JP2006206630A - Ethylene-acenaphthylene random copolymer and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylene-acenaphthylene copolymer excellent in optical properties and its manufacturing method. <P>SOLUTION: The ethylene-acenaphthylene random copolymer is obtained by copolymerizing ethylene and an acenaphthylene derivative represented by formula [1] (wherein R<SP>1</SP>and R<SP>2</SP>are each a hydrogen atom or a 1-10C hydrocarbon group, and R<SP>3</SP>to R<SP>8</SP>are each a hydrogen atom, a halogen atom or a 1-10C hydrocarbon group), and the method for manufacturing the ethylene-acenaphthylene random copolymer comprises copolymerizing ethylene and the acenaphthylene derivative represented by formula [I] in the presence of a catalyst for polymerization obtained by bringing a component (A) of a metallocene compound component of a group 4 metal in the periodic table of elements, a component (B) of a specific organoaluminum compound component and/or a component (C) of a specific boron compound into contact with each other. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an ethylene-acenaphthylene random copolymer excellent in optical properties and a method for producing the same.

Conventionally, as a copolymer of ethylene and acenaphthylene, a graft copolymer produced by graft polymerization and a copolymer produced using a Ziegler-Natta catalyst are known.
For example, Non-Patent Document 1 describes an ethylene-acenaphthylene graft copolymer produced by melt-kneading polyethylene and acenaphthylene.
Patent Document 1 discloses an ethylene-acenaphthylene copolymer produced using a catalyst composed of titanium tetrachloride and an organoaluminum compound. Patent Document 2 discloses a catalyst composed of vanadium oxytrichloride and an organoaluminum compound. An ethylene-acenaphthylene copolymer produced using the above is described.

Mituo Akiyama, Senkiti Kawakubo, Mitiko Kondo, “Kinetic analysis of graft polymerization of acenaphthylene onto polyethylene by roll kneading and solution polymerization of acenaphthylene”, Review Of the Electrical Communication Laboratory (Japan), Nippon Telegraph and Telephone Public Corporation, 1964, Vol. 12, No. 11-12, pp. 693-706 Hungarian Patent No. 154798 US Pat. No. 4,093,678

However, the ethylene-acenaphthylene graft copolymer produced by melt-kneading polyethylene and acenaphthylene contains by-products generated by the decomposition reaction of the acenaphthylene graft chain during melt-kneading. There was a problem that the optical properties of the inferior were inferior.
In addition, the ethylene-acenaphthylene copolymer produced using a Ziegler-Natta catalyst contains a considerable amount of ethylene and acenaphthylene homopolymers according to the crystallinity by X-ray diffraction (XRD), There was a problem that optical properties such as transparency were inferior.
Under such circumstances, the problem to be solved by the present invention, that is, an object of the present invention is to provide an ethylene-acenaphthylene copolymer excellent in optical characteristics and a method for producing the same.

（ただし、Ｒ¹およびＲ²はそれぞれ独立に、水素原子または炭素原子数１〜１０の炭化水素基を表し、Ｒ³〜Ｒ⁸はそれぞれ独立に、水素原子、ハロゲン原子または炭素原子数１〜１０の炭化水素基を表す。） That is, the first of the present invention relates to an ethylene-acenaphthylene random copolymer obtained by copolymerizing ethylene and an acenaphthylene derivative represented by the following general formula [1].

(However, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ^{3 to} R ⁸ each independently represent a hydrogen atom, a halogen atom or 1 to 1 carbon atom. Represents 10 hydrocarbon groups.)

The second of the present invention is ethylene and acenaphthylene represented by the above general formula [1] in the presence of a polymerization catalyst obtained by contacting the following component (A), component (B) and / or component (C). The present invention relates to a method for producing an ethylene-acenaphthylene random copolymer in which a derivative is copolymerized.
Component (A): Metallocene compound of group 4 metal of the Periodic Table of Elements Component (B): One or more organoaluminum compounds selected from the group consisting of the following (B1) to (B3) (B1) General formula E ¹ _a Organoaluminum compound represented by AlZ _3-a (B2) General formula {-Al (E ² ) -O—} Cyclic aluminoxane represented by _b (B3) General formula E ³ {-Al (E ³ ) -O-} _c linear aluminoxane represented by AlE ³ ₂ (where E ¹ , E ² and E ³ are each a hydrocarbon group, and a plurality of E ¹ , a plurality of E ² and a plurality of E ³ are Z may be the same or different, Z represents a hydrogen atom or a halogen atom, and when there are a plurality of Z, the plurality of Z may be the same or different. 3 represents a number satisfying 3, b represents an integer of 2 or more, c is 1 or more It represents the number.)
Component (C): One or more boron compounds selected from the group consisting of the following (C1) to (C3) (C1) General formula BQ ¹ Q ² Q ³ Boron compound (C2) General formula G ⁺ ( Boron compound represented by BQ ¹ Q ² Q ³ Q ⁴ ) ^- (C3) General formula (L-H) ⁺ Boron compound represented by (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (B is 3 It represents a boron atom valent valence state, the Q ¹ to Q ⁴ each independently represents a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, Q ¹ to Q ⁴ good be different even in the same .G ⁺ represents an inorganic or organic cation, L represents a neutral Lewis base, represents the (L-H) ⁺ is a Bronsted acid.)

  ADVANTAGE OF THE INVENTION According to this invention, the ethylene-acenaphthylene random copolymer excellent in the optical characteristic and its manufacturing method are provided.

（ただし、Ｒ¹およびＲ²はそれぞれ独立に、水素原子または炭素原子数１〜１０の炭化水素基を表し、Ｒ³〜Ｒ⁸はそれぞれ独立に、水素原子、ハロゲン原子または炭素原子数１〜１０の炭化水素基を表す。） The ethylene-acenaphthylene random copolymer of the present invention is obtained by copolymerizing ethylene and an acenaphthylene derivative represented by the following general formula [1].

(However, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ^{3 to} R ⁸ each independently represent a hydrogen atom, a halogen atom or 1 to 1 carbon atom. Represents 10 hydrocarbon groups.)

In the general formula [1], R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group include an alkyl group. Examples of the alkyl group having 1 to 10 carbon atoms include a linear alkyl group such as a methyl group, an ethyl group, and an n-butyl group, an isopropyl group, Examples thereof include branched alkyl groups such as isobutyl group, tert-butyl group and neopentyl group, and cyclic alkyl groups such as cyclohexyl group and cyclooctyl group. R ¹ and R ² are preferably each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a linear unsubstituted alkyl group having 1 to 4 carbon atoms, More preferred is a hydrogen atom or a methyl group, and particularly preferred is a hydrogen atom.

In the general formula [1], R ^{3 to} R ⁸ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, Preferably they are a fluorine atom, a chlorine atom, or a bromine atom.

In the general formula [1], examples of the hydrocarbon group represented by R ^{3 to} R ⁸ include an alkyl group and an aryl group, and these include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonate group, a silyl group, It may be substituted with a cyano group or the like. Examples of the alkyl group used for the hydrocarbon group of R ^{3 to} R ⁸ include a linear alkyl group such as a methyl group, an ethyl group, and an n-butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, and a neopentyl group. And a branched alkyl group such as a cyclohexyl group and a cycloalkyl group such as a cyclooctyl group. Examples of the aryl group used for the hydrocarbon group of R ^{3 to} R ⁸ include a phenyl group, a tolyl group, and a mesityl group. R ^{3 to} R ⁸ are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom, a methyl group, or a phenyl group, and still more preferably. Is a hydrogen atom or a methyl group.

Two or more groups arbitrarily selected from R ^{3 to} R ⁸ may be bonded to each other, and in this case, two adjacent groups are bonded to each other to form an alicyclic structure or an aromatic ring structure. These ring structures may further have a substituent.

  In the ethylene-acenaphthylene random copolymer of the present invention, the copolymer composition of the structural unit derived from the acenaphthylene derivative is not particularly limited, but is usually 0.1 mol% or more and less than 50 mol% from the viewpoint of excellent optical characteristics. . Preferably they are 1 mol% or more and less than 50 mol%, More preferably, they are 4 mol% or more and less than 50 mol%.

In the ethylene-acenaphthylene random copolymer of the present invention, the copolymer composition of the structural unit derived from the acenaphthylene derivative represents mol% of the structural unit derived from the acenaphthylene derivative in the entire monomer constituting the copolymer. , 1,1,2,2-tetrachloroethane-d ₂ as a solvent and determined by a ¹³ C-NMR spectrum. Ratio of the area of peak (II) appearing at 28.0 to 31.0 ppm to the area of peak (I) appearing at 32.0 to 50.0 ppm in the ¹³ C-NMR spectrum of the copolymer of the present invention [100 (I ) / {(I) + (II)}] determines the copolymer composition.
In the ¹³ C-NMR spectrum of the copolymer of the present invention, when the peak position of 1,1,2,2-tetrachloroethane-d ₂ is 74.2 ppm, the peak appearing at 32.0-50.0 ppm (I ) Is attributed to a carbon atom derived from an acenaphthylene derivative separated by two or more methylene groups in the skeleton of the copolymer, and the peak (II) appearing at 28.0 to 31.0 ppm is the skeleton of the copolymer In the methylene group derived from ethylene.

  The melting point of the ethylene-acenaphthylene random copolymer of the present invention is measured by a differential scanning calorimeter (DSC). When the copolymer composition of the structural unit derived from the acenaphthylene derivative in the ethylene-acenaphthylene random copolymer is less than 14 mol%, the melting point is usually observed. The melting point of the ethylene-acenaphthylene random copolymer is not particularly limited, but is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower. Further, when the structural unit derived from the acenaphthylene derivative is 14 mol% or more, the melting point is not observed.

  The intrinsic viscosity [η] measured with a 135 ° C. tetralin solution of the ethylene-acenaphthylene random copolymer of the present invention is not particularly limited, but is preferably 0.1 from the viewpoint of excellent tensile strength and workability. It is-10.0 dl / g, More preferably, it is 0.2-8.0 dl / g, More preferably, it is 0.2-5.0 dl / g.

The ethylene-acenaphthylene random copolymer of the present invention comprises ethylene and the above general formula [A] in the presence of a polymerization catalyst obtained by contacting the following component (A), component (B) and / or component (C). 1] is produced by copolymerizing the acenaphthylene derivative represented by [1].
Component (A): Metallocene compound of group 4 metal of the Periodic Table of Elements Component (B): One or more organoaluminum compounds selected from the group consisting of the following (B1) to (B3) (B1) General formula E ¹ _a Organoaluminum compound represented by AlZ _3-a (B2) General formula {-Al (E ² ) -O—} Cyclic aluminoxane represented by _b (B3) General formula E ³ {-Al (E ³ ) -O-} _c linear aluminoxane represented by AlE ³ ₂ (where E ¹ , E ² and E ³ are each a hydrocarbon group, and a plurality of E ¹ , a plurality of E ² and a plurality of E ³ are Z may be the same or different, Z represents a hydrogen atom or a halogen atom, and when there are a plurality of Z, the plurality of Z may be the same or different. 3 represents a number satisfying 3, b represents an integer of 2 or more, c is 1 or more It represents the number.)
Component (C): One or more boron compounds selected from the group consisting of the following (C1) to (C3) (C1) General formula BQ ¹ Q ² Q ³ Boron compound (C2) General formula G ⁺ ( Boron compound represented by BQ ¹ Q ² Q ³ Q ⁴ ) ^- (C3) General formula (L-H) ⁺ Boron compound represented by (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (B is 3 It represents a boron atom valent valence state, the Q ¹ to Q ⁴ each independently represents a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, Q ¹ to Q ⁴ good be different even in the same .G ⁺ represents an inorganic or organic cation, L represents a neutral Lewis base, represents the (L-H) ⁺ is a Bronsted acid.)

[Component (A) Metallocene Compound]
The component (A) used in the present invention is a metallocene compound of a Group 4 metal of the Periodic Table of Elements (IUPAC 1989), preferably a metal atom selected from the group consisting of a titanium atom, a zirconium atom and a hafnium atom. And a half metallocene compound bonded to a group having one cyclopentadiene type anion skeleton or a metallocene compound bonded to a group having two cyclopentadiene type anion skeletons.

（上記一般式［２］〜［６］において、Ｍ¹〜Ｍ⁷はそれぞれ元素周期律表第４族の原子を表し、Ａ¹〜Ａ⁵およびＡ⁷はそれぞれ元素周期律表第１６族の原子を表し、Ｊ¹〜Ｊ⁶はそれぞれ元素周期律表第１４族の原子を表す。Ｔ⁶は元素周期律表第１５族の原子を表す。Ｃｐ¹〜Ｃｐ⁷はそれぞれ独立に、シクロペンタジエン形アニオン骨格を有する基を表す。Ｘ¹〜Ｘ⁴、Ｘ⁸〜Ｘ¹¹、Ｒ¹¹〜Ｒ¹⁶、Ｒ²¹〜Ｒ²⁶、Ｒ³¹〜Ｒ³⁶、Ｒ⁴¹〜Ｒ⁴⁶、Ｒ⁵¹〜Ｒ⁵⁶、Ｒ⁶¹〜Ｒ⁶³およびＲ⁷¹〜Ｒ⁷⁵はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、置換シリル基、炭化水素オキシ基、２置換アミノ基、炭化水素チオ基または炭化水素セレノ基を表し、Ｒ¹¹〜Ｒ¹⁶、Ｒ²¹〜Ｒ²⁶、Ｒ³¹〜Ｒ³⁶、Ｒ⁴¹〜Ｒ⁴⁶、Ｒ⁵¹〜Ｒ⁵⁶、Ｒ⁶¹〜Ｒ⁶³およびＲ⁷¹〜Ｒ⁷⁵はそれぞれ任意に結合して単環構造または多環構造を形成してもよい。該単環構造または多環構造は、芳香族環構造であっても、非芳香族環構造であってもよい。Ｘ⁵〜Ｘ⁷はそれぞれ元素周期律表第１６族の原子を表す。） As the half metallocene compound, a compound represented by any one of the following general formulas [2] to [6] is preferable.

(In the above general formulas [2] to [6], M ^{1 to} M ⁷ each represent an atom of Group 4 of the Periodic Table of Elements, and A ^{1 to} A ⁵ and A ⁷ each represent Group 16 of the Periodic Table of Elements. J ^{1 to} J ⁶ each represent an atom of Group 14 of the Periodic Table of Elements, T ⁶ represents an atom of Group 15 of the Periodic Table of Elements, and Cp ^{1 to} Cp ⁷ each independently represent cyclopentadiene. Represents a group having an anionic skeleton X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted silyl group, a hydrocarbon oxy group, a disubstituted amino group, a hydrocarbon thio group, or a hydrocarbon seleno group. the ^{stands, R 11 ~R 16, R 21} ~R 26, R 31 ~R 36, R 41 ~R 46, R 51 ~R 56, R 61 ~R 63 And R ⁷¹ to R ⁷⁵ each may be bonded to form a monocyclic structure or polycyclic structure optionally. The monocyclic structure or a polycyclic structure, be an aromatic ring structure, non-aromatic ring (The structure may also be used. X ^{5 to} X ⁷ each represent an atom of Group 16 of the Periodic Table of Elements.)

In the general formulas [2] to [6], M ^{1 to} M ⁷ are atoms of Group 4 of the periodic table, and examples thereof include a titanium atom, a zirconium atom, and a hafnium atom. M ^{1 to} M ⁷ are preferably titanium atoms or zirconium atoms.

In the general formulas [2] to [6], examples of the group 16 atom of the periodic table of the elements represented by A ^{1 to} A ⁵ and A ⁷ include an oxygen atom, a sulfur atom, and a selenium atom. Preferably it is an oxygen atom.

In the general formulas [2] to [6], examples of the atoms belonging to Group 14 of the periodic table of the elements represented by J ^{1 to} J ⁶ include a carbon atom, a silicon atom, and a germanium atom. Preferably, they are a carbon atom or a silicon atom.

T ⁶ in the general formula [5] is an atom of Group 15 of the Periodic Table of Elements, and examples thereof include a nitrogen atom and a phosphorus atom, and preferably a nitrogen atom.

In the general formulas [2] to [5], Cp ^{1 to} Cp ⁶ are each independently a group having a cyclopentadiene-type anion skeleton, such as a (substituted) cyclopentadienyl group, a (substituted) indenyl group, ( Substituted) fluorenyl group and the like. Specifically, for example, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, ethylcyclopentadienyl group, n-propylcyclo Pentadienyl group, isopropylcyclopentadienyl group, n-butylcyclopentadienyl group, sec-butylcyclopentadienyl group, tert-butylcyclopentadienyl group, phenylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, tert -Butyldimethylsilylcyclopentadienyl group, indenyl group, methyl indenyl group, dimethyl indenyl group, n-propyl indenyl group, isopropyl indenyl group, n-butyl indenyl group, tert-butyl group Denyl group, phenylindenyl group, methylphenylindenyl group, naphthylindenyl group, trimethylsilylindenyl group, tetrahydroindenyl group, fluorenyl group, methylfluorenyl group, dimethylfluorenyl group, tert-butylfluorenyl Group, di-tert-butylfluorenyl group, phenylfluorenyl group, diphenylfluorenyl group, trimethylsilylfluorenyl group, bistrimethylsilylfluorenyl group, etc., preferably cyclopentadienyl group, methyl A cyclopentadienyl group, an n-butylcyclopentadienyl group, a tert-butylcyclopentadienyl group, a tetramethylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, or a fluorenyl group.

In the general formula [2] ~ [5], Cp 1 ~Cp polydentate of η ⁶ is not particularly limited, it may be any possible values of Cp ¹ ~ CP ^6. For example, 5 seats, 4 seats, 3 seats, 2 seats and single seats are mentioned, preferably 5 seats, 3 seats or single seats, more preferably 5 seats or 3 seats.

In the general formula [6], Cp ⁷ is a group having a cyclopentadiene-type anion skeleton, and examples thereof include a (substituted) cyclopentadienyl group, a (substituted) indenyl group, and a (substituted) fluorenyl group. Specifically, for example, cyclopentadienyl group, methylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,3,4-trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group , Pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, n-propylcyclopentadienyl group, isopropylcyclopentadienyl group, n-butylcyclopentadienyl group, sec-butylcyclopentadienyl group, tert- Butylcyclopentadienyl group, phenylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, tert-butyldimethylsilylcyclopentadienyl group, indenyl group, methylindenyl group, dimethylindenyl group, n-propylindenyl group, isopropyl Ndenyl group, n-butyl indenyl group, tert-butyl indenyl group, phenyl indenyl group, methyl phenyl indenyl group, naphthyl indenyl group, trimethylsilyl indenyl group, tetrahydroindenyl group, fluorenyl group, methyl fluorenyl Group, dimethylfluorenyl group, tert-butylfluorenyl group, di-tert-butylfluorenyl group, phenylfluorenyl group, diphenylfluorenyl group, trimethylsilylfluorenyl group, bistrimethylsilylfluorenyl group Preferably, cyclopentadienyl group, methylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, tert-butylcyclopentadienyl group, penta Methylcyclopentadienyl An indenyl group, tetrahydroindenyl group or a fluorenyl group.

In the general formula [6], the multidentate of η of Cp ⁷ is not particularly limited, may be any possible values of Cp ^7. For example, 5 seats, 4 seats, 3 seats, 2 seats and single seats are mentioned, preferably 5 seats, 3 seats or single seats, more preferably 5 seats or 3 seats.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] Examples of the halogen atom in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a chlorine atom or a bromine atom, more preferably It is a chlorine atom.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] Examples of the hydrocarbon group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include an alkyl group, an aralkyl group, and an aryl group.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] Examples of the alkyl group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Isobutyl, n-pentyl, neopentyl, tert-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl, n-eicosyl, cyclohexyl, cyclo An octyl group, a cyclodecyl group, a cyclododecyl group, etc. are mentioned.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorobutyl group. Examples thereof include a fluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group.
Any of the hydrogen atoms of these alkyl groups may be substituted with, for example, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, an aralkyloxy group such as a benzyloxy group, or the like.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] The alkyl group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, An isobutyl group or a tert-pentyl group.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] Examples of the aralkyl group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, and a (4-methylphenyl) methyl group. , (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4- (Dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6- Trimethylphenyl) methyl group, (3,4,5-trimethyl) Tilphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n- (Butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (N-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylme Group, anthracenylmethyl group and the like.
The hydrogen atoms of these aralkyl groups are, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, benzyloxy group May be substituted with an aralkyloxy group or the like.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] The aralkyl group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably a benzyl group.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] Examples of the aryl group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4- Xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group 2,3,4-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4, 6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, Tylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n- Examples include octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and the like.
The hydrogen atoms of these aryl groups are all halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms and iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, benzyloxy groups and the like. It may be substituted with an aralkyloxy group or the like.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] The aryl group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ⁵⁶ , the substituted silyl group in R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ is a silyl group substituted with a hydrocarbon group, and the hydrocarbon group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. A halogen atom, an methoxy group, an alkoxy group such as an ethoxy group, an aryloxy group such as a phenoxy group, an aralkyloxy group such as a benzyloxy group, and the like. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, and an n-hexyl group. And an alkyl group having 1 to 20 carbon atoms such as a cyclohexyl group and an aryl group such as a phenyl group.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] Examples of the substituted silyl group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include a monosubstituted silyl group having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group, phenylsilyl group, dimethylsilyl group, diethyl C2-C20 disubstituted silyl group such as silyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec -Butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclo Examples thereof include a hexylsilyl group and a triphenylsilyl group, and a trisubstituted silyl group having 3 to 20 carbon atoms is preferable, and a trimethylsilyl group, a tert-butyldimethylsilyl group, or a triphenylsilyl group is more preferable.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in general formulas [2] to [6] Examples of the hydrocarbon oxy group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include an alkoxy group, an aralkyloxy group, and an aryloxy group.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [4] to [6]. Examples of the alkoxy group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group. N-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecyloxy group, n-pentadecyloxy group, n-eicosyloxy group and the like.
These alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be substituted.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] The alkoxy group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ is, for example, preferably an alkoxy group having 1 to 20 carbon atoms, more preferably a methoxy group, an ethoxy group, an isopropoxy group or a tert-butoxy group. It is.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] Examples of the aralkyloxy group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, and (4-methylphenyl) Methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3, 4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3, 6-Trimethylpheny L) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4) , 5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (Ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (N-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, Fuchirumetokishi group, anthracenylmethoxy methoxy group and the like.
These aralkyloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ^56, the aralkyl group in R ⁶¹ to R ⁶³ and R ⁷¹ to R ^75, for example, preferably an aralkyl group having 7 to 20 carbon atoms, more preferably a benzyloxy group.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] Examples of the aryloxy group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, and a 2,3-dimethylphenoxy group. 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methyl Phenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2-tert-butyl-3,4 -Dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert-butyl-3-methylphenoxy group, 2 -Tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy Group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3, , 6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, 2-tert-butyl-3,5,6- Trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butyl Examples include phenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, naphthoxy group, anthracenoxy group and the like.
These aryloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ^{As the} aryloxy group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ , for example, an aryloxy group having 6 to 20 carbon atoms is preferable.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ are amino groups substituted with two hydrocarbon groups or amino groups substituted with two silyl groups, the hydrocarbon group Alternatively, the silyl group is a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, an aralkyloxy group such as a benzyloxy group, or the like. May be substituted. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, and an n-hexyl group. Group, an alkyl group having 1 to 20 carbon atoms such as a cyclohexyl group, an aryl group having 6 to 20 carbon atoms such as a phenyl group, an aralkyl group having 7 to 10 carbon atoms such as a benzyl group, and the like, and a silyl group Examples thereof include a trimethylsilyl group and a tert-butyldimethylsilyl group. Examples of the disubstituted amino group include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butyl. Amino group, diisobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group, etc. Preferred are dimethylamino group, diethylamino group, diisopropylamino group, di-tert-butylamino group or bistrimethylsilylamino group.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] Examples of the hydrocarbon thio group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include an alkylthio group, an aralkylthio group, and an arylthio group.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ^{As the} alkylthio group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ , for example, methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, Examples include n-pentylthio group, neopentylthio group, n-hexylthio group, n-octylthio group, n-dodecylthio group, n-pentadecylthio group, n-eicosylthio group and the like.
These alkylthio groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be substituted.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] The alkylthio group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ is preferably an alkylthio group having 1 to 20 carbon atoms, more preferably a methylthio group, an ethylthio group, an isopropylthio group or a tert-butylthio group. .

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ^As the aralkylthio group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ , for example, benzylthio group, (2-methylphenyl) methylthio group, (3-methylphenyl) methylthio group, (4-methylphenyl) methylthio Group, (2,3-dimethylphenyl) methylthio group, (2,4-dimethylphenyl) methylthio group, (2,5-dimethylphenyl) methylthio group, (2,6-dimethylphenyl) methylthio group, (3,4) -Dimethylphenyl) methylthio group, (3,5-dimethylphenyl) methylthio group, (2,3,4-trimethylphenyl) methylthio group, (2,3,5-trimethylphenyl) methylthio group, (2,3,6) -Trimethylphenyl) methylthio group, (2,4,5-trimethylphenyl) methylthio group, (2,4,6-trimethylphenyl) methylthio group, (3,4,5-trimethylphenyl) methylthio group, (2,3 , 4,5-tetramethylphenyl) methylthio group, (2,3,4,6-tetramethylphenyl) methylthio group, (2,3,5,6-tetramethylphenyl) methylthio group, (pentamethylphenyl) methylthio Group, (ethylphenyl) methylthio group, (n-propylphenyl) methylthio group, (isopropylphenyl) methylthio group, (n-butylphenyl) methylthio group, (sec-butylphenyl) methylthio group, (tert-butylphenyl) methylthio Group, (n-hexylphenyl) methylthio group, (n-octylphenyl) Methylthio group, (n- decylphenyl) methylthio group, naphthylmethyl thio group, anthracenylmethyl thio group and the like.
All of these aralkylthio groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ^{As the} aralkylthio group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ^75, an aralkylthio group having 7 to 20 carbon atoms is preferable, and a benzylthio group is more preferable.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in general formulas [2] to [6] Examples of the arylthio group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include a phenylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, a 4-methylphenylthio group, and 2,3-dimethyl. Phenylthio group, 2,4-dimethylphenylthio group, 2,5-dimethylphenylthio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 2 -Tert-butyl-3-methylphenylthio group, 2-tert-butyl-4-methylphenylthio group, 2-tert-butyl-5-methylphenylthio group, 2-tert-butyl-6-methylphenylthio group , 2, 3, 4-trimethylphenylthio group, 2,3,5-trimethylphenylthio group, 2,3,6-trimethylphenylthio group, 2,4,5-trimethylphenylthio group, 2,4,6-trimethylphenylthio group 2-tert-butyl-3,4-dimethylphenylthio group, 2-tert-butyl-3,5-dimethylphenylthio group, 2-tert-butyl-3,6-dimethylphenylthio group, 2,6- Di-tert-butyl-3-methylphenylthio group, 2-tert-butyl-4,5-dimethylphenylthio group, 2,6-di-tert-butyl-4-methylphenylthio group, 3,4,5 -Trimethylphenylthio group, 2,3,4,5-tetramethylphenylthio group, 2-tert-butyl-3,4,5-trimethylphenylthio group, 2,3,4,6 Tetramethylphenylthio group, 2-tert-butyl-3,4,6-trimethylphenylthio group, 2,6-di-tert-butyl-3,4-dimethylphenylthio group, 2,3,5,6- Tetramethylphenylthio group, 2-tert-butyl-3,5,6-trimethylphenylthio group, 2,6-di-tert-butyl-3,5-dimethylphenylthio group, pentamethylphenylthio group, ethylphenyl Thio group, n-propylphenylthio group, isopropylphenylthio group, n-butylphenylthio group, sec-butylphenylthio group, tert-butylphenylthio group, n-hexylphenylthio group, n-octylphenylthio group, n-decylphenylthio group, n-tetradecylphenylthio group, naphthylthio group, anthracenylthio group, etc. It is below.
These arylthio groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be substituted.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] The arylthio group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ is preferably an arylthio group having 6 to 20 carbon atoms.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] Examples of the hydrocarbon seleno group in ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ include an alkyl seleno group, an aralkyl seleno group, and an aryl seleno group.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ^56, the alkyl seleno group in R ⁶¹ to R ⁶³ and R ⁷¹ to R ^75, for example, methylseleno group, Echirusereno group, n- propyl seleno group, an isopropyl seleno group, n- Buchirusereno group, sec- Buchirusereno group, tert- Examples thereof include butylseleno group, n-pentylseleno group, neopentylseleno group, n-hexylseleno group, n-octylseleno group, n-dodecylseleno group, n-pentadecylseleno group, n-eicosylseleno group and the like.
These alkylseleno groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ^56, the alkyl seleno group in R ⁶¹ to R ⁶³ and R ⁷¹ to R ^75, preferably an alkyl seleno group having 1 to 20 carbon atoms, more preferably methylseleno group, Echirusereno group, an isopropyl seleno group or tert- Buchirusereno group It is.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ^56, the aralkyl seleno group in R ⁶¹ to R ⁶³ and R ⁷¹ to R ^75, for example, benzyl seleno group, (2-methylphenyl) methylseleno group, (3-methylphenyl) methylseleno group, (4-methylphenyl) Methylseleno group, (2,3-dimethylphenyl) methylseleno group, (2,4-dimethylphenyl) methylseleno group, (2,5-dimethylphenyl) methylseleno group, (2,6-dimethylphenyl) methylseleno group, (3, 4-dimethylphenyl) methylseleno group, (3,5-dimethylphenyl) methylseleno group, (2,3,4-trimethylphenyl) methylseleno group, (2,3,5-trimethylphenyl) me Tylseleno group, (2,3,4-trimethylphenyl) methylseleno group, (2,4,5-trimethylphenyl) methylseleno group, (2,4,6-trimethylphenyl) methylseleno group, (3,4,5-trimethyl) Phenyl) methylseleno group, (2,3,4,5-tetramethylphenyl) methylseleno group, (2,3,4,6-tetramethylphenyl) methylseleno group, (2,3,5,6-tetramethylphenyl) Methylseleno group, (pentamethylphenyl) methylseleno group, (ethylphenyl) methylseleno group, (n-propylphenyl) methylseleno group, (isopropylphenyl) methylseleno group, (n-butylphenyl) methylseleno group, (sec-butylphenyl) methylseleno group Group, (tert-butylphenyl) methylseleno group, (n- Hexyl phenyl) methylseleno group, (n- octylphenyl) methylseleno group, (n- decylphenyl) methylseleno group, naphthylmethyl seleno group, anthracenylmethyl seleno group and the like.
These aralkylseleno groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ^56, the aralkyl seleno group in R ⁶¹ to R ⁶³ and R ⁷¹ to R ^75, preferably an aralkyl seleno group having 7 to 20 carbon atoms, more preferably a benzyl seleno group.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ^56, the aryl seleno group for R ⁶¹ to R ⁶³ and R ⁷¹ to R ^75, for example, a phenyl seleno group, 2-methylphenyl seleno group, 3-methylphenyl seleno group, 4-methylphenyl seleno group, 2,3 -Dimethylphenylseleno group, 2,4-dimethylphenylseleno group, 2,5-dimethylphenylseleno group, 2,6-dimethylphenylseleno group, 3,4-dimethylphenylseleno group, 3,5-dimethylphenylseleno group 2-tert-butyl-3-methylphenylseleno group, 2-tert-butyl-4-methylphenylseleno group, 2-tert-butyl-5-methylphenylseleno group, 2-tert-butyl-6-methyl Tilphenylseleno group, 2,3,4-trimethylphenylseleno group, 2,3,5-trimethylphenylseleno group, 2,3,6-trimethylphenylseleno group, 2,4,5-trimethylphenylseleno group, 2 , 4,6-trimethylphenylseleno group, 2-tert-butyl-3,4-dimethylphenylseleno group, 2-tert-butyl-3,5-dimethylphenylseleno group, 2-tert-butyl-3,6- Dimethylphenylseleno group, 2,6-di-tert-butyl-3-methylphenylseleno group, 2-tert-butyl-4,5-dimethylphenylseleno group, 2,6-di-tert-butyl-4-methyl Phenylseleno group, 3,4,5-trimethylphenylseleno group, 2,3,4,5-tetramethylphenylseleno group, 2-tert-butyl -3,4,5-trimethylphenylseleno group, 2,3,4,6-tetramethylphenylseleno group, 2-tert-butyl-3,4,6-trimethylphenylseleno group, 2,6-di-tert -Butyl-3,4-dimethylphenylseleno group, 2,3,5,6-tetramethylphenylseleno group, 2-tert-butyl-3,5,6-trimethylphenylseleno group, 2,6-di-tert -Butyl-3,5-dimethylphenylseleno group, pentamethylphenylseleno group, ethylphenylseleno group, n-propylphenylseleno group, isopropylphenylseleno group, n-butylphenylseleno group, sec-butylphenylseleno group, tert -Butylphenylseleno group, n-hexylphenylseleno group, n-octylphenylseleno group, n-decyl Enirusereno group, n- tetradecyl phenylselenocysteine group, Nafuchirusereno group, anthracenyl seleno group and the like.
These arylseleno groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R in the general formulas [2] to [6] ^56, the aryl seleno group for R ⁶¹ to R ⁶³ and R ⁷¹ to R ^75, preferably an aryl seleno group having 6 to 20 carbon atoms, more preferably a phenyl seleno group.

X ^{5 to} X ⁷ in the general formulas [3] and [4] each represent an atom of group 16 of the periodic table of the elements, and examples thereof include an oxygen atom, a sulfur atom, and a selenium atom, preferably an oxygen atom or sulfur An atom, and more preferably an oxygen atom.

  Examples of the metal compound represented by the general formula [2] include methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl). -2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, methylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium Dichloride, me Len (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, Methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (tetramethyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tetramethyl) Lucyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride , Methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2- Phenoxy) titanium dichloride,

Isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadiene) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, iso Ropyridene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride Isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropyl Riden (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) ) Titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5) -Methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride Id, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) ) Titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium Dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3 Phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) ( 3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopenta (Dienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride and the like, and (cyclopentadienyl) of the above compound is converted to (methylcyclopentadienyl), (dimethy Lucyclopentadienyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (tert-butylcyclopentadienyl), (trimethylsilylcyclopentadienyl), (tert-butyldimethylsilylcyclo) Examples thereof include compounds substituted with (pentadienyl), (indenyl), (methylindenyl), (phenylindenyl) or (fluorenyl). Moreover, the compound etc. which replaced the dichloride of the said compound with dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamide), or bis (diethylamide) can be mentioned. Furthermore, the compound which replaced the titanium of the said compound with the zirconium or hafnium can be mentioned.

  Examples of the metal compound represented by the general formula [2] include dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy). ) Titanium dichloride, dimethylsilene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Jime Lucylylene (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride , Dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride , Dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamil-2-phenoxy) titani Mudichloride, dimethylsilylene (cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) ) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3- tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, di Methylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3) -Trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetra Tilcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (Tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride or the like, or (cyclopentadienyl) of the above compound is converted to (methylcyclopentadienyl), (dimethylcyclopentadienyl), (trimethyl Cyclopentadienyl), (n-butylcyclopentadienyl), (tert-butylcyclopentadienyl), (trimethylsilylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (indenyl), (Methyly Denier), it can be exemplified compounds obtained by replacing the (phenylindenyl) or (fluorenyl). Moreover, the compound etc. which replaced 2-phenoxy of the said compound by 3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy, or 3-tert-butyldimethylsilyl-2-phenoxy can be mentioned. Moreover, the compound etc. which replaced the dimethylsilylene of the said compound with diethylsilylene, diphenylsilylene, or dimethoxysilylene can be mentioned. Moreover, the compound etc. which replaced the dichloride of the said compound with dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino), or bis (diethylamino) can be mentioned. Furthermore, the compound etc. which replaced the titanium of the said compound with the zirconium or hafnium, etc. can be mentioned.

  Examples of the metal compound represented by the general formula [3] include μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (cyclopentadienyl) ( 2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (cyclopentadiene) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (Methylcyclopentadie L) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titani Mukuroraido}, .mu. Okisobisu {isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide},

μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) ) Titanium methoxide}, μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium methoxide} , Μ Oxobis {dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide} and the like, and (cyclopentadienyl) of the above compound is changed to (dimethylcyclopentadienyl), (trimethylcyclo Pentadienyl), (n-butylcyclopentadienyl), (tert-butylcyclopentadienyl), (trimethylsilylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (indenyl), ( Examples thereof include compounds substituted with (methylindenyl), (phenylindenyl) or (fluorenyl). In addition, (2-phenoxy) of the above compound is changed to (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), ( And compounds substituted with (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy). Moreover, the compound etc. which substituted the chloride of the said compound by methyl, benzyl, phenoxide, dimethylamino, or diethylamino can be mentioned. Furthermore, the compound etc. which replaced the titanium of the said compound with the zirconium or hafnium, etc. can be mentioned.

  Examples of the metal compound represented by the general formula [4] include di-μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (cyclopentadiene). Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropyl Riden (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium}, Di-μ-oxobis {isopropylidene (tetramethylcyclopentadieny ) (3-tert-butyl-5-methyl-2-phenoxy) titanium},

Di-μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) ) Titanium}, di-μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5 -Methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-pheno Si) Titanium} and the like, and (cyclopentadienyl), (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (tert-butylcyclopentadienyl) in the above compound. Examples include compounds substituted with (enyl), (trimethylsilylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (indenyl), (methylindenyl), (phenylindenyl) or (fluorenyl). Can do. In addition, (2-phenoxy) of the above compound is changed to (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), ( And compounds substituted with (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy). Furthermore, the compound etc. which replaced the titanium of the said compound with the zirconium or hafnium, etc. can be mentioned.

  The metal compounds represented by the general formulas [2] to [4] are synthesized by, for example, the method described in JP-A-9-87313.

  Examples of the metal compound represented by the general formula [5] include dimethylsilylene (cyclopentadienyl) (methylamido) titanium dichloride, dimethylsilylene (cyclopentadienyl) (ethylamido) titanium dichloride, dimethylsilylene (cyclopentadiene). Enyl) (isopropylamido) titanium dichloride, dimethylsilylene (cyclopentadienyl) (tert-butylamido) titanium dichloride, dimethylsilylene (cyclopentadienyl) (cyclohexylamido) titanium dichloride, dimethylsilylene (cyclopentadienyl) (cyclo Octylamide) titanium dichloride, dimethylsilylene (cyclopentadienyl) (cyclododecylamide) titanium dichloride, diethylsilylene Cyclopentadienyl) (methylamido) titanium dichloride, diethylsilylene (cyclopentadienyl) (ethylamido) titanium dichloride, diethylsilylene (cyclopentadienyl) (isopropylamido) titanium dichloride, diethylsilylene (cyclopentadienyl) (tert -Butylamido) titanium dichloride, diethylsilylene (cyclopentadienyl) (cyclohexylamido) titanium dichloride, diethylsilylene (cyclopentadienyl) (cyclooctylamido) titanium dichloride, diethylsilylene (cyclopentadienyl) (cyclododecylamide) Titanium dichloride, diisopropylsilylene (cyclopentadienyl) (methylamido) titanium dichlori , Diisopropylsilylene (cyclopentadienyl) (ethylamide) titanium dichloride, diisopropylsilylene (cyclopentadienyl) (isopropylamido) titanium dichloride, diisopropylsilylene (cyclopentadienyl) (tert-butylamido) titanium dichloride, diisopropylsilylene (cyclohexane) Pentadienyl) (cyclohexylamide) titanium dichloride, diisopropylsilylene (cyclopentadienyl) (cyclooctylamide) titanium dichloride, diisopropylsilylene (cyclopentadienyl) (cyclododecylamide) titanium dichloride, di-tert-butylphenylsilylene (Cyclopentadienyl) (methylamido) titanium dichloride, di-te rt-Butylphenylsilylene (cyclopentadienyl) (ethylamido) titanium dichloride, di-tert-butylphenylsilylene (cyclopentadienyl) (isopropylamido) titanium dichloride, di-tert-butylphenylsilylene (cyclopentadienyl) (Tert-butylamido) titanium dichloride, di-tert-butylphenylsilylene (cyclopentadienyl) (cyclohexylamido) titanium dichloride, di-tert-butylphenylsilylene (cyclopentadienyl) (cyclooctylamido) titanium dichloride, di -Tert-butylphenylsilylene (cyclopentadienyl) (cyclododecylamide) titanium dichloride, diphenylsilylene (cyclopentadiene) Nyl) (methylamido) titanium dichloride, diphenylsilylene (cyclopentadienyl) (ethylamido) titanium dichloride, diphenylsilylene (cyclopentadienyl) (isopropylamido) titanium dichloride, diphenylsilylene (cyclopentadienyl) (tert-butylamide) Titanium dichloride, diphenylsilylene (cyclopentadienyl) (cyclohexylamide) titanium dichloride, diphenylsilylene (cyclopentadienyl) (cyclooctylamide) titanium dichloride, diphenylsilylene (cyclopentadienyl) (cyclododecylamide) titanium dichloride, etc. Or (cyclopentadienyl) of the above compound (methylcyclopentadienyl), (dimethylsilane) Lopentadienyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (tert-butylcyclopentadienyl), (trimethylsilylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl) , (Indenyl), (methylindenyl), (phenylindenyl) or (fluorenyl). Moreover, the compound etc. which replaced the dichloride of the said compound with dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino), or bis (diethylamino) can be mentioned. Furthermore, the compound which replaced the titanium of the said compound with the zirconium or hafnium can be mentioned.

  The metal compound represented by the general formula [5] is synthesized by, for example, the method described in International Publication Number (WO) No. 9104257.

  Examples of the metal compound represented by the general formula [6] include (cyclopentadienyl) (phenoxy) titanium dichloride, (cyclopentadienyl) (2-methylphenoxy) titanium dichloride, (cyclopentadienyl) ( 2-ethylphenoxy) titanium dichloride, (cyclopentadienyl) (4-ethylphenoxy) titanium dichloride, (cyclopentadienyl) (2-isopropylphenoxy) titanium dichloride, (cyclopentadienyl) (4-isopropylphenoxy) Titanium dichloride, (cyclopentadienyl) (2-tert-butylphenoxy) titanium dichloride, (cyclopentadienyl) (4-tert-butylphenoxy) titanium dichloride, (cyclopentadiene) ) (2-phenylphenoxy) titanium dichloride, (cyclopentadienyl) (4-phenylphenoxy) titanium dichloride, (cyclopentadienyl) (2,6-dimethylphenoxy) titanium dichloride, (cyclopentadienyl) ( 3,5-dimethylphenoxy) titanium dichloride, (cyclopentadienyl) (2,6-diisopropylphenoxy) titanium dichloride, (cyclopentadienyl) (2,6-di-tert-butylphenoxy) titanium dichloride, (cyclo Pentadienyl) (2,6-diphenylphenoxy) titanium dichloride, (cyclopentadienyl) (2,4,6-trimethylphenoxy) titanium dichloride, (2,4,6-tri-tert-butylpheno) Si) Titanium dichloride, (cyclopentadienyl) (2,4,6-triphenylphenoxy) titanium dichloride, titanium dichloride, (cyclopentadienyl) (2,6-di-tert-butyl-4-methylphenoxy) Titanium dichloride and the like, and (cyclopentadienyl) of the above compound are converted to (methylcyclopentadienyl), (n-butylcyclopentadienyl), (tert-butylcyclopentadienyl), (1,3-dimethylcyclo Pentadienyl), (1,3,4-trimethylcyclopentadienyl), (pentamethylcyclopentadienyl), (indenyl), (methylindenyl), (phenylindenyl), (fluorenyl) or (3 , 6-Di-tert-butylfluorenyl) Etc. In addition, (2-phenoxy) of the above compound is changed to (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), ( And compounds substituted with (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy). Moreover, the compound etc. which replaced the dichloride of the said compound with dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino), or bis (diethylamino) can be mentioned. Furthermore, the compound etc. which replaced the titanium of the said compound with the zirconium or hafnium, etc. can be mentioned.

  The metal compound represented by the general formula [6] is synthesized by, for example, the method described in JP-A-11-166010.

（上記一般式［７］において、Ｍ⁸は元素周期律表第４族の金属原子を表し、Ｊ⁸は元素周期律表第１４族の原子を表す。Ｃｐ⁸およびＣｐ⁹はそれぞれ独立に、シクロペンタジエン形アニオン骨格を有する基を表す。Ｘ¹²およびＸ¹³、Ｒ⁸¹およびＲ⁸²はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、置換シリル基または炭化水素オキシ基を表す。Ｒ⁸¹およびＲ⁸²は任意に結合して単環構造または多環構造を形成してもよい。該単環構造または多環構造は、芳香族環であっても、非芳香族環であってもよい。） As the metallocene compound in which the metal atom of Group 4 of the periodic table is bonded to a group having two cyclopentadiene type anion skeletons, a metal compound represented by the following general formula [7] is preferable.

(In the above general formula [7], M ⁸ represents a metal atom of Group 4 of the Periodic Table of Elements, J ⁸ represents an atom of Group 14 of the Periodic Table of Elements. Cp ⁸ and Cp ⁹ are each independently, respectively .X ¹² and X ^13, R ⁸¹ and R ⁸² represents a group having a cyclopentadiene type anion skeleton independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted silyl group or a hydrocarbon oxy group .R ⁸¹ And R ⁸² may be bonded together to form a monocyclic structure or a polycyclic structure, which may be an aromatic ring or a non-aromatic ring. .)

M ⁸ in the general formula [7] is an atom of Group 4 of the periodic table, and examples thereof include a titanium atom, a zirconium atom, and a hafnium atom. M ⁸ is preferably a titanium atom or a zirconium atom.

In the general formula [7], examples of the atoms belonging to Group 14 of the periodic table of the elements represented by J ⁸ include a carbon atom, a silicon atom, and a germanium atom. Preferably, they are a carbon atom or a silicon atom.

In the general formula [7], Cp ⁸ and Cp ⁹ are each independently a group having a cyclopentadiene-type anion skeleton, such as a cyclopentadienyl group, a 3-methylcyclopentadienyl group, and 2,4-dimethylcyclo Pentadienyl group, 2,4,5-trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-propylcyclopentadienyl group, 2-isopropylcyclopentadienyl An enyl group, a 2-n-butylcyclopentadienyl group, a 2-sec-butylcyclopentadienyl group, a 2-tert-butylcyclopentadienyl group, a 2-phenylcyclopentadienyl group, a 2-trimethylsilylcyclopentadienyl group, tert-butyldimethylsilylcyclopentadienyl group, Indenyl group, 2-methylindenyl group, 4-methylindenyl group, 2,4-dimethylindenyl group, 4-n-propylindenyl group, 4-isopropylindenyl group, 4-n-butylindenyl group 4-tert-butylindenyl group, 4-phenylindenyl group, 2-methyl-4-phenylindenyl group, 4-naphthylindenyl group, 2-trimethylsilylindenyl group, 4,5,6,7- Tetrahydroindenyl group, fluorenyl group, methylfluorenyl group, 2,7-dimethylfluorenyl group, 2,7-di-tert-butylfluorenyl group, 2,7-diphenylfluorenyl group, 2, 7-bistrimethylsilylfluorenyl group and the like, preferably (substituted) cyclopentadienyl group, (substituted) indenyl group or (substituted) fluor An alkenyl group such as, more preferably indenyl group, 2-methylindenyl group, 4-phenyl indenyl group, 2-methyl-4-phenyl indenyl group, 4-naphthyl indenyl group or a tetrahydroindenyl group.

In the general formula [7], the multidentate of η of Cp ⁸ and Cp ⁹ is not particularly limited, it may be any possible values of Cp ⁸ and Cp ^9. For example, 5 seats, 4 seats, 3 seats, 2 seats and single seats are mentioned, preferably 5 seats, 3 seats or single seats, more preferably 5 seats.

X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] are each independently a hydrogen atom, a halogen atom, a hydrocarbon group (however, it does not include a group having a cyclopentadiene type anion skeleton) or It is a hydrocarbon oxy group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. Examples of the hydrocarbon group herein include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Moreover, as a hydrocarbon oxy group, an alkoxy group, an aryloxy group, an aralkyloxy group etc. are mentioned, for example.

Examples of the alkyl group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. Tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl Groups and the like.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorobutyl group. Examples thereof include a fluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group.
Any of these alkyl groups may be substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, an aralkyloxy group such as a benzyloxy group, or the like.

The alkyl group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] is preferably an alkyl group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group, or an isopropyl group. , Tert-butyl group, isobutyl group or tert-pentyl group.

As the aralkyl group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7], for example, benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4 -Methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group , (3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, 2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetra Methylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) Methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentyl) Phenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthyl A methyl group, an anthracenylmethyl group, etc. are mentioned.
These aralkyl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be substituted.

The aralkyl group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably a benzyl group.

Examples of the aryl group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, and 2,3-xylyl. Group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3 , 5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group , Sec -Butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecyl group A phenyl group, a naphthyl group, an anthracenyl group, etc. are mentioned.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be substituted.

The aryl group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group.

Examples of the alkenyl group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] include a vinyl group, an allyl group, a 3-butenyl group, and a 4-pentenyl group. An alkenyl group having 2 to 20 carbon atoms is preferable, and a vinyl group and an allyl group are more preferable.

Examples of the alkoxy group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a sec-butoxy group. Group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecyloxy group, n-pentadecyloxy group, n-eicosyloxy group, etc. Is mentioned.
These alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be substituted.

The alkoxy group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably a methoxy group, an ethoxy group, or isopropoxy. Group or tert-butoxy group.

Examples of the aryloxy group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] include, for example, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2 3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert -Butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4 -Trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethyl Tylphenoxy group, 2,4,6-trimethylphenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3, 6-dimethylphenoxy group, 2,6-di-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy Group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetra Methylphenoxy group, 2-tert-butyl-3,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, , 3,5,6-tetramethylphenoxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group , Ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group , Naphthoxy group, anthracenoxy group and the like.
These aryloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

The aryloxy group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] is preferably an aryloxy group having 6 to 20 carbon atoms, and more preferably a phenoxy group.

Examples of the aralkyloxy group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] include a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) Methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group , (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) L) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n- (Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group Naphthylmethoxy group, anthracenylmethoxy group and the like.
These aralkyloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

The aralkyloxy group used for X ¹² and X ¹³ , R ⁸¹ and R ⁸² in the general formula [7] is preferably an aralkyloxy group having 7 to 20 carbon atoms, and more preferably a benzyloxy group.

  Examples of the metal compound represented by the general formula [7] include dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2-methylcyclopentadienyl) zirconium dichloride, and dimethylsilylene bis (3-methyl). Cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (3-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2,3- Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,5-dimethylcyclope) Tadienyl) zirconium dichloride, dimethylsilylene bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2,3-ethylmethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2,4-ethylmethyl) Cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,5-ethylmethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3,5-ethylmethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2, 3,4-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride Dimethylsilylene bis (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (indenyl) zirconium dichloride, dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, and the like, dimethylsilylene And the like in which is substituted with diethylsilylene or diphenylsilylene. Further, the dichloride of the above compound is difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, Examples thereof include compounds in which di-tert-butoxide, diphenoxide, or di (2,6-di-tert-butylphenoxide) is substituted. Furthermore, the compound etc. which replaced the zirconium atom with the titanium atom or the hafnium atom can be mentioned.

  Examples of the metal compound represented by the general formula [7] include isopropylidenebis (cyclopentadienyl) zirconium dichloride, isopropylidenebis (2-methylcyclopentadienyl) zirconium dichloride, and isopropylidenebis (3-methyl). Cyclopentadienyl) zirconium dichloride, isopropylidenebis (2-n-butylcyclopentadienyl) zirconium dichloride, isopropylidenebis (3-n-butylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2,3- Dimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2,5-dimethylcyclope) Tadienyl) zirconium dichloride, isopropylidenebis (3,4-dimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2,3-ethylmethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2,4-ethylmethyl) Cyclopentadienyl) zirconium dichloride, isopropylidenebis (2,5-ethylmethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (3,5-ethylmethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2, 3,4-trimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride Isopropylidenebis (tetramethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (indenyl) zirconium dichloride, isopropylidenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidenebis (2-phenyl) Indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene (methylcyclopentadienyl) (indenyl) ) Zirconium dichloride, isopropylidene (n-butylcyclopentadienyl) (indenyl) dichloride, isopropylidene Tetramethylcyclopentadienyl) (indenyl) dichloride or isopropylidene of the compound include compounds obtained by replacing the diphenylmethylene. Further, the dichloride of the above compound is difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, Examples thereof include compounds in which di-tert-butoxide, diphenoxide, or di (2,6-di-tert-butylphenoxide) is substituted. Furthermore, the compound etc. which replaced the zirconium atom with the titanium atom or the hafnium atom can be mentioned.

  The metal compound represented by the general formula [7] is preferably a zirconium compound having a (substituted) indenyl group having 9 to 30 carbon atoms, more preferably isopropylidenebis (indenyl) zirconium dichloride, isopropylidenebis ( 4-phenylindenyl) zirconium dichloride or isopropylidenebis (2-methyl-4-phenylindenyl) zirconium dichloride.

[Component (B) Organoaluminum compound]
In the present invention, the component (B) is at least one organoaluminum compound selected from the group consisting of the following (B1) to (B3).
(B1) the general formula E ¹ _a AlZ organoaluminum compound represented by the _3-a (B2) general formula {-Al (E ²⁾ -O-} cyclic aluminoxane represented by _b (B3) formula E ³ {-Al (E ³ ) —O—} _c Linear aluminoxane represented by AlE ³ ₂ (where E ¹ , E ² and E ³ are each a hydrocarbon group, and a plurality of E ¹ , a plurality of E ² and a plurality of E ³ may be the same or different, Z represents a hydrogen atom or a halogen atom, and when there are a plurality of Z, the plurality of Z may be the same or different. A represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.)

The hydrocarbon group in E ¹ , E ² and E ³ of (B1) to (B3) is preferably a hydrocarbon group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

Examples of the organoaluminum compound (B1) represented by the general formula E ¹ _a AlZ _3-a include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, and dimethylaluminum chloride. Dialkylaluminum chloride such as diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, alkylaluminum dichloride such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, dimethylaluminum Yes Ride, diethylaluminum hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, dialkylaluminum hydride such as dihexyl aluminum hydride and the like.
Trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.

Cyclic aluminoxane (B2) having a structure represented by the general formula {-Al (E ² ) —O—} _b , represented by the general formula E ³ {-Al (E ³ ) —O—} _c AlE ³ ₂ Examples of E ² and E ³ in the linear aluminoxane (B3) having the following structure include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal pentyl group, and a neopentyl group. Of the alkyl group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ² and E ³ are a methyl group or an isobutyl group, b is 2 to 40, and c is 1 to 40.

  The aluminoxanes of (B2) and (B3) are produced by various methods. The method is not particularly limited, and can be made according to a known method. For example, a method in which a solution in which a trialkylaluminum (eg, trimethylaluminum) is dissolved in an appropriate organic solvent (benzene, aliphatic hydrocarbon, etc.) is brought into contact with water, a trialkylaluminum (eg, trimethylaluminum, etc.) The method of making it contact with the metal salt (for example, copper sulfate hydrate etc.) containing crystal water is mentioned.

[Component (C) Boron Compound]
In the present invention, the component (C) is one or more boron compounds selected from the group consisting of the following (C1) to (C3).
(C1) Boron compound represented by general formula BQ ¹ Q ² Q ³ (C2) Boron compound represented by general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (C3) General formula (LH ) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (wherein B represents a trivalent boron atom, Q ^{1 to} Q ⁴ are each independently a halogen atom, carbonized) Represents a hydrogen group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, and Q ^{1 to} Q ⁴ may be the same or different, and G ⁺ represents an inorganic or organic cation. , L represents a neutral Lewis base, and (L—H) ⁺ represents a Bronsted acid.)

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are each independently a halogen atom, a hydrocarbon group, A halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different; Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or the number of carbon atoms A substituted amino group substituted with an alkoxy group having 1 to 20 carbon atoms or a hydrocarbon group having 2 to 20 carbon atoms, more preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms or a carbon group A halogenated hydrocarbon group containing a carbon atom having 1 to 20 atoms. More preferably, it is a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably a fluorinated aryl group having 6 to 20 carbon atoms containing at least one fluorine atom. It is.

Examples of the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2, 3,4,5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, etc. Most preferred is tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , B is a trivalent boron atom, and Q ^{1 to} Q ⁴ are the above (C1 ) Is the same as Q ^{1 to} Q ^{3 in the} formula ( ¹ ) and G ⁺ is an inorganic or organic cation.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , examples of G ⁺ that is an inorganic cation include ferrocenium cation, alkyl-substituted ferrocenium cation, A silver cation etc. are mentioned, As G ^<+> which is an organic cation, a triphenylmethyl cation etc. are mentioned, for example. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. Examples of (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5- Tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5 -Bistrifluoromethylphenyl) borate and the like.

  Specific examples of these combinations include lithium tetrakis (3,5-bistrifluoromethylphenyl) borate, sodium tetrakis (3,5-bistrifluoromethylphenyl) borate, and potassium tetrakis (3,5-bistrifluoromethylphenyl). ) Borate, silver tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, tetrabutylphosphonium tetrakis (pentafluorophenyl) borate , Tetraphenylphosphonium tetrakis (pentafluorophenyl) borate, tetramethylammonium tetrakis (pentafluorophenyl) borate, trimethyls Honium tetrakis (pentafluorophenyl) borate, diphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-bistrifluoromethylphenyl) borate, etc. Most preferred is triphenylcarbenium tetrakis (pentafluorophenyl) borate.

In the boron compound (C3) represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , B is a trivalent valence state boron atom, and Q ^{1 to} Q ⁴ are The same as Q ^{1 to} Q ³ in (C1) above, L is a neutral Lewis base, and (LH) ⁺ is a Bronsted acid.

In the boron compound (C3) represented by the general formula (L—H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , (L—H) ⁺ that is a Bronsted acid includes, for example, a trialkyl-substituted ammonium. , N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, etc., and (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ includes the same as described above.

  Specific examples of these combinations include, for example, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n -Butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N -2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) Borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethyl) Phenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like, most preferably tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) It is borate.

  In the present invention, the component (C) boron compound is preferably (C2) or (C3), particularly preferably triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl). ) Borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

[Polymerization method]
In the present invention, a polymerization catalyst obtained by contacting a metallocene compound of a metal of Group 4 of the Periodic Table of Elements (A) with a component (B) an organoaluminum compound and / or a component (C) a boron compound is used. . When a polymerization catalyst obtained by bringing two components of component (A) and component (B) into contact with each other is used, the component (B) may be the above cyclic aluminoxane (B2) and / or linear aluminoxane (B3). Is preferably used. Another preferred embodiment of the polymerization catalyst includes a polymerization catalyst obtained by bringing the component (A), the component (B) and the component (C) into contact with each other. In this case, the component (B) The organoaluminum compound (B1) is preferred.

As for the usage-amount of each component, the molar ratio of a component (B) / component (A) is 0.1-10000 normally, Preferably it is 5-2000, The molar ratio of a component (C) / component (A) However, each component is used so that it is 0.01-100 normally, Preferably it is 0.5-10.
The concentration of each component is generally 0.01 to 500 μmol / g, preferably 0.05 to 100 μmol / g, and more preferably 0.05 to 50 μmol / g, as the component (A). A component (B) is 0.01-10000 micromol / g normally in conversion of an aluminum atom, Preferably it is 0.1-5000 micromol / g, More preferably, it is 0.1-2000 micromol / g. A component (C) is 0.01-500 micromol / g normally, Preferably it is 0.05-200 micromol / g, More preferably, it is 0.05-100 micromol / g.

  The polymerization catalyst used in the present invention may further be a combination of an inorganic compound such as silica gel or alumina and an organic compound particulate material composed of a styrene polymer as a carrier.

  The polymerization method for copolymerizing the ethylene and acenaphthylene derivatives of the present invention is not particularly limited. For example, batch or continuous gas phase polymerization method, bulk polymerization method, solution polymerization method or slurry using an appropriate polymerization solvent Any polymerization method such as a polymerization method can be employed. When a polymerization solvent is used, any compound that does not deactivate the catalyst can be used as a polymerization solvent. Examples of such a polymerization solvent include benzene, toluene, pentane, hexane, heptane, and cyclohexane. Mention may be made of hydrocarbon solvents.

  Although it does not specifically limit about polymerization temperature, Generally -100-250 degreeC, Preferably -50-200 degreeC is employ | adopted. The polymerization pressure is not particularly limited, but is generally 10 MPa or less, preferably 0.1 MPa to 5.0 MPa. Further, hydrogen or the like can be used as a chain transfer agent in order to adjust the molecular weight of the copolymer.

  The ethylene-acenaphthylene random copolymer of the present invention can be used after being processed into an extrusion molded product, an injection molded product or the like. As the extrusion molding method, a known molding method may be used. For example, a resin melted from a linear die or an inflation molding method of extruding a resin melted from a circular die and winding a film or sheet inflated into a cylindrical shape. And a molding method such as a T-die molding method or a calendar molding method for winding the film or sheet.

  Various additives can be blended in the ethylene-acenaphthylene random copolymer of the present invention depending on the purpose. For example, weathering agents, lubricants, pigments, dyes, antistatic agents, antioxidants, antifogging agents, rust preventives, surfactants, lubricants, conductive agents and the like can be mentioned. In addition, a known polymer such as radical polymerization low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-α-olefin copolymer elastomer, and polypropylene may be blended within a range that does not impair the effects of the present invention. it can.

  Examples of the optical product parts using the ethylene-acenaphthylene random copolymer of the present invention include a CD pickup lens, a DVD pickup lens, a FAX lens, a laser printer lens, a CCD camera lens, and a projector. Examples include lenses, oligon mirrors, and prisms.

  Hereinafter, the present invention will be described specifically by way of examples.

  The measured value of each item in an Example was measured with the following method.

(1) Intrinsic viscosity ([η]: dl / g)
Using an Ubbelohde viscometer, it was measured at 135 ° C. in tetralin.

(2) Melting point (Tm: ° C)
Using a differential scanning calorimeter (DSC, SSC-5200 manufactured by Seiko Denshi Kogyo Co., Ltd.), the measurement was performed under the following conditions.
Condition adjustment: After raising the temperature from 20 ° C. to 200 ° C. at 20 ° C./min, holding at 200 ° C. for 10 minutes, then lowering the temperature from 200 ° C. to −100 ° C. at 20 ° C./min, then at −100 ° C. for 10 minutes Retained.
Melting point measurement: Immediately after adjusting the state, the temperature was raised from −100 ° C. to 200 ° C. at 20 ° C./min.

(3) Copolymer composition (mol% of structural units derived from acenaphthylene in the whole monomer constituting the copolymer)
The copolymer composition of acenaphthylene in the ethylene-acenaphthylene random copolymer was determined by ¹³ C-NMR (AVANCE 600 manufactured by Bruker) analysis.
Measuring solvent 1,1,2,2-tetrachloroethane-d ₂
Measurement temperature 135 ℃
Sample concentration 200mg / 3ml
Reference substance 1,1,2,2-tetrachloroethane-d ₂ (74.2 ppm)

(4) Transparency The transparency of the ethylene-acenaphthylene random copolymer is pre-heated at 180 ° C. for 1 minute, and then hot-pressed for 1 minute under a pressure of 3 to 5 MPa. Visual evaluation was performed.

(5) Refractive index The refractive index of the ethylene-acenaphthylene random copolymer is a film having a thickness of about 100 μm formed by preheating at 180 ° C. for 3 minutes and then hot pressing under a pressure of 3 to 5 MPa for 3 minutes. An Abbe refractometer type 3 (manufactured by Atago Co., Ltd.) was examined as a test piece cut into a size of 10 mm × 30 mm.

Each compound used in the following examples is as follows.
As acenaphthylene, what was purchased from Tokyo Chemical Industry Co., Ltd. was recrystallized with a heptane solvent and used. For triisobutylaluminum, a 1 mol / l toluene solution was purchased from Tosoh Finechem Co., Ltd. and used. N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was purchased from Tosoh Finechem Co., Ltd. and used in a 0.01 mol / l toluene slurry. The isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (complex 1) synthesized according to the method described in JP-A-9-87313 was used. Rec-isopropylidenebis (indenyl) zirconium dichloride (complex 2) purchased from Strem Co. was used. Dimethylsilylene (tetramethylcyclopentadienyl) (tert-butylamido) titanium dichloride (complex 3) was purchased from Boulder Scientific.

[Example 1]
A 400 ml stirred stainless steel autoclave was replaced with argon gas, 30 ml of a 1 mol / l acenaphthylene toluene solution and 170 ml of purified toluene were charged, 1.0 MPa of ethylene gas was fed, and the inside of the autoclave was adjusted to 60 ° C. . 2.0 ml (2 mmol) of a toluene solution of triisobutylaluminum, 0.5 ml (5 μmol) of a toluene solution of isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (complex 1) ) And 1.0 ml (10 μmol) of a toluene slurry of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate were sequentially added and polymerized at 60 ° C. for 30 minutes. During this time, ethylene gas was continuously fed so that the pressure in the system was constant. The reaction solution was slowly poured into a mixture of 1 ml of hydrochloric acid (4 mol / l) and 2 liters of ethanol, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, 7.2 g of a copolymer was obtained. The copolymerization composition of acenaphthylene was 7 mol%, and the catalytic activity per mole of the titanium compound was 2900 kg / mol-Ti · h. [Η] of the copolymer was 1.3 dl / g, the melting point (Tm) was 77 ° C., and the glass transition point (Tg) could not be substantially observed. As a result of pressing this copolymer, a transparent press sheet was obtained, and the refractive index was 1.56.

[Example 2]
In Example 1, the same apparatus and the same procedure as in Example 1 were used except that the amount of acenaphthylene in toluene solution was changed from 30 ml to 20 ml and the purified amount of toluene was changed from 170 ml to 180 ml. As a result, 8.2 g of a copolymer was obtained. The catalytic activity per mole of titanium compound was 3300 kg / mol-Ti · h. [Η] of this copolymer was 1.9 dl / g, the melting point (Tm) was 101 ° C., the glass transition point (Tg) was not substantially observed, and the copolymer composition of acenaphthylene was 4 mol%. It was. As a result of pressing this copolymer, a transparent press sheet was obtained.

[Example 3]
In Example 1, the same apparatus and the same procedure as in Example 1 were used except that the amount of acenaphthylene in toluene solution was changed from 30 ml to 40 ml and the purified amount of toluene was changed from 170 ml to 160 ml. As a result, 5.5 g of a copolymer was obtained. The catalytic activity per mole of titanium compound was 2200 kg / mol-Ti · h. [Η] of the copolymer was 1.1 dl / g, the melting point (Tm) was 59 ° C., the glass transition point (Tg) was 4 ° C., and the copolymer composition of acenaphthylene was 9 mol%. As a result of pressing this copolymer, a transparent press sheet was obtained, and the refractive index was 1.58.

[Example 4]
In Example 1, the same apparatus and the same procedure as Example 1 were carried out except that the amount of acenaphthylene in toluene solution was changed from 30 ml to 60 ml and the purified amount of toluene was changed from 170 ml to 140 ml. As a result, 4.8 g of a copolymer was obtained. The catalytic activity per mole of titanium compound was 1900 kg / mol-Ti · h. [Η] of this copolymer was 0.9 dl / g, the melting point (Tm) could not be substantially observed, the glass transition point (Tg) was 12 ° C., and the copolymer composition of acenaphthylene was 14 mol%. It was. As a result of pressing this copolymer, a transparent press sheet was obtained, and the refractive index was 1.60.

[Example 5]
In Example 1, the amount of acenaphthylene in toluene solution was changed from 30 ml to 100 ml, the amount of purified toluene was changed from 170 ml to 100 ml, and isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl -2-Phenoxy) Titanium dichloride (complex 1) The same apparatus and procedure as in Example 1 was used, except that the amount of the toluene solution charged was changed from 0.5 ml to 1.0 ml. As a result, 9.3 g of a copolymer was obtained. The catalytic activity per mole of titanium compound was 1900 kg / mol-Ti · h. [Η] of this copolymer was 1.0 dl / g, the melting point (Tm) could not be substantially observed, the glass transition point (Tg) was 24 ° C., and the copolymer composition of acenaphthylene was 18 mol%. It was. As a result of pressing this copolymer, a transparent press sheet was obtained.

[Example 6]
In Example 1, the amount of acenaphthylene in toluene solution was changed from 30 ml to 120 ml, the amount of purified toluene charged was changed from 170 ml to 20 ml, and isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl). -2-Phenoxy) Titanium dichloride (complex 1) The same apparatus and procedure as in Example 1 was used, except that the amount of the toluene solution charged was changed from 0.5 ml to 1.0 ml. As a result, 7.2 g of a copolymer was obtained. The catalytic activity per mole of titanium compound was 1400 kg / mol-Ti · h. [Η] of this copolymer was 0.4 dl / g, the melting point (Tm) could not be substantially observed, the glass transition point (Tg) was 75 ° C., and the copolymer composition of acenaphthylene was 32 mol%. It was. As a result of pressing this copolymer, a transparent press sheet was obtained.

[Example 7]
In Example 1, 0.5 ml (5 μmol) of a toluene solution of isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (complex 1) was added to rec-isopropylidenebis ( The same apparatus and the same procedure as in Example 1 were followed except that the toluene solution of indenyl) zirconium dichloride (complex 2) was changed to 0.5 ml (5 μmol). As a result, 24.5 g of a copolymer was obtained. The catalytic activity per mole of zirconium compound was 9800 kg / mol-Zr · h. The [η] of this copolymer was 0.8 dl / g, the melting point (Tm) was 110 ° C., the glass transition point (Tg) could not be substantially observed, and the copolymer composition of acenaphthylene was 3 mol%. It was. As a result of pressing this copolymer, a transparent press sheet was obtained.

[Example 8]
In Example 1, 0.5 ml (5 μmol) of a toluene solution of isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (complex 1) was added to dimethylsilylene (tetramethylcyclohexane). The same apparatus and the same procedure as in Example 1 were used except that the toluene solution was changed to 0.5 ml (5 μmol) of pentadienyl) (tert-butylamido) titanium dichloride (complex 3). As a result, 13.2 g of a copolymer was obtained. The catalytic activity per mole of titanium compound was 5300 kg / mol-Ti · h. [Η] of this copolymer was 4.6 dl / g, melting point (Tm) was 112 ° C., glass transition point (Tg) could not be observed substantially, and the copolymer composition of acenaphthylene was 2 mol%. It was. As a result of pressing this copolymer, a transparent press sheet was obtained.

[Comparative Example 1]
In Example 1, 2.0 ml (2 mmol) of a toluene solution of triisobutylaluminum was changed to 5.0 ml (5 mmol) of a toluene solution of diethylaluminum chloride, and isopropylidene (cyclopentadienyl) (3-tert-butyl-5 -Methyl-2-phenoxy) The same apparatus and procedure as in Example 1 except that 0.5 ml (5 μmol) of the toluene solution of titanium dichloride (complex 1) was changed to 2 ml (200 μmol) of the toluene solution of oxyvanadium trichloride. I went there. As a result, 32 g of a polymer was obtained. The melting point (Tm) of this polymer was 138 ° C., the glass transition point (Tg) could not be observed substantially, and the copolymer composition of acenaphthylene was 0 mol%. Since this polymer was opaque, the refractive index could not be measured.

[Comparative Example 2]
In Example 1, 2.0 ml (2 mmol) of a toluene solution of triisobutylaluminum was changed to 5.0 ml (5 mmol) of a toluene solution of diethylaluminum chloride, and isopropylidene (cyclopentadienyl) (3-tert-butyl-5 The same apparatus and procedure as in Example 1 except that 0.5 ml (5 μmol) of the toluene solution of -methyl-2-phenoxy) titanium dichloride (complex 1) was changed to 2 ml (200 μmol) of the titanium tetrachloride toluene solution. went. As a result, 13 g of a polymer was obtained. The melting point (Tm) of this polymer was 127 ° C., the glass transition point (Tg) could not be observed substantially, and the copolymer composition of acenaphthylene was 0 mol%. Since this polymer was opaque, the refractive index could not be measured.

Claims (7)

An ethylene-acenaphthylene random copolymer obtained by copolymerizing ethylene and an acenaphthylene derivative represented by the following general formula [1].

(However, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ^{3 to} R ⁸ each independently represent a hydrogen atom, a halogen atom or 1 to 1 carbon atom. Represents 10 hydrocarbon groups.)   The ethylene-acenaphthylene random copolymer according to claim 1, wherein the melting point measured by a differential scanning calorimeter (DSC) is 130 ° C or lower, or the melting point is not substantially observed. Ethylene which copolymerizes ethylene and the acenaphthylene derivative represented by the general formula [1] in the presence of a polymerization catalyst obtained by contacting the following component (A), component (B) and / or component (C) A method for producing an acenaphthylene random copolymer.
Component (A): Metallocene compound of group 4 metal of the Periodic Table of Elements Component (B): One or more organoaluminum compounds selected from the group consisting of the following (B1) to (B3) (B1) General formula E ¹ _a Organoaluminum compound represented by AlZ _3-a (B2) General formula {-Al (E ² ) -O—} Cyclic aluminoxane represented by _b (B3) General formula E ³ {-Al (E ³ ) -O-} _c linear aluminoxane represented by AlE ³ ₂ (where E ¹ , E ² and E ³ are each a hydrocarbon group, and a plurality of E ¹ , a plurality of E ² and a plurality of E ³ are Z may be the same or different, Z represents a hydrogen atom or a halogen atom, and when there are a plurality of Z, the plurality of Z may be the same or different. 3 represents a number satisfying 3, b represents an integer of 2 or more, c is 1 or more It represents the number.)
Component (C): One or more boron compounds selected from the group consisting of the following (C1) to (C3) (C1) General formula BQ ¹ Q ² Q ³ Boron compound (C2) General formula G ⁺ ( Boron compound represented by BQ ¹ Q ² Q ³ Q ⁴ ) ^- (C3) General formula (L-H) ⁺ Boron compound represented by (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (B is 3 It represents a boron atom valent valence state, the Q ¹ to Q ⁴ each independently represents a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, Q ¹ to Q ⁴ good be different even in the same .G ⁺ represents an inorganic or organic cation, L represents a neutral Lewis base, represents the (L-H) ⁺ is a Bronsted acid.)   The method for producing an ethylene-acenaphthylene random copolymer according to claim 3, wherein the metallocene compound (A) is a half metallocene compound. The method for producing an ethylene-acenaphthylene random copolymer according to claim 3, wherein the metallocene compound (A) is a compound represented by any one of the following general formulas [2] to [6].

(In the above general formulas [2] to [6], M ^{1 to} M ⁷ each represent an atom of Group 4 of the Periodic Table of Elements, and A ^{1 to} A ⁵ and A ⁷ each represent Group 16 of the Periodic Table of Elements. J ^{1 to} J ⁶ each represent an atom of Group 14 of the Periodic Table of Elements, T ⁶ represents an atom of Group 15 of the Periodic Table of Elements, and Cp ^{1 to} Cp ⁷ each independently represent cyclopentadiene. Represents a group having an anionic skeleton X ^{1 to} X ⁴ , X ^{8 to} X ¹¹ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ , R ^{51 to} R ⁵⁶ , R ^{61 to} R ⁶³ and R ^{71 to} R ⁷⁵ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted silyl group, a hydrocarbon oxy group, a disubstituted amino group, a hydrocarbon thio group, or a hydrocarbon seleno group. the ^{stands, R 11 ~R 16, R 21} ~R 26, R 31 ~R 36, R 41 ~R 46, R 51 ~R 56, R 61 ~R 63 And R ⁷¹ to R ⁷⁵ each may be bonded to form a monocyclic structure or polycyclic structure optionally. The monocyclic structure or a polycyclic structure, be an aromatic ring structure, non-aromatic ring (The structure may also be used. X ^{5 to} X ⁷ each represent an atom of Group 16 of the Periodic Table of Elements.)   The ethylene-acenaphthylene random according to claim 3, wherein the metallocene compound (A) is a metallocene compound in which a metal atom of Group 4 of the Periodic Table of the Elements is bonded to a group having two cyclopentadiene type anion skeletons. A method for producing a copolymer. The method for producing an ethylene-acenaphthylene random copolymer according to claim 3, wherein the metallocene compound (A) is a metal compound represented by the following general formula [7].

(In the above general formula [7], M ⁸ represents a metal atom of Group 4 of the Periodic Table of Elements, J ⁸ represents an atom of Group 14 of the Periodic Table of Elements. Cp ⁸ and Cp ⁹ are each independently, respectively .X ¹² and X ^13, R ⁸¹ and R ⁸² represents a group having a cyclopentadiene type anion skeleton independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted silyl group or a hydrocarbon oxy group .R ⁸¹ And R ⁸² may be bonded together to form a monocyclic structure or a polycyclic structure, which may be an aromatic ring or a non-aromatic ring. .)