreviation of the substituent (U) is ζ, the abbreviation of the substituent (R) at the position adjacent to the cyclopentadienyl ring (2) partial bridge is η, and the cyclopentadienyl ring (2) is a partial oxygen atom-bonded alkyl substituent ( The abbreviation of Alk) is Θ, and the abbreviations of the substituents are shown in [Table 1] to [Table 8].

Specific examples of the metal portion MX _{n is, TiF 2, TiCl 2, TiBr} 2, TiI 2, Ti (Me) 2, Ti (Bn) 2, Ti (Allyl) 2, Ti (CH 2 -tBu) 2 , Ti (η ⁴ -1,3-butadienyl), Ti (η ⁴ -1,3-pentadienyl), Ti (η ⁴ -2,4-hexadienyl), Ti (η ⁴ -1,4-diphenyl-1, _{3-pentadienyl), Ti (CH 2 -Si (} Me) 3) 2, Ti (ОMe) 2, Ti (ОiPr) 2, Ti (NMe 2) 2, Ti (ОMs) 2, Ti (ОTs) 2, Ti (OTF) ₂ , ZrF ₂ , ZrCl ₂ , ZrBr ₂ , ZrI ₂ , Zr (Me) ₂ , Zr (Bn) ₂ , Zr (Allyl) ₂ , Zr (CH ₂ -tBu) ₂ , Zr (η ⁴ −1 , 3-butadienyl), Zr (η ⁴ -1,3- pentadienyl) Zr (η ⁴ -2,4- hexadienyl), Zr (η ⁴ -1,4- _{diphenyl-1,3-pentadienyl), Zr (CH 2 -Si (} Me) 3) 2, Zr (ОMe) 2, Zr _{(ОiPr) 2, Zr (NMe} 2) 2, Zr (ОMs) 2, Zr (ОTs) 2, Zr (ОTf) 2, HfF 2, HfCl 2, HfBr 2, HfI 2, Hf (Me) 2, Hf ( Bn) ₂ , Hf (Allyl) ₂ , Hf (CH ₂ -tBu) ₂ , Hf (η ⁴ -1,3-butadienyl), Hf (η ⁴ -1,3-pentadienyl), Hf (η ⁴ -2, 4-hexadienyl), Hf (η ⁴ -1,4-diphenyl-1,3-pentadienyl), Hf (CH ₂ —Si (Me) ₃ ) ₂ , Hf (ОMe) ₂ , Hf (ОiPr) ₂ , Hf ( NMe ₂ ) ₂ , Hf (ОMs) ₂ , Hf (ОTs) ₂ , Hf (ОTf ₂ ). Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si (Me) ₃ is a trimethylsilyl group, OMe is a methoxy group, OiPr is an iso-propoxy group, NMe ₂ is a dimethylamino group, and OMs is methanesulfonate OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

According to the above notation, the cyclopentadienyl ring (1) part is α-11 in [Table 1], the bridging part is β-3 in [Table 2], and the cyclopentadienyl ring (2) part is Γ-12 in [Table 3], cyclopentadienyl ring (2) partial aromatic substituent (Ar) is δ-1, in [Table 4], cyclopentadienyl ring (2) partial aromatic substituent Substituent (T) in positions 3 and 5 is ε-4 in [Table 5], and substituent (U) in position 4 in cyclopentadienyl ring (2) partial aromatic substituent is in [Table 6]. Ζ-20, cyclopentadienyl ring (2) The substituent (R) adjacent to the partial bridging portion is composed of a combination of η-1 in [Table 7], and MX _{n of} the metal portion is ZrCl ₂ Exemplifies the following compound [1].

シクロペンタジエニル環（１）部分が［表１］中のα−１８、架橋部分が［表２］中のβ−１６、シクロペンタジエニル環（２）部分が［表３］中のγ−６、シクロペンタジエニル環（２）部分芳香族置換基（Ａｒ）が［表４］中のδ−８、シクロペンタジエニル環（２）部分架橋部隣接位の置換基（Ｒ）が［表７］中のη−１０、シクロペンタジエニル環（２）部分酸素原子結合アルキル置換基（Ａｌｋ）が［表８］中のΘ−１０の組み合わせで構成され、金属部分のＭＸ_nがＺｒ（ＮＭｅ）₂の場合は、下記化合物［２］を例示している。

The cyclopentadienyl ring (1) moiety is α-18 in [Table 1], the bridging moiety is β-16 in [Table 2], and the cyclopentadienyl ring (2) moiety is γ in [Table 3]. -6, Cyclopentadienyl ring (2) Partial aromatic substituent (Ar) is δ-8 in [Table 4], Cyclopentadienyl ring (2) Substituent (R) at the position adjacent to the partial bridge is Η-10 in [Table 7], cyclopentadienyl ring (2) Partial oxygen atom-bonded alkyl substituent (Alk) is composed of the combination of Θ-10 in [Table 8], and MX _{n of} the metal portion is In the case of Zr (NMe) ₂ , the following compound [2] is exemplified.

また、シクロペンタジエニル環（１）部分が［表１］中のα−１６、架橋部分が［表２］中のβ−３２、シクロペンタジエニル環（２）部分が［表３］中のγ−１０、シクロペンタジエニル環（２）部分芳香族置換基（Ａｒ）が［表４］中のδ−２、シクロペンタジエニル環（２）部分架橋部隣接位の置換基（Ｒ）が［表７］中のη−１２の組み合わせで構成され、金属部分のＭＸ_nがＨｆＭｅ₂の場合は、下記化合物［３］を例示している。

Further, the cyclopentadienyl ring (1) portion is α-16 in [Table 1], the bridging portion is β-32 in [Table 2], and the cyclopentadienyl ring (2) portion is in [Table 3]. Γ-10, cyclopentadienyl ring (2) partial aromatic substituent (Ar) is δ-2 in [Table 4], cyclopentadienyl ring (2) substituent adjacent to the partial bridging moiety (R ) Is composed of a combination of η-12 in [Table 7], and MX _{n of} the metal portion is HfMe ₂ , the following compound [3] is exemplified.

また、シクロペンタジエニル環（１）部分が［表１］中のα−２０、架橋部分が［表２］中のβ−１３、シクロペンタジエニル環（２）部分が［表３］中のγ−８、シクロペンタジエニル環（２）部分芳香族置換基（Ａｒ）が［表４］中のδ−１、シクロペンタジエニル環（２）部分芳香族置換基中３，５位の置換基（Ｔ）が［表５］中のε―９およびε−１６、シクロペンタジエニル環（２）部分芳香族置換基中４位の置換基（Ｕ）が［表６］中のζ―１５、シクロペンタジエニル環（２）部分架橋部隣接位の置換基（Ｒ）が［表７］中のη−８、シクロペンタジエニル環（２）部分酸素原子結合アルキル置換基（Ａｌｋ）が［表８］中のΘ−１１の組み合わせで構成され、金属部分のＭＸ_nがＴｉ（η⁴−１，３−ペンタジエニル）の場合は、下記化合物［４］を例示している。

Further, the cyclopentadienyl ring (1) part is α-20 in [Table 1], the bridging part is β-13 in [Table 2], and the cyclopentadienyl ring (2) part is in [Table 3]. Γ-8, cyclopentadienyl ring (2) partial aromatic substituent (Ar) is δ-1, [5] in the cyclopentadienyl ring (2) partial aromatic substituent in [Table 4] The substituent (T) in ε-9 and ε-16 in [Table 5], and the cyclopentadienyl ring (2) the 4-position substituent (U) in the partial aromatic substituent is in [Table 6] ζ-15, the substituent (R) adjacent to the cyclopentadienyl ring (2) partial bridge portion is η-8 in [Table 7], the cyclopentadienyl ring (2) partial oxygen atom-bonded alkyl substituent ( Alk) is composed of a combination of Θ-11 in [Table 8], and MX _{n of} the metal part is Ti (η ⁴ -1,3-pentadienyl), Compound [4] is exemplified.

上記の遷移金属化合物が特異な性能を示す理由は現時点では明らかではないが、本願発明者は下記の様に推測している。

The reason why the above transition metal compound exhibits unique performance is not clear at present, but the inventor of the present application estimates as follows.

  The transition metal compound of the present invention is characterized by having (i) a heteroatom-containing electron-donating substituent at a metallocene specific site. This is considered to give potential such as improved reactivity with α-olefins, particularly higher α-olefins having a large number of carbon atoms, which is considered to be due to the flow of electrons into the vicinity of the central metal via the conjugated system. On the other hand, (ii) a substituent near the electron-donating substituent is considered to reduce the interaction between the electron-donating substituent and a Lewis acidic compound such as an organometallic compound described later or the central metal of the transition metal compound. Therefore, it is considered that only the performance improvement effect by introducing the electron donating substituent can be selectively expressed.

((B-1) Organometallic compound)
As the organometallic compound (B-1) used in the present invention, specifically, periodic table groups 1, 2, 12, and 13 represented by the following general formulas (B-1a) to (B-1c) And compounds containing at least one atom of:
R ^a _p Al (OR ^b1 ) _q H _r Y _s (B-1a)
(In the general formula (B-1a), R ^a and R ^b1 may be the same as or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; P is 0 <p ≦ 3, q is 0 ≦ q <3, r is 0 ≦ r <3, s is 0 ≦ s <3, and m + n + p + q = 3. Organoaluminum compounds;
M ³ AlR ^c ₄ (B-1b)
(In the general formula (B-1b), M ³ represents Li, Na or K, and R ^c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). Complex alkylated product of alkali metal of group 1 of the table and aluminum;
R ^{d Re} M ⁴ (B-1c)
(In the general formula (B-1c), R ^d and R ^e may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ⁴ represents Mg. , Zn or Cd.) Dialkyl compounds with Group 2 alkaline earth metals or Group 12 metals.

Examples of the organoaluminum compound belonging to the general formula (B-1a) include the following compounds.
R ^a _p Al (OR ^b1 ) _3-p (B-1a-1)
(In the formula (B-1a-1), R ^a and R ^b1 may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably Is a number of 1.5 ≦ p ≦ 3.)
R ^a _p AlY _3-p (B-1a-2)
(In the formula (B-1a-2), Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably 0 <p <3. An organoaluminum compound represented by:
R ^a _p AlH _3-p (B-1a-3)
(In the formula (B-1a-3), Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number satisfying 2 ≦ p <3). An organoaluminum compound represented,
R ^a _p Al (OR ^b1 ) _q Y _s (B-1a-4)
(In the formula (B-1a-4), R ^a and R ^b1 may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y represents a halogen atom. An organic aluminum compound represented by the following formula: p is an atom, p is 0 <p ≦ 3, q is a number 0 ≦ q <3, s is a number 0 ≦ s <3, and p + q + s = 3.

More specifically, as the organoaluminum compound belonging to the general formula (B-1a), trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum Tri-n-alkylaluminum such as;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 A tri-branched alkylaluminum such as methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as diisobutylaluminum hydride;
_{(I-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Tri isoprenylaluminum represented by like Trialkenyl aluminum such as;
Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
R ^a _2.5 Al (OR ^b1 ) Partially alkoxylated alkylaluminum having an average composition represented by _0.5 (wherein R ^a and R ^b1 may be the same as or different from each other and have the same number of carbon atoms) 1 to 15, preferably 1 to 4 hydrocarbon groups);
Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6- Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

A compound similar to (B-1a) can also be used in the present invention. Examples of such a compound include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to the general formula (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .
Examples of the compound belonging to the general formula (B-1c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n- Examples thereof include butyl zinc, diisobutyl zinc, bis (pentafluorophenyl) zinc, dimethyl cadmium, diethyl cadmium and the like.

  In addition, examples of the organometallic compound (B-1) include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium. Chloride, butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

  In addition, a compound capable of forming the organoaluminum compound in the polymerization system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium is used as the organometallic compound (B-1). It can also be used as

Of the organometallic compounds (B-1), organoaluminum compounds are preferred from the viewpoint of catalytic activity.
The organometallic compound (B-1) as described above is used singly or in combination of two or more.

((B-2) Organoaluminum oxy compound)
The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. May be.

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.

  (2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

  (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or unreacted organoaluminum compound by distillation from the recovered solution of the above aluminoxane, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (B-1a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
The above organoaluminum compounds are used singly or in combination of two or more.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable. These solvents can be used alone or in combination.

  The organoaluminum oxy compound (B-2) according to the present invention is represented by an aluminoxane having a structure represented by the following general formula (B-2a) or (B-2b), and the following general formula (B-2c). And an aluminoxane selected from at least one of aluminoxanes having a repeating unit represented by the following general formula (B-2d) as a structure.

（一般式中、Ｒ^cは、それぞれ独立に、炭素原子数１〜１０、好ましくは１〜４の炭化水素基であり、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、イソプロペニル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、シクロヘキシル基、シクロオクチル基、フェニル基、トリル基、エチルフェニル基などの炭化水素基を例示することができる。これら例示したもののうちで、メチル基、エチル基、イソブチル基が好ましく、特にメチル基が好ましく、前記一般式（Ｂ−２ａ）、（Ｂ−２ｂ）および（Ｂ−２ｃ）中、Ｒ^cの一部が塩素、臭素などのハロゲン原子で置換され、かつハロゲン含有率が４０重量％以下であってもよい。（Ｂ−２ｃ）および（Ｂ−２ｄ）中の、片方が原子と繋がっていない直線は、図示していない別の原子との結合を示す。

(In the general formula, each R ^c is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, isopropenyl. Group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, Examples thereof include hydrocarbon groups such as cyclooctyl group, phenyl group, tolyl group, ethylphenyl group, etc. Among those exemplified, methyl group, ethyl group, and isobutyl group are preferable, and methyl group is particularly preferable. In the general formulas (B-2a), (B-2b) and (B-2c), a part of R ^c is substituted with a halogen atom such as chlorine or bromine. And the halogen content may be 40% by weight or less, in (B-2c) and (B-2d), a straight line that is not connected to one atom is connected to another atom not shown. Indicates binding.

In the general formulas (B-2a) and (B-2b), r represents an integer of 2 to 500, preferably 6 to 300, particularly preferably 10 to 100.
In the general formulas (B-2c) and (B-2d), s and t each represent an integer of 1 or more.

  The aluminoxane having the repeating unit represented by the general formula (B-2c) and the repeating unit represented by the general formula (B-2d) has a molecular weight measured by a freezing point depression method of benzene of 200 to 2000. It is preferable to be within.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, it is preferably insoluble or hardly soluble in benzene. )

  Examples of the organoaluminum oxy compound (B-2) used in the present invention also include an organoaluminum oxy compound containing boron represented by the following general formula (B-2e).

（一般式（Ｂ−２ｅ）中、Ｒ¹⁵は炭素原子数が１〜１０の炭化水素基を示し、４つのＲ¹⁶は、互いに同一でも異なっていてもよく、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数が１〜１０の炭化水素基を示す。）

(In the general formula (B-2e), R ¹⁵ represents a hydrocarbon group having 1 to 10 carbon atoms, and four R ^{16 s} may be the same as or different from each other. And represents a hydrocarbon group having 1 to 10 atoms or carbon atoms.)

The organoaluminum oxy compound containing boron represented by the general formula (B-2e) comprises an alkyl boronic acid represented by the following general formula (B-2f) and an organoaluminum compound in an inert gas atmosphere. In an inert solvent at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.
R ¹⁵ -B (ОH) ₂ (B-2f)
(In the general formula (B-2f), R ¹⁵ represents the same group as R ¹⁵ in the general formula (B-2e).)

  Specific examples of the alkyl boronic acid represented by the general formula (B-2f) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n- Examples include hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.

  Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (B-1a).

  As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

In addition to the transition metal compound [A], when an organoaluminum oxy compound (B-2) such as methylaluminoxane as a promoter component is used in combination, the olefin compound exhibits a very high polymerization activity.
The above organoaluminum oxy compounds (B-2) are used singly or in combination of two or more.

((B-3) Compound that reacts with transition metal compound [A] to form an ion pair)
As the compound (B-3) (hereinafter referred to as “ionized ionic compound”) which forms an ion pair by reacting with the transition metal compound [A] used in the present invention, JP-A-1-501950, Lewis described in JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US-5321106, etc. Examples thereof include acids, ionic compounds, borane compounds and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group, trifluoromethyl group, etc.) is used. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, Examples include tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.
Examples of the ionic compound include compounds represented by the following general formula (B-3a).

（一般式［Ｂ−３ａ］中、Ｒ¹⁷はＨ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオンまたは遷移金属を有するフェロセニウムカチオンであり、Ｒ¹⁸〜Ｒ²¹は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。）。

(In formula [B-3a], R ¹⁷ is H ^+, a ferrocenium cation having carbonium cations, oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation or a transition metal, R ¹⁸ ~ R ²¹ may be the same or different from each other, and is an organic group, preferably an aryl group or a substituted aryl group.

  Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

  Specific examples of the ammonium cation include lower alkyls such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation, and di (n-octadecyl) methylammonium cation. Trialkylammonium cations of alkyl; N, N-dialkylanilinium cations such as N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation A dialkylammonium cation such as a di (isopropyl) ammonium cation or a dicyclohexylammonium cation;

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ¹⁷ is preferably a carbonium cation or an ammonium cation, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

  Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). ) Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (M, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethyl) Enyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron, di (octadecyl) methylammonium tetraphenylboron, di (octadecyl) methylammonium tetrakis (p-tolyl) boron, di (octadecyl) methylammonium tetrakis (O-tolyl) boron, di (octadecyl) methylammonium tetrakis (pentafluorophenyl) boron, di (octadecyl) methylammonium tetrakis (2,4-dimethylphenyl) boron, di (octadecyl) methylammonium tetrakis (3,5- Dimethylphenyl) boron, di (octadecyl) methylammonium tetrakis (4-trifluoromethylphenyl) boron, di (octadecyl) methylammonium tetrakis (3,5-ditrif Oro-methylphenyl) has a higher alkyl of lower of said di (octadecyl) methylammonium boron or the like can be exemplified an alkyl ammonium salt.

  Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4, Examples thereof include 6-pentamethylanilinium tetra (phenyl) boron.

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Mention may also be made of cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the following formula (B-3b) or (B-3c), and the like.

（式（Ｂ−３ｂ）中、Ｅｔはエチル基を示す。）

(In the formula (B-3b), Et represents an ethyl group.)

（式（Ｂ−３ｃ）中、Ｅｔはエチル基を示す。）

(In the formula (B-3c), Et represents an ethyl group.)

Specifically as a borane compound which is an example of an ionized ionic compound (compound (B-3)), for example, decaborane;
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate Salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

Specific examples of carborane compounds that are examples of ionized ionic compounds include, for example, 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3- Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2 , 7-dicarbaound decaborane, undecahydride-7,8-dimethyl-7,8-dicarbaound decaborane, dodecahydride-11-methyl-2,7-dicarbound decaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n- Til) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6- Carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 7-carbaundecaborate, tri (n-butyl) ammonium 7,8-dicarbaundecaborate, tri (n -Butyl) ammonium 2,9-dicarbaundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl -7,9-Dicarbaound Decabo , Tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate , Tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundeborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate, etc. Anion salts;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundeborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III , Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecarboxylate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8 -Dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [Tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundeca Borate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undeca) Metal carborane anions such as idride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) And the like.

  The heteropoly compound that is an example of the ionized ionic compound includes an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. A compound. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germano-tungstovanadic acid, phosphomolybdo-tungstovanadic acid, germano-molybdo-tungstovanadic acid, phosphomolybdotungstic acid , Phosphomolybdoniobic acid, and salts of these acids, but not limited thereto. In addition, the salt includes, for example, an alkali metal of Group 1 of the periodic table or an alkaline earth metal of Group 2, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium. , Salts with strontium, barium and the like, and organic salts such as triphenylethyl salt.

  An isopoly compound which is an example of an ionized ionic compound is a compound composed of a metal ion of one kind of atom selected from vanadium, niobium, molybdenum and tungsten, and is regarded as a molecular ionic species of a metal oxide. Can do. Specific examples include vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids, but are not limited thereto. The salt includes, for example, metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. And organic salts such as triphenylethyl salt.

The above ionized ionic compounds (compound (B-3) that forms an ion pair by reacting with the transition metal compound [A]) are used singly or in combination of two or more.
Moreover, the catalyst for olefin polymerization according to the present invention includes the transition metal compound [A], an organometallic compound (B-1), an organoaluminum oxy compound (B-2), and an ionized ionic compound (B-3). In addition to at least one compound [B] selected from the group consisting of:

[[C] carrier]
The carrier [C] used in the present invention is an inorganic or organic compound and is a granular or particulate solid. By supporting the transition metal compound [A] and the compound [B] on the carrier [C], a polymer having a good morphology can be obtained.

As the inorganic compound, porous oxides, solid aluminoxane compounds, inorganic halides, clays, clay minerals, or ion-exchangeable layered compounds are preferable.
Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , and a composite or mixture containing these. Furthermore, natural or synthetic zeolites, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO _2- TiO ₂ -MgO or the like can be used. Of these, the porous oxide is preferably one containing SiO ₂ and / or Al ₂ O ₃ as a main component.

The porous oxide contains a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCo ₃ , MgCo ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO _3). ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but the porous oxide preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area. It is desirable to be in the range of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, and the pore volume to be in the range of 0.3 to 3.0 cm ³ / g. Such a porous oxide is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Examples of the solid aluminoxane compound include aluminoxane selected from at least one of the aluminoxanes represented by the above (B-2a) to (B-2d).
The solid aluminoxane used in the present invention is different from conventionally known olefin polymerization catalyst carriers, and does not contain inorganic solid components such as silica and alumina, and organic polymer components such as polyethylene and polystyrene. Shows solidified as. The meaning of “solid” used in the present invention is to maintain a substantially solid state in a reaction environment in which the aluminoxane component (B-2) is used. More specifically, for example, when preparing the solid catalyst component for olefin polymerization by bringing the component [A] and the component [B] into contact as described later, an inert hydrocarbon solvent such as hexane or toluene used for the reaction. Among these, it represents that component [B] is in a solid state under a specific temperature and pressure environment. Further, for example, when suspension polymerization is performed using a solid catalyst component for olefin polymerization prepared by using the component [B] as described later, a specific temperature and pressure in a hydrocarbon solvent such as hexane, heptane, and toluene. It is also a necessary requirement that the component [B] contained in the catalyst component in the environment is in a solid state. The same applies to bulk polymerization in which polymerization is performed in a liquefied monomer instead of a solvent, and gas phase polymerization in which polymerization is performed in a monomer gas.

  Whether the component [B] is in a solid state under the above environment is the simplest method for visual confirmation, but for example, it is often difficult to visually confirm during polymerization. In that case, for example, it is possible to judge from the properties of the polymer powder obtained after polymerization, the state of adhesion to the reactor, and the like. On the contrary, if the properties of the polymer powder are good and there is little adhesion to the reactor, even if some of the component [B] elutes in the polymerization environment, the gist of the present invention is not deviated. The index for judging the properties of the polymer powder includes the bulk density, the particle shape, the surface shape, the degree of presence of the amorphous polymer, etc., and the polymer bulk density is preferable from the viewpoint of quantitativeness. The bulk density in this invention is 0.01-0.9 normally, Preferably it is 0.05-0.6, More preferably, it exists in the range of 0.1-0.5.

  The solid aluminoxane used in the present invention is usually dissolved in a proportion of 0 to 40 mol%, preferably 0 to 20 mol%, particularly preferably 0 to 10 mol with respect to n-hexane maintained at a temperature of 25 ° C. % Range is satisfied.

  The dissolution ratio of the solid aluminoxane used in the present invention with respect to n-hexane was determined by adding 2 g of solid aluminoxane support to 50 ml of n-hexane maintained at 25 ° C., followed by stirring for 2 hours, and then G-4 glass. The solution portion was separated using a filter manufactured, and the aluminum concentration in the filtrate was measured. Therefore, the dissolution ratio is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of the aluminoxane used.

  As the solid aluminoxane according to the present invention, a known solid aluminoxane can be used without limitation. Known manufacturing methods include, for example, JP-B-7-43001, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000. -38410, JP-A-2000-95810, WO201055552 and the like.

The average particle size of the solid aluminoxane according to the present invention is generally 0.01 to 50000 μm, preferably 1 to 1000 μm, particularly preferably 1 to 200 μm.
The average particle size of the solid aluminoxane can be determined by observing the particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and weight averaging. For the particle size of the solid aluminoxane, the maximum length of the Pythagorean method was measured from the particle image. That is, in each of the horizontal direction and the vertical direction, the length of the particle image sandwiched between two parallel lines is measured, and it can be calculated by the following formula.
Particle size = ((horizontal length) ² + (vertical length) ² ) ^0.5

The weight average particle diameter of the solid aluminoxane is obtained by the following formula using the particle diameter obtained above.
Average particle size = Σnd ⁴ / Σnd ³ (where n: number of particles, d: particle size)

The solid aluminoxane preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 800 m ² / g, and a pore volume of 0.1 to 2.5 cm ³ / g. desirable.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.

  The clay is usually composed mainly of clay minerals. Moreover, the said ion exchange layered compound is a compound which has a crystal structure where the surface comprised by the ionic bond etc. was piled up in parallel with weak mutual binding force, and the ion to contain is exchangeable. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

Examples of the clay, clay mineral, or ion-exchangeable layered compound include ionic crystalline compounds having a layered crystal structure such as a hexagonal close packing type, an antimony type, a CdCl ₂ type, and a CdI ₂ type.

In addition, as clay and clay minerals, kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysingelite, pyrophyllite, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, Halloysite, etc.
Examples of the ion-exchange layered compounds include α-Zr (HASO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ). ₂ , α-Ti (HASO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti ( Examples thereof include crystalline acidic salts of polyvalent metals such as NH ₄ PO ₄ ) ₂ · H ₂ O.

Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of not less than 0.1 cc / g and not less than 0.3 to 5 cc / g as measured by mercury porosimetry. It is particularly preferred. Here, the pore volume is measured in a range of pore radius of 20 to 30000 mm by mercury porosimetry using a mercury porosimeter.
When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.

  The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. . Such bulky ions play a role of supporting pillars to support the layered structure, and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl _4, and metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) _3. R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (ОH) ₂₄ ] ⁷⁺ , [Zr ₄ (ОH) ₁₄ ] ²⁺ , [Fe ₃ O (ОCOCH ₃ ) ₆ ] ⁺ Etc. These compounds are used alone or in combination of two or more. In addition, when intercalating these compounds, metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R represents a hydrocarbon group, etc.) are hydrolyzed. The obtained polymer and colloidal inorganic compounds such as SiO ₂ can coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
As described above, the carrier [C] is an inorganic or organic compound, and examples of the organic compound include granular or particulate solids having a particle size in the range of 10 to 300 μm. Specifically, a polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or vinylcyclohexane or styrene as a main component. As examples, polymers produced as follows, and modified products thereof can be exemplified.

  The catalyst for olefin polymerization according to the present invention comprises the transition metal compound [A], the compound [B], and the carrier [C] as necessary, and the following specific organic compound component [D] as necessary. It can also be included.

[[D] Organic compound component]
In the present invention, if necessary, the organic compound component [D] improves the polymerization performance of the olefin polymerization catalyst of the present invention and the physical properties of the produced polymer (for example, the molecular weight of the produced polymer). Used for the purpose. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

As the alcohols and the phenolic compounds, those represented by R ²² —OH are usually used, wherein R ²² is a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, a carbon atom). The number is 6 to 50) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols).

As alcohols, R ²² is preferably a halogenated hydrocarbon group. Moreover, as a phenolic compound, what substituted the (alpha) and (alpha) '-position of the hydroxyl group with the C1-C20 hydrocarbon is preferable.

As the carboxylic acid, those represented by R ²³ —COOH are usually used. R ²³ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

As the phosphorus compound, phosphoric acids having a P—O—H bond, P—OR, phosphates having a P═O bond, and phosphine oxide compounds are preferably used.
Examples of the sulfonate include those represented by the following general formula (Da).

（一般式（Ｄ−ａ）中、Ｍ⁵は周期律表第１〜１４族の原子であり、Ｒ²⁴は水素、炭素原子数１〜２０の炭化水素基または炭素原子数１〜２０のハロゲン化炭化水素基であり、Ｚは水素原子、ハロゲン原子、炭素原子数が１〜２０の炭化水素基または炭素原子数が１〜２０のハロゲン化炭化水素基であり、ｔは１〜７の整数であり、ｕは１〜７の整数であり、また、ｔ−ｕ≧１である。）

(In General Formula (Da), M ⁵ is an atom of Groups 1 to 14 in the periodic table, and R ²⁴ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and t is an integer of 1 to 7 And u is an integer from 1 to 7 and tu ≧ 1.)

<Production method of polyolefin>
In the polyolefin production method according to the present invention, a polyolefin is obtained by including a step of polymerizing (homopolymerizing or copolymerizing) an olefin in the presence of the olefin polymerization catalyst as described above. As described above, in the present specification, the olefin refers to any compound having a polymerizable double bond.

The method for using each component constituting the catalyst of the present invention in polymerization and the order of addition to the polymerization vessel are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the transition metal compound [A] alone to the polymerization vessel.
(2) A method of adding the transition metal compound [A] and the compound [B] to the polymerization vessel in any order.
(3) A method in which the catalyst component having the transition metal compound [A] supported on the carrier [C] and the compound [B] are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having the compound [B] supported on the carrier [C] and the transition metal compound [A] are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] are supported on a carrier [C] is added to a polymerization vessel.
(6) A method of adding a catalyst component in which a transition metal compound [A] and a compound [B] are supported on a carrier [C], and a compound [B] to a polymerization vessel in an arbitrary order. In this case, the compound [B] supported on the carrier [C] and the compound [B] added alone may be the same or different.
(7) A method in which the catalyst component having the compound [B] supported on the carrier [C] and the transition metal compound [A] are added to the polymerization vessel in any order.
(8) A method in which the catalyst component having the compound [B] supported on the carrier [C], the transition metal compound [A], and the compound [B] are added to the polymerization vessel in any order. In this case, the compound [B] supported on the carrier [C] and the compound [B] added alone may be the same or different.
(9) A method in which a component having the transition metal compound [A] supported on the carrier [C] and a component having the compound [B] supported on the carrier [C] are added to the polymerization vessel in any order.
(10) A method of adding a component in which the transition metal compound [A] is supported on the carrier [C], a component in which the compound [B] is supported on the carrier [C], and the compound [B] to an arbitrary sequential polymerization apparatus. In this case, the compound [B] supported on the carrier [C] and the compound [B] added alone may be the same or different.
(11) A method of adding the transition metal compound [A], the compound [B], and the organic compound component [D] to the polymerization vessel in an arbitrary order.
(12) A method in which the component [B] and the organic compound component [D] previously contacted and the transition metal compound [A] are added to the polymerization vessel in an arbitrary order.
(13) A method of adding the component [B] and the organic compound component [D] supported on the carrier [C] and the transition metal compound [A] to the polymerization vessel in an arbitrary order.
(14) A method in which the catalyst component obtained by previously contacting the transition metal compound [A] and the compound [B] and the organic compound component [D] are added to the polymerization vessel in an arbitrary order.
(15) A method in which the transition metal compound [A] and the compound [B] are contacted in advance, and the compound [B] and the organic compound component [D] are added to the polymerization vessel in any order.
(16) A catalyst component in which the transition metal compound [A] and the compound [B] are contacted in advance, and a component in which the compound [B] and the organic compound component [D] are contacted in advance are added to the polymerization reactor in an arbitrary order. Method. In this case, the compound [B] brought into contact with the transition metal compound [A] and the compound [B] brought into contact with the organic compound component [D] may be the same or different.
(17) A method in which the component having the transition metal compound [A] supported on the carrier [C], the compound [B], and the organic compound component [D] are added to the polymerization vessel in any order.
(18) A method in which a component in which the transition metal compound [A] is supported on the carrier [C] and a component in which the compound [B] and the organic compound component [D] are contacted in advance are added to the polymerization vessel in any order.
(19) A method in which a catalyst component obtained by previously contacting a transition metal compound [A], a compound [B], and an organic compound component [D] in an arbitrary order is added to a polymerization vessel.
(20) A method in which the transition metal compound [A], the compound [B] and the organic compound component [D] are contacted in advance, and the compound [B] is added to the polymerization vessel in any order. In this case, the compound [B] brought into contact with the transition metal compound [A] and the organic compound component [D] and the compound [B] added alone may be the same or different.
(21) A method in which a catalyst in which a transition metal compound [A], a compound [B], and an organic compound component [D] are supported on a carrier [C] is added to a polymerization vessel.
(22) A method in which a transition metal compound [A], a compound [B], a catalyst component in which an organic compound component [D] is supported on a carrier [C], and a component [B] are added to the polymerization vessel in an arbitrary order. In this case, the compound [B] supported on the carrier [C] and the compound [B] added alone may be the same or different.

  The solid catalyst component in which the transition metal compound [A] is supported on the carrier [C] and the solid catalyst component in which the transition metal compound [A] and the compound [B] are supported on the carrier [C] It may be polymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

  In the present invention, the polymerization (homopolymerization or copolymerization) can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and the like aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and mixtures thereof; and polymerization (homopolymerization or The olefin itself used for the copolymerization) can also be used as a solvent.

When the olefin polymerization is performed using the olefin polymerization catalyst as described above, the transition metal compound [A] is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻¹⁰ liter per reaction volume. Used in such an amount as to be ^-3 mol.

  The organometallic compound (B-1) usually has a molar ratio [(B-1) / M] of the organometallic compound (B-1) and all transition metal atoms (M) in the transition metal compound [A]. It is used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. The organoaluminum oxy compound (B-2) is a molar ratio of the aluminum atom in the organoaluminum oxy compound (B-2) to the total transition metal (M) in the transition metal compound [A] [(B-2). / M] is usually used in an amount of 10 to 500,000, preferably 20 to 100,000. The compound that reacts with the transition metal compound [A] to form an ion pair (ionized ionic compound) (B-3) includes the ionized ionic compound (B-3) and the transition metal in the transition metal compound [A]. The molar ratio [(B-3) / M] with the atom (M) is usually 1 to 10, preferably 1 to 5.

  The organic compound component [D] has a molar ratio [[D] / (B-1)] with the organometallic compound (B-1) of usually 0.01 to 10, preferably 0.1 to 5. Used in various amounts. The organic compound component [D] has a molar ratio [[D] / (B-2)] with the organoaluminum oxy compound (B-2) of usually 0.001 to 2, preferably 0.005 to 1. Used in such amounts. The organic compound component [D] has a molar ratio [[D] / (B-3)] with the ionized ionic compound (B-3) of usually 0.01 to 10, preferably 0.1 to 5. Used in such amounts.

Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² -G, preferably from normal pressure to 50 kg / cm ² -G, and the polymerization reaction is carried out in any of batch, semi-continuous and continuous methods. Can also be done. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  The molecular weight of the resulting polyolefin can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the compound [B] to be used.

The olefin that can be polymerized by the olefin polymerization catalyst of the present invention is not particularly limited as long as it has a polymerizable double bond, but has 2 to 30, preferably 2 to 20, more preferably carbon atoms. Are 2 to 10 linear or branched α-olefins such as ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl- 1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene;
Cyclic olefins having 3 to 30, preferably 3 to 20, more preferably 3 to 10 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like.

  The catalyst for olefin polymerization of the present invention is used for homopolymerization of ethylene or copolymerization of ethylene with an olefin having 3 to 20 carbon atoms, preferably a linear or branched α-olefin having 3 to 10 carbon atoms. Is more preferable. The α-olefin may be used alone or in combination of two or more.

  In the case of copolymerization of ethylene and an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, the α-olefin (hereinafter also referred to as olefin A) is not particularly limited as long as the effects of the present invention are exhibited. Are, for example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene and 1-decene. preferable. These α-olefins may be used alone or in combination of two or more. Among these, at least one selected from 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene is more preferable.

  When ethylene is used and the olefin A is used, the ratio of ethylene to the olefin A used is ethylene: the olefin A (molar ratio), usually 1:10 to 5000: 1, preferably 1: 5. 1000: 1.

The catalyst for olefin polymerization of the present invention may polymerize a chain-like unsaturated hydrocarbon having a polar group (for example, a carbonyl group, a hydroxyl group, an ether bond group, etc.). For example, acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 17-octadecenoic acid, 18-nonadecenoic acid, 19-eicosenoic acid, 20-henicosenoic acid, 21-docosenoic acid, 22-tricosenoic acid, methacrylic acid, 2-methylpentenoic acid, 2,2-dimethyl-3-butenoic acid, 2,2-dimethyl-4-pentenoic acid, -Vinylbenzoic acid, 4-vinylbenzoic acid, 2,6-heptadienoic acid, 2- (4-isopropylbenzylidene) -4-pentenoic acid, allylmalonic acid, 2- (10-undecenyl) malonic acid, fumaric acid, itaconic acid , Unsaturated carboxylic acids such as bicyclo [2.2.1] -5-heptene-2-carboxylic acid, bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid, and sodium salts thereof , Potassium salts, lithium salts, zinc salts, magnesium salts, calcium salts and the like, and methyl esters, ethyl esters, n-propyl esters, isopropyl esters, n-butyl esters, isobutyl esters of these unsaturated carboxylic acids, ( Unsaturated carboxylic acid esters such as 5-norbornen-2-yl) ester When the acid is a dicarboxylic acid, it may be a monoester or a diester), and amides of these unsaturated carboxylic acids, unsaturated carboxylic amides such as N, N-dimethylamide When the saturated carboxylic acid is a dicarboxylic acid, it may be a monoamide or a diamide);
Maleic anhydride, itaconic anhydride, allyl succinic anhydride, isobutenyl succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1 ] Unsaturated carboxylic acid anhydrides such as -5-heptene-2,3-dicarboxylic acid anhydride;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate;
Allyl esters such as allyl acetate, allyl propionate, allyl caproate, allyl caprate, allyl laurate, allyl stearate;
Halogenated olefins such as vinyl chloride, vinyl fluoride, vinyl bromide, vinyl iodide, allyl bromide, allyl chloride, allyl fluoride, allyl bromide;
halogenated styrenes such as o-chlorostyrene and p-chlorostyrene;
Silylated olefins such as allyltrimethylsilane, diallyldimethylsilane, 3-butenyltrimethylsilane, allyltriisopropylsilane, allyltriphenylsilane;
Unsaturated nitriles such as acrylonitrile, 2-cyanobicyclo [2.2.1] -5-heptene, 2,3-dicyanobicyclo [2.2.1] -5-heptene;
Unsaturated alcohol compounds such as allyl alcohol, 3-butenol, 4-pentenol, 5-hexenol, 6-hebutenol, 7-octenol, 8-nonenol, 9-decenol, 10-undecenol, 11-dodecenol, 12-tridecenol And unsaturated esters thereof such as acetates, benzoates, propionates, caproates, caprates, laurates, stearates;
Substituted phenols such as vinylphenol and allylphenol, and unsaturated esters such as acetate, benzoate, propionate, caproate, caprate, laurate, and stearate;
Substituted benzyl alcohols such as vinyl benzyl alcohol and allyl benzyl alcohol, and unsaturated esters thereof such as acetate, benzoate, propionate, caproate, caprate, laurate and stearate;
Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether, allyl methyl ether, allyl propyl ether, allyl butyl ether, allyl methallyl ether, methoxy styrene, ethoxy styrene, allyl anisole;
Unsaturated epoxides such as butadiene monoxide, 1,2-epoxy-7-octene, 3-vinyl 7-oxabicyclo [4.1.0] heptane;
Unsaturated aldehydes such as acrolein and undecenal, and unsaturated acetals such as dimethyl acetal and diethyl acetal;
Unsaturated ketones such as methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, and allyl benzyl ketone, and unsaturated acetals such as dimethyl acetal and diethyl acetal;
Unsaturated thioethers such as allyl methyl sulfide, allyl phenyl sulfide, allyl isopropyl sulfide, allyl n-propyl sulfide, 4-pentenyl phenyl sulfide;
Unsaturated sulfoxides such as allyl phenyl sulfoxide;
Unsaturated sulfones such as allyl phenyl sulfone;
Unsaturated phosphines such as allyldiphenylphosphine;
And unsaturated phosphine oxides such as allyldiphenylphosphine oxide.

Furthermore, unsaturated hydrocarbons having two or more polar groups listed above, such as vinyl trifluoroacetate, allyl trifluoroacetate, methyl 4- (3-butenyloxy) benzoate, glycidyl acrylate, allyl glycidyl ether, (2H-perfluoropropyl) -2-propenyl ether, linalool oxide, 3-allyloxy-1,2-propanediol, 2- (allyloxy) ethanol, N-allylmorpholine, allylglycine, N-vinylpyrrolidone, allyltrichlorosilane, Acrylic trimethylsilane, allyldimethyl (diisopropylamino) silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, allyloxytriphenylsilane and the like are also polymerized (homopolymerized or co-polymerized) by the olefin polymerization catalyst of the present invention. If) may be.
The olefin polymerization catalyst of the present invention may polymerize (homopolymerization or copolymerization) vinylcyclohexane, diene or polyene.

Examples of the diene or the polyene include cyclic or chain compounds having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and having two or more double bonds. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 , 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene;
7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene;
Further, mono- or poly-aromatic vinyl compounds such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, etc. Alkyl styrene;
Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene;
And 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like.

  As described above, the transition metal compound [A] of the present invention has a novel structure in which a specific substituent is introduced at a specific position of the metallocene skeleton, and includes the compound [A]. The catalyst for use has α-olefin copolymerizability that is particularly superior to transition metal compounds having a conventional metallocene skeleton (having no specific substituent at a specific position), and good olefin polymerization activity. A low-density ethylene copolymer having a sufficient molecular weight can be produced.

  This effect is remarkable due to the effect of introducing a heteroatom-containing electron donating substituent into the metallocene specific site in the transition metal compound [A] represented by the general formula (A-1) or (A-2). It is considered that this is due to the effect of improving the α-olefin copolymerizability and (ii) the activity-inhibiting phenomenon due to the introduction of heteroatoms by the effect of introducing substituents in the vicinity.

[Olefin polymer]
According to the present invention, in the presence of a catalyst for olefin polymerization containing a useful and novel transition metal compound [A] having the specific structure described above, one or more α-olefins having 2 to 30 carbon atoms are used. Preferably, the olefin polymer is made efficient by homopolymerizing ethylene or copolymerizing ethylene with at least one olefin A selected from α-olefins having 3 to 20 carbon atoms. Can be manufactured well.

  As one aspect of the olefin polymer of the present invention, an ethylene-based polymer containing an ethylene-derived constitutional unit preferably in the range of 90 to 100 mol%, more preferably 92 to 100 mol%, still more preferably 95 to 100 mol%. Coalescence is mentioned. The ethylene-based polymer preferably contains the olefin A-derived structural units in a total amount of 0 to 10 mol%, more preferably 0 to 8 mol%, and still more preferably 0 to 5 mol%. However, the total of the content of the structural unit derived from ethylene and the content of the structural unit derived from the olefin A is 100 mol%. The ethylene-based polymer in which the structural unit derived from the olefin A is in the above range is excellent in molding processability. Further, other structural units may be included without departing from the spirit of the present invention. These contents can be measured by nuclear magnetic resonance spectroscopy or, if there is a reference substance, infrared spectroscopy.

  Among these polymers, ethylene homopolymer, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / 1-octene polymer, ethylene / 1 -Hexene polymer, ethylene / 4-methyl-1-pentene polymer, ethylene / propylene / 1-octene polymer, ethylene / propylene / 1-hexene polymer, ethylene / propylene / 4-methyl-1-pentene polymer Is particularly preferred. Moreover, what is called a block copolymer (impact copolymer) obtained by mixing or manufacturing continuously 2 or more types selected from these polymers may be sufficient.

  Among the polymers having the structural units described above, the ethylene-based polymer of the present invention is preferably an α-olefin polymer consisting essentially of structural units derived from an α-olefin having 2 to 20 carbon atoms. “Substantially” means that the proportion of the structural unit derived from the α-olefin having 2 to 20 carbon atoms is 95% by weight or more with respect to all the structural units.

  In the olefin polymer of the present invention, the weight average molecular weight measured by a gel permeation chromatography (GPC) method is not particularly limited, but is preferably 10,000 to 5,000,000, more preferably 10,000. ˜2,000,000, particularly preferably 20,000 to 1,000,000. The molecular weight distribution (Mw / Mn), which is the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn), is not particularly limited, but is preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 1. 5.

In the olefin polymer of the present invention, the density is not particularly limited, it is preferably not more than 875kg / m ³ or more 975 kg / m ^3.
In the olefin polymer of the present invention, the intrinsic viscosity [η] in 135 ° C. decalin is not particularly limited, but is preferably 0.1 to 40 dl / g, more preferably 0.5 to 15 dl / g, and particularly preferably 1 10 dl / g.

  In the olefin polymer of the present invention, the melt mass flow rate (MFR; unit is g / 10 minutes) measured under conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-89 is not particularly limited, but preferably 0 It is 0.001 g / 10 min or more and 300 g / 10 min or less, more preferably 0.001 g / 10 min or more and 200 g / 10 min or less.

Further, according to ASTM D1238-89, the value (I10 / I2) obtained by dividing the MFR value measured under the condition of 190 ° C. and 10 kg load by the MFR value measured under the condition of 190 ° C. and 2.16 kg load is 5 It is preferably 0.0 or more and less than 300.
Details of the measurement conditions of the above physical property values are as described in the examples.

The following examples further illustrate the present invention. In addition, this invention is not limited to description of a following example.
The compounds described in the synthesis examples are 270 MHz, ¹ H-NMR (JEOL; GSH-270), gas chromatograph mass spectrometer (GC-MS) (Shimadzu Corporation; GCMS-QP5050A and Shimadzu Corporation; GCMS-QP2010 Ultra), It identified using FD-mass spectrometry (JEOL SX-102A).
Moreover, the method to measure the physical property and property of the polymer obtained by superposition | polymerization of an olefin in presence of the catalyst containing the transition metal compound of this invention was described below.

・ Density (kg / m ³ )
A sheet of 0.5 mm thickness was formed at a pressure of 100 kg / cm ² using a hydraulic heat press machine manufactured by Shindo Metal Industry Co., Ltd. set at 190 ° C. (spacer shape: 240 × 240 × 0.5 (mm) thick plate 45 × 45 × 0.5 (mm), 9 pieces), and cooled by compressing at a pressure of 100 kg / cm ² using another hydraulic heat press machine manufactured by Shinfuji Metal Industry Co., Ltd. set to 20 ° C. A sample for measurement was prepared. As the hot plate, a 5 mm thick SUS plate was used.
The press sheet was heat-treated at 120 ° C. for 1 hour, linearly cooled to room temperature over 1 hour, and then measured with a density gradient tube.

-Weight average molecular weight (Mw), number average molecular weight (Mn)
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). It was calculated from the molecular weight distribution curve obtained by “Alliance GPC 2000” gel permeation chromatograph (high temperature size exclusion chromatograph) manufactured by Waters Co., and operating conditions are as follows:

[Devices used and conditions]
Measuring device: Gel permeation chromatograph alliance GPC2000 (Waters)
Analysis software: Chromatography data system Empower (trademark, Waters)
Column; TSKgel GMH6-HT × 2 + TSKgel GMH6-HT × 2
(Inner diameter 7.5mm x length 30cm, Tosoh Corporation)
Mobile phase: o-dichlorobenzene [= ОDCB] (Wako Pure Chemicals special grade reagent)
Detector: Differential refractometer (built-in device)
Column temperature: 140 ° C
Flow rate: 1.0 mL / min
Injection volume: 500 μL
Sampling time interval; 1 second Sample concentration; 0.15% (w / v)
Molecular weight calibration Monodisperse polystyrene (Tosoh Corp.) / Molecular weight 495 to molecular weight 20.6 million Molecular weight distribution and various average molecular weights Polym. Sci. , B5, 753. (1967) was calculated as a polyethylene molecular weight conversion according to the general calibration procedure described in (1967).

-Comonomer content The comonomer content of the copolymer was measured by FT-IR (FT-IR410 infrared spectrophotometer manufactured by JASCO Corporation). FT-IR uses, as a measurement sample, a film obtained by dissolving and stretching the copolymer-forming polymer obtained in Examples in a hot press heated to 135 ° C. and then cooling under pressure at room temperature. The measurement was performed at a wavelength of 5000 cm ^{−1 to} 400 cm ⁻¹ . Hexene _{content, C-CH 2 CH 2 CH} 2 CH 3 skeleton vibration based on hexene (1378 cm ^-1) as a key band, absorbance key band (D1378) and the internal standard band (4321cm ^-1: CH stretching vibration And the absorbance (D4321) of the combined sound of the methylene and methyl bending vibrations [D1378 / D4321].

  A calibration curve specifying the relationship between the comonomer content and the [D1378 / D4321] is used to specify the comonomer content. The calibration curve is prepared in advance based on the [D1378 / D4321] results obtained by performing FT-IR measurement on ethylene copolymers having various compositions whose comonomer content is specified by 13C NMR by the above method.

<(1) Synthesis of transition metal compound>
[Example 1]
[Example 1-1]
A 200 mL reactor that had been thoroughly dried and purged with argon was charged with 0.42 g (17.2 mmol) of magnesium pieces and stirred vigorously for 30 minutes while heating under reduced pressure. After cooling to room temperature, a piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. To this solution, J. Org. Am. Chem. Soc. 2006, 128, 16486. Slowly add a diluted solution of 4.67 g (15.6 mmol) of 1-bromo-3,5-di-tert-butyl-4-methoxybenzene synthesized in the described manner in 25 mL of tetrahydrofuran, and heat to reflux in an oil bath for 1 hour. did. After the reaction solution was cooled to -78 ° C, 2.00 mL (18.0 mmol) of trimethoxyborane was slowly added, and stirring was continued for 21 hours while slowly returning to room temperature. A 1.0 M aqueous hydrochloric acid solution was added, and the soluble component was extracted with diethyl ether. The obtained fraction was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled off to obtain the residue obtained by Organometallics 2006, 25, 1217. 4-bromo-2-methyl-1-indanone 2.70 g (12.0 mmol), tripotassium phosphate 6.69 g (31.5 mmol), palladium acetate 0.03 g (0.13 mmol) synthesized by the method described 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos) 0.08 g (0.18 mmol), 30 mL of tetrahydrofuran and 6 mL of distilled water were charged, and the mixture was heated to reflux for 2 hours in an oil bath. After the reaction solution was cooled to room temperature, a saturated aqueous ammonium chloride solution was added, the soluble component was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtration of magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 4.09 g of the desired product represented by the following formula (1a) (hereinafter referred to as compound (1a)) was obtained. Yield 93%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.75 (1H, dd, J = 7.5 and 1.2 Hz, Ar—H), 7.61 (1 H, dd, J = 7.5 and 1.2 Hz, Ar—H) ), 7.45 (1H, t, J = 7.5Hz, Ar-H), 7.33 (2H, s, Ar-H), 3.76 (3H, s, -OCH 3), 3.56 -3.39 (1H, m, CH- CH 3), 2.85-2.65 (2H, m, Ar-CH 2 -C), 1.48 (18H, s, -C (CH 3) 3 ), 1.33 (3H, d, J = 7.3 Hz, CH—CH ₃ ) ppm

[Example 1-2]
In a sufficiently dry, argon-substituted 200 mL reactor, 4.07 g (11.2 mmol) of the compound (1a) obtained in Example 1-1, 15 mL of tetrahydrofuran, and 5 mL of methanol were charged and stirred. The solution was cooled to 0 ° C., 0.85 g (22.6 mmol) of sodium hydroborate was slowly added little by little, and the mixture was stirred at room temperature for 2 hours. This solution was cooled to 0 ° C., 1.0 M hydrochloric acid aqueous solution was slowly added, and the soluble portion was extracted with ethyl acetate. The obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 20 mL of toluene and 0.05 g (0.24 mmol) of p-toluenesulfonic acid monohydrate were added to the residue obtained by distilling the filtrate, and heated in an oil bath for 1 hour. Refluxed. After the reaction solution was cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 3.51 g of the desired product represented by the following formula (1b) (hereinafter referred to as the compound (1b)) was obtained. Yield 90%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.41 (2H, s, Ar—H), 7.35-7.17 (2H, m, Ar—H), 7.12 (1H, dd, J = 7.4and1.3Hz, Ar-H), 6.53 (1H, dd, J = 2.9and1.4Hz, Ar-CH = C), 3.75 (3H, s, -OCH 3), 3.38 (2H, s, Ar-CH 2 -C), 2.15 (3H, s, CH-CH 3), 1.47 (18H, s, -C (CH 3) 3) ppm

[Example 1-3]
In a 100 mL reactor sufficiently dried and purged with argon, 1.05 g (3.00 mmol) of the compound (1b) obtained in Example 1-2 and 15 mL of tetrahydrofuran were charged and stirred. The solution was cooled to −78 ° C., and 2.00 mL of n-butyllithium solution (hexane solution, 1.55 M, 3.10 mmol) was added to the solution and stirred at room temperature for 2 hours. To this solution, 0.30 mL (3.19 mmol) of 1,3-dimethyl-2-imidazolidinone was added, followed by cooling to -78 ° C., and chlorodimethyl (2,3,4,5-tetrahydrofuran purchased from Aldrich). 0.67 mL (3.03 mmol) of methyl-2,4-cyclopentadien-1-yl) silane was added, and stirring was continued for 18 hours while slowly returning to room temperature. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtration of magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. The obtained residue was washed with methanol, and the target compound (hereinafter referred to as compound) represented by the following formula (1c) was obtained. (1c)) was obtained as 0.91 g (58% yield) isomer mixture.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.41 (2H, s, Ar—H), 7.36 (1H, d, J = 7.5 Hz, Ar—H), 7.23 (1H, d, J = 7.5 Hz, Ar-H), 7.13 (1H, t, J = 7.5 Hz, Ar-H), 6.77 (1H, s, Ar-CH = C), 3.75 (3H _{, s, -OCH 3), 3.70} (1H, s, CH-Si-CH), 3.26 (1H, s, CH-Si-CH), 2.24 (3H, s, C-CH 3 ), 2.02 (3H, s, C—CH ₃ ), 1.99 (3H, s, C—CH ₃ ), 1.84 (6H, s, C—CH ₃ ), 1.48 (18H, _{s, -C (CH 3) 3} ), - 0.25 (3H, s, Si-CH 3), - 0.28 (3H, s, Si-CH 3) ppm

[Example 1-4]
In a 100 mL reactor sufficiently dried and purged with argon, 0.26 g (0.50 mmol) of the compound (1c) obtained in Example 1-3, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. To this solution, 0.65 mL of n-butyllithium solution (hexane solution, 1.63 M, 1.06 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 10 mL of diethyl ether was added to the obtained solid. This solution was cooled to 0 ° C., 0.12 g (0.51 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After the solvent of the reaction solution was distilled off, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, a suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure, which was expressed by the following formula (1). 0.17 g (yield 64%) of a yellow powdery compound (hereinafter referred to as metallocene compound (1)) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.56 (2H, s, Ar—H), 7.54 (1H, d, J = 8.7 Hz, Ar—H), 7.29 (1H, dd, J = 7.0 and 0.8 Hz, Ar—H), 7.04 (1H, dd, J = 8.7 and 7.0 Hz, Ar—H), 7.01 (1 H, s, Ar—H), 3.74 _{(3H, s, -OCH 3)} , 2.29 (3H, s, Ar-CH 3), 2.09 (3H, s, Ar-CH 3), 2.01 (3H, s, Ar-CH 3 ), 1.93 (3H, s, Ar—CH ₃ ), 1.91 (3H, s, Ar—CH ₃ ), 1.48 (18H, s, —C (CH ₃ ) ₃ ), 1.22 (3H, s, Si-CH 3), 1.10 (3H, s, Si-CH 3) ppm
FD-mass spectrometry (M ⁺ ): 686

[Example 2]
[Example 2-1]
A 200 mL reactor thoroughly dried and purged with argon was charged with 0.53 g (22.0 mmol) of magnesium pieces and stirred vigorously for 30 minutes while heating under reduced pressure. After cooling to room temperature, a piece of iodine and 22 mL of tetrahydrofuran were charged and stirred. To this solution, Eur. J. et al. Org. Chem. 2006, 2727. And slowly adding a 30 ml diluted solution of 5.69 g (20.0 mmol) of 4-bromo-2,6-di-iso-propyl-N, N-dimethylaniline synthesized by the method described in WO2007 / 034975, The mixture was heated to reflux for 1 hour in an oil bath at 80 ° C. After the reaction solution was cooled to -78 ° C, 2.50 mL (22.5 mmol) of trimethoxyborane was slowly added, and stirring was continued for 18 hours while slowly returning to room temperature. In this reaction solution, Organometallics 2006, 25, 1217. 7.71 g (17.7 mmol) of 7-bromo-2-methylindene synthesized by the described method, 8.42 g (39.7 mmol) of tripotassium phosphate, 0.08 g (0.36 mmol) of palladium acetate, 2-dicyclohexyl Phosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos) 0.22 g (0.53 mmol) and distilled water 10 mL were charged, and the mixture was heated to reflux for 2 hours in an oil bath. The reaction mixture was cooled to room temperature, 1.0 M aqueous hydrochloric acid solution was added, the soluble portion was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, methanol was added to the residue obtained by distilling off the filtrate to prepare a suspension, the insoluble matter was filtered off, and the residue was dried under reduced pressure to obtain the following formula (2a). ) (4.52 g, yield 76%) was obtained (hereinafter referred to as compound (2a)).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.35-7.19 (4H, m, Ar—H), 7.14 (1H, dd, J = 7.4 and 1.3 Hz, Ar—H), 6. 58-6.50 (1H, m, Ar- CH = C), 3.49-3.31 (4H, m, Ar-CH 2 -C and -CH (CH 3) 2), 2.89 (6H , S, —NC (CH ₃ ) ₂ ), 2.15 (3H, s, CH—CH ₃ ), 1.25 (12H, d, J = 6.9 Hz, —CH (CH ₃ ) ₂ ) ppm

[Example 2-2]
In a 100 mL reactor thoroughly dried and purged with argon, 1.01 g (3.02 mmol) of the compound (2a) obtained in Example 2-1 and 15 mL of tetrahydrofuran were charged and stirred. To this solution under ice cooling, 1.85 mL of n-butyllithium solution (hexane solution, 1.63 M, 3.02 mmol) was added and stirred at room temperature for 2 hours. To this solution, 0.30 mL (3.19 mmol) of 1,3-dimethyl-2-imidazolidinone was added, cooled to −30 ° C., and chlorodimethyl (2,3,4,5-tetrahydrofuran purchased from Aldrich). Methyl-2,4-cyclopentadien-1-yl) silane (0.67 mL, 3.03 mmol) was added, and stirring was continued for 17 hours while slowly returning to room temperature. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 0.91 g of the desired product represented by the following formula (2b) (hereinafter referred to as the compound (2b)) was obtained. (Yield 59%) as an isomer mixture.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.43-7.10 (5H, m, Ar—H), 6.78 (1H, s, Ar—CH═C), 3.69 (1H, s, CH-Si-CH), 3.40 (2H, sep, J = 6.9Hz, -CH (CH 3) 2), 3.26 (1H, s, CH-Si-CH), 2.90 (6H _{, s, -NC (CH 3)} 2), 2.24 (3H, s, C-CH 3), 2.02 (3H, s, C-CH 3), 1.99 (3H, s, C- _{CH 3), 1.85 (6H,} s, C-CH 3), 1.26 (12H, dd, J = 6.9and4.2Hz, -CH (CH 3) 2), - 0.25 (3H, _{s, Si-CH 3),} - 0.28 (3H, s, Si-CH 3) ppm

[Example 2-3]
In a 100 mL reactor sufficiently dried and purged with argon, 0.26 g (0.50 mmol) of the compound (2b) obtained in Example 2-2, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. To this solution, 0.65 mL of n-butyllithium solution (hexane solution, 1.63 M, 1.06 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.12 g (0.51 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 15 hours. After the solvent of the reaction solution was distilled off, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, a suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to show the following formula (2). 0.13 g (yield 38%) of a yellow powdery compound (hereinafter referred to as metallocene compound (2)) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.53 (1H, d, J = 8.6 Hz, Ar—H), 7.42 (2H, s, Ar—H), 7.32 (1H, d, J = 6.9Hz, Ar-H) , 7.04 (2H, m, Ar-H), 3.38 (2H, sep, J = 6.9Hz, -CH (CH 3) 2), 2.89 (6H, s, -NC (CH 3) 2), 2.29 (3H, s, Ar-CH 3), 2.09 (3H, s, Ar-CH 3), 2.02 (3H, s, _{Ar-CH 3), 1.93 (} 3H, s, Ar-CH 3), 1.92 (3H, s, Ar-CH 3), 1.32 (6H, d, J = 6.9Hz, -CH _{(CH 3) 2), 1.22} (6H, d, J = 6.9Hz, -CH (CH 3) 2), 1.21 (3H, s, Si-CH 3), 1.10 (3H, s, Si-CH ₃ ) ppm
FD-mass spectrometry (M ⁺ ): 671

[Comparative Example 1]
Dimethylsilylene (tetramethylcyclopentadienyl) (2-methylindenyl) zirconium dichloride (metallocene compound (3)) is obtained from Organometallics 2003, 22, 2790. Synthesized by the method described.

[Comparative Example 2]
[Comparative Example 2-1]
Organometallics 2006, 25, 1217. In a 200 mL reactor thoroughly dried and purged with argon. 6.76 g (30.0 mmol) of 4-bromo-2-methyl-1-indanone synthesized by the method described, 5.00 g (43.9 mmol) of cyclopentylboronic acid, 18.2 g (120 mmol) of cesium fluoride, palladium acetate 0.67 g (3.0 mmol), 1.7 g (6.0 mmol) of tri-tert-butylphosphonium tetrafluoroborate, 60 mL of toluene and 12 mL of distilled water were charged, and the mixture was heated to reflux for 28 hours in an oil bath. After cooling the reaction solution to room temperature, insoluble components were filtered through celite and washed thoroughly with ethyl acetate. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 1.44 g of the desired product (hereinafter referred to as compound (4a)) represented by the following formula (4a) was obtained. Yield 22%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.60 (1H, d, J = 7.5 Hz, Ar—H), 7.50 (1H, d, J = 7.5 Hz, Ar—H), 7. 34 (1H, t, J = 7.5 Hz, Ar-H), 3.45-3.35 (1H, m, C (O) CH), 3.23-3.14 (1H, m, ArCH) , 2.78-2.63 (2H, m, ArCH 2), 2.10-1.58 (8H, m, (CH 2) 4), 1.32 (3H, d, J = 7.3Hz, CH ₃ ) ppm

[Comparative Example 2-2]
In a 50 mL reactor that was sufficiently dried and purged with argon, 1.44 g (6.73 mmol) of the compound (4a) obtained in Comparative Example 2-1, 8 mL of tetrahydrofuran, and 4 mL of methanol were charged and stirred. The solution was cooled to 0 ° C., 0.87 g (23 mmol) of sodium hydroborate was slowly added little by little, and the mixture was stirred at room temperature for 2 hours. This solution was cooled to 0 ° C., 1.0 M hydrochloric acid aqueous solution was slowly added, and the soluble portion was extracted with ethyl acetate. The obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 20 mL of toluene and 40 mg (0.21 mmol) of p-toluenesulfonic acid monohydrate were added to the residue obtained by distilling the filtrate, and the mixture was heated to reflux for 1 hour in an oil bath. . After the reaction solution was cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 1.07 g (the compound (4b)) of the desired product represented by the following formula (4b) was obtained. Yield 80%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.19 (1H, t, J = 7.6 Hz, Ar—H), 7.09 (1H, d, J = 7.6 Hz, Ar—H), 7. 02 (1H, d, J = 7.6 Hz, Ar—H), 6.49-6.48 (1H, m, Ar—CH═C), 3.28 (2H, s, Ar—CH ₂ —C) ), 3.21-3.09 (1H, m, Ar-CH), 2.16 (3H, s, CH 3), 2.09-2.02 (2H, m, CH 2), 1.86 −1.60 (6H, m, CH ₂ ) ppm

[Comparative Example 2-3]
In a 30 mL reactor sufficiently dried and purged with argon, 0.67 g (3.4 mmol) of the compound (4b) obtained in Comparative Example 2-2 and 8 mL of tetrahydrofuran were charged and stirred. The solution was cooled to −78 ° C., and 2.1 mL of n-butyllithium solution (hexane solution, 1.60 M, 3.4 mmol) was added to the solution, followed by stirring at room temperature for 2 hours. This solution was mixed with 0.43 mL (4.0 mmol) of 1,3-dimethyl-2-imidazolidinone, chlorodimethyl (2,3,4,5-tetramethyl-2,4-cyclopentadiene-purchased from Aldrich). To a diluted solution of 1-yl) silane (0.89 mL, 4.0 mmol) in tetrahydrofuran (8 mL) was slowly added while cooling at −78 ° C., and the mixture was stirred at room temperature for 19 hours. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 0.57 g of the desired product (hereinafter referred to as compound (4c)) represented by the following formula (4c) was obtained. Yield 45%) as an isomer mixture.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.25-7.02 (3H, m, Ar—H), 6.74 (1H, s, Ar—CH═C), 3.87 (3H, s, _{-OCH 3), 3.63 (1H,} s, Si-CH), 3.30-3.23 (2H, m, Ar-CH, Si-CH), 2.25-1.70 (23H, m _{, (CH 2) 4, C} -CH 3), - 0.31 (3H, s, Si-CH 3), - 0.36 (3H, s, Si-CH 3) ppm

[Comparative Example 2-4]
In a 30 mL reactor sufficiently dried and purged with argon, 0.19 g (0.50 mmol) of the compound (4c) obtained in Comparative Example 2-3, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. To this solution, 0.69 mL of n-butyllithium solution (hexane solution, 1.60 M, 1.1 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.12 g (0.50 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After the solvent of the reaction solution was distilled off, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, the components precipitated by adding n-hexane were collected with a glass filter and dried under reduced pressure to give a yellow powdery compound represented by the following formula (4) (hereinafter referred to as metallocene compound). 0.13 g (yield 48%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.41 (1H, d, J = 8.4 Hz, Ar—H), 7.15 (1H, d, J = 7.1 Hz, Ar—H), 7. 00 (1H, s, Ar-H), 6.93 (1H, dd, J = 8.4 and 7.1 Hz, Ar-H), 3, 33-3.21 (1H, m, Ar-CH), 2 .32 (3H, s, Ar- CH 3), 2.16-2.07 (5H, m, CH 2, Ar-CH 3), 1.97-1.62 (15H, m, CH 2, Ar _{-CH 3), 1.18 (3H,} s, Si-CH 3), 1.09 (3H, s, Si-CH 3) ppm
FD-mass spectrometry (M ⁺ ): 536

[Comparative Example 3]
[Comparative Example 3-1]
In a 100 mL reactor thoroughly dried and purged with argon, Organometallics 2006, 25, 1217. 4.Bromo-2-methyl-1-indanone 3.60 g (16.0 mmol), 2- (1-cyclohexenyl) -4,4,5,5-tetramethyl-1,3, synthesized by the method described 2-dioxaborolane 5.00 g (24.0 mmol), tripotassium phosphate 6.79 g (32.0 mmol), palladium acetate 0.37 g (0.16 mmol), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos) 0.13 g (0.32 mmol), tetrahydrofuran 30 mL, and distilled water 7.5 mL were charged and heated under reflux in an oil bath for 11 hours. After cooling the reaction solution to room temperature, insoluble components were filtered through celite and washed thoroughly with dichloromethane. A saturated aqueous ammonium chloride solution was added, and the soluble portion was extracted with dichloromethane. The obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate is purified by silica gel column chromatography to quantitatively obtain the desired product (hereinafter referred to as compound (5a)) represented by the following formula (5a). It was.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.64 (1H, dd, J = 7.5 and 1.3 Hz, Ar—H), 7.42 (1 H, dd, J = 7.5 and 1.3 Hz, Ar—H) ), 7.33 (1H, t, J = 7.5 Hz, Ar-H), 5.83-5.80 (1H, m, Ar-C = CH), 3.46-3.36 (1H, _{m, CH-CH 3),} 2.75-2.64 (2H, m, Ar-CH 2 -C), 2.34-1.58 (8H, m, (CH 2) 2), 1.31 (3H, d, J = 7.3 Hz, CH—CH ₃ ) ppm

[Comparative Example 3-2]
In a 100 mL reactor sufficiently dried and purged with argon, 2.27 g (10.0 mmol) of the compound (5a) obtained in Comparative Example 3-1, 10 mL of tetrahydrofuran and 5 mL of methanol were charged and stirred. This solution was cooled to 0 ° C., 0.40 g (11 mmol) of sodium hydroborate was slowly added little by little, and the mixture was stirred at room temperature for 3 hours. This solution was cooled to 0 ° C., 1.0 M hydrochloric acid aqueous solution was slowly added, and the soluble portion was extracted with ethyl acetate. The obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 20 mL of toluene and 40 mg (0.20 mmol) of p-toluenesulfonic acid monohydrate were added to the residue obtained by distilling the filtrate, and the mixture was heated to reflux for 1 hour in an oil bath. . After the reaction solution was cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 1.40 g (the compound (5b)) of the desired product represented by the following formula (5b) was obtained. Yield 66%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.21-7.10 (2H, m, Ar—H), 6.98-6.94 (1H, m, Ar—H), 6.48-6. 46 (1H, m, Ar- CH = C), 5.89-5.86 (1H, m, Ar-C = CH), 3.32 (2H, s, Ar-CH 2 -C), 2. _{37-2.19 (4H, m, CH 2} -C = C-CH 2), 2.14 (3H, s, CH 3), 1.82-1.65 (4H, m, (CH 2) 2 ) Ppm

[Comparative Example 3-3]
In a 30 mL reactor sufficiently dried and purged with argon, 0.42 g (2.0 mmol) of the compound (5b) obtained in Comparative Example 3-2 and 4 mL of tetrahydrofuran were charged and stirred. The solution was cooled to −78 ° C., and 1.2 mL of n-butyllithium solution (hexane solution, 1.63 M, 2.0 mmol) was added to the solution and stirred at room temperature for 3 hours. This solution was mixed with 0.18 mL (2.4 mmol) of 1,3-dimethyl-2-imidazolidinone and chlorodimethyl (2,3,4,5-tetramethyl-2,4-cyclopentadiene-purchased from Aldrich). To a diluted solution of 1-yl) silane (0.53 mL, 2.4 mmol) in tetrahydrofuran (4 mL) was slowly added while cooling at −78 ° C., and the mixture was stirred at room temperature for 18 hours. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 0.46 g (the compound (5c)) of the desired product represented by the following formula (5c) was obtained. (Yield 58%) as an isomer mixture.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.04-7.02 (2H, m, Ar—H), 6.73 (1H, s, Ar—CH═C), 5.81 (1H, s, Ar-C = CH), 3.64 (1H, s, Si-CH), 3.23 (1H, s, Si-CH), 2.33-1.71 (23H, m, (CH 2) 4 _{, C-CH 3), -} 0.30 (3H, s, Si-CH 3), - 0.34 (3H, s, Si-CH 3) ppm

[Comparative Example 3-4]
In a 50 mL reactor that was sufficiently dried and purged with argon, 0.19 g (0.50 mmol) of the compound (5c) obtained in Comparative Example 3-3, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. To this solution, 0.67 mL of n-butyllithium solution (hexane solution, 1.63 M, 1.1 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.12 g (0.50 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 18 hours. After the solvent of the reaction solution was distilled off, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, the components precipitated by adding n-hexane were collected with a glass filter and dried under reduced pressure to give a yellow powdery compound represented by the following formula (5) (hereinafter referred to as metallocene compound). 0.14 g (yield 50%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.43 (1H, d, J = 8.7 Hz, Ar—H), 7.13 (1H, d, J = 7.0 Hz, Ar—H), 7. 04 (1H, s, Ar-H), 6.93 (1H, dd, J = 8.7 and 7.0 Hz, Ar-H), 6.12-6.09 (1H, m, Ar-C = CH) , 2.62-2.23 (7H, m, CH 2 -C = C-CH 2, Ar-CH 3), 2.07 (3H, s, Ar-CH 3), 1.98 (3H, s _{, Ar-CH 3), 1.89} (3H, s, Ar-CH 3), 1.88 (3H, s, Ar-CH 3), 1.84-1.65 (4H, m, CH 2) , 1.18 (3H, s, Si -CH 3), 1.09 (3H, s, Si-CH 3) ppm
FD-mass spectrometry (M ⁺ ): 548

[Comparative Example 4]
[Comparative Example 4-1]
In a 100 mL reactor thoroughly dried and purged with argon, Organometallics 2006, 25, 1217. 1.04 g (5.02 mmol) of 2-methyl-4-phenylindene synthesized by the method described above and 15 mL of tetrahydrofuran were charged and stirred. The solution was cooled to 0 ° C., and 3.20 mL of n-butyllithium solution (hexane solution, 1.60 M, 5.12 mmol) was added to the solution and stirred at room temperature for 3 hours. This solution was added to a dilute solution of 1.20 mL (5.43 mmol) of chlorodimethyl (2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl) silane purchased from Aldrich, in 8 mL of tetrahydrofuran. The mixture was slowly added with cooling at −78 ° C., and stirred at room temperature for 16 hours. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 0.65 g of the desired product (hereinafter referred to as the compound (6a)) represented by the following formula (6a) was obtained. (Yield 34%) as an isomer mixture.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.57-7.11 (8H, m, Ar—H), 6.79-6.67 (1H, m, Ar—CH═C), 3.78- 3.17 (2H, m, CH- Si-CH), 2.26-2.18 (3H, m, C-CH 3), 2.02 (3H, s, C-CH 3), 1.99 (3H, s, C-CH 3), 1.89 (6H, s, C-CH 3), - 0.25 (3H, s, Si-CH 3), - 0.29 (3H, s, Si -CH ₃₎ ppm

[Comparative Example 4-2]
In a 100 mL reactor sufficiently dried and purged with argon, 0.19 g (0.50 mmol) of the compound (6a) obtained in Comparative Example 4-1, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. The solution was cooled to 0 ° C., 0.63 mL of n-butyllithium solution (hexane solution, 1.60 M, 1.01 mmol) was added, and stirring was continued in an oil bath at 40 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.12 g (0.50 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 18 hours. After the solvent of the reaction solution was distilled off, 10 mL of dichloromethane was added to the resulting solid to prepare a suspension, and insoluble matter was removed with Celite on a glass filter. After concentrating the obtained solution under reduced pressure, a suspension was prepared by adding 5 mL of n-hexane, insoluble matters were filtered off with a glass filter, and the residue was dried under reduced pressure, thereby obtaining the following formula (6). 0.17 g (yield 63%) of the yellow powdery compound shown (hereinafter referred to as metallocene compound (6)) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.72-7.63 (2H, m, Ar—H), 7.56 (1H, d, J = 8.7 Hz, Ar—H), 7.51- 7.27 (4H, m, Ar- H), 7.10-7.00 (2H, m, Ar-H), 2.29 (3H, s, Ar-CH 3), 2.09 (3H, _{s, Ar-CH 3),} 2.00 (3H, s, Ar-CH 3), 1.93 (3H, s, Ar-CH 3), 1.90 (3H, s, Ar-CH 3), 1.22 (3H, s, Si- CH 3), 1.11 (3H, s, Si-CH 3) ppm
FD-mass spectrometry (M ⁺ ): 544

[Comparative Example 5]
[Comparative Example 5-1]
In a 100 mL reactor sufficiently dried and purged with argon, 1.00 g (5.56 mmol) of a 2-methyl-benzo [e] indene isomer mixture purchased from Tokyo Chemical Industry and 15 mL of tetrahydrofuran were charged and stirred. The solution was cooled to 0 ° C., and 3.50 mL of n-butyllithium solution (hexane solution, 1.60 M, 5.60 mmol) was added to the solution and stirred at room temperature for 3 hours. This solution was added to a diluted solution of chlorodimethyl (2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl) silane (1.20 mL, 5.43 mmol) purchased from Aldrich in 10 mL of tetrahydrofuran. The mixture was slowly added with cooling at −78 ° C., and stirred at room temperature for 15 hours. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 1.13 g (the compound (7a)) of the desired product represented by the following formula (7a) was obtained. Yield 57%) as an isomer mixture.
¹ H NMR (270 MHz, CDCl ₃ ) δ 8.20-6.56 (7H, m, Ar—H and Ar—CH═C), 3.94-3.20 (2H, m, CH—Si—CH) ), 2.42-2.21 (3H, m, C-CH 3), 2.11-1.67 (12H, s, C-CH 3), - 0.29 (3H, s, Si-CH _{3), - 0.35 (3H,} s, Si-CH 3) ppm

[Comparative Example 5-2]
In a 100 mL reactor that had been sufficiently dried and purged with argon, 0.18 g (0.51 mmol) of the compound (7a) obtained in Comparative Example 5-1, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. The solution was cooled to 0 ° C., 0.63 mL of n-butyllithium solution (hexane solution, 1.60 M, 1.01 mmol) was added, and stirring was continued in an oil bath at 40 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.12 g (0.50 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 18 hours. After the solvent of the reaction solution was distilled off, 10 mL of dichloromethane was added to the resulting solid to prepare a suspension, and insoluble matter was removed with Celite on a glass filter. After concentrating the obtained solution under reduced pressure, a suspension is prepared by adding 5 mL of n-hexane, insoluble matter is separated by filtration with a glass filter, and the residue is dried under reduced pressure to obtain the following formula (7). As a result, 0.09 g (yield 34%) of a yellow powdery compound (hereinafter referred to as metallocene compound (7)) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 8.11 (1H, d, J = 8.0 Hz, Ar—H), 7.75 (1H, d, J = 8.1 Hz, Ar—H), 7. 60 (1H, dt, J = 7.5 and 1.3 Hz, Ar-H), 7.55-7.43 (2H, m, Ar-H), 7.41 (1H, s, Ar-H), 7 .28 (1H, d, J = 9.5 Hz, Ar—H), 2.39 (3H, s, Ar—CH ₃ ), 2.10 (3H, s, Ar—CH ₃ ), 1.96 ( _{3H, s, Ar-CH 3} ), 1.93 (3H, s, Ar-CH 3), 1.81 (3H, s, Ar-CH 3), 1.22 (3H, s, Si-CH 3 ), 1.11 (3H, s, Si-CH 3) ppm
FD-mass spectrometry (M ⁺ ): 518

[Comparative Example 6]
[Comparative Example 6-1]
1.27 g (4) of 4- (3,5-di-tert-butylphenyl) -2-methylindene synthesized by the method described in JP-T-2004-502699 in a 30 mL reactor thoroughly dried and purged with argon 0.000 mmol) and 8 mL of tetrahydrofuran were charged and stirred. The solution was cooled to −78 ° C., 2.5 mL of n-butyllithium solution (hexane solution, 1.60 M, 4.0 mmol) was added to the solution, and the mixture was stirred at room temperature for 2 hours. This solution was mixed with 0.35-mL (4.8 mmol) of 1,3-dimethyl-2-imidazolidinone, chlorodimethyl (2,3,4,5-tetramethyl-2,4-cyclopentadiene-purchased from Aldrich). To a diluted solution of 1-yl) silane (1.1 mL, 4.8 mmol) in tetrahydrofuran (8 mL) was slowly added while cooling at −78 ° C., and the mixture was stirred at room temperature for 16 hours. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, n-hexane was added to the residue obtained by distilling the filtrate, and the deposited components were recovered and dried under reduced pressure to obtain the target compound represented by the following formula (8a) (hereinafter referred to as compound (8a). )) Was obtained as 0.64 g (yield 32%) of the isomer mixture.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.41-7.37 (4H, m, Ar—H), 7.28 (1H, s, Ar—H), 7.15 (1H, t, J = 7.6 Hz, Ar—H), 6.76 (1H, s, Ar—CH═C), 3.70 (1H, s, Si—CH), 3.26 (1H, s, Si—CH), 2.24 (3H, s, C- CH 3), 2.02 (3H, s, C-CH 3), 1.99 (3H, s, C-CH 3), 1.85 (6H, s, _{C-CH 3), 1.38 (} 18H, s, -C (CH 3) 3), - 0.25 (3H, s, Si-CH 3), - 0.28 (3H, s, Si-CH ₃ ) ppm

[Comparative Example 6-2]
In a 50 mL reactor that had been thoroughly dried and purged with argon, 0.25 g (0.50 mmol) of the compound (8a) obtained in Comparative Example 6-1, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. To this solution, 0.69 mL of n-butyllithium solution (hexane solution, 1.60 M, 1.1 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.12 g (0.50 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 18 hours. After the solvent of the reaction solution was distilled off, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, the components precipitated by adding n-hexane were collected with a glass filter and dried under reduced pressure to give a yellow powdery compound represented by the following formula (8) (hereinafter referred to as metallocene compound). 0.14 g (42% yield) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.57-7.54 (3H, m, Ar—H), 7.44 (1H, t, J = 1.8 Hz, Ar—H), 7.35— 7.32 (1H, m, Ar- H), 7.08-7.02 (2H, m, Ar-H), 2.29 (3H, s, Ar-CH 3), 2.09 (3H, _{s, Ar-CH 3),} 2.01 (3H, s, Ar-CH 3), 1.94 (3H, s, Ar-CH 3), 1.92 (3H, s, Ar-CH 3), 1.38 (18H, s, -C ( CH 3) 3), 1.22 (3H, s, Si-CH 3), 1.10 (3H, s, Si-CH 3) ppm
FD-mass spectrometry (M ⁺ ): 656

[Comparative Example 7]
[Comparative Example 7-1]
0.69 g of 4- (3,5-bis (trifluoromethyl) phenyl) -2-methylindene synthesized by the method described in JP-T-2004-502699 was placed in a 30 mL reactor sufficiently dried and purged with argon. 2.0 mmol) and 4 mL of tetrahydrofuran were charged and stirred. The solution was cooled to −78 ° C., and 1.3 mL of n-butyllithium solution (hexane solution, 1.55 M, 2.0 mmol) was added to the solution and stirred at room temperature for 2 hours. This solution was mixed with 0.18 mL (2.4 mmol) of 1,3-dimethyl-2-imidazolidinone and chlorodimethyl (2,3,4,5-tetramethyl-2,4-cyclopentadiene-purchased from Aldrich). To a diluted solution of 1-yl) silane (0.53 mL, 2.4 mmol) in tetrahydrofuran (4 mL) was slowly added while cooling at −78 ° C., and the mixture was stirred at room temperature for 18 hours. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 0.37 g of the desired product (hereinafter referred to as the compound (9a)) represented by the following formula (9a) was obtained. (Yield 36%) as an isomer mixture.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.95 (2H, s, Ar—H), 7.85 (1H, s, Ar—H), 7.45 (1H, d, J = 7.6 Hz, Ar-H), 7.22-19 (2H, m, Ar-H), 6.62 (1H, s, Ar-CH = C), 3.73 (1H, s, Si-CH), 3. 23 (1H, s, Si- CH), 2.25-1.82 (15H, m, C-CH 3), - 0.22 (3H, s, Si-CH 3), - 0.28 (3H _{, s, Si-CH 3)} ppm

[Comparative Example 7-2]
In a 50 mL reactor sufficiently dried and purged with argon, 0.37 g (0.72 mmol) of the compound (9a) obtained in Comparative Example 7-1, 10 mL of toluene, and 0.13 mL of tetrahydrofuran were charged and stirred. To this solution, 1.02 mL of n-butyllithium solution (hexane solution, 1.55 M, 1.58 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.17 g (0.72 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 18 hours. After the solvent of the reaction solution was distilled off, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, the components deposited by adding n-hexane were collected with a glass filter and dried under reduced pressure to give a yellow powdery compound represented by the following formula (9) (hereinafter referred to as metallocene compound). 0.23 g (yield 47%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 8.14 (2H, s, Ar—H), 7.88 (1H, s, Ar—H), 7.66 (1H, d, J = 8.8 Hz, Ar-H), 7.33 (1H, d, J = 7.0 Hz, Ar-H), 7.08 (1H, dd, J = 8.8 and 7.0 Hz, Ar-H), 6.89 (1H) , s, Ar-H), 2.33 (3H, s, Ar-CH 3), 2.10 (3H, s, Ar-CH 3), 2.01 (3H, s, Ar-CH 3), 1.92 (3H, s, Ar- CH 3), 1.91 (3H, s, Ar-CH 3), 1.24 (3H, s, Si-CH 3), 1.13 (3H, s, Si-CH ₃₎ ppm
FD-mass spectrometry (M ⁺ ): 680

[Comparative Example 8]
[Comparative Example 8-1]
Organometallics 2006, 25, 1217. In a 200 mL reactor thoroughly dried and purged with argon. 2.70 g (12.0 mmol) of 4-bromo-2-methyl-1-indanone synthesized by the method described, 2.19 g (14.4 mmol) of 4-methoxyphenylboronic acid, 6.14 g of tripotassium phosphate (28 0.9 mmol), 0.03 g (0.13 mmol) of palladium acetate, 0.08 g (0.18 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos), 30 mL of tetrahydrofuran, and 6 mL of distilled water. The mixture was heated and refluxed for 2 hours in an oil bath. After the reaction solution was cooled to room temperature, a saturated aqueous ammonium chloride solution was added, the soluble component was extracted with ethyl acetate, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 2.93 g of the desired product (hereinafter referred to as compound (10a)) represented by the following formula (10a) was obtained. Yield 97%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.74 (1H, dd, J = 7.5 and 1.2 Hz, Ar—H), 7.58 (1 H, dd, J = 7.5 and 1.2 Hz, Ar—H) ), 7.49-7.35 (3H, m, Ar-H), 7.06-6.96 (2H, m, Ar-H), 3.87 (3H, s, -OCH 3), 3 .50-3.34 (1H, m, CH—CH ₃ ), 2.84-2.62 (2H, m, Ar—CH ₂ —C), 1.31 (3H, d, J = 7.3 Hz) , CH-CH ₃₎ ppm

[Comparative Example 8-2]
In a sufficiently dry, argon-substituted 200 mL reactor, 2.93 g (11.6 mmol) of the compound (10a) obtained in Comparative Example 8-1, 15 mL of tetrahydrofuran, and 5 mL of methanol were charged and stirred. The solution was cooled to 0 ° C., 0.88 g (23.4 mmol) of sodium hydroborate was slowly added little by little, and the mixture was stirred at room temperature for 1 hour. This solution was cooled to 0 ° C., 1.0 M hydrochloric acid aqueous solution was slowly added, and the soluble portion was extracted with ethyl acetate. The obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 20 mL of toluene and 0.06 g (0.30 mmol) of p-toluenesulfonic acid monohydrate were added to the residue obtained by distilling the filtrate, and heated in an oil bath for 1 hour. Refluxed. After the reaction solution was cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled off to obtain 2.65 g (yield 97%) of the desired product (hereinafter referred to as compound (10b)) represented by the following formula 10b).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.52-7.40 (2H, m, Ar—H), 7.34-7.06 (3H, m, Ar—H), 7.03-6. 93 (2H, m, Ar- H), 6.52 (1H, dd, J = 3.0and1.5Hz, Ar-CH = C), 3.85 (3H, s, -OCH 3), 3.36 (2H, s, Ar-CH 2 -C), 2.13 (3H, s, CH-CH 3) ppm

[Comparative Example 8-3]
In a 100 mL reactor sufficiently dried and purged with argon, 0.71 g (3.01 mmol) of the compound (10b) obtained in Comparative Example 8-2 and 15 mL of tetrahydrofuran were charged and stirred. The solution was cooled to −78 ° C., 1.90 mL of n-butyllithium solution (hexane solution, 1.63 M, 3.10 mmol) was added to the solution, and the mixture was stirred at room temperature for 2 hours. To this solution, 0.30 mL (3.19 mmol) of 1,3-dimethyl-2-imidazolidinone was added, cooled to −20 ° C., and chlorodimethyl (2,3,4,5-tetrahydrofuran purchased from Aldrich). 0.67 mL (3.03 mmol) of methyl-2,4-cyclopentadien-1-yl) silane was added, and the mixture was stirred at room temperature for 16 hours. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography. As a result, 1.03 g (the compound (10c)) of the target compound represented by the following formula (10c) was obtained. (Yield 83%) as an isomer mixture.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.54-6.93 (7H, m, Ar—H), 6.80-6.70 (1H, m, Ar—CH═C), 3.87 ( _{3H, s, -OCH 3),} 3.74-3.12 (2H, m, CH-Si-CH), 2.32-1.64 (15H, m, C-CH 3), - 0.26 (3H, s, Si-CH 3), - 0.29 (3H, s, Si-CH 3) ppm

[Comparative Example 8-4]
In a 100 mL reactor sufficiently dried and purged with argon, 0.21 g (0.50 mmol) of the compound (10c) obtained in Comparative Example 8-3, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. To this solution, 0.65 mL of n-butyllithium solution (hexane solution, 1.63 M, 1.06 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.12 g (0.51 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 18 hours. After the solvent of the reaction solution was distilled off, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, a suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure. 0.19 g (yield 65%) of a yellow powdery compound (hereinafter referred to as metallocene compound (10)) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.66-7.58 (2H, m, Ar—H), 7.53 (1H, d, J = 8.7 Hz, Ar—H), 7.26 ( 1H, dd, J = 7.0and0.8Hz, Ar-H), 7.08-6.94 (4H, m, Ar-H), 3.85 (3H, s, -OCH 3), 2.29 (3H, s, Ar-CH 3), 2.09 (3H, s, Ar-CH 3), 2.00 (3H, s, Ar-CH 3), 1.92 (3H, s, Ar-CH _{3), 1.90 (3H, s} , Ar-CH 3), 1.22 (3H, s, Si-CH 3), 1.11 (3H, s, Si-CH 3) ppm
FD-mass spectrometry (M ⁺ ): 574

[Comparative Example 9]
[Comparative Example 9-1]
In a 30 mL reactor thoroughly dried and purged with argon, Organometallics 2006, 25, 1217. 4- (4- (N, N-dimethylamino) phenyl) -2-methylindene (0.50 g, 2.0 mmol) synthesized by the method described above and 4 mL of tetrahydrofuran were charged and stirred. The solution was cooled to −78 ° C., and 1.4 mL of n-butyllithium solution (hexane solution, 1.63 M, 2.2 mmol) was added to the solution and stirred at room temperature for 2 hours. This solution was mixed with 0.18 mL (2.4 mmol) of 1,3-dimethyl-2-imidazolidinone and chlorodimethyl (2,3,4,5-tetramethyl-2,4-cyclopentadiene-purchased from Aldrich). To a diluted solution of 1-yl) silane (0.53 mL, 2.4 mmol) in tetrahydrofuran (4 mL) was slowly added while cooling at −78 ° C., and the mixture was stirred at room temperature for 18 hours. A saturated aqueous ammonium chloride solution was added, the soluble component was extracted with n-hexane, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtration of magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography, and the target product (hereinafter referred to as compound (11a)) represented by the following formula (11a) was obtained as an isomer mixture. Obtained quantitatively.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.45-7.42 (2H, m, Ar—H), 7.42-7.09 (3H, m, Ar—H), 6.85-6. 80 (3H, m, Ar-H, Ar-CH = C), 3.69 (1H, s, Si-CH), 3.26 (1H, s, Si-CH), 2.23-1.82 (15H, m, C-CH 3), - 0.27 (3H, s, Si-CH 3), - 0.30 (3H, s, Si-CH 3) ppm

[Comparative Example 9-2]
In a 50 mL reactor sufficiently dried and purged with argon, 0.21 g (0.50 mmol) of the compound (11a) obtained in Comparative Example 9-1, 10 mL of toluene, and 0.1 mL of tetrahydrofuran were charged and stirred. To this solution, 0.67 mL of n-butyllithium solution (hexane solution, 1.63 M, 1.1 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 ° C. for 3 hours. After the solvent of the reaction solution was distilled off, 10 mL of diethyl ether was added to the obtained solid. The solution was cooled to 0 ° C., 0.12 g (0.50 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 16 hours. After the solvent of the reaction solution was distilled off, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, the components deposited by adding n-hexane were collected with a glass filter and dried under reduced pressure, whereby an orange powdery compound represented by the following formula (11) (hereinafter metallocene compound) 91 mg (yield 31%) was obtained.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.61-7.47 (2H, m, Ar—H), 7.25 (1H, d, J = 4.3 Hz, Ar—H), 7.08— 6.99 (2H, m, Ar- H), 6.83 (2H, d, J = 8.6Hz, Ar-H), 2.99 (6H, s, -NCH 3), 2.29 (3H _{, s, Ar-CH 3)} , 2.09 (3H, s, Ar-CH 3), 2.00 (3H, s, Ar-CH 3), 1.92 (3H, s, Ar-CH 3) , 1.90 (3H, s, Ar -CH 3), 1.21 (3H, s, Si-CH 3), 1.10 (3H, s, Si-CH 3) ppm
FD-mass spectrometry (M ⁺ ): 587

Example 3
<(2) Preparation of solid carrier>
[Example 3-1]
Using a reactor equipped with a stirrer with an internal volume of 270 L, under a nitrogen atmosphere, silica gel (manufactured by Fuji Silysia Chemical Co., Ltd .: 50% cumulative volume distribution of laser light diffraction scattering method, particle size 70 μm, specific surface area 340 m ² / g, pore volume 10 kg of 1.3 cm ³ / g, dried at 250 ° C. for 10 hours) was suspended in 77 L of toluene, and then cooled to 0 to 5 ° C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atom) was added dropwise over 30 minutes. At this time, the system temperature was kept at 0 to 5 ° C.

Subsequently, after making it contact at 0-5 degreeC for 30 minutes, the system temperature was heated up to 95 degreeC over 1.5 hours, and it was made to contact at 95 degreeC continuously for 4 hours. Thereafter, the temperature was lowered to room temperature, the supernatant was removed by decantation, and further washed twice with toluene, and then a total amount of 115 liters of a solid support toluene slurry was prepared.
When a part of the obtained slurry component was collected and analyzed, the solid content concentration was 122.6 g / L.

<(3) Preparation of solid catalyst component for olefin polymerization>
[Example 3-2]
A reactor equipped with a stirrer with an internal volume of 200 mL sufficiently purged with nitrogen was charged with 30 mL of toluene and 8.2 mL of the solid carrier slurry obtained in Example 3-1 (solid content weight 1.0 g). Next, a toluene solution of the metallocene compound 1 (0.025 mmol) obtained in Example 1 was added and contacted at a system temperature of 20 to 25 ° C. for 1 hour. The supernatant was removed by decantation, and heptane was further removed. After being used and washed twice, a total amount of 50 ml of the solid catalyst component for olefin polymerization (1) slurry was prepared.

Example 4
A solid catalyst component (2) slurry for olefin polymerization was prepared in the same manner as in Example 3, except that the metallocene compound 2 obtained in Example 2 was used.

[Comparative Example 10]
A solid catalyst component (3) slurry for olefin polymerization was prepared in the same manner as in Example 3 except that the metallocene compound 3 obtained in Comparative Example 1 was used.

[Comparative Example 11]
A solid catalyst component (4) slurry for olefin polymerization was prepared in the same manner as in Example 3 except that the metallocene compound 4 obtained in Comparative Example 2 was used.

[Comparative Example 12]
A solid catalyst component (5) slurry for olefin polymerization was prepared in the same manner as in Example 3 except that the metallocene compound 5 obtained in Comparative Example 3 was used.

[Comparative Example 13]
A solid catalyst component (6) slurry for olefin polymerization was prepared in the same manner as in Example 3 except that the metallocene compound 6 obtained in Comparative Example 4 was used.

[Comparative Example 14]
A solid catalyst component for olefin polymerization (7) slurry was prepared in the same manner as in Example 3 except that the metallocene compound 7 obtained in Comparative Example 5 was used.

[Comparative Example 15]
A solid catalyst component (8) slurry for olefin polymerization was prepared in the same manner as in Example 3 except that the metallocene compound 8 obtained in Comparative Example 6 was used.

[Comparative Example 16]
A solid catalyst component (9) slurry for olefin polymerization was prepared in the same manner as in Example 3 except that the metallocene compound 9 obtained in Comparative Example 7 was used.

[Comparative Example 17]
A solid catalyst component (10) slurry for olefin polymerization was prepared in the same manner as in Example 3 except that the metallocene compound 10 obtained in Comparative Example 8 was used.

[Comparative Example 18]
A solid catalyst component (11) slurry for olefin polymerization was prepared in the same manner as in Example 3 except that the metallocene compound 11 obtained in Comparative Example 9 was used.

<(4) Olefin polymerization>
Example 5
500 mL of heptane was charged into a 1 L stainless steel autoclave sufficiently purged with nitrogen, and the system was substituted with ethylene. Then, 0.375 mmol of triisobutylaluminum, 10 mL of 1-hexene and the solid catalyst component (1) 20 mg was added, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the conditions of a total pressure of 0.8 MPaG and 80 ° C. The polymer was recovered by filtration and dried at 80 ° C. for 10 hours under reduced pressure to obtain 52.1 g of an ethylene polymer.
The analysis results of the obtained ethylene polymer are shown in [Table 9].

Example 6
An ethylene polymer was obtained in the same manner as in Example 5 except that the solid catalyst component (2) was used.
The analysis results of the obtained ethylene polymer are shown in [Table 9].

[Comparative Examples 19-27]
An ethylene polymer was obtained in the same manner as in Example 5 except that the solid catalyst components (3) to (11) obtained in Comparative Examples 10 to 18 were used as the solid catalyst component.
The yield and analysis results of the obtained ethylene polymer are shown in [Table 9].

  In Examples 5 and 6 using the metallocene compound (1) described in Example 1 and the metallocene compound (2) described in Example 2 within the scope of the present claims, good polymerization activity was exhibited, and A polymer having a high hexene content was obtained, and the resulting decrease in the density of the polymer was observed. On the other hand, in Comparative Examples 22 and 24 using the metallocene compound (6) described in Comparative Example 4 and (8) described in Comparative Example 6, good polymerization activity is exhibited, but the copolymerizability is the same as that of the present invention. Low compared to the case of using a metallocene compound. This suggests the necessity of an electron-donating substituent in order to exhibit the effects of the present invention.

  However, in Comparative Examples 26 and 27 using the metallocene compound (10) described in Comparative Example 8 and the metallocene compound ((11) described in Comparative Example 9 that do not have a specific substituent in the vicinity of the electron-donating substituent. Therefore, it was suggested that an electron donating substituent and a bulky substituent in the vicinity of the electron donating substituent are necessary to exert the effect of the present invention. This is because the effect suppresses the interaction between the co-catalyst such as an aluminum compound in the polymerization environment and the central metal of the transition metal compound and the electron-donating substituent by the steric effect of the bulky substituent, As a result, it is considered that only an electronic effect on the metal center appears.

  By using a catalyst for olefin polymerization containing a novel transition metal compound into which a specific substituent according to the present invention is introduced, when copolymerizing ethylene and α-olefin, molecular weight with good olefin polymerization activity And high comonomer content polyethylene can be produced with high productivity. The obtained polyolefin is excellent in impact resistance, light weight, transparency balance, and the like, and is expected to be applicable to various uses. Therefore, it can be said that the present invention has extremely high industrial value.

Claims (11)

A transition metal compound [A] represented by the following general formula (A-1).

(In general formula (A-1),
M represents a titanium atom, a zirconium atom, or a hafnium atom;
n represents the number of X, and the number is a value satisfying the valence of M of 1 to 4,
X is independently a hydrogen atom, halogen atom, hydrocarbon group, halogen-containing group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, boron-containing group, aluminum-containing group, or conjugated diene. A divalent derivative group, and when n is 2 or more, they may be bonded to each other to form a ring;
Q represents a divalent hydrocarbon group, a divalent silicon-containing group, or a divalent germanium-containing group;
R ^{1 to} R ⁶ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group. Which may be the same or different, of which adjacent substituents may be joined together to form a saturated ring,
R ^{a1 to} R ^a4 represent a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group ( Provided that R ^a2 and R ^a3 are not a hydrogen atom), these may be the same or different, and adjacent substituents may be bonded to each other to form a ring;
R ^a5 is a substituent represented by the following general formula (A-1a), or a heterocycle optionally having a 5-membered ring having a mother skeleton containing at least one element selected from nitrogen, oxygen, and sulfur. Showing the ring,
Z is a saturated or unsaturated divalent or trivalent hydrocarbon having 3 or 4 carbon atoms that forms a condensed ring which may have the same substituent as R ^{1 to} R ⁶ with respect to the carbon atom to which it is bonded. The substituents may be bonded to R ^a1 and R ^a4 to form a ring. )

(In General Formula (A-1a), Y represents an element selected from oxygen, nitrogen, and sulfur;
m is an integer of 1 to 2 that satisfies the valence of Y;
R ^b is a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a silicon-containing group, an ether bond-containing hydrocarbon group, or a tertiary amino group-containing hydrocarbon group, and is bonded to R ^a2 or R ^a3 to be substituted. A ring which may have a group may be formed,
When m is 2, they may be the same or different, and R ^b may be bonded to each other to form a ring that may have a substituent. ) The transition metal compound [A] according to claim 1, which is represented by the following general formula (A-2).

(In the general formula (A-2), M, X, n, Q, R ^{1 to} R ⁶ , and R ^{a1 to} R ^a5 are M, X, n, Q, and R ^{1 in the} general formula (A-1), respectively. ~ R ⁶ , R ^{a1 to} R ^a5 have the same meaning,
R ^{7 to} R ⁹ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group. These may be the same or different, and adjacent substituents may be bonded to each other to form a ring, and R ⁷ may be bonded to R ^a1 and R ^a4 to form a ring. Also good. ) The transition metal compound [A] according to claim 2, wherein in the general formula (A-2), R ^a5 is a substituent represented by the general formula (A-1a). In the general formula (A-2),
M is a zirconium atom or a hafnium atom,
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group,
The transition metal compound [A] according to claim 3, wherein Q is a divalent hydrocarbon group or a divalent silicon-containing group. In the general formula (A-2),
R ^{1 to} R ⁶ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group, which may be the same or different,
In general formula (A-1a),
The transition metal compound [A] according to claim 4, wherein Y is an element selected from oxygen and nitrogen. In the general formula (A-2),
Q is a divalent silicon-containing group,
R ^{1 to} R ⁴ are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, but not all are hydrogen at the same time,
R ⁵ and R ⁶ are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R ^{7 to} R ⁹ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an oxygen-containing group,
R ^a1 and R ^a4 are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group,
R ^a2 and R ^a3 are hydrocarbon groups having 1 to 40 carbon atoms or silicon-containing groups,
In general formula (A-1a),
R ^b is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may combine with at least one selected from R ^a2 and R ^a3 to form a saturated ring;
The transition metal compound [A] according to claim 5, wherein m is 2, and when R ^b is bonded to each other to form a ring, the transition metal compound [A] is a saturated ring. In the general formula (A-2),
R ^{1 to} R ⁵ , R ^a2 and R ^a3 are hydrocarbon groups having 1 to 10 carbon atoms,
R ⁶ , R ^a1 and R ^a4 are hydrogen atoms;
The transition metal compound [A] according to claim 6, wherein R ^a5 is an alkoxy group, a dialkylamino group or a pyrrolidinyl group.   An olefin polymerization catalyst comprising the transition metal compound [A] according to any one of claims 1 to 7.   Further, at least selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with a transition metal compound [A] to form an ion pair. The olefin polymerization catalyst according to claim 8, comprising one kind of compound [B].   A method for producing an olefin polymer, comprising a step of polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 8 or 9.   The method for producing an olefin polymer according to claim 10, wherein the polymerization of the olefin is homopolymerization of ethylene or copolymerization of ethylene and an α-olefin having 3 to 20 carbon atoms.