JP2009091570A - Block copolymer and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a block copolymer with excellent heat resistance containing a cyclopentane ring structure in the main chain. <P>SOLUTION: The block copolymer comprises the following blocks (b1) and (b2) and/or (b3). Block (b1): a homopolymer block (b1-1) or a random copolymer block (b1-2) of a compound represented by formula (1). Block (b2): a single polymer block or a random copolymer block comprising a polymerization unit of the compound represented by formula (1) and having a different attribute from that of the above (b1-1) or the above (b1-2). Block (b3): a single polymer block or a random copolymer block of one kind of olefin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a block copolymer having a main chain containing a cyclopentane ring structure and a method for producing the same.

  A block copolymer synthesized from ethylene and cyclopentene is known as a block copolymer having a polymer chain containing a cyclopentane ring structure in the main chain. This block copolymer is chemically composed of a block composed of ethylene polymer units and a block composed of polymer units of 1,2-cyclopentylene in which all the carbon atoms constituting the cyclopentane ring are bonded to hydrogen atoms. It is a bonded block copolymer (for example, see Non-Patent Document 1).

Macromolecules, Volume 35, 2002, 9640-9647

However, a block copolymer in which a polymer unit containing a cyclopentane ring structure is a polymer unit derived from a specific diene compound and having a structure different from that of a polymer unit derived from cyclopentene is known. It is not done.
Under such circumstances, the problem to be solved by the present invention, that is, the object of the present invention, is that the polymer unit containing a cyclopentane ring structure contained in the main chain is a polymer unit derived from a specific diene compound, An object of the present invention is to provide a block copolymer excellent in heat resistance, which is a polymer unit having a structure different from that derived from cyclopentene, and a method for producing the same.

（１）
（式中、Ｙ¹およびＹ²はそれぞれ独立に、水素原子、ハロゲン原子、アルコキシカルボニル基、アラルキルオキシカルボニル基、アリールオキシカルボニル基、ヒドロキシル基、ニトリル基、アルデヒド基、アルキル基、アラルキル基、アリール基、シリル基、シロキシ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アシル基、アミノ基、置換されたアミノ基、アミド基、イミド基、チオール基、アルキルチオ基、アラルキルチオ基、アリールチオ基、アルキルチオキシカルボニル基またはアリールチオキシカルボニル基を表し、Ｙ¹とＹ²とは互いに結合して環を形成していてもよい。Ａ¹、Ａ²、Ａ³、Ａ⁴、Ａ⁵、Ａ⁶、Ａ⁷、Ａ⁸、Ａ⁹、Ａ¹⁰およびＡ¹¹はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アミノ基、置換されたアミノ基、アミド基、イミド基またはアルキルチオ基を表し、Ａ³とＡ⁴とは、または、Ａ⁵とＡ⁶とは、互いに結合して環を形成していてもよい。ｍは０または１を表し、ｎは０〜２０の整数を表す。） The present invention is a block copolymer comprising the following block (b1), block (b2) and / or block (b3).
Block (b1): a homopolymer block (b1-1) or a random copolymer block (b1-2) comprising polymerized units of at least one compound represented by the following formula (1)
Block (b2): a homopolymer block (b2-1) having an attribute different from that of the homopolymer block (b1-1) comprising polymerized units of at least one compound represented by the following formula (1), or Random copolymer block (b2-2) having attributes different from those of the random copolymer block (b1-2)
Block (b3): homopolymer block (b3-1) or random copolymer block (b3-2) comprising polymerized units of at least one olefin

(1)
Wherein Y ¹ and Y ² are each independently a hydrogen atom, halogen atom, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, hydroxyl group, nitrile group, aldehyde group, alkyl group, aralkyl group, aryl Group, silyl group, siloxy group, alkoxy group, aralkyloxy group, aryloxy group, acyl group, amino group, substituted amino group, amide group, imide group, thiol group, alkylthio group, aralkylthio group, arylthio group, Represents an alkylthioxycarbonyl group or an arylthioxycarbonyl group, and Y ¹ and Y ² may be bonded to each other to form a ring A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ each ^{a 7, a 8, a 9} , a 10 and a ¹¹ are independently a hydrogen atom, a halogen atom, an alkyl group, a Alkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an amino group, substituted amino group, an amido group, an imido group, or an alkylthio group, and A ³ and A ^4, or a A ⁵ A ⁶ may be bonded to each other to form a ring, m represents 0 or 1, and n represents an integer of 0 to 20.)

（３）
（式中、Ｙ¹およびＹ²はそれぞれ独立に、水素原子、ハロゲン原子、アルコキシカルボニル基、アラルキルオキシカルボニル基、アリールオキシカルボニル基、ヒドロキシル基、ニトリル基、アルデヒド基、アルキル基、アラルキル基、アリール基、シリル基、シロキシ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アシル基、アミノ基、置換されたアミノ基、アミド基、イミド基、チオール基、アルキルチオ基、アラルキルチオ基、アリールチオ基、アルキルチオキシカルボニル基またはアリールチオキシカルボニル基を表し、Ｙ¹とＹ²とは互いに結合して環を形成していてもよい。Ａ¹、Ａ²、Ａ³、Ａ⁴、Ａ⁵、Ａ⁶、Ａ⁷、Ａ⁸、Ａ⁹、Ａ¹⁰およびＡ¹¹はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アミノ基、置換されたアミノ基、アミド基、イミド基またはアルキルチオ基を表し、Ａ³とＡ⁴とは、または、Ａ⁵とＡ⁶とは、互いに結合して環を形成していてもよい。ｍは０または１を表し、ｎは０〜２０の整数を表す。） Moreover, this invention is a manufacturing method of the said block copolymer which consists of arbitrary orders of the following process (I) and the following process (B) and / or process (C).
Step (a): Step of polymerizing at least one diene compound represented by the following formula (3) to produce a homopolymer block (b1-1) or a random copolymer block (b1-2) (B): A homopolymer block (b2-1) having an attribute different from that of the homopolymer block obtained by polymerizing at least one diene compound represented by the following formula (3), or the random copolymer: Step of generating a random copolymer block (b2-2) having an attribute different from that of the block Step (c): Polymerizing at least one kind of olefin to produce a homopolymer block (b3-1) or copolymer of olefin Step of generating block (b3-2)

(3)
Wherein Y ¹ and Y ² are each independently a hydrogen atom, halogen atom, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, hydroxyl group, nitrile group, aldehyde group, alkyl group, aralkyl group, aryl Group, silyl group, siloxy group, alkoxy group, aralkyloxy group, aryloxy group, acyl group, amino group, substituted amino group, amide group, imide group, thiol group, alkylthio group, aralkylthio group, arylthio group, Represents an alkylthioxycarbonyl group or an arylthioxycarbonyl group, and Y ¹ and Y ² may be bonded to each other to form a ring A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ each ^{a 7, a 8, a 9} , a 10 and a ¹¹ are independently a hydrogen atom, a halogen atom, an alkyl group, a Alkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an amino group, substituted amino group, an amido group, an imido group, or an alkylthio group, and A ³ and A ^4, or a A ⁵ A ⁶ may be bonded to each other to form a ring, m represents 0 or 1, and n represents an integer of 0 to 20.)

  According to the present invention, the polymer unit containing a cyclopentane ring structure contained in the main chain is a polymer unit derived from a specific diene compound and has a structure different from that polymer unit derived from cyclopentene. A block copolymer excellent in heat resistance, which is a unit, can be obtained.

As halogen atoms represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ in Formula (1) and Formula (3) , Fluorine atom, chlorine atom, bromine atom, and iodine atom. Among them, preferred is a fluorine atom.

As an alkyl group represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ in Formula (1) and Formula (3) Linear alkyl groups such as methyl, ethyl and n-butyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl and neopentyl; and cyclohexyl and cyclooctyl Examples of such cyclic alkyl groups are as follows.

As an aralkyl group represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ in Formula (1) and Formula (3) , Benzyl group, phenethyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 2,6-dimethylbenzyl group, and 3,5-dimethylbenzyl group.

As an aryl group represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ in Formula (1) and Formula (3) , Phenyl, tolyl, 1-biphenyl, 2-biphenyl, 3-biphenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, and mesityl it can.

As an alkoxy group represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ in Formula (1) and Formula (3) Linear alkoxy groups such as methoxy, ethoxy and n-butoxy; branched alkoxy groups such as isopropoxy, isobutoxy, tert-butoxy and neopentoxy; and cyclohexyloxy and cyclo A cyclic alkoxy group such as an octyloxy group can be exemplified.

Aralkyloxy groups represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ in Formula (1) and Formula (3) Benzyloxy group, phenethyloxy group, 2-methylbenzyloxy group, 3-methylbenzyloxy group, 4-methylbenzyloxy group, 2,6-dimethylbenzyloxy group, and 3,5-dimethylbenzyloxy group It can be illustrated.

Aryloxy groups represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ in Formula (1) and Formula (3) As phenoxy group, 2-methylphenoxy group, 2-ethylphenoxy group, 2-n-propylphenoxy group, 2-isopropylphenoxy group, 2-n-butylphenoxy group, 2-isobutylphenoxy group, 2-tert-butyl Phenoxy group, 3-methylphenoxy group, 3-isopropylphenoxy group, 3-n-butylphenoxy group, 3-tert-butylphenoxy group, 4-methylphenoxy group, 4-isopropylphenoxy group, 4-n-butylphenoxy group 4-tert-butylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group 2,6-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-di-tert-butylphenoxy group, and naphthoxy group.

In formulas (1) and (3), the substituted groups represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ As amino groups, N-methylamino group, N-ethylamino group, Nn-butylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-butylamino group N-isopropylamino group, N-isobutylamino group, N-tert-butylamino group, N-neopentylamino group, N, N-diisopropylamino group, N, N-diisobutylamino group, N, N-di- Amino such as tert-butylamino group, N, N-dineopentylamino group, N-cyclohexylamino group, N-cyclooctylamino group, N, N-dicyclohexylamino group and N, N-dicyclooctylamino group Group It can be illustrated.

As an amide group represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ in Formula (1) and Formula (3) , Ethaneamide group, n-butanamide group, N-methylethaneamide group, N-ethylethaneamide group, Nn-butylethaneamide group, isopropanamide group, isobutanamide group, tert-butanamide group, neopentanamide group N-isopropylethaneamide group, N-isobutylmethaneamide group, N-tert-butylethaneamide group, N-neopentylethaneamide group, cyclohexaneamide group, cyclooctaneamide group, N-cyclohexylethaneamide group and N- An amide group such as a cyclooctylethaneamide group can be exemplified.

As an imide group represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ in Formula (1) and Formula (3) And imide groups such as succinimide group, maleimide group and phthalimide group.

As an alkylthio group represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ in Formula (1) and Formula (3) Linear alkylthio groups such as methylthio group, ethylthio group and n-butylthio group; branched alkylthio groups such as isopropylthio group, isobutylthio group, tert-butylthio group, and neopentylthio group; and cyclohexylthio group And a cyclic alkylthio group such as a cyclooctylthio group.

A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ are each a halogen atom, a hydroxyl group, a thiol group, an amino group, or a carboxyl group. , A carbamoyl group, a formyl group, a nitro group, a sulfonate group, a silyl group, a siloxy group, and a cyano group.

Among them, as A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , and A ¹¹ , a hydrogen atom, a halogen atom, or a carbon atom number of 1 to 10 The alkyl group is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

A ³ and A ⁴ or A ⁵ and A ⁶ may be bonded to each other to form a ring. Examples of the ring include aliphatic rings such as cyclobutane, cyclopentane and cyclohexane, and aromatic rings. These rings may have a substituent.

A ⁸ in formula (3) and — (CH ₂ ) _n (CA ⁹ A ¹⁰ ) _m H are preferably in a cis configuration.

Examples of the halogen atom represented by Y ¹ and Y ² in Formula (1) and Formula (3) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, preferred is a fluorine atom.

Linear alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and n-butoxycarbonyl group as the alkoxycarbonyl group represented by Y ¹ and Y ² in formula (1) and formula (3); isopropoxycarbonyl Illustrating branched alkoxycarbonyl groups such as cyclohexyloxycarbonyl groups and cyclooctyloxycarbonyl groups; and branched alkoxycarbonyl groups such as isobutoxycarbonyl groups, tert-butoxycarbonyl groups, and neopentoxycarbonyl groups; Can do.

As the aralkyloxycarbonyl group represented by Y ¹ and Y ² in formula (1) and formula (3), benzyloxycarbonyl group, phenethyloxycarbonyl group, 2-methylbenzyloxycarbonyl group, 3-methylbenzyloxycarbonyl group , 4-methylbenzyloxycarbonyl group, 2,6-dimethylbenzyloxycarbonyl group, and 3,5-dimethylbenzyloxycarbonyl group.

Examples of the aryloxycarbonyl group represented by Y ¹ and Y ² in Formula (1) and Formula (3) include a phenyloxycarbonyl group, a tolyloxycarbonyl group, and a mesityloxycarbonyl group.

In the formula (1) and formula (3), as the alkyl group represented by Y ¹ and Y ² , 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- Examples thereof include branched alkyl groups such as butyl group and neopentyl group; and cyclic alkyl groups such as cyclohexyl group and cyclooctyl group.

As the aralkyl group represented by Y ¹ and Y ² in Formula (1) and Formula (3), benzyl group, phenethyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 2,6 -A dimethylbenzyl group and a 3, 5- dimethylbenzyl group can be illustrated.

Examples of the aryl group represented by Y ¹ and Y ² in Formula (1) and Formula (3) include a phenyl group, a tolyl group, and a mesityl group.

As silyl groups represented by Y ¹ and Y ² in formula (1) and formula (3), monosubstituted silyl groups such as methylsilyl group, ethylsilyl group and phenylsilyl group; dimethylsilyl group, diethylsilyl group, and diphenyl A disubstituted silyl group such as a silyl group; trimethylsilyl group, trimethoxysilyl group, dimethylmethoxysilyl group, methyldimethoxysilyl group, triethylsilyl group, triethoxysilyl group, tri-n-propylsilyl group, triisopropylsilyl group, Of tri-n-butylsilyl group, tri-sec-butylsilyl group, tert-butyldimethylsilyl group, triisobutylsilyl group; tert-butyldiphenylsilyl group, sexyldimethylsilyl group, tricyclohexylsilyl group, and triphenylsilyl group Such as 3-substitution An example is a tolyl group. Among them, preferably a trialkylsilyl group, more preferably a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a sexyldimethylsilyl group, or a triisopropylsilyl group. is there.

As the siloxy groups represented by Y ¹ and Y ² in the formulas (1) and (3), trimethylsiloxy group, trimethoxysiloxy group, dimethylmethoxysiloxy group, methyldimethoxysiloxy group, triethylsiloxy group, triethoxysiloxy group , Tri-n-propylsiloxy group, triisopropylsiloxy group, tri-n-butylsiloxy group, tri-sec-butylsiloxy group, tert-butyldimethylsiloxy group, triisobutylsiloxy group; tert-butyldiphenylsiloxy group, Illustrative are siloxy groups such as a sildimethylsiloxy group, a tricyclohexylsiloxy group, and a triphenylsiloxy group. Among them, preferably a trialkylsiloxy group, more preferably a trimethylsiloxy group, a triethylsiloxy group, a triphenylsiloxy group, a tert-butyldimethylsiloxy group, a tert-butyldiphenylsiloxy group, a sexyldimethylsiloxy group, or a triisopropylsiloxy group It is.

In the formulas (1) and (3), the alkoxy groups represented by Y ¹ and Y ² are linear alkoxy groups such as methoxy, ethoxy and n-butoxy groups; isopropoxy groups, isobutoxy groups, tert -Butoxy groups and branched alkoxy groups such as neopentoxy groups; and cyclic alkoxy groups such as cyclohexyloxy groups and cyclooctyloxy groups.

As the aralkyloxy group represented by Y ¹ and Y ² in Formula (1) and Formula (3), benzyloxy group, phenethyloxy group, 2-methylbenzyloxy group, 3-methylbenzyloxy group, 4-methylbenzyl Examples thereof include a ruoxy group, a 2,6-dimethylbenzyloxy group, and a 3,5-dimethylbenzyloxy group.

In the formulas (1) and (3), the aryloxy groups represented by Y ¹ and Y ² are phenoxy group, 2-methylphenoxy group, 2-ethylphenoxy group, 2-n-propylphenoxy group, 2-isopropyl. Phenoxy group, 2-n-butylphenoxy group, 2-isobutylphenoxy group, 2-tert-butylphenoxy group, 3-methylphenoxy group, 3-isopropylphenoxy group, 3-n-butylphenoxy group, 3-tert-butyl Phenoxy group, 4-methylphenoxy group, 4-isopropylphenoxy group, 4-n-butylphenoxy group, 4-tert-butylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5 -Dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,5-dimethylphenoxy group Examples include a group, 2,6-diisopropylphenoxy group, 2,6-di-tert-butylphenoxy group, and naphthoxy group.

As the acyl groups represented by Y ¹ and Y ² in the formulas (1) and (3), an acetyl group, an n-propanoyl group, an n-butanoyl group, an n-pentanoyl group, an n-hexanoyl group, 2-methylpropanoyl group Examples include noyl group, pivaloyl group, 2-methylbutanoyl group, benzoyl group, 1-naphthoyl group, and 2-naphthoyl group.

Examples of the substituted amino group represented by Y ¹ and Y ² in the formula (1) and the formula (3) include N-methylamino group, N-ethylamino group, and Nn-butylamino group. Linear alkylamino groups; branched alkylamino groups such as N-isopropylamino group, N-isobutylamino group, N-tert-butylamino group, and N-neopentylamino group; N-cyclohexylamino group and N- Cyclic alkylamino groups such as cyclooctylamino group; linear alkylamino groups such as N, N-dimethylamino group, N, N-diethylamino group, and N, N-di-n-butylamino group; N , N-diisopropylamino group, N, N-diisobutylamino group, N, N-di-tert-butylamino group, and N, N-dineopentylamino group Examples thereof include branched alkylamino groups such as these; and cyclic alkylamino groups such as N, N-dicyclohexylamino groups and N, N-dicyclooctylamino groups.

As the amide group represented by Y ¹ and Y ² in the formulas (1) and (3), an ethaneamide group, an n-butanamide group, an N-methylethaneamide group, an N-ethylethaneamide group, an Nn-butyl group Ethanamide group, isopropanamide group, isobutanamide group, tert-butanamide group, neopentanamide group, N-isopropylethanamide group, N-isobutylethanamide group, N-tert-butylethanamide group, N-neopentyl group Examples of the amide group include an ethaneamide group, an N-cyclohexaneamide group, an N-cyclooctaneamide group, an N, N-dicyclohexaneamide group, and an N, N-dicyclooctaneamide group.

Examples of the imide group represented by Y ¹ and Y ² in Formula (1) and Formula (3) include imide groups such as a maleimide group, a phthalimide group, and a succinimide group.

As the alkylthio group represented by Y ¹ and Y ² in the formulas (1) and (3), a linear alkylthio group such as a methylthio group, an ethylthio group and an n-butylthio group; an isopropylthio group, an isobutylthio group, Examples thereof include branched alkylthio groups such as tert-butylthio group and neopentylthio group; and cyclic alkylthio groups such as cyclohexylthio group and cyclooctylthio group.

Examples of the aralkylthio group represented by Y ¹ and Y ² in Formula (1) and Formula (3) include benzylthio group, 1-naphthylmethylthio group, 2-naphthylmethylthio group, and 9-fluorenylmethylthio group. Can do.

Examples of the arylthio group represented by Y ¹ and Y ² in Formula (1) and Formula (3) include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-fluorenylthio group.

As the alkylthioxycarbonyl group represented by Y ¹ and Y ² in formula (1) and formula (3), a methylthioxycarbonyl group, an ethylthioxycarbonyl group, an isopropylthioxycarbonyl group, a tert-butylthioxycarbonyl group, And cyclohexylthiooxycarbonyl group.

Examples of the arylthioxycarbonyl group represented by Y ¹ and Y ² in Formula (1) and Formula (3) include a phenylthioxycarbonyl group.

In Formula (1) and Formula (3), Y ¹ and Y ² may each independently have a substituent. Examples of the substituent include a hydrogen atom, halogen atom, hydroxyl group, nitrile group, aldehyde group, alkyl group, aralkyl group, aryl group, silyl group, siloxy, alkoxy group, aralkyloxy group, aryloxy group, acyl group, amino group, Examples include amide groups, imide groups, thiol groups, alkylthio groups, aralkylthio groups, arylthio groups, alkylthioxycarbonyl groups, and arylthioxycarbonyl groups.

In Formula (1) and Formula (3), Y ¹ and Y ² may be bonded to each other to form a ring. As the ring, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, decahydronaphthalene ring, norbornane ring, 1,2,3,4-tetrahydronaphthalene A ring composed of a hydrocarbon such as a ring, a norbornene ring, an ethylidene norbornene ring, an indane ring, a fluorene ring, and an acenaphthylene ring; a cyclopropan-1-one ring, a cyclobutan-1-one ring, a cyclopentan-1-one ring, Cyclohexane-1-one ring, cycloheptan-1-one ring, cyclooctane-1-one ring, cyclononan-1-one ring, cyclodecan-1-one ring, cyclopropane-1,2-dione ring, cyclobutane-1 , 3-dione ring, cyclopentane-1,3-dione , Cyclohexane-1,3-dione ring, cycloheptane-1,3-dione ring, cyclooctane-1,3-dione ring, cyclononane-1,3-dione ring, cyclodecane-1,3-dione ring, indane- Ketones such as 1-one ring, indan-2-one ring, indan-1,3-dione ring, tetralin-1-one ring, tetralin-1,3-dione ring, and tetralin-1,4-dione ring Ring containing group: oxirane ring, oxetane ring, oxolane ring, oxane ring, 1,3-dioxetane ring, 1,3-dioxolane ring, 1,3-dioxane ring, 1,4-dioxane ring, 1,3,5 -Trioxane ring, phthalane ring, coumaran ring, chroman ring, isochroman ring, xanthene ring, 1,3-benzodioxane ring, 1,4-benzodioxane ring and benzodio Ring having an ether bond such as SORUN ring;

  Pyrazolidine ring, morpholine ring, imidazolidine ring, pyrrolidine ring, piperidine ring, hexahydropyrimidine ring, piperazine ring, indoline ring, indazoline ring, 1,2,3,4-tetrahydroquinoline ring, 1,2,3,4 Tetrahydroisoquinoline ring, N-methylpyrazolidine ring, N-methylmorpholine ring, N, N′-dimethylpyrazolidine ring, N-methylimidazolidine ring, N, N′-dimethylimidazolidine ring, N-methylpyrrolidine Ring, N-methylpiperidine ring, N-methylhexahydropyrimidine ring, N, N′-dimethylhexahydropyrimidine ring, N-methylpiperazine ring, N, N′-diethylpiperazine ring, N-ethylpyrazolidine ring, N, N'-diethylpyrazolidine ring, N-ethylimidazolidine ring, N, N'-diethyl Imidazolidine ring, N-ethylpyrrolidine ring, N-ethylpiperidine ring, N-ethylpiperazine ring, N-ethylhexahydropyrimidine ring, N, N′-diethylhexahydropyrimidine ring, N, N′-diethylpiperazine ring, N-phenylpyrazolidine ring, N, N'-diphenylpyrazolidine ring, N-phenylimidazolidine ring, N, N'-diphenylimidazolidine ring, N-phenylpyrrolidine ring, N-phenylpiperidine ring, N- Phenylhexahydropyrimidine ring, N, N'-diphenylhexahydropyrimidine ring, N-phenylpiperazine ring, N-methylindoline ring, N-methylindazoline ring, N, N'-dimethylindazoline ring, N-methyl- 1,2,3,4-tetrahydroquinoline ring and N-methyl-1,2,3,4 Rings containing amino groups or substituted amino groups such as tetrahydroisoquinoline ring: α-lactone ring, β-lactone ring, γ-lactone ring, δ-lactone ring, ε-caprolactone ring, 1,3-dioxolane-4 -One ring, 1,4-dioxane-2-one ring, 1,4-dioxane-2,5-dione ring, 1,3-dihydroisobenzofuran-1-one ring, 2,3-dihydro-1-benzofuran A ring having an ester bond such as a 2-one ring, a 3,4-dihydro-2H-1-benzopyran-3-one ring, and a 3,4-dihydro-1H-2-benzopyran-3-one ring; A ring having a carbonate bond such as a 1,3-dioxane-2-one ring and a 1,3-dioxolan-2-one ring;

  α-lactam ring, β-lactam ring, γ-lactam ring, δ-lactam ring, ε-caprolactam ring, imidazolidin-4-one ring, pyrazolidin-3-one ring, piperazin-2-one ring, piperazine-2 , 5-dione ring, 1,2,3,4-tetrahydroquinolin-3-one ring, 1,2,3,4-tetrahydroisoquinolin-1-one ring, 1,2,3,4-tetrahydro-1- Isoquinolin-3-one ring, N-methyl-α-lactam ring, N-methyl-β-lactam ring, N-methyl-γ-lactam ring, N-methyl-δ-lactam ring, N-methyl-ε-caprolactam Ring, N-methylimidazolidin-4-one ring, N-methylpiperazin-2-one ring, N-methylpiperazine-2,5-dione ring, N-methyl-1,2,3,4-tetrahydroquinoline- 3-one ring Includes amide groups such as N-methyl-1,2,3,4-tetrahydroisoquinolin-1-one ring and N-methyl-1,2,3,4-tetrahydro-1-isoquinolin-3-one ring Ring; hexahydropyrimidine-2,4,6-trione ring, N-methylhexahydropyrimidine-2,4,6-trione ring, N, N′-dimethylhexahydropyrimidine-2,4,6-trione ring, N-ethylhexahydropyrimidine-2,4,6-trione ring, N, N′-diethylhexahydropyrimidine-2,4,6-trione ring, N-phenylhexahydropyrimidine-2,4,6-trione ring And a ring containing an imide group such as an N, N′-diphenylhexahydropyrimidine-2,4,6-trione ring; a ring such as a 1,3-oxazolidine-2-one ring Examples include rings having a retane bond; and rings having a urea bond such as an imidazolidin-2-one ring and a hexahydropyrimidin-2-one ring. These rings may have a substituent.

  Among these, a hydrocarbon ring, a ring containing a ketone group, a ring having an ether bond, a ring having an ester bond, a ring containing an amide group, a ring containing an imide group, or a ring having a urea bond is preferable.

  The compound represented by the formula (3) may be a known compound. Examples of the compound include 5,5-diallylmeldrum acid, 5-allyl-5-((2E) -2-butenyl) meldrum acid, 5-allyl-5-((2E) -2-pentenyl) meldrum acid, 5 -Allyl-5-((2E) -2-hexenyl) meldrum acid, 5-allyl-5-((2E) -2-heptenyl) meldrum acid, 5-allyl-5-((2E) -2-octenyl ) Meldrum's acid, 5-allyl-5-((2E) -2-nonenyl) meldrum acid, 5-allyl-5-((2E) -2-denyl) meldrum acid, 5-allyl-5-((2E) -2-undenyl) meldrum acid, Meldrum acid derivatives such as 5-allyl-5-((2E) -2-dodenyl) meldrum acid; dimethyl 2,2-diallylmalonate, diethyl 2,2-diallylmalonate, 2,2-dia Di-n-propyl lumalonate, diisopropyl 2,2-diallylmalonate, di-n-butyl 2,2-diallylmalonate, diisobutyl 2,2-diallylmalonate, di-tert-2,2-diallylmalonate Butyl, 2-allyl-2-((2E) -2-butenyl) malonate, 2-allyl-2-((2E) -2-pentenyl) malonate, 2-allyl-2-((2E) 2-hexenyl) malonate diethyl, 2-allyl-2-((2E) -2-heptenyl) malonate, 2-allyl-2-((2E) -2-octenyl) diethyl malonate, 2- Diethyl allyl-2-((2E) -2-nonenyl) malonate, diethyl 2-allyl-2-((2E) -2-denyl) malonate, 2-allyl-2-((2E) -2-undenyl ) Ma Phosphate, diethyl 2-allyl -2 - ((2E) -2- Dodeniru) malonic acid diester derivatives, such as malonic acid diethyl;

  2,2-diallyl-1,3-dioxane, 4,4-diallyl-1,3-dioxane, 5,5-diallyl-1,3-dioxane, 2,2-diallyl-1,4-dioxane, 2, 2-diallyl-1,3-dioxolane, 4,4-diallyl-1,3-dioxolane, 2,2-dimethyl-5,5-diallyl-1,3-dioxane, 2-allyl-2-((2E) -2-butenyl) -1,3-dioxane, 4-allyl-4-((2E) -2-butenyl) -1,3-dioxane, 5-allyl-5-((2E) -2-butenyl)- 1,3-dioxane, 2-allyl-2-((2E) -2-butenyl) -1,4-dioxane, 2-allyl-2-((2E) -2-butenyl) -1,3-dioxolane, 4-Allyl-4-((2E) -2-butenyl) -1,3-dio Solane, 2,2-dimethyl-5-allyl-5-((2E) -2-butenyl) -1,3-dioxane, 2-allyl-2-((2E) -2-pentenyl) -1,3- Dioxane, 4-allyl-4-((2E) -2-butenyl) -1,3-dioxane, 5-allyl-5-((2E) -2-pentenyl) -1,3-dioxane, 2-allyl- 2-((2E) -2-pentenyl) -1,4-dioxane, 2-allyl-2-((2E) -2-pentenyl) -1,3-dioxolane, 4-allyl-4-((2E) -2-pentenyl) -1,3-dioxolane, 2,2-dimethyl-5-allyl-5-((2E) -2-pentenyl) -1,3-dioxane, 2,2-dimethyl-5-allyl- 5-((2E) -2-hexenyl) -1,3-dioxane, 2,2- Methyl-5-allyl-5-((2E) -2-heptenyl) -1,3-dioxane, 2,2-dimethyl-5-allyl-5-((2E) -2-octenyl) -1,3- Dioxane, 2,2-dimethyl-5-allyl-5-((2E) -2-nonenyl) -1,3-dioxane, 2,2-dimethyl-5-allyl-5-((2E) -2-denyl ) -1,3-dioxane, 2,2-dimethyl-5-allyl-5-((2E) -2-unenyl) -1,3-dioxane, 2,2-dimethyl-5-allyl-5-(( 2E) -2-dodenyl) -1,3-dioxane, 2,2-dimethyl-5-allyl-5-((2E) -2-tridenyl) -1,3-dioxane, 2,2-dimethyl-4, 4-diallyl-1,3-dioxane, 2,2-dimethyl-4,4-diallyl-1, 3-dioxolane, 2,2-diethyl-4,4-diallyl-1,3-dioxane, 2,2-diethyl-5,5-diallyl-1,3-dioxane, 2,2-diethyl-4,4- Diallyl-1,3-dioxolane, 2-methyl-4,4-diallyl-1,3-dioxane, 2-methyl-5,5-diallyl-1,3-dioxane, 2-methyl-4,4-diallyl- 1,3-dioxolane, 2-ethyl-4,4-diallyl-1,3-dioxane, 2-ethyl-5,5-diallyl-1,3-dioxane, 2-ethyl-4,4-diallyl-1, 3-dioxolane, 2-n-propyl-4,4-diallyl-1,3-dioxane, 2-n-propyl-5,5-diallyl-1,3-dioxane, 2-n-propyl-4,4- Diallyl-1,3-dioxolane, 2- Sopropyl-4,4-diallyl-1,3-dioxane, 2-isopropyl-5,5-diallyl-1,3-dioxane, 2-isopropyl-4,4-diallyl-1,3-dioxolane, 2-n- Butyl-4,4-diallyl-1,3-dioxane, 2-n-butyl-5,5-diallyl-1,3-dioxane, and 2-n-butyl-4,4-diallyl-1,3-dioxolane A compound having an ether bond such as

  2,2-diallylcyclobutane-1,3-dione, 2,2-diallylcyclopentane-1,3-dione, 2,2-diallylcyclohexane-1,3-dione, 2,2-diallylcycloheptane-1, 3-dione, 2,2-diallylcyclooctane-1,3-dione, 2,2-diallylcyclononane-1,3-dione, 2-allyl-2-((2E) -2-butenyl) cyclohexane-1 , 3-dione, 2-allyl-2-((2E) -2-pentenyl) cyclohexane-1,3-dione, 2-allyl-2-((2E) -2-hexenyl) cyclohexane-1,3- Dione, 2-allyl-2-((2E) -2-heptenyl) cyclohexane-1,3-dione, 2-allyl-2-((2E) -2-octenyl) cyclohexane-1,3-dione, 2- Ryl-2-((2E) -2-nonenyl) cyclohexane-1,3-dione, 2-allyl-2-((2E) -2-denyl) cyclohexane-1,3-dione, 2-allyl-2- ((2E) -2-unenyl) cyclohexane-1,3-dione, 2-allyl-2-((2E) -2-dodenyl) cyclohexane-1,3-dione, 2-allyl-2-((2E) -2-tridenyl) cyclohexane-1,3-dione, 2-allyl-2-((2E) -2-tetradenyl) cyclohexane-1,3-dione, 2-allyl-2-((2E) -2-hexadenyl ) Cyclohexane-1,3-dione, 2,2-diallylindane-1,3-dione, 2-allyl-2-((2E) -2-butenyl) indan-1,3-dione, 2-allyl-2 -((2E) -2- Nthenyl) indan-1,3-dione, 2-allyl-2-((2E) -2-hexenyl) indan-1,3-dione, 2-allyl-2-((2E) -2-heptenyl) indan -1,3-dione, 2-allyl-2-((2E) -2-octenyl) indan-1,3-dione, 2-allyl-2-((2E) -2-nonenyl) indan-1,3 -Dione, 2-allyl-2-((2E) -2-denyl) indan-1,3-dione, 2-allyl-2-((2E) -2-unenyl) indane-1,3-dione, 2 -Allyl-2-((2E) -2-dodenyl) indan-1,3-dione, 2-allyl-2-((2E) -2-tridenyl) indan-1,3-dione, 2-allyl-2 -((2E) -2-tetradenyl) indan-1,3-dione, 2-a Compounds containing a ketone group such as ril-2-((2E) -2-hexadenyl) indan-1,3-dione;

  Propanediamide derivatives such as 2,2-diallylpropanediamide, 2-allyl-2-((2E) -2-butenyl) propanediamide; N-methyl-2,2-diallylpropanediamide, N-ethyl-2 , 2-diallylpropanediamide, N-alkyl-substituted propanediamide derivatives such as N-methyl-2-allyl-2-((2E) -2-butenyl) propanediamide; N, N-dimethyl-2,2- N, N-dialkyl-substituted propanediamide derivatives such as diallylpropanediamide, N, N-dimethyl-2-allyl-2-((2E) -2-butenyl) propanediamide; N, N′-dimethyl-2,2 -Diallylpropanediamide, N, N'-diethyl-2,2-diallylpropanediamide, N, N'-di-n-propyl-2,2-di Rylpropanediamide, N, N′-diisopropyl-2,2-diallylpropanediamide, N, N′-di-n-butyl-2,2-diallylpropanediamide, N, N′-diisobutyl-2,2-diallyl Propanediamide, N, N'-di-tert-butyl-2,2-diallylpropanediamide, N, N'-dineopentyl-2,2-diallylpropanediamide, N, N'-dicyclohexyl-2,2-diallylpropane Diamide, N, N′-di-n-hexyl-2,2-diallylpropanediamide, N, N′-dicyclopentyl-2,2-diallylpropanediamide, N, N′-diethyl-2-allyl-2- ((2E) -2-butenyl) propanediamide, N, N′-diethyl-2-allyl-2-((2E) -2-pentenyl) propane Amide, N, N′-diethyl-2-allyl-2-((2E) -2-hexenyl) propanediamide, N, N′-diethyl-2-allyl-2-((2E) -2-heptenyl) Propanediamide, N, N′-diethyl-2-allyl-2-((2E) -2-octenyl) propanediamide, N, N′-diethyl-2-allyl-2-((2E) -2-nonenyl) Propanediamide, N, N′-diethyl-2-allyl-2-((2E) -2-denyl) propanediamide, N, N′-diethyl-2-allyl-2-((2E) -2-undenyl) N, N′-dialkyl-substituted propanediamide derivatives such as propanediamide, N, N′-diethyl-2-allyl-2-((2E) -2-dodenyl) propanediamide;

  N, N, such as N, N, N′-trimethyl-2,2-diallylpropanediamide, N, N, N′-trimethyl-2-allyl-2-((2E) -2-butenyl) propanediamide N′-trialkyl-substituted propanediamide derivatives; N, N, N ′, N′-tetramethyl-2,2-diallylpropanediamide, N, N, N ′, N′-tetramethyl-2-allyl-2- N, N, N ′, N′-tetraalkyl-substituted propanediamide derivatives such as ((2E) -2-butenyl) propanediamide; N-phenyl-2,2-diallylpropanediamide, N-phenyl-2-allyl N-aryl substituted propanediamide derivatives such as -2-((2E) -2-butenyl) propanediamide; N, N′-diphenyl-2,2-diallylpropanediamide, N, N, N'-diaryl substituted propanediamide derivatives such as' -diphenyl-2-allyl-2-((2E) -2-butenyl) propanediamide; N-benzyl-2,2-diallylpropanediamide, N- N-aralkyl-substituted propanediamide derivatives such as benzyl-2-allyl-2-((2E) -2-butenyl) propanediamide; N, N′-dibenzyl-2,2-diallylpropanediamide, N, N ′ N, N′-diaralkyl-substituted propanediamide derivatives such as dibenzyl-2-allyl-2-((2E) -2-butenyl) propanediamide; 5,5-diallylbarbituric acid, 5-allyl-5 ((2E) -2-butenyl) barbituric acid derivatives such as barbituric acid; N-methyl-5,5-diallylbarbituric acid, N Ethyl-5,5-diallyl barbituric acid, N- methyl-5-allyl -5 - ((2E) -2- butenyl) N- alkyl-substituted barbituric acid derivatives, such as barbituric acid;

  N, N′-dimethyl-5,5-diallylbarbituric acid, N, N′-diethyl-5,5-diallylbarbituric acid, N, N′-di-n-propyl-5,5-diallylbarbituric acid Acid, N, N′-diisopropyl-5,5-diallylbarbituric acid, N, N′-di-n-butyl-5,5-diallylbarbituric acid, N, N′-diisobutyl-5,5-diallyl Barbituric acid, N, N′-di-tert-butyl-5,5-diallylbarbituric acid, N, N′-dineopentyl-5,5-diallylbarbituric acid, N, N′-dicyclohexyl-5,5 Diallyl barbituric acid, N, N′-di-n-hexyl-5,5-diallylbarbituric acid, N, N′-dicyclopentyl-5,5-diallylbarbituric acid, N, N′-dimethyl- 5-ant -5-((2E) -2-butenyl) barbituric acid, N, N'-dimethyl-5-allyl-5-((2E) -2-pentenyl) barbituric acid, N, N'-dimethyl-5 -Allyl-5-((2E) -2-hexenyl) barbituric acid, N, N'-dimethyl-5-allyl-5-((2E) -2-heptenyl) barbituric acid, N, N'- Dimethyl-5-allyl-5-((2E) -2-octenyl) barbituric acid, N, N′-dimethyl-5-allyl-5-((2E) -2-nonenyl) barbituric acid, N, N '-Dimethyl-5-allyl-5-((2E) -2-denyl) barbituric acid, N, N'-dimethyl-5-allyl-5-((2E) -2-unenyl) barbituric acid, N , N′-dimethyl-5-allyl-5-((2E) -2-dodenyl) N, N′-dialkyl-substituted barbituric acid derivatives such as rubituric acid; N-phenyl-5,5-diallylbarbituric acid, N-phenyl-5-allyl-5-((2E) -2-butenyl) barbi N-aryl substituted barbituric acid derivatives such as tool acid; N, N′-diphenyl-5,5-diallylbarbituric acid, N, N′-diphenyl-5-allyl-5-((2E) -2- N, N′-diaryl substituted barbituric acid derivatives such as butenyl) barbituric acid;

  N-aralkyl-substituted barbituric acid derivatives such as N-benzyl-5,5-diallylbarbituric acid, N-benzyl-5-allyl-5-((2E) -2-butenyl) barbituric acid; N, N N, N'-diaralkyl-substituted barbiturates such as' -dibenzyl-5,5-diallylbarbituric acid, N, N'-dibenzyl-5-allyl-5-((2E) -2-butenyl) barbituric acid Acid derivatives; pyrazolidine-3,5-diones such as 4,4-diallylpyrazolidine-3,5-dione, 4-allyl-4-((2E) -2-butenyl) pyrazolidine-3,5-dione Derivatives; such as N-methyl-4,4-diallylpyrazolidine-3,5-dione, N-methyl-4-allyl-4-((2E) -2-butenyl) pyrazolidine-3,5-dione N-A Kill-substituted pyrazolidine-3,5-dione derivatives; N, N′-dimethyl-4,4-diallylpyrazolidine-3,5-dione, N, N′-diethyl-4,4-diallylpyrazolidine-3 , 5-dione, N, N′-di-n-propyl-4,4-diallylpyrazolidine-3,5-dione, N, N′-diisopropyl-4,4-diallylpyrazolidine-3,5 -Dione, N, N'-di-n-butyl-4,4-diallylpyrazolidine-3,5-dione, N, N'-diisobutyl-4,4-diallylpyrazolidine-3,5-dione N, N′-di-tert-butyl-4,4-diallylpyrazolidine-3,5-dione, N, N′-dineopentyl-4,4-diallylpyrazolidine-3,5-dione, N , N′-Dicyclopentyl-4,4-diallylpyrazo Din-3,5-dione, N, N′-di-n-hexyl-4,4-diallylpyrazolidine-3,5-dione, N, N′-dicyclohexyl-4,4-diallylpyrazolidine- N, N′-dialkyl substituted pyrazolidine-3,5-dione derivatives such as 3,5-dione;

  N-phenyl-4,4-diallylpyrazolidine-3,5-dione, N-phenyl-4-allyl-4-((2E) -2-butenyl) pyrazolidine-3,5-dione, N- (2 N-aryl substituted pyrazolidines such as -naphthyl) -4,4-diallylpyrazolidine-3,5-dione, N- (2-anthracenyl) -4,4-diallylpyrazolidine-3,5-dione 3,5-dione derivatives; N, N′-diphenyl-4,4-diallylpyrazolidine-3,5-dione, N, N′-diphenyl-4-allyl-4-((2E) -2-butenyl ) Pyrazolidine-3,5-dione, N, N′-diphenyl-4-allyl-4-((2E) -2-pentenyl) pyrazolidine-3,5-dione, N, N′-diphenyl-4-allyl- 4-((2E) -2-hexeni ) Pyrazolidine-3,5-dione, N, N′-diphenyl-4-allyl-4-((2E) -2-heptenyl) pyrazolidine-3,5-dione, N, N′-diphenyl-4-allyl- 4-((2E) -2-octenyl) pyrazolidine-3,5-dione, N, N′-diphenyl-4-allyl-4-((2E) -2-nonenyl) pyrazolidine-3,5-dione, N , N′-diphenyl-4-allyl-4-((2E) -2-denyl) pyrazolidine-3,5-dione, N, N′-diphenyl-4-allyl-4-((2E) -2-undenyl ) Pyrazolidine-3,5-dione, N, N′-diphenyl-4-allyl-4-((2E) -2-dodenyl) pyrazolidine-3,5-dione, N, N′-bis (2-naphthyl) -4,4-diallylpyrazolidine-3 N, N′-diaryl substituted pyrazolidine-3,5-dione derivatives such as 5-dione, N, N′-di (2-anthracenyl) -4,4-diallylpyrazolidine-3,5-dione; N -Benzyl-4,4-diallylpyrazolidine-3,5-dione, N-benzyl-4-allyl-4-((2E) -2-butenyl) pyrazolidine-3,5-dione, N- (9- N-aralkyl-substituted pyrazolidine-3,5-dione derivatives such as fluorenylmethyl) -4,4-diallylpyrazolidine-3,5-dione; N, N′-dibenzyl-4,4-diallylpyrazo Lysine-3,5-dione, N, N′-dibenzyl-4-allyl-4-((2E) -2-butenyl) pyrazolidine-3,5-dione, N, N′-bis (9-fluorenyl) Methyl) -4,4-diallylpi N, N'-diaralkyl-substituted pyrazolidine-3,5-dione derivatives such as lazolidine-3,5-dione;

  9,9-diallylfluorene, 2,7-di-tert-butyl-9,9-diallylfluorene, 2,7-difluoro-9,9-diallylfluorene, 2,7-dichloro-9,9-diallylfluorene, 2,7-dibromo-9,9-diallylfluorene, 2,7-diiodo-9,9-diallylfluorene, 2-iodo-7-bromo-9,9-diallylfluorene, 2- (N, N-diphenylamino) ) -7-Bromo-9,9-diallylfluorene, 3,6-di-tert-butyl-9,9-diallylfluorene, 3,6-difluoro-9,9-diallylfluorene, 3,6-dichloro-9 , 9-diallylfluorene, 3,6-dibromo-9,9-diallylfluorene, 3,6-diiodo-9,9-diallylfluorene, 3-iodo-6-bromo- , 9-diallylfluorene, 3- (N, N-diphenylamino) -6-bromo-9,9-diallylfluorene, 9,9-diallyl-10,10-dimethyl-9,10-dihydroanthracene, 9-allyl -9-((2E) -2-butenyl) -fluorene, 9-allyl-9-((2E) -2-pentenyl) -fluorene, 9-allyl-9-((2E) -2-hexenyl)- Fluorene, 9-allyl-9-((2E) -2-octenyl) -fluorene, 9-allyl-9-((2E) -2-nonenyl) -fluorene, 9-allyl-9-((2E) -2 -Denyl) -fluorene, 9-allyl-9-((2E) -2-unenyl) -fluorene, 9-allyl-9-((2E) -2-dodenyl) -fluorene, 9-allyl-9-(( 2E) -2-Tride Le) - can be exemplified a fluorene derivative such as fluorene.

  Among these, particularly preferred are barbituric acid derivatives, N-alkyl substituted barbituric acid derivatives, N, N′-dialkyl substituted barbituric acid derivatives, N-aryl substituted barbituric acid derivatives, N, N′-diaryl substituted barbiturates. Acid derivatives, N-aralkyl substituted barbituric acid derivatives, N, N′-diaralkyl substituted barbituric acid derivatives, N, N′-dialkyl substituted pyrazolidine-3,5-dione derivatives, N, N′-diaryl substituted pyrazolidine-3 , 5-dione derivatives or fluorene derivatives.

  Examples of olefins in the present invention include linear olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene; Branched olefins such as 1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, and vinylcyclohexane; and cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene And cyclic olefins such as norbornene, limonene, α-pinene, β-pinene, camphene, cis-cyclooctene, trans-cyclooctene, cis-cyclononene, trans-cyclononene, cis-cyclodecene, and trans-cyclodecene But it can. Among them, preferred is a linear olefin or cyclic olefin having 2 to 20 carbon atoms, more preferred is a linear olefin or cyclic olefin having 2 to 8 carbon atoms, and particularly preferred are ethylene, propylene, 1 -Butene, 1-pentene, cyclopentene, 1-hexene, 4-methyl-1-pentene, or 1-octene.

  The olefins include conjugated dienes such as butadiene and isoprene; chain nonconjugated dienes such as 1,4-pentadiene and 1,5-hexadiene; and cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclononadiene, They may be used in combination with cyclic non-conjugated dienes such as ethylidene norbornene, norbornadiene, and dicyclopentadiene.

The “olefin polymerized unit” in the present invention is a structure produced by a polymerization reaction caused by cleavage of an olefin carbon-carbon double bond, that is, a polymerized unit in an olefin addition polymer (for example, an ethylene addition polymer). (Polymerized unit of —CH ₂ CH ₂ — in a certain polyethylene)

（２）
（式中、Ｙ¹およびＹ²はそれぞれ独立に、水素原子、ハロゲン原子、アルコキシカルボニル基、アラルキルオキシカルボニル基、アリールオキシカルボニル基、ヒドロキシル基、ニトリル基、アルデヒド基、アルキル基、アラルキル基、アリール基、シリル基、シロキシ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アシル基、アミノ基、置換されたアミノ基、アミド基、イミド基、チオール基、アルキルチオ基、アラルキルチオ基、アリールチオ基、アルキルチオキシカルボニル基またはアリールチオキシカルボニル基を表し、Ｙ¹とＹ²とは互いに結合して環を形成していてもよい。Ａ¹、Ａ²、Ａ³、Ａ⁴、Ａ⁵、Ａ⁶、Ａ⁷、Ａ⁸、Ａ⁹、Ａ¹⁰およびＡ¹¹はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アミノ基、置換されたアミノ基、アミド基、イミド基またはアルキルチオ基を表し、Ａ³とＡ⁴とは、または、Ａ⁵とＡ⁶とは、互いに結合して環を形成していてもよい。ｍは０または１を表し、ｎは０〜２０の整数を表す。） From the viewpoint of enhancing the heat resistance of the block copolymer of the present invention, at least one of the polymer units represented by the formula (1) is preferably such that A ⁷ and A ⁸ on the cyclopentane ring are trans-type. Is a polymerization unit represented by the following formula (2).

(2)
Wherein Y ¹ and Y ² are each independently a hydrogen atom, halogen atom, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, hydroxyl group, nitrile group, aldehyde group, alkyl group, aralkyl group, aryl Group, silyl group, siloxy group, alkoxy group, aralkyloxy group, aryloxy group, acyl group, amino group, substituted amino group, amide group, imide group, thiol group, alkylthio group, aralkylthio group, arylthio group, Represents an alkylthioxycarbonyl group or an arylthioxycarbonyl group, and Y ¹ and Y ² may be bonded to each other to form a ring A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ each ^{a 7, a 8, a 9} , a 10 and a ¹¹ are independently a hydrogen atom, a halogen atom, an alkyl group, a Alkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an amino group, substituted amino group, an amido group, an imido group, or an alkylthio group, and A ³ and A ^4, or a A ⁵ A ⁶ may be bonded to each other to form a ring, m represents 0 or 1, and n represents an integer of 0 to 20.)

The ratio of the trans-type arrangement is determined by a ¹³ C-NMR spectrum using a deuterated chloroform solution of the random copolymer of the present invention. In the spectrum, when the peak position of deuterated chloroform as a solvent is 77 ppm, the peak (i) appearing at 45 to 48 ppm is a cyclohexane to which each of A ⁷ and A ⁸ taking a trans configuration is bonded. The peak (ii) assigned to each carbon atom on the pentane ring and appearing at 39 to 42 ppm is the carbon atom on the cyclopentane ring to which each of A ⁷ and A ⁸ taking a cis configuration is bonded. Is attributed to Therefore, the proportion (%) of the trans-type arrangement is the ratio of the area of peak (i) to the total area of peaks (i) and (ii) [100 (i) / {(i) + (ii)} ].

  The homopolymer block (b1-1) in the present invention is a block composed of one type of polymerization unit represented by the formula (1), and one type of diene compound represented by the formula (3) is polymerized. Is generated by The diene compound constituting the homopolymer block (b1-1) is preferably a barbituric acid derivative, an N-alkyl substituted barbituric acid derivative, an N, N′-dialkyl substituted barbituric acid derivative, or an N-aryl substituted barbituric Acid derivatives, N, N'-diaryl substituted barbituric acid derivatives, N-aralkyl substituted barbituric acid derivatives, N, N'-diaralkyl substituted barbituric acid derivatives, N, N'-dialkyl substituted pyrazolidine-3,5-diones Derivatives, N, N′-diaryl substituted pyrazolidine-3,5-dione derivatives, or fluorene derivatives.

  The random copolymer block (b1-2) in the present invention is a block formed by randomly combining at least two kinds of polymer units represented by the formula (1), and is represented by at least the formula (3). It is produced by random copolymerization of two types of diene compounds. The combination of the diene compounds constituting the random copolymer block (b1-2) is preferably 5,5-diallylmerdramic acid and 2,2-dimethyl-5,5-diallyl-1,3-dioxane, 5-diallylmeldrum acid and dimethyl 2,2-diallylmalonic acid, 5,5-diallylmeldrum acid and 2,2-diallyl-1,3-dioxane, 5,5-diallylmeldrum acid and 5,5- Diallyl barbituric acid, 5,5-diallylmeldrum acid and N, N′-dimethyl-4,4-diallylpyrazolidine-3,5-dione, 5,5-diallylmeldrum acid and 9,9-diallyl Fluorene, 2,2-dimethyl-5,5-diallyl-1,3-dioxane and dimethyl 2,2-diallylmalonate, 2,2-dimethyl-5,5-diallyl-1,3-dioxane and 2,2 Diallyl-1,3-dioxane, 2,2-dimethyl-5,5-diallyl-1,3-dioxane and 5,5-diallylbarbituric acid, 2,2-dimethyl-5,5-diallyl-1,3 -Dioxane and N, N'-dimethyl-4,4-diallylpyrazolidine-3,5-dione, 2,2-dimethyl-5,5-diallyl-1,3-dioxane and 9,9-diallylfluorene, 2,2-diallylmalonate dimethyl and 2,2-diallyl-1,3-dioxane, 2,2-diallylmalonate dimethyl and 5,5-diallylbarbituric acid, 2,2-diallylmalonate dimethyl and N, N′-dimethyl-4,4-diallylpyrazolidine-3,5-dione, dimethyl 2,2-diallylmalonate and 9,9-diallylfluorene, 2,2-diallyl-1,3-dioxane and 5 5-diallylbarbituric acid, 2,2-diallyl-1,3-dioxane and N, N′-dimethyl-4,4-diallylpyrazolidine-3,5-dione, 2,2-diallyl-1,3 -Dioxane and 9,9-diallylfluorene, 5,5-diallylbarbituric acid and N, N'-dimethyl-4,4-diallylpyrazolidine-3,5-dione, 5,5-diallylbarbituric acid It is 9,9-diallylfluorene or a combination of N, N′-dimethyl-4,4-diallylpyrazolidine-3,5-dione and 9,9-diallylfluorene.

  The homopolymer block (b2-1) in the present invention is a block having an attribute different from that of the homopolymer block (b1-1), comprising one type of polymer unit represented by the formula (1), It is produced by polymerizing one kind of diene compound represented by the formula (3). The diene compound constituting the homopolymer block (b2-1) is preferably a barbituric acid derivative, an N-alkyl substituted barbituric acid derivative, an N, N′-dialkyl substituted barbituric acid derivative, an N-aryl substituted barbituric Acid derivatives, N, N'-diaryl substituted barbituric acid derivatives, N-aralkyl substituted barbituric acid derivatives, N, N'-diaralkyl substituted barbituric acid derivatives, N, N'-dialkyl substituted pyrazolidine-3,5-diones Derivatives, N, N′-diaryl substituted pyrazolidine-3,5-dione derivatives, or fluorene derivatives.

  As the attributes of the homopolymer blocks (b1-1) and (b2-1), the type of polymerization unit represented by the formula (1) (that is, the type of diene compound represented by the formula (3)), The average molecular weight of the homopolymer block, the molecular weight distribution of the homopolymer block, and the content of the trans-type arrangement represented by the formula (2) can be exemplified. That is, the homopolymer block (b1-1) and the homopolymer block (b2-1) are different in at least one of these attributes.

  The random copolymer block (b2-2) in the present invention is different from the random copolymer block (b1-2) in which at least two kinds of polymer units represented by the formula (1) are randomly combined. A block having an attribute, which is generated by random copolymerization of at least two diene compounds represented by the formula (3). The combination of the diene compounds constituting the random copolymer block (b2-2) is preferably 5,5-diallylmeldrum acid and 2,2-dimethyl-5,5-diallyl-1,3-dioxane, 5-diallylmeldrum acid and dimethyl 2,2-diallylmalonic acid, 5,5-diallylmeldrum acid and 2,2-diallyl-1,3-dioxane, 5,5-diallylmeldrum acid and 5,5- Diallyl barbituric acid, 5,5-diallylmeldrum acid and N, N′-dimethyl-4,4-diallylpyrazolidine-3,5-dione, 5,5-diallylmeldrum acid and 9,9-diallyl Fluorene, 2,2-dimethyl-5,5-diallyl-1,3-dioxane and dimethyl 2,2-diallylmalonate, 2,2-dimethyl-5,5-diallyl-1,3-dioxane and 2,2 Diallyl-1,3-dioxane, 2,2-dimethyl-5,5-diallyl-1,3-dioxane and 5,5-diallylbarbituric acid, 2,2-dimethyl-5,5-diallyl-1,3 -Dioxane and N, N'-dimethyl-4,4-diallylpyrazolidine-3,5-dione, 2,2-dimethyl-5,5-diallyl-1,3-dioxane and 9,9-diallylfluorene, 2,2-diallylmalonate dimethyl and 2,2-diallyl-1,3-dioxane, 2,2-diallylmalonate dimethyl and 5,5-diallylbarbituric acid, 2,2-diallylmalonate dimethyl and N, N′-dimethyl-4,4-diallylpyrazolidine-3,5-dione, dimethyl 2,2-diallylmalonate and 9,9-diallylfluorene, 2,2-diallyl-1,3-dioxane and 5 5-diallylbarbituric acid, 2,2-diallyl-1,3-dioxane and N, N′-dimethyl-4,4-diallylpyrazolidine-3,5-dione, 2,2-diallyl-1,3 -Dioxane and 9,9-diallylfluorene, 5,5-diallylbarbituric acid and N, N'-dimethyl-4,4-diallylpyrazolidine-3,5-dione, 5,5-diallylbarbituric acid It is 9,9-diallylfluorene or a combination of N, N′-dimethyl-4,4-diallylpyrazolidine-3,5-dione and 9,9-diallylfluorene.

  As an attribute of the random copolymer blocks (b1-2) and (b2-2), a combination of a plurality of types of polymerization units represented by formula (1) (that is, a plurality of types represented by formula (3)) Examples of the combination of the diene compounds), the average molecular weight of the random copolymer block, the molecular weight distribution of the random copolymer block, and the content of the trans-type arrangement represented by the formula (2). That is, the random copolymer block (b1-2) and the random copolymer block (b2-2) are different in at least one of these attributes.

  The homopolymer block (b3-1) in the present invention is a block composed of polymerized units of one kind of olefin, and is produced by polymerizing one kind of olefin. The olefin constituting the homopolymer block (b3-1) is preferably ethylene, propylene, 1-butene, 1-pentene, cyclopentene, 1-hexene, 4-methyl-1-pentene, or 1-octene.

  The random copolymer block (b3-2) in the present invention is a block formed by randomly combining at least two types of olefin polymerization units, and is produced by random copolymerization of at least two types of olefins. . The combination of olefins constituting the random copolymer block (b3-2) is preferably ethylene and propylene, ethylene and 1-butene, ethylene and 1-pentene, ethylene and cyclopentene, ethylene and 1-hexene, ethylene and 4- Methyl-1-pentene, ethylene and 1-octene, propylene and 1-butene, propylene and 1-pentene, propylene and cyclopentene, propylene and 1-hexene, propylene and 4-methyl-1-pentene, propylene and 1-octene, 1-butene and 1-pentene, 1-butene and cyclopentene, 1-butene and 1-hexene, 1-butene and 4-methyl-1-pentene, 1-butene and 1-octene, 1-pentene and cyclopentene, 1-butene Pentene and 1-hexene, 1-pentene and 4-methyl-1-pentene, 1-pe N-ten and 1-octene, cyclopentene and 1-hexene, cyclopentene and 4-methyl-1-pentene, cyclopentene and 1-octene, 1-hexene and 4-methyl-1-pentene, 1-hexene and 1-octene, or 4 -A combination of methyl-1-pentene and 1-octene.

In the method for producing a block copolymer of the present invention, the order in which the step (a), the step (b) and / or the step (c) are performed is not limited, and the following order can be exemplified.
(1) Step (a) and step (b) are performed in this order.
(2) Step (a) and step (c) are performed in this order.
(3) Step (A), Step (B), and Step (C) are performed in this order.
Among these, the preferred order is (1) or (2).

  As block copolymers of the present invention, block copolymers of two different Meldrum acid derivatives, block copolymers of Meldrum acid derivatives and barbituric acid derivatives, Meldrum acid derivatives and N, N′-dialkyl-substituted pyrazolidine-3 , 5-dione derivative block copolymer, Meldrum acid derivative and fluorene derivative block copolymer, Meldrum acid derivative and linear olefin block copolymer, Meldrum acid derivative and cyclic olefin block copolymer Polymer, block copolymer of two different barbituric acid derivatives, block copolymer of barbituric acid derivative and N, N'-dialkyl-substituted pyrazolidine-3,5-dione derivative, barbituric acid derivative and fluorene derivative Block copolymers with barbituric acid derivatives and linear olefins A block copolymer of a barbituric acid derivative and a cyclic olefin, a block copolymer of two different N, N′-dialkyl-substituted pyrazolidine-3,5-dione derivatives, N, N′— Block copolymer of dialkyl-substituted pyrazolidine-3,5-dione derivative and fluorene derivative, block copolymer of N, N'-dialkyl-substituted pyrazolidine-3,5-dione derivative and linear olefin, N, N A block copolymer of a '-dialkyl-substituted pyrazolidine-3,5-dione derivative and a cyclic olefin, a block copolymer of two different fluorene derivatives, a block copolymer of a fluorene derivative and a linear olefin, and a fluorene derivative A block copolymer with a cyclic olefin can be exemplified.

Among these, the following block copolymers are preferable.
(1) a block copolymer of a 2,2-diallylindane-1,3-dione homopolymer block (b1-1) and a 1-hexene homopolymer block (b3-1);
(2) 2,2-dimethyl-5-allyl-5-((2E) -2-butenyl) -1,3-dioxane homopolymer block (b1-1) and 2,2-dimethyl-5,5 Block copolymer with diallyl-1,3-dioxane homopolymer block (b2-1): or (3) 5,5-diallylbarbituric acid homopolymer block (b1-1) and 1- Block copolymer with hexene homopolymer block (b3-1).

The block copolymer of the present invention is not a simple mixture of the block (b1) and the block (b2) and / or the block (b3), but a heavy chain in which one end or both ends of each block are covalently bonded to each other. It is a coalescence. The block copolymer of the present invention is produced, for example, by a production method in which the following steps (A) to (C) are carried out in this order using a polymerization catalyst described later.
(A) a step of polymerizing one kind of diene compound represented by the formula (3) to form a homopolymer block (b1-1) of the diene compound;
(B) In the presence of the homopolymer block (b1-1), another one type of diene compound represented by the formula (3) is polymerized, and one end of the homopolymer block (b1-1) An intermediate polymer block (b1-1) (b2-1) in which one end of a homopolymer block (b2-1) of another type of diene compound produced in this step is covalently bonded. And (c) one kind of olefin is polymerized in the presence of the intermediate polymer block, and the other end of (b2-1) of the intermediate polymer block and the olefin generated in this step. A step of producing block copolymers (b1-1) (b2-1) (b3-1) in which one end of the homopolymer block (b3-1) is covalently bonded.

  The reason for the formation of the covalent bond is that the terminal of the homopolymer block (b1-1) in the step (a) continues to have polymerization activity unless it is deactivated as in living polymerization. The diene compound added in the step (b) is polymerized in a chain, and the end of the intermediate polymer block (b1-1) (b2-1) in the step (b) is deactivated as in the living polymerization. This is because the olefin added in the step (c) is polymerized in a chain manner since the polymerization activity continues unless it is treated. In addition, since the terminal of the block copolymer (b1-1) (b2-1) (b3-1) produced | generated at a process (c) also has polymerization activity, unless it deactivates like living polymerization, For example, by pouring the polymerization reaction mixture into methanol, the active terminal is deactivated, and the polymerization reaction is stopped.

  The polymerization in the method for producing a block copolymer of the present invention is preferably carried out in the presence of a polymerization catalyst produced by contacting a transition metal compound with an organoaluminum compound and / or a boron compound.

  Conditions such as the type and concentration of the polymerization catalyst, the concentration of the compound (monomer) to be polymerized, and the polymerization temperature and time in the steps (b), (b) and (c) can be determined for each step. .

  As the transition metal compound, a known transition metal compound containing one or more atoms among iron atom, cobalt atom, nickel atom, palladium atom and copper atom, formula [I], formula [II] (formula Examples of the transition metal compound represented by each of the formula (III) and the transition metal compound (included in [I]), and combinations of two or more of these transition metal compounds.

［Ｉ］
（式［Ｉ］中、Ｍ¹は鉄原子、コバルト原子、ニッケル原子、パラジウム原子または銅原子を表し、Ｒ³およびＲ⁴はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、アルコキシ基、アラルキルオキシ基またはアリールオキシ基を表し、Ｒ⁵、Ｒ⁶、Ｒ⁷およびＲ⁸はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アラルキルオキシカルボニル基、アリールオキシカルボニル基、アミノ基、置換されたアミノ基、アミド基またはアルキルチオ基を表し、Ｒ⁷とＲ⁸とは互いに結合して環を形成していてもよい。）

[I]
(In formula [I], M ¹ represents an iron atom, a cobalt atom, a nickel atom, a palladium atom or a copper atom, and R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group. Group, alkoxy group, aralkyloxy group or aryloxy group, R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aralkyl group. Represents an oxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an amino group, a substituted amino group, an amide group or an alkylthio group, and R ⁷ and R ⁸ are bonded to each other And may form a ring.)

［ＩＩ］
（式［ＩＩ］中、Ｍ¹は鉄原子、コバルト原子、ニッケル原子、パラジウム原子または銅原子を表し、Ｒ³およびＲ⁴はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、アルコキシ基、アラルキルオキシ基またはアリールオキシ基を表し、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³およびＲ¹⁴はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アラルキルオキシカルボニル基、アリールオキシカルボニル基、アミノ基、置換されたアミノ基、アミド基またはアルキルチオ基を表し、Ｒ⁷とＲ⁸とは互いに結合して環を形成していてもよい。）

[II]
(In the formula [II], M ¹ represents an iron atom, a cobalt atom, a nickel atom, a palladium atom or a copper atom, and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group. Group, alkoxy group, aralkyloxy group or aryloxy group, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, halogen atom, alkyl Group, aralkyl group, aryl group, alkoxy group, aralkyloxy group, aryloxy group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, amino group, substituted amino group, amide group or alkylthio group R ⁷ and R ⁸ may be bonded to each other to form a ring.

［ＩＩＩ］
（式［ＩＩＩ］中、Ｍ¹は鉄原子、コバルト原子、ニッケル原子、パラジウム原子または銅原子を表し、Ｒ³およびＲ⁴はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、アルコキシ基、アラルキルオキシ基またはアリールオキシ基を表し、Ｒ¹⁵〜Ｒ²¹はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アラルキルオキシカルボニル基、アリールオキシカルボニル基、アミノ基、置換されたアミノ基、アミド基、またはアルキルチオ基を表し、Ｒ¹⁵〜Ｒ²¹のいずれか２つ以上は互いに結合して環を形成していてもよい。）

[III]
(In the formula [III], M ¹ represents an iron atom, a cobalt atom, a nickel atom, a palladium atom or a copper atom, and R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group. A group, an alkoxy group, an aralkyloxy group or an aryloxy group, wherein R ^{15 to} R ²¹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group. , an acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an amino group, substituted amino group, an amide group or an alkylthio group, any two or more of R ¹⁵ to R ²¹ may bond to each other, And may form a ring.)

M ^{1 in the} formulas [I] and [II] is preferably a nickel atom or a palladium atom.

M ¹ in the formula [III] is preferably an iron atom or a cobalt atom.

The alkyl group, aralkyl group, aryl group, alkoxy group, aralkyloxy group and aryloxy group of R ³ and R ^{4 in} the formulas [I] to [III] are a halogen atom, an alkyloxy group, an aryloxy group, an aralkyloxy group. , A nitro group, an amino group, an amide group, an imide group, a sulfonyl group and an alkylthio group.

R ^{5 to} R ²¹ in formulas [I] to [III] are alkyl groups, aralkyl groups, aryl groups, alkoxy groups, aralkyloxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aralkyloxycarbonyl groups, aryloxycarbonyls. Groups, amino groups, substituted amino groups, amide groups, and alkylthio groups are halogen atoms, alkyloxy groups, aryloxy groups, aralkyloxy groups, nitro groups, amino groups, substituted amino groups, amide groups, imides It may have a substituent such as a group, a sulfonyl group and an alkylthio group.

Examples of the halogen atom of R ^{3 to} R ^{21 in} the formulas [I] to [III] include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the alkyl group of R ^{3 to} R ^{21 in} the formulas [I] to [III], 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 branched alkyl groups such as neopentyl group; and cyclic alkyl groups such as cyclohexyl group and cyclooctyl group. Among them, preferred is an alkyl group having 1 to 16 carbon atoms, more preferred is a linear alkyl group having 1 to 8 carbon atoms, and further preferred is a methyl group or an ethyl group.

As the aralkyl group of R ^{3 to} R ^{21 in} the formulas [I] to [III], a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, 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, (2,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (3,4,5-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, Examples include n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, and anthracenylmethyl group. Among them, preferably an aralkyl group having 7 to 20 carbon atoms, more preferably a benzyl group.

As the aryl groups of R ^{3 to} R ^{21 in} the formulas [I] to [III], 3-methylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 2,3-dimethylphenyl group, 2,4 -Dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,6-dimethylphenyl group, 2,6-di-tert-butylphenyl group, mesityl Group, phenyl group, 2-methylphenyl group, 2-ethylphenyl group, 2-n-propylphenyl group, 2-isopropylphenyl group, 2-n-butylphenyl group, 2-isobutylphenyl group, 2-n-hexyl Phenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenyl group, 2,6-di-n-propylphenyl group, 2,6 Diisopropylphenyl group, 2,6-di-n-butylphenyl group, 2,6-diisobutylphenyl group, 2,6-di-n-hexylphenyl group, 2-methyl-6-ethylphenyl group, 2-methyl- 6-n-propylphenyl group, 2-methyl-6-isopropylphenyl group, 2-methyl-6-butylphenyl group, 2-ethyl-6-n-propylphenyl group, 2-ethyl-6-isopropylphenyl group, 2-ethyl-6-n-butylphenyl group, 2-n-propyl-6-isopropylphenyl group, 2-n-propyl-6-n-butylphenyl group, 2-isopropyl-6-n-butylphenyl group, 2,4,6-trimethylphenyl group, 2,4-dimethyl-6- (2-methylphenyl) phenyl group, 2,4-dimethyl-6- (2-ethylphenyl) phenyl Nyl group, 2,4-dimethyl-6- (2-n-propylphenyl) phenyl group, 2,4-dimethyl-6- (2-isopropylphenyl) phenyl group, 2,4-dimethyl-6- (2, 6-dimethylphenyl) phenyl group, 2,4-dimethyl-6- (2,6-diethylphenyl) phenyl group, 2,4-dimethyl-6- (2,6-di-n-propylphenyl) phenyl group, 2,4-dimethyl-6- (2,6-diisopropylphenyl) phenyl group, 2,4-dimethyl-6- (2-methyl-6-ethylphenyl) phenyl group, 2,4-dimethyl-6- (2 -Methyl-6-n-propylphenyl) phenyl group, 2,4-dimethyl-6- (2-methyl-6-isopropylphenyl) phenyl group, 2,4-dimethyl-6- (2-ethyl-6-n) -Propylfe Nyl) phenyl group, 2,4-dimethyl-6- (2-ethyl-6-isopropylphenyl) phenyl group, 2,4-dimethyl-6- (1-naphthyl) phenyl group, 1-naphthyl group, 2-naphthyl Group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 2,3-dimethyl- 1-naphthyl group, 2,4-dimethyl-1-naphthyl group, 2,5-dimethyl-1-naphthyl group, 2,6-dimethyl-1-naphthyl group, 3,4-dimethyl-1-naphthyl group, 3 , 5-dimethyl-1-naphthyl group, 3,6-dimethyl-1-naphthyl group, 2-methyl-1-anthracenyl group, 3-methyl-10-anthracenyl group, 4-methyl-10-anthracenyl group 2,3-dimethyl-10-anthracenyl group, 2,4-dimethyl-10-anthracenyl group, 2,5-dimethyl-1-10-anthracenyl group, 2,6-dimethyl-10-anthracenyl group, 3,4- Examples thereof include a dimethyl-10-anthracenyl group, a 3,5-dimethyl-10-anthracenyl group, a 3,6-dimethyl-10-anthracenyl group, and a 2-methyl-10-anthracenyl group. Among them, preferred is an aryl group having 6 to 20 carbon atoms, and more preferred are a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-isopropylphenyl group, 4-tert. -Butylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 3,6-dimethylphenyl group, 2,6-diisopropylphenyl group, 2,6-di-tert-butylphenyl group, 3 , 5-di-tert-butylphenyl group or mesityl group, more preferably phenyl group, 2,6-dimethylphenyl group, mesityl group or 2,6-diisopropylphenyl group.

As the alkoxy groups of R ^{3 to} R ^{21 in} the formulas [I] to [III], linear alkoxy groups such as methoxy group, ethoxy group, and n-butoxy group; isopropoxy group, isobutoxy group, tert-butoxy group And branched alkoxy groups such as neopentyloxy group; and cyclic alkoxy groups such as cyclohexyloxy group and cyclooctyloxy group. Among them, preferred is an alkoxy group having 1 to 16 carbon atoms, more preferred is a linear alkoxy group having 1 to 8 carbon atoms, and further preferred is a methoxy group or an ethoxy group.

As the aralkyloxy group of R ^{3 to} R ^{21 in} the formulas [I] to [III], a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, a (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, (2,4,5-trimethylphenyl) methoxy, (2,4,6-trimethylphenyl) methoxy, (3,4,5-to Methylphenyl) 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, and anthracenylmethoxy group It can be illustrated. Among them, an aralkyloxy group having 7 to 20 carbon atoms is preferable, and a benzyloxy group is more preferable.

As the aryloxy groups of R ^{3 to} R ^{21 in} the formulas [I] to [III], a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, 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-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-trimethylphenoxy group, 2,4,6-to Methylphenoxy 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 Group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl- 3,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenol Xyl 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, and anthracenoxy group can do. Among these, an aryloxy group having 6 to 20 carbon atoms is preferable.

Illustrative of the acyl groups of R ^{5 to} R ²¹ of formulas [I]-[III] are acetyl, propanoyl, butanoyl, isobutanoyl, pentanoyl, isopentanoyl, benzoyl, and phenylacetyl groups Can do.

As the alkoxycarbonyl group of R ^{5 to} R ^{21 in} the formulas [I] to [III], a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, Examples thereof include t-butoxycarbonyl group, n-pentoxycarbonyl group, neopentoxycarbonyl group, cyclopentoxycarbonyl group, n-hexoxycarbonyl group, and cyclohexoxycarbonyl group.

Examples of the aralkyloxycarbonyl group of R ^{5 to} R ^{21 in} the formulas [I] to [III] include a benzyloxycarbonyl group, a phenethyloxycarbonyl group, and a cumyloxycarbonyl group.

A phenoxycarbonyl group can be illustrated as an aryloxycarbonyl group of R < ⁵ > -R < ²¹ > of Formula [I]-[III].

As substituted amino groups of R ^{5 to} R ^{21 in} the formulas [I] to [III], an N-methylamino group, an N-ethylamino group, an Nn-butylamino group, an N, N-dimethylamino group, Linear alkylamino groups such as N, N-diethylamino and N, N-di-n-butylamino; N, N-diisopropylamino, N, N-diisobutylamino, N, N-di A branched alkylamino group such as a tert-butylamino group and an N, N-dineopentylamino group; and a cyclic alkyl such as an N, N-dicyclohexylamino group and an N, N-dicyclooctylamino group An amino group can be illustrated.

As the amide group of R ^{5 to} R ^{21 in} the formulas [I] to [III], an ethaneamide group, an Nn-butylethaneamide group, an N-methylethaneamide group, an N-ethylethaneamide group, an Nn-butyl group Examples thereof include a hexaneamide group, an isopropanamide group, an isobutanamide group, a tert-butanamide group, and a neopentanamide group.

Examples of the alkylthio group of R ^{5 to} R ^{21 in} the formulas [I] to [III] include a methylthio group, an ethylthio group, an isopropylthio group, a tert-butylthio group, a benzylthio group, and a 9-fluorenylmethylthio group. .

The transition metal compound is preferably represented by the formula [II] from the viewpoint of producing a random copolymer containing a polymer unit represented by the formula (2) in which A ⁷ and A ⁸ are in a trans configuration. More preferably, from the viewpoint of producing a random copolymer having a high content of the above polymerized units, R ⁹ and R ^{10 in} the formula [II] are each independently an aryl group, and R ¹¹ and R ¹² Are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aralkyloxy group, an amino group, a substituted amino group or an alkylthio group, and more preferably R in the formula [II] ⁹ and R ¹⁰ are each independently an aryl group, and R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group or an aralkyl group.

A ring formed by bonding R ⁷ and R ⁸ in formulas [I] and [II] and any two or more of R ^{15 to} R ²¹ in formula [III] are bonded to each other. Examples of the ring include an aliphatic ring and an aromatic ring. These rings may have a substituent such as a halogen atom, an alkyloxy group, an aryloxy group, an aralkyloxy group, a nitro group, an amino group, a substituted amino group, an amide group, a sulfonyl group, and an alkylthio group. Good.

Examples of the divalent group constituting the aliphatic ring formed by bonding R ⁷ and R ⁸ to each other include a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, Propane-1,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,2-diyl group, pentane-1,3 -Diyl group, pentane-1,4-diyl group, pentane-1,5-diyl group, ethylene-1,2-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1,3-diyl group, norbornane -1,2-diyl group, norborn-5-ene-2,3-diyl group, but-1-ene-1,2-diyl group, but-1-ene-1,3-diyl group, buta-1 -Ene-2,3-diyl group, but-2-ene-1,2-diyl group, But-2-ene-1,3-diyl group, but-2-ene-2,3-diyl group, buta-1,3-diene-1,2-diyl group, buta-1,3-diene-1 , 3-diyl group, buta-1,3-diene-1,4-diyl group, 2,3-dimethyl-2-butene-2,3-diyl group, and 2-pentene-2,4-diyl group. It can be illustrated.

Examples of the divalent group constituting the aromatic ring formed by combining R ⁷ and R ⁸ with each other include a benzene-1,2-diyl group, a 3-methylbenzene-1,2-diyl group, 4-methylbenzene-1,2-diyl group, 3-ethylbenzene-1,2-diyl group, 4-ethylbenzene-1,2-diyl group, 3-n-propylbenzene-1,2-diyl group, 4- n-propylbenzene-1,2-diyl group, 3-n-butylbenzene-1,2-diyl group, 4-n-butylbenzene-1,2-diyl group, 3-isopropylbenzene-1,2-diyl Group, 4-isopropylbenzene-1,2-diyl group, 3-isobutylbenzene-1,2-diyl group, 4-isobutylbenzene-1,2-diyl group, 3-tert-butylbenzene-1,2-diyl Group, 4-tert-bu Tylbenzene-1,2-diyl group, benzene-1,3-diyl group, 2-methylbenzene-1,3-diyl group, 4-methylbenzene-1,3-diyl group, methylenebenzene-1,2-diyl Group, benzene-1,2-dimethylene group, benzene-1,3-dimethylene group and naphthalene-1,8-diyl group.

As the divalent group constituting the aliphatic ring formed by bonding any two or more of R ^{15 to} R ²¹ to each other, a methylene group, an ethane-1,2-diyl group, propane-1, 3-diyl group, propane-1,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,2-diyl group, Pentane-1,3-diyl group, pentane-1,4-diyl group, pentane-1,5-diyl group, ethylene-1,2-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1,3 -Diyl group, norbornane-1,2-diyl group, norborn-5-ene-2,3-diyl group, but-1-ene-1,2-diyl group, but-1-ene-1,3-diyl Group, but-1-ene-2,3-diyl group, but-2-ene- 1,2-diyl group, but-2-ene-1,3-diyl group, but-2-ene-2,3-diyl group, buta-1,3-diene-1,2-diyl group, butane 1,3-diene-1,3-diyl group, buta-1,3-diene-1,4-diyl group, 2,3-dimethyl-2-butene-2,3-diyl group, and 2-pentene- A 2,4-diyl group can be exemplified.

As a divalent group constituting the aromatic ring formed by bonding any two or more of R ^{15 to} R ²¹ to each other, a benzene-1,2-diyl group, 3-methylbenzene-1, 2-diyl group, 4-methylbenzene-1,2-diyl group, 3-ethylbenzene-1,2-diyl group, 4-ethylbenzene-1,2-diyl group, 3-n-propylbenzene-1,2- Diyl group, 4-n-propylbenzene-1,2-diyl group, 3-n-butylbenzene-1,2-diyl group, 4-n-butylbenzene-1,2-diyl group, 3-isopropylbenzene- 1,2-diyl group, 4-isopropylbenzene-1,2-diyl group, 3-isobutylbenzene-1,2-diyl group, 4-isobutylbenzene-1,2-diyl group, 3-tert-butylbenzene- 1,2-diyl group 4-tert-butylbenzene-1,2-diyl group, benzene-1,3-diyl group, 2-methylbenzene-1,3-diyl group, 4-methylbenzene-1,3-diyl group, methylenebenzene Examples include -1,2-diyl group, benzene-1,2-dimethylene group, benzene-1,3-dimethylene group and naphthalene-1,8-diyl group.

As a transition metal compound in which M ¹ represented by the formula [I] or [II] is a palladium atom, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (aniline-κN)] Palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2-methylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2- Diylidene) bis (2-ethylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2-normalpropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2-isopropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2- Nor Rubutylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2-isobutylaniline-κN)] palladium, chloro (methyl) [N, N′- (Ethane-1,2-diylidene) bis (2-normalhexylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (4-methylaniline-κN) ] Palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2,6-dimethylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1) , 2-Diylidene) bis (2,6-diethylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2,6-dinormalpropyla) Phosphorus-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2,6-diisopropylaniline-κN)] palladium, chloro (methyl) [N, N′- (Ethane-1,2-diylidene) bis (2,6-dinormalbutylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2,6- Diisobutylaniline-κN)] palladium,

  Chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2,6-dinorhexylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1, 2-Diylidene) bis (2-methyl-6-ethylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2-methyl-6-normalpropylaniline) -ΚN)] palladium, chloro (methyl) [N, N '-(ethane-1,2-diylidene) bis (2-methyl-6-isopropylaniline-κN)] palladium, chloro (methyl) [N, N' -(Ethane-1,2-diylidene) bis (2-methyl-6-butylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2-ethane Til-6-normalpropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2-ethyl-6-isopropylaniline-κN)] palladium, chloro ( Methyl) [N, N ′-(ethane-1,2-diylidene) bis (2-ethyl-6-normalbutylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2) -Diylidene) bis (2-normalpropyl-6-isopropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2-normalpropyl-6-normalbutyl) Aniline-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis (2-isopropyl-6-normalbutyla) Nilin-κN)] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis {2,4-dimethyl-6- (2-methylphenyl) aniline-κN}] palladium, chloro (Methyl) [N, N ′-(ethane-1,2-diylidene) bis {2,4-dimethyl-6- (2-ethylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′ -(Ethane-1,2-diylidene) bis {2,4-dimethyl-6- (2-normalpropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(ethane-1,2) -Diylidene) bis {2,4-dimethyl-6- (2-isopropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis {2,4 - Methyl-6- (2,6-dimethylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis {2,4-dimethyl-6- (2 , 6-Diethylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis {2,4-dimethyl-6- (2,6-dinormalpropyl) Phenyl) aniline-κN}] palladium,

  Chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis {2,4-dimethyl-6- (2,6-diisopropylphenyl) aniline-κN}] palladium, chloro (methyl) [N , N ′-(ethane-1,2-diylidene) bis {2,4-dimethyl-6- (2-methyl-6-ethylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N′- (Ethane-1,2-diylidene) bis {2,4-dimethyl-6- (2-methyl-6-normalpropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(ethane- 1,2-diylidene) bis {2,4-dimethyl-6- (2-methyl-6-isopropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(ethane-1,2- Jiri ) Bis {2,4-dimethyl-6- (2-ethyl-6-normalpropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis {2,4-Dimethyl-6- (2-ethyl-6-isopropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(ethane-1,2-diylidene) bis {2,4 -Dimethyl-6- (1-naphthyl) aniline-κN}] palladium,

  Chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (aniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (2 -Methylaniline-κN)] palladium, chloro (methyl) [N, N '-(butane-2,3-diylidene) bis (2-ethylaniline-κN)] palladium, chloro (methyl) [N, N'- (Butane-2,3-diylidene) bis (2-normalpropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (2-isopropylaniline-κN) ] Palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (2-normalbutylaniline-κN)] palladium, chloro (methyl) [N, N ′-(bu -2,3-diylidene) bis (2-isobutylaniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (2-normalhexylaniline-κN)] Palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (4-methylaniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2,3- Diylidene) bis (2,6-dimethylaniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (2,6-diethylaniline-κN)] palladium, chloro (Methyl) [N, N ′-(butane-2,3-diylidene) bis (2,6-dinormalpropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(butane 2,3-diylidene) bis (2,6-diisopropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (2,6-dinormalbutylaniline- [kappa] N)] palladium, chloro (methyl) [N, N '-(butane-2,3-diylidene) bis (2,6-diisobutylaniline-κN)] palladium, chloro (methyl) [N, N'-(butane -2,3-diylidene) bis (2,6-dinormalhexylaniline-κN)] palladium, chloro (methyl) [N, N '-(butane-2,3-diylidene) bis (2-methyl-6- Ethylaniline-κN)] palladium,

  Chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (2-methyl-6-normalpropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2) , 3-Diylidene) bis (2-methyl-6-isopropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (2-methyl-6-normalbutyl) Aniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (2-ethyl-6-normalpropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (2-ethyl-6-isopropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2,3-dii) Ridene) bis (2-ethyl-6-normalbutylaniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis (2-normalpropyl-6-isopropylaniline) [kappa] N)] palladium, chloro (methyl) [N, N '-(butane-2,3-diylidene) bis (2-normalpropyl-6-normalbutylaniline- [kappa] N)] palladium, chloro (methyl) [N, N '-(Butane-2,3-diylidene) bis (2-isopropyl-6-normalbutylaniline-κN)] palladium, chloro (methyl) [N, N'-(butane-2,3-diylidene) bis (2 , 4,6-trimethylaniline-κN)] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis {2,4-dimethyl-6 -(2-Methylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis {2,4-dimethyl-6- (2-ethylphenyl) aniline -ΚN}] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis {2,4-dimethyl-6- (2-normalpropylphenyl) aniline-κN}] palladium, chloro (Methyl) [N, N ′-(butane-2,3-diylidene) bis {2,4-dimethyl-6- (2-isopropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′ -(Butane-2,3-diylidene) bis {2,4-dimethyl-6- (2,6-dimethylphenyl) aniline-κN}] palladium,

  Chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis {2,4-dimethyl-6- (2,6-diethylphenyl) aniline-κN}] palladium, chloro (methyl) [N , N ′-(butane-2,3-diylidene) bis {2,4-dimethyl-6- (2,6-dinormalpropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N′- (Butane-2,3-diylidene) bis {2,4-dimethyl-6- (2,6-diisopropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(butane-2,3 -Diylidene) bis {2,4-dimethyl-6- (2-methyl-6-ethylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis {2,4 Dimethyl-6- (2-methyl-6-normalpropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis {2,4-dimethyl-6 -(2-Methyl-6-isopropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis {2,4-dimethyl-6- (2- Ethyl-6-normalpropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis {2,4-dimethyl-6- (2-ethyl-6) -Isopropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(butane-2,3-diylidene) bis {2,4-dimethyl-6- (1-naphthyl) anily -κN}] palladium,

  Chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bisaniline-κN] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthyl) Len-1,2-diylidene) bis (2-methylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2- Ethylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2-normalpropylaniline-κN)] palladium, chloro (methyl ) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2-isopropylaniline-κN)] palladium, chloro (methyl) [N, N′— (1,2-dihydroacenaphthylene-1,2-diylidene) bis (4-methylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1, 2-diylidene) bis (2-normalbutylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2-isobutylaniline) κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2-normalhexylaniline-κN)] palladium, chloro (methyl) [N , N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2,6-dimethylaniline-κN)] palladium, chloro (methyl) [N, N ′-( 1,2-dihydroacenaphthylene-1,2-diylidene) bis (2,6-diethylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1) , 2-diylidene) bis (2,6-dinormalpropylaniline-κN)] palladium,

  Chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2,6-diisopropylaniline-κN)] palladium, chloro (methyl) [N, N′- (1,2-dihydroacenaphthylene-1,2-diylidene) bis (2,6-dinormalbutylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthy Len-1,2-diylidene) bis (2,6-diisobutylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis ( 2,6-dinormalhexylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2-methyl-6- Tylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2-methyl-6-normalpropylaniline-κN)] palladium, Chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2-methyl-6-isopropylaniline-κN)] palladium, chloro (methyl) [N, N '-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2-methyl-6-normalbutylaniline-κN)] palladium, chloro (methyl) [N, N'-(1,2- Dihydroacenaphthylene-1,2-diylidene) bis (2-ethyl-6-normalpropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-di-) Droacenaphthylene-1,2-diylidene) bis (2-ethyl-6-isopropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2) -Diylidene) bis (2-ethyl-6-normalbutylaniline-κN)] palladium,

  Chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2-normalpropyl-6-isopropylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2-normalpropyl-6-normalbutylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1, 2-dihydroacenaphthylene-1,2-diylidene) bis (2-isopropyl-6-normalbutylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene- 1,2-diylidene) bis (2,4,6-trimethylaniline-κN)] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene) 1,2-diylidene) bis {2,4-dimethyl-6- (2-methylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1) , 2-Diylidene) bis {2,4-dimethyl-6- (2-ethylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1, 2-Diylidene) bis {2,4-dimethyl-6- (2-normalpropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1, 2-diylidene) bis {2,4-dimethyl-6- (2-isopropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1, -Diylidene) bis {2,4-dimethyl-6- (2,6-dimethylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1, 2-Diylidene) bis {2,4-dimethyl-6- (2,6-diethylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1) , 2-diylidene) bis {2,4-dimethyl-6- (2,6-dinormalpropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthy Len-1,2-diylidene) bis {2,4-dimethyl-6- (2,6-diisopropylphenyl) aniline-κN}] palladium,

  Chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis {2,4-dimethyl-6- (2-methyl-6-ethylphenyl) aniline-κN} ] Palladium, chloro (methyl) [N, N '-(1,2-dihydroacenaphthylene-1,2-diylidene) bis {2,4-dimethyl-6- (2-methyl-6-normalpropylphenyl)] Aniline-κN}] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis {2,4-dimethyl-6- (2-methyl-6- Isopropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis {2,4-dimethyl-6- (2-ethyl) -6-no Malpropylphenyl) aniline-κN}] palladium, chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis {2,4-dimethyl-6- (2- Ethyl-6-isopropylphenyl) aniline-κN}] palladium and chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis {2,4-dimethyl- 6- (1-naphthyl) aniline-κN}] palladium.

As a transition metal compound in which M ¹ represented by the formula [I] or [II] is a nickel atom, an iron atom, a copper atom or a cobalt atom, the palladium atom in the palladium compound is a nickel atom, an iron atom, a copper atom or A compound substituted with a cobalt atom can be exemplified.

As a transition metal compound in which M ¹ represented by the formula [III] is an iron atom, 2,6-bis- [1- (2,6-dimethylphenylimino) ethyl] pyridine iron dichloride, 2,6-bis- [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron dichloride, 2,6-bis- [1- (2-tert-butyl-phenylimino) ethyl] pyridine iron dichloride, [hydrotris (3,5- [Dimethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-dimethylpyrazolyl) borate] iron bromide, [hydrotris (3,5-dimethylpyrazolyl) borate] iron iodide, [hydrotris (3,5-dimethylpyrazolyl) borate ] Iron methyl, [Hydrotris (3,5 [Dimethylpyrazolyl) borate] ethyl iron, [hydrotris (3,5-dimethylpyrazolyl) borate] iron allyl, [hydrotris (3,5-dimethylpyrazolyl) borate] iron methallyl, [hydrotris (3,5-diethylpyrazolyl) borate Iron chloride, [hydrotris (3,5-diethylpyrazolyl) borate] iron bromide, [hydrotris (3,5-diethylpyrazolyl) borate] iron iodide, [hydrotris (3,5-diethylpyrazolyl) borate] iron methyl, [Hydrotris (3,5-diethylpyrazolyl) borate] iron ethyl, [hydrotris (3,5-diethylpyrazolyl) borate] iron allyl, [hydrotris (3,5-diethylpyrazolyl) Borate] iron methallyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron chloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron bromide, [hydrotris (3,5 -Di-tert-butylpyrazolyl) borate] iron iodide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron methyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron Examples thereof include ethyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron allyl, and [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron methallyl.

As the transition metal compound in which M ¹ represented by the formula [III] is a nickel atom, a palladium atom, a copper atom, or a cobalt atom, the iron atom in the iron compound is a nickel atom, a palladium atom, a copper atom, or cobalt. Examples include compounds substituted with atoms.

  Two or more kinds of the transition metal compounds may be combined.

The organoaluminum compound may be a known compound. Examples of the organoaluminum compound include the following compounds (A1) to (A3) and combinations of two or more thereof.
(A1) an organoaluminum compound represented by the formula E ¹ _d AlX ² _3-d ;
(A2) a cyclic aluminoxane represented by the formula {—Al (E ² ) —O—} _e ; and (A3) a formula E ³ {—Al (E ³ ) —O—} _f AlE ³ ₂ Linear aluminoxane;
(In the formula, E ¹ , E ² and E ³ each represent a hydrocarbon group, and when a plurality of E ¹ , a plurality of E ² or a plurality of E ³ are present, they are the same or different from each other. X ² is hydrogen. An atom or a halogen atom, and when there are a plurality of X ² , they are the same or different, d represents a number satisfying 0 <d ≦ 3, e is an integer of 2 or more, preferably an integer of 2 to 40 F is an integer of 1 or more, preferably an integer of 1 to 40.)

The hydrocarbon group of E ¹ , E ² and E ³ is preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. Examples of E ¹ , E ² and E ³ are alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, and neopentyl. it can. Of these, a methyl group or an isobutyl group is preferable.

  Examples of the organoaluminum compound represented by (A1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride Dialkylaluminum chlorides such as methyl, diisobutylaluminum chloride, and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, and hexylaluminum dichloride; Mini um hydride, diethylaluminum hydride, can be exemplified dipropyl aluminum hydride, diisobutylaluminum hydride, and the dialkyl aluminum hydride such as dihexyl aluminum hydride. Among them, preferred is trialkylaluminum, and more preferred is triethylaluminum or triisobutylaluminum.

  The organoaluminum compounds represented by (A2) and (A3) can be produced by various methods. Their production methods are not particularly limited, and may be known production methods. As a production method, a method in which a trialkylaluminum such as trimethylaluminum is dissolved in a suitable organic solvent such as benzene and an aliphatic hydrocarbon is brought into contact with water. A trialkylaluminum such as trimethylaluminum is produced. An example is a method of producing by contacting with a metal salt containing water of crystallization, such as copper sulfate hydrate.

The boron compound may be a known compound. Examples of the boron compound include compounds represented by the following (B1) to (B3) and combinations of two or more thereof.
(B1) a boron compound represented by the formula BQ ¹ Q ² Q ³ ;
(B2) a boron compound represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ ; and (B3) a formula (JH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ Boron compounds;
(In the formula, B represents a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ each independently represent a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silyl group, a siloxy group, an alkoxy group, Represents an amino group, a substituted amino group, an amide group, or an imide group, G ⁺ represents an inorganic or organic cation, J represents a neutral Lewis base, and (J—H) ⁺ represents a Bronsted acid. .)

Q ^{1 to} Q ⁴ in (B1) to (B3) are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom. -20 silyl group or siloxy group, amino group substituted with a hydrocarbon group having 2 to 20 carbon atoms, amide group substituted with a hydrocarbon group having 2 to 20 carbon atoms, or 2 to 20 carbon atoms More preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon 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.

  Examples of the boron compound represented by (B1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5-tetrafluorophenyl). Examples include borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, and phenylbis (pentafluorophenyl) borane. Of these, tris (pentafluorophenyl) borane is most preferable.

Examples of G ⁺ that is an inorganic cation in the boron compound represented by (B2) include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation. An example of G ⁺ that is an organic cation is a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, particularly preferably a triphenylmethyl cation.

As (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ in the (B2), 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, and tetrakis ( 3,5-bistrifluoromethylphenyl) borate can be exemplified.

  Examples of the boron compound represented by (B2) include lithium tetrakis (3,5-bistrifluoromethylphenyl) borate, sodium tetrakis (3,5-bistrifluoromethylphenyl) borate, potassium tetrakis (3,5-bistrifluoromethyl). Phenyl) 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, trimethylsulfate Illustrative examples include nium tetrakis (pentafluorophenyl) borate, diphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and triphenylcarbenium tetrakis (3,5-bistrifluoromethylphenyl) borate can do. Of these, triphenylcarbenium tetrakis (pentafluorophenyl) borate is most preferable.

Examples of (JH) ⁺ in (B3) include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, and triarylphosphonium. (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ The same thing as the above can be illustrated.

  Examples of the boron compound represented by (B3) include 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-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethyl) Nyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and An example is tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate. Among these, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate is most preferable.

  The boron compound in the present invention is preferably a boron compound represented by the above (B2) or (B3), and particularly preferably triphenylcarbenium tetrakis (pentafluorophenyl) borate or tri (n-butyl) ammonium tetrakis. (Pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

  The weight average molecular weight (Mw) of the block copolymer of the present invention is preferably 1,000 to 10,000,000, more preferably 2,000 to 5,000,000, most preferably 4, 000 to 3,000,000.

  The weight average molecular weight (Mw) of each of the blocks (b1), (b2) and (b3) constituting the block copolymer of the present invention is preferably 95 to 2,000,000, more preferably 1 From 1,000 to 1,000,000, most preferably from 2,000 to 500,000.

  The molecular weight distribution (Mw) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of each of the block copolymer of the present invention, block (b1), block (b2) and block (b3) / Mn) is preferably 1.0 to 50, more preferably 1.0 to 20, and most preferably 1.0 to 10.

  The block copolymer of the present invention preferably exhibits at least one glass transition point. The glass transition point is preferably −20 ° C. or higher, more preferably 20 ° C. or higher, and most preferably 50 ° C. or higher.

  In the present invention, the method for contacting the compound represented by the formula (3), the olefin, the transition metal compound, the organoaluminum compound and / or the boron compound is not particularly limited.

  When forming a polymerization catalyst by bringing a transition metal compound into contact with an organoaluminum compound, from the viewpoint of increasing the activity of the polymerization catalyst, as the organoaluminum compound, (A2) cyclic aluminoxane, (A3) linear aluminoxane, or these The combination of is preferable. When obtaining a polymerization catalyst by bringing a transition metal compound, an organoaluminum compound and a boron compound into contact, the organoaluminum compound (A1) is preferred as the organoaluminum compound from the same viewpoint.

  The amount of the organoaluminum compound used is usually 0.1 to 10,000 mole parts, preferably 5 to 2,000 mole parts, per mole part of the transition metal compound. The usage-amount of a boron compound is 0.01-100 mol part normally per 1 mol part of transition metal compounds, Preferably it is 0.5-10 mol part.

  Each of the transition metal compound, organoaluminum compound, and boron compound may be used as a solution. Examples of the solvent for the solution include methylene chloride, chloroform, toluene, pentane, hexane, and heptane. Among these, methylene chloride, chloroform, or toluene is preferable.

  The density | concentration of a transition metal compound solution is 0.01-500 micromol / L normally, Preferably it is 0.05-100 micromol / L, More preferably, it is 0.05-50 micromol / L. The concentration of the organoaluminum compound solution is usually 0.01 to 10,000 μmol / L, preferably 0.1 to 5,000 μmol / L, more preferably 0.1 to 2,000 μmol, in terms of aluminum atoms. / L. The density | concentration of a boron compound solution is 0.01-500 micromol / L normally, Preferably it is 0.05-200 micromol / L, More preferably, it is 0.05-100 micromol / L.

  The polymerization catalyst may be combined with a carrier made of an inorganic compound or an organic compound particulate material. Examples of the inorganic compound include silica gel and alumina. A styrene polymer can be illustrated as an organic compound.

  Examples of the polymerization method in the present invention include batch type or continuous type gas phase polymerization method, bulk polymerization method, and solution polymerization method or slurry polymerization method using an appropriate polymerization solvent. The polymerization solvent is a solvent that does not deactivate the polymerization catalyst, and examples of the solvent include hydrocarbon solvents such as benzene, toluene, pentane, hexane, heptane, and cyclohexane, and halogenated solvents such as dichloromethane and chloroform. be able to.

  The polymerization temperature in the present invention is generally −100 to 250 ° C., preferably −50 to 200 ° C. The polymerization time is generally from 1 minute to 72 hours.

  In the production method of the present invention, a chain transfer agent such as hydrogen may be used in order to adjust the molecular weight of the obtained random copolymer.

  The copolymer of the present invention can be used as an extrusion molded product or an injection molded product. The extrusion molding method may be a known molding method. As extrusion molding methods, an inflation molding method in which a molten resin is extruded from a circular die and a film or sheet expanded in a cylindrical shape is wound, or a molten resin is extruded from a linear die and a T die in which the film or sheet is wound up. Examples thereof include a molding method and a calendar molding method.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples.
[Example 1]
Chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2,6-diisopropylaniline-κN)] palladium (transition metal compound, “Reque de Travo” 6.6 mg (0.01 mmol) synthesized with reference to “Recueil des Travaux Chimiques de Pays-Bas”, Vol. 113, 1994, p. 88, sodium tetrakis (3,5- 10.6 mg (0.012 mmol) of bistrifluoromethylphenyl) borate (boron compound, synthesized with reference to “Organometallics” Vol. 11, 1992, page 3920) and 0.25 mL of methylene chloride In a Schlenk flask. To this, 90.5 mg (0.4 mmol) of 2,2-diallylindane-1,3-dione (diene compound represented by the formula (3)) was added, and the mixture was allowed to stand at −5 ° C. for 4 days. The whole amount of the diene compound was polymerized. The resulting reaction mixture is cooled to −20 ° C., 50 mL (0.4 mmol, olefin) of 1-hexene and 0.25 mL of methylene chloride are added thereto, and the mixture is stirred for 36 hours to polymerize the total amount of 1-hexene. I let you. The obtained reaction mixture was poured into methanol, and the resulting precipitate was filtered and dried, and a homopolymer comprising 2,2-diallylindane-1,3-dione and a polymerized unit represented by the formula (1) A block copolymer comprising a block (b1-1) and a 1-hexene homopolymer block (b3-1) was obtained. The block copolymer had a number average molecular weight of 14,300 and a molecular weight distribution of 1.46. Separately, the first reaction mixture was post-treated in the same manner as above to obtain a homopolymer of 2,2-diallylindane-1,3-dione. The number average molecular weight of the homopolymer was 9300, and the molecular weight distribution was 1.22.

The block copolymer having a unit represented by the formula (1) means that a signal group in the range of 23 to 50 ppm in the spectrum of the ¹³ C-NMR analysis has a structure represented by the formula (1). It confirmed by assigning as a linear hydrocarbon and a five-membered cyclic hydrocarbon.
Measuring solvent: chloroform-d ₁
Measurement temperature: room temperature Sample concentration: 50 mg / 0.5 ml
Reference material: chloroform-d ₁ (77 ppm)

The number average molecular weight and molecular weight distribution were measured by gel permeation chromatography (GPC) under the following conditions. A calibration curve was prepared using standard polystyrene.
Measuring instrument: manufactured by JASCO (Degasser: DG-980-50, pump: PU-980, autosampler: AS-950, column oven: CO-966, RI detector: RI-930, UV detector: UV-975 )
Column: Shodex-806L x 2 manufactured by Showa Denko KK Measurement temperature: 40 ° C
Solvent: Chloroform Sample concentration: 1 mg / 1 ml

[Example 2]
Chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2,6-diisopropylaniline-κN)] palladium (transition metal compound) 13.2 mg (0. 02 mmol) and 21.2 mg (0.024 mmol) of sodium tetrakis (3,5-bistrifluoromethylphenyl) borate (boron compound) were placed in a 25 mL Schlenk tube. To this was added 1.0 mL of methylene chloride and the mixture was stirred for 10 minutes. The obtained mixture was cooled to −20 ° C., and 2,2-dimethyl-5-allyl-5-((2E) -2-butenyl) -1,3-dioxane (represented by the formula (3)) was obtained. Compound) 168.2 mg was added and stirred at −20 ° C. for 22 hours. To the obtained reaction mixture, 157.0 mg of 2,2-dimethyl-5,5-diallyl-1,3-dioxane (a compound represented by the formula (3)) was added, and the temperature was lowered to -30 ° C. Stir at temperature for 55 hours. The resulting reaction mixture was poured into methanol, and the resulting precipitate was filtered off and dried, and 2,2-dimethyl-5-allyl-5-((2E) -2-butenyl) -1,3-dioxane alone 257 mg of a block copolymer consisting of the polymer block (b1-1) and 2,2-dimethyl-5,5-diallyl-1,3-dioxane homopolymer block (b2-1) was obtained. The block copolymer is soluble in chloroform, methylene chloride and tetrahydrofuran, insoluble in hexane and methanol, and has a number average molecular weight of 22800, a molecular weight distribution of 1.28, and a temperature range of -20 ° C to 180 ° C. It had a glass transition point. All the polymer units represented by the formula (1) contained in the block copolymer had a trans-type arrangement represented by the formula (2). Separately, the first reaction mixture was worked up as described above to obtain a homopolymer of 2,2-dimethyl-5-allyl-5-((2E) -2-butenyl) -1,3-dioxane. The homopolymer had a number average molecular weight of 12,400 and a molecular weight distribution of 1.13.

The glass transition point was measured under the following conditions by differential scanning calorimetry (DSC) measurement using a model having the name SSC-5200 manufactured by Seiko Denshi Kogyo Co., Ltd.
(1) The temperature is raised from 25 ° C. to 180 ° C. at a rate of 10 ° C./min and held at 180 ° C. for 5 minutes.
(2) Cool from 180 ° C. to −20 ° C. at a rate of 20 ° C./min and hold at −20 ° C. for 5 minutes.
(3) The glass transition point is measured from −20 ° C. to 180 ° C. at a rate of 10 ° C./min.

The proportion of the transformer type arrangement was determined under the following conditions by ¹³ C-NMR analysis using a model named LA-500 manufactured by JEOL.
Measuring solvent: chloroform-d ₁
Measurement temperature: room temperature Sample concentration: 50 mg / 0.5 ml
Reference material: chloroform-d ₁ (77 ppm)

[Example 3]
Chloro (methyl) [N, N ′-(1,2-dihydroacenaphthylene-1,2-diylidene) bis (2,6-diisopropylaniline-κN)] palladium (transition metal compound) 50 mg (0.076 mmol) Then, an excess amount of sodium tetrakis (3,5-bistrifluoromethylphenyl) borate (boron compound) 80 mg (0.09 mmol) with respect to the transition metal compound was placed in a Schlenk flask. To this was added 2.75 mL of methylene chloride and stirred at room temperature for 5 minutes. The obtained reaction mixture was filtered and separated into a filtrate and an insoluble component (mainly containing unreacted boron compound and NaCl generated by the reaction). The filtrate was cooled to −20 ° C., 117 mg (0.56 mmol) of 5,5-diallylbarbituric acid (compound represented by formula (3)) was added thereto, and the resulting suspension was added to −20 ° C. For 2 days. The reaction mixture was filtered to remove unreacted 5,5-diallylbarbituric acid, and 5 mL of hexane was added to the filtrate. The temperature of the obtained solution was lowered from −20 ° C. to −40 ° C. over 1 hour. The solution is allowed to stand at −40 ° C. for 4 days, and a red solid compound in which one molecule of 5,5-diallylbarbituric acid, one equivalent of a cation complex of a transition metal compound, and one equivalent of an anion of a boron compound are combined. 78 mg (0.046 mmol) were obtained. The polymerization rate (polymerization rate) of 5,5-diallylbarbituric acid was 54%. A solution was prepared by placing 17 mg (0.01 mmol) of the solid compound and 0.5 mL of methylene chloride in a Schlenk flask. When 0.08 mL (0.7 mmol) of 1-hexene was added to the solution and reacted at −20 ° C. for 1.5 days, 1-hexene reacted almost completely. The obtained reaction mixture (solution) was poured into methanol, and the resulting precipitate was filtered and dried under reduced pressure to obtain a homopolymer block (b1-1) of 5,5-diallylbarbituric acid and 1-hexene alone. A block copolymer comprising the polymer block (b2-1) was obtained. The block copolymer has a number average molecular weight of 8,200 and a molecular weight distribution of 1.12. The block copolymer is composed of 1 mol% of polymer units represented by the formula (1) of 5,5-diallylbarbituric acid. And 99 mol% of 1-hexene polymerized units (the total of both polymerized units is 100 mol%).

The polymerization unit amount was determined under the following conditions using ¹ H-NMR (LA-500 manufactured by JEOL Ltd.).
Measuring solvent: chloroform-d ₁
Measurement temperature: room temperature Sample concentration: 50 mg / 0.5 ml
Reference material: chloroform-d ₁ (77 ppm)

Claims (8)

A block copolymer comprising the following block (b1), block (b2) and / or block (b3).
Block (b1): a homopolymer block (b1-1) or a random copolymer block (b1-2) comprising polymerized units of at least one compound represented by the following formula (1)
Block (b2): a homopolymer block (b2-1) having an attribute different from that of the homopolymer block (b1-1) comprising polymerized units of at least one compound represented by the following formula (1), or Random copolymer block (b2-2) having attributes different from those of the random copolymer block (b1-2)
Block (b3): homopolymer block (b3-1) or random copolymer block (b3-2) comprising polymerized units of at least one olefin

(1)
Wherein Y ¹ and Y ² are each independently a hydrogen atom, halogen atom, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, hydroxyl group, nitrile group, aldehyde group, alkyl group, aralkyl group, aryl Group, silyl group, siloxy group, alkoxy group, aralkyloxy group, aryloxy group, acyl group, amino group, substituted amino group, amide group, imide group, thiol group, alkylthio group, aralkylthio group, arylthio group, Represents an alkylthioxycarbonyl group or an arylthioxycarbonyl group, and Y ¹ and Y ² may be bonded to each other to form a ring A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ each ^{a 7, a 8, a 9} , a 10 and a ¹¹ are independently a hydrogen atom, a halogen atom, an alkyl group, a Alkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an amino group, substituted amino group, an amido group, an imido group, or an alkylthio group, and A ³ and A ^4, or a A ⁵ A ⁶ may be bonded to each other to form a ring, m represents 0 or 1, and n represents an integer of 0 to 20.) 2. The polymer unit represented by the following formula (2) in which at least one polymer unit of the polymer units represented by the formula (1) is in a trans configuration is A ⁷ and A ^8: The block copolymer as described.

(2)
Wherein Y ¹ and Y ² are each independently a hydrogen atom, halogen atom, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, hydroxyl group, nitrile group, aldehyde group, alkyl group, aralkyl group, aryl Group, silyl group, siloxy group, alkoxy group, aralkyloxy group, aryloxy group, acyl group, amino group, substituted amino group, amide group, imide group, thiol group, alkylthio group, aralkylthio group, arylthio group, Represents an alkylthioxycarbonyl group or an arylthioxycarbonyl group, and Y ¹ and Y ² may be bonded to each other to form a ring A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ each ^{a 7, a 8, a 9} , a 10 and a ¹¹ are independently a hydrogen atom, a halogen atom, an alkyl group, a Alkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an amino group, substituted amino group, an amido group, an imido group, or an alkylthio group, and A ³ and A ^4, or a A ⁵ A ⁶ may be bonded to each other to form a ring, m represents 0 or 1, and n represents an integer of 0 to 20.) Block co-polymerization consisting of the following block (b1) and the following block (b2) and / or block (b3), comprising any order of the following step (b) and the following step (b) and / or step (c) Manufacturing method of coalescence.
Step (a): Step of polymerizing at least one diene compound represented by the following formula (3) to produce a homopolymer block (b1-1) or a random copolymer block (b1-2) (B): A homopolymer block (b2-1) having an attribute different from that of the homopolymer block obtained by polymerizing at least one diene compound represented by the following formula (3), or the random copolymer: Step of generating a random copolymer block (b2-2) having an attribute different from that of the block Step (c): Polymerizing at least one kind of olefin to produce a homopolymer block (b3-1) or copolymer of olefin Step of generating block (b3-2) Block (b1): homopolymer block comprising polymerized units of at least one compound represented by the following formula (1) b1-1) or a random copolymer block (b1-2)
Block (b2): a homopolymer block (b2-1) having an attribute different from that of the homopolymer block (b1-1) comprising polymerized units of at least one compound represented by the following formula (1), or Random copolymer block (b2-2) having attributes different from those of the random copolymer block (b1-2)
Block (b3): homopolymer block (b3-1) or random copolymer block (b3-2) comprising polymerized units of at least one olefin

(1)

(3)
(In the formulas (1) and (3), Y ¹ and Y ² are each independently a hydrogen atom, halogen atom, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, hydroxyl group, nitrile group, aldehyde group, Alkyl group, aralkyl group, aryl group, silyl group, siloxy group, alkoxy group, aralkyloxy group, aryloxy group, acyl group, amino group, substituted amino group, amide group, imide group, thiol group, alkylthio group, Represents an aralkylthio group, an arylthio group, an alkylthioxycarbonyl group or an arylthioxycarbonyl group, and Y ¹ and Y ² may be bonded to each other to form a ring A ¹ , A ² , A ³ , A ^{4, a 5, a 6,} a 7, a 8, a 9, a 10 and a ¹¹ each independently represent a hydrogen atom, a halogen Child, alkyl group, aralkyl group, aryl group, alkoxy group, aralkyloxy group, aryloxy group, amino group, substituted amino group, an amido group, an imido group, or an alkylthio group, and A ³ and A ^4, Alternatively, A ⁵ and A ⁶ may be bonded to each other to form a ring, m represents 0 or 1, and n represents an integer of 0 to 20.) The polymer unit represented by the following formula (2) in which at least one polymer unit among the polymer units represented by the formula (1) is a trans configuration is A ⁷ and A ^8: The manufacturing method of the block copolymer of description.

(2)
Wherein Y ¹ and Y ² are each independently a hydrogen atom, halogen atom, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, hydroxyl group, nitrile group, aldehyde group, alkyl group, aralkyl group, aryl Group, silyl group, siloxy group, alkoxy group, aralkyloxy group, aryloxy group, acyl group, amino group, substituted amino group, amide group, imide group, thiol group, alkylthio group, aralkylthio group, arylthio group, Represents an alkylthioxycarbonyl group or an arylthioxycarbonyl group, and Y ¹ and Y ² may be bonded to each other to form a ring A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ each ^{a 7, a 8, a 9} , a 10 and a ¹¹ are independently a hydrogen atom, a halogen atom, an alkyl group, a Alkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an amino group, substituted amino group, an amido group, an imido group, or an alkylthio group, and A ³ and A ^4, or a A ⁵ A ⁶ may be bonded to each other to form a ring, m represents 0 or 1, and n represents an integer of 0 to 20.)   The method for producing a block copolymer according to claim 3 or 4, wherein the polymerization is carried out in the presence of a polymerization catalyst produced by contacting the transition metal compound with an organoaluminum compound and / or a boron compound. 6. The method for producing a block copolymer according to claim 5, wherein the transition metal compound is a compound represented by the following formula [I].

[I]
(In the formula, M ¹ represents an iron atom, cobalt atom, nickel atom, palladium atom or copper atom transition metal atom, and R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group. , An aryl group, an alkoxy group, an aralkyloxy group, or an aryloxy group, wherein R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, Represents an alkoxy group, an aralkyloxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an amino group, a substituted amino group, an amide group, or an alkylthio group, and R ⁷ and R ⁸ may be bonded to each other to form a ring.) The method for producing a block copolymer according to claim 5, wherein the transition metal compound is a compound represented by the following formula [II].

[II]
(In the formula, M ¹ represents an iron atom, cobalt atom, nickel atom, palladium atom or copper atom transition metal atom, and R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group. , An aryl group, an alkoxy group, an aralkyloxy group, or an aryloxy group, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently a hydrogen atom, Halogen atom, alkyl group, aralkyl group, aryl group, alkoxy group, aralkyloxy group, aryloxy group, acyl group, alkoxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, amino group, substituted amino group, amide Represents a group or an alkylthio group, and R ⁷ and R ⁸ may be bonded to each other to form a ring.) The method for producing a block copolymer according to claim 5, wherein the transition metal compound is a compound represented by the following formula [III].

[III]
(In the formula, M ¹ represents an iron atom, cobalt atom, nickel atom, palladium atom or copper atom transition metal atom, and R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group. , An aryl group, an alkoxy group, an aralkyloxy group, or an aryloxy group, R ^{15 to} R ²¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an amino group, substituted amino group, an amide group or an alkylthio group, any two or more of R ¹⁵ to R ^21, May be bonded to each other to form a ring.)