JP5095476B2 - Poly (diene-arylene) and process for producing the same - Google Patents

Description

  The present invention relates to a method for producing poly (diene-arylene), diene-aryl, and poly (diene-arylene), and in particular, poly (diene-arylene) having a repeating unit composed of diene-aryl in the main chain and the production thereof. Regarding the method.

Poly (diene-arylene) s such as poly (vinylphenylene) and poly (vinylidenephenylene) are of interest because the arylene groups contained in the repeating units have excellent thermal and chemical stability. In addition, poly (diene-arylene) has developed a π-electron conjugated system, and has attracted attention for its unique physical properties.
Poly (diene-arylene) is expected to have various applications as, for example, a conductive polymer.
Poly (diene-arylene) is expected to be applied to polymer light emitting devices. In this field, an element called a polymer light-emitting electrochemical element (LEC) has recently been proposed, and has attracted attention because of its high luminous efficiency. The structure consists of a conductive polymer, a polymer membrane composed of polyethylene oxide and supporting salt having ion conductivity between both electrodes, positive and negative charges injected from the electrode and positive and negative ions of the supporting salt as a dopant. It is presumed that the operation principle is that a pn junction is formed in the film by the movement of. If ionic conductivity can be further imparted to the conductive polymer having electron conductivity, the device can be manufactured with a single material instead of the composite film as described above, which has a great advantage in terms of process.
For example, the use of poly (p-phenylene-vinylene) for a light emitting element is reported in Chemical & Engineering News, January 19, 1998, page 9 (Patent Document 1).
Conventionally, methods for producing poly (diene-arylene) and the like have been limited. As a related method for producing polyphenylene, for example, oxidative cationic polymerization called cobasic method is known as a condensation polymerization method using benzene as a monomer. P. Kovacic, et al. Chem. Rev. , 1987, 87, 357-379 (Patent Document 2), generally using an oxidizing agent such as cupric chloride and a Lewis acid catalyst such as aluminum chloride. As a result. Polyphenylene produced by the oxidation of benzene is said to have a low molecular weight with a branched chain.
Also, electrochemical oxidation polymerization (a method of applying a voltage between electrodes using a cupric chloride-lithium arsenium hexafluoride electrolyte to obtain a polymer on the electrodes), a method of condensation polymerization of substituted benzene derivatives As the Wurzfiti reaction (method of condensing dihalogenobenzene with an alkali metal), Ullmann reaction (method of condensing diiodobenzene with metal copper), and the Grignard reaction called the Yamamoto method (chlorinating a glynarial derivative of dihalogenobenzene) A method of condensing with a nickel bipyridyl complex), a diazonium coupling method (a method of condensing a diazonium derivative by treatment with sodium nitrite / hydrochloric acid and then with copper chloride), a method via a precursor, a dehydration reaction of a polymer of cyclohexadiene, Biotechnological methods (oxidizing benzene with bacteria Synthesizing hydroxy-1,3-diene The carbonate radical polymerization, and a method) for synthesizing by heating the intermediate polymer obtained has been proposed.
Chemical & Engineering News, January 19, 1998, page 9 P. Kovacic, et al. Chem. Rev. , 1987, 87, 357-379.

However, no polymer is known in which the repeating unit is arylene-didiene-arylene. In such a polymer, different substituents can be introduced into the arylene group in the repeating unit, and various modifications are expected to be facilitated.
For example, JP-A-9-309945 discloses a polyphenylene copolymer. In this publication, polyphenylene copolymers are synthesized using various monoarylenes as repeating units.

Therefore, an object of the present invention is to provide poly (diene-arylene) in which the repeating unit is diene-arylene.
In one aspect of the present invention, there is provided a poly (diene-arylene) having a repeating unit represented by the following formula (I) or (II).
(In formula, Ar < ¹ > and Ar < ² > are respectively mutually independent, and are the same or different, may have a substituent, may have 1-5 nitrogen atoms, and may be 4-18. Arylene having 1 carbon atom;
R ¹ and R ² are each independently the same or different and each may have a hydrogen atom, a substituent, a C _{1 to} C ₂₀ hydrocarbon group, or a substituent. C ₁ -C ₂₀ alkoxy group, represented by which may have a substituent, C ₆ -C ₂₀ aryloxy group, an amine group, a hydroxyl group or the formula ^{-Si (R 3) (R 4} ) (R 5) Groups (wherein R ³ , R ⁴ and R ⁵ are each independently the same or different and are each a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ arylalkyl group, a C ₁ -C ₂₀ alkoxy group) a is a C ₆ -C ₂₀ arylalkyl group.)
However, in the case of the repeating unit represented by the formula (I), R ¹ and R ² may be interrupted with an oxygen atom, and may have a substituent, C _{4 to} C _20. May form a saturated or unsaturated ring;
A represents a hydrogen atom; a halogen atom; an optionally substituted C _{1 to} C ₂₀ hydrocarbon group; an optionally substituted C _{1 to} C ₂₀ alkoxy group; and a substituted group. may be in, C ₆ -C ₂₀ aryloxy group; which may have a substituent group C ₆ -C ₂₀ alkylaryl group; which may have a substituent, an alkoxycarbonyl group; substituents may have a, C ₆ -C ₂₀ aryloxycarbonyl group; a cyano group (-CN); a carbamoyl group _{(-C (= O) NH 2} ); haloformyl (-C (= O) -X, In the formula, X represents a halogen atom.); A formyl group (—C (═O) —H);
n is an integer of 2 or more. )

In the present invention, it is preferable that Ar ¹ and Ar ² are each independently a phenylene group which may be the same or different and may have a substituent.
Further, a repeating unit represented by the above formula (I), and, R ¹ and R ² are, together, may be interrupted by oxygen atoms, which may have a substituent, C ₄ ~ preferably forms a C ₂₀ saturated or unsaturated ring.
Furthermore, C ₁ -C ₂₀ hydrocarbon group, linear or branched C ₁ -C ₂₀ alkyl group, linear or branched C ₂ -C ₂₀ alkenyl group, a linear or branched C ₂ -C ₂₀ alkynyl group, a linear Or branched C ₃ -C ₂₀ allyl group, linear or branched C ₄ -C ₂₀ alkyl dienyl group, linear or branched C ₄ -C ₂₀ polyenyl group, C ₆ -C ₁₈ aryl group, C ₆ -C ₂₀ alkyl group aryl group, C ₆ -C ₂₀ arylalkyl group, preferably a C ₄ -C ₂₀ cycloalkyl group or C ₄ -C ₂₀ cycloalkenyl group.

In another aspect of the present invention, there is provided a resin composition comprising the poly (diene-arylene) and a synthetic organic polymer.
Furthermore, in another aspect of the present invention, there is provided a diene-aryl represented by the following formula (III) or (IV).
(In formula, Ar < ¹ > and Ar < ² > are respectively mutually independent, and are the same or different, may have a substituent, may have 1-5 nitrogen atoms, and may be 4-18. Arylene having 1 carbon atom;
R ¹ and R ² are each independently the same or different and each may have a hydrogen atom, a substituent, a C _{1 to} C ₂₀ hydrocarbon group, or a substituent. C ₁ -C ₂₀ alkoxy group, represented by which may have a substituent, C ₆ -C ₂₀ aryloxy group, an amine group, a hydroxyl group or the formula ^{-Si (R 3) (R 4} ) (R 5) Groups (wherein R ³ , R ⁴ and R ⁵ are each independently the same or different and are each a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ arylalkyl group, a C ₁ -C ₂₀ alkoxy group) a is a C ₆ -C ₂₀ arylalkyl group.)
However, in the case of diene-aryl represented by the formula (III), R ¹ and R ² may be interrupted by an oxygen atom, and may have a substituent, C _{4 to} C ₂₀ may form saturated or unsaturated rings;
A represents a hydrogen atom; a halogen atom; an optionally substituted C _{1 to} C ₂₀ hydrocarbon group; an optionally substituted C _{1 to} C ₂₀ alkoxy group; and a substituted group. C ₆ -C ₂₀ aryloxy group which may be substituted; C ₆ -C ₂₀ alkyl aryloxy group which may have substituent; C ₁ -C ₂₀ alkoxy which may have substituent which may have a substituent, C ₆ -C ₂₀ aryloxycarbonyl group; a carbonyl group a cyano group (-CN); a carbamoyl group _{(-C (= O) NH 2} ); haloformyl (-C (= O) -X, wherein X represents a halogen atom.); A formyl group (-C (= O) -H);
X ¹ and X ² are each independently of each other, the same or different, and are leaving groups. )

In another aspect of the present invention, there is provided a process for producing a poly (diene-arylene) represented by the following formula (I) or (II):
(In formula, Ar < ¹ > and Ar < ² > are respectively mutually independent, and are the same or different, may have a substituent, may have 1-5 nitrogen atoms, and may be 4-18. Arylene having 1 carbon atom;
R ¹ and R ² are each independently the same or different and each may have a hydrogen atom, a substituent, a C _{1 to} C ₂₀ hydrocarbon group, or a substituent. C ₁ -C ₂₀ alkoxy group, represented by which may have a substituent, C ₆ -C ₂₀ aryloxy group, an amine group, a hydroxyl group or the formula ^{-Si (R 3) (R 4} ) (R 5) Groups (wherein R ³ , R ⁴ and R ⁵ are each independently the same or different and are each a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ arylalkyl group, a C ₁ -C ₂₀ alkoxy group) a is a C ₆ -C ₂₀ arylalkyl group.)
However, in the case of the repeating unit represented by the formula (I), R ¹ and R ² may be interrupted with an oxygen atom, and may have a substituent, C _{4 to} C _20. May form a saturated or unsaturated ring;
A represents a hydrogen atom; a halogen atom; an optionally substituted C _{1 to} C ₂₀ hydrocarbon group; an optionally substituted C _{1 to} C ₂₀ alkoxy group; and a substituted group. C ₆ -C ₂₀ aryloxy group which may be substituted; C ₆ -C ₂₀ alkyl aryloxy group which may have substituent; C ₁ -C ₂₀ alkoxy which may have substituent which may have a substituent, C ₆ -C ₂₀ aryloxycarbonyl group; a carbonyl group a cyano group (-CN); a carbamoyl group _{(-C (= O) NH 2} ); haloformyl (-C (= O) -X, wherein X represents a halogen atom.); A formyl group (-C (= O) -H);
n is an integer of 2 or more. )
There is provided a method for producing poly (diene-arylene), characterized in that a diene-aryl represented by the following formula (III) or (IV) is polymerized.
(Wherein Ar ¹ , Ar ² , R ¹ , R ² and A each have the above meaning,
X ¹ and X ² are each independently of each other, the same or different, and are leaving groups. )

In another aspect of the present invention, a metallacyclopentadiene represented by the following formula (V) or (VI) is used:
(In the formula, M represents a group 3 to group 5 of the periodic table or a lanthanide series metal;
L ¹ and L ² are independent of each other and are the same or different and represent an anionic ligand, provided that L ¹ and L ² may be bridged;
Ar ¹ and Ar ² are each independently the same or different and may have a substituent, may have 1 to 5 nitrogen atoms, and may have 4 to 18 carbon atoms. An arylene having
R ¹ and R ² are each independently the same or different and each may have a hydrogen atom, a substituent, a C _{1 to} C ₂₀ hydrocarbon group, or a substituent. C ₁ -C ₂₀ alkoxy group, represented by which may have a substituent, C ₆ -C ₂₀ aryloxy group, an amine group, a hydroxyl group or the formula ^{-Si (R 3) (R 4} ) (R 5) Groups (wherein R ³ , R ⁴ and R ⁵ are each independently the same or different and are each a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ arylalkyl group, a C ₁ -C ₂₀ alkoxy group) a is a C ₆ -C ₂₀ arylalkyl group.)
However, in the case of the metallacyclopentadiene represented by the formula (V), R ¹ and R ² may be interrupted by an oxygen atom and may have a substituent, C ₄ -C ₂₀ may form saturated or unsaturated rings;
X ¹ and X ² are each independently of each other, the same or different, and are leaving groups. )
Reaction with a compound represented by the following formula (VII)
(In the formula, A ¹ is a hydrogen atom; a halogen atom; an optionally substituted C _{3 to} C ₂₀ allyl group; an optionally substituted C _{6 to} C ₂₀ arylmethyl group. It is.
W is a leaving group. )
There is provided a process for producing a diene-aryl, characterized in that a diene-aryl represented by the following formula (IIIa) or (IVa) is produced.
(In the formula, Ar ¹ , Ar ² , R ¹ , R ² , A, X ¹ and X ² each have the above-mentioned meaning.)

In the present invention, M is a periodic table group 4 or lanthanide series metal,
The anionic ligand is preferably a delocalized cyclic η ⁵ -coordinated ligand, a C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₂₀ aryloxy group or a dialkylamide group.
The delocalized cyclic η ⁵ -coordinated ligand is preferably a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, which may be substituted.
Furthermore, the reaction is preferably allowed to proceed in the presence of a compound containing a metal of Groups 9 to 15 of the periodic table.

  The poly (diene-arylene) of the present invention has a wide range of uses as a conductive resin. Moreover, it can shape | mold and use in various shapes as a resin composition.

In one aspect of the present invention, there is provided a poly (diene-arylene) represented by the above formula (I) or (II).
Ar ¹ and Ar ² are each independently the same or different and may have a substituent, may have 1 to 5 nitrogen atoms, and may have 4 to 18 carbon atoms. Arylene having Ar ¹ and Ar ² are preferably 5- to 18-membered rings, and more preferably 6- to 14-membered rings. When it has a nitrogen atom, it is preferable that it is 1-3, and it is still more preferable that it is 1-2.

  Arylene may be a carbocyclic ring or a heterocyclic ring having 1 to 5 nitrogen atoms. Arylene may be a single ring or a condensed ring. Examples of arylene include phenylene (1,3- and 1,4-phenylene), 5-amino-1,3-phenylene, 4-benzoyl-1,3-phenylene, 5-benzoyl-1,3-phenylene, 2-benzoyl-1,4-phenylene, 4,4′-biphenyldiyl, 2-carboxy-methyl-1,4-phenylene, 4-carboxymethyl-1,3-phenylene, 5-carboxymethyl-1, 3-phenylene, 1,3-naphthalenediyl, 1,4-naphthalenediyl, 5-phenoxy-1,3-phenylene, 2-phenyl-1,3-phenylene, 4-phenyl-1,3-phenylene, 5- Phenyl-1,3-phenylene, 2-phenyl-1,4-phenylene, 2,6-pyridinediyl, 2,4-pyridinediyl, 3,5-pyridinediyl 3,6-pyridinediyl, 5,8-quinolinediyl, 2,4-toluene-diyl, there are 2,5-xylene-diyl and the like. Examples of isomers not specifically listed other than the 1,3-position and 1,4-position of the above-described arylene include 2,4-quinolinediyl, 2,5-quinolinediyl, 2,6-quinolinediyl, and the like. Arylene is preferably phenylene, naphthalenediyl or pyridinediyl which may have a substituent, and more preferably phenylene or naphthalenediyl which may have a substituent.

Examples of the substituent for the arylene of Ar ¹ and Ar ² include a C _{1 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ alkoxy group, a C _{6 to} C ₂₀ aryloxy group, an amine group, a hydroxyl group, and a formula —Si ( Groups represented by R ³ ) (R ⁴ ) (R ⁵ ) (wherein R ³ , R ⁴ and R ⁵ are each independently the same or different and represent a C ₁ -C ₂₀ alkyl group, C ₆ -C ₂₀ arylalkyl group, C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₂₀ arylalkyl group.) can be mentioned.
The arylene substituent is not limited to these, and can be introduced into the arylene before or after the production of the monomer diene-aryl, particularly bis (aryl) diene, and does not inhibit the reaction. As long as it is, it is not limited. Further, by appropriately introducing a protecting group, various substituents can be introduced by a known reaction such as a nucleophilic substitution reaction with a normal aromatic compound.

R ¹ and R ² are each independently the same or different and may have a substituent, a C _{1 to} C ₂₀ hydrocarbon group, or may have a substituent, C ₁ to A C ₂₀ alkoxy group, a C ₆ -C ₂₀ aryloxy group, an amine group, a hydroxyl group or a group represented by the formula —Si (R ³ ) (R ⁴ ) (R ⁵ ) which may have a substituent (formula R ³ , R ⁴ and R ⁵ are independently of each other and the same or different and each represents a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ arylalkyl group, a C ₁ -C ₂₀ alkoxy group, C ₆ ~C ₂₀ aryl alkyl group.) a.

In the present specification, the C _{1 to} C ₂₀ hydrocarbon group may be a saturated or unsaturated acyclic group or a saturated or unsaturated cyclic group. When the C ₁ -C ₂₀ hydrocarbon group is acyclic, it may be linear or branched. C ₁ -C ₂₀ hydrocarbon groups include C ₁ -C ₂₀ alkyl groups, C ₂ -C ₂₀ alkenyl groups, C ₂ -C ₂₀ alkynyl groups, C ₃ -C ₂₀ allyl groups, C ₄ -C ₂₀ alkyl groups. enyl, C ₄ -C ₂₀ polyenyl group, C ₆ -C ₁₈ aryl group, C ₆ -C ₂₀ alkylaryl group, C ₆ -C ₂₀ arylalkyl group, C ₄ -C ₂₀ cycloalkyl group, C ₄ -C ₂₀ cycloalkenyl groups and the like are included.

Examples of alkyl groups useful in the practice of the present invention include, but are not limited to, methyl, ethyl, propyl, n-butyl, t-butyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2,2 , 2-trifluoroethyl, benzyl, 2-phenoxyethyl and the like.
Examples of aryl groups useful in the practice of the present invention include, but are not limited to, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, naphthyl, biphenyl, 4-phenoxyphenyl, 4-fluorophenyl, 3 -Carbomethoxyphenyl, 4-carbomethoxyphenyl and the like.
Examples of alkoxy groups useful in the practice of the present invention include, but are not limited to, methoxy, ethoxy, 2-methoxyethoxy, t-butoxy and the like. Examples of aryloxy groups useful in the practice of the present invention include, but are not limited to, phenoxy, naphthoxy, phenylphenoxy, 4-methylphenoxy, and the like.
Examples of amine groups useful in the practice of the present invention include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.
The group represented by the formula —Si (R ³ ) (R ⁴ ) (R ⁵ ) is not limited, but trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenylmethylsilyl, triphenylsilyl. , Triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxyphenyl and the like.
A substituent may be introduced into the C ₁ -C ₂₀ hydrocarbon group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryloxy group, and examples of the substituent include a halogen atom and a hydroxyl group. And amino groups.

However, in the case of the repeating unit represented by the formula (I), R ¹ and R ² may be interrupted with an oxygen atom, and may have a substituent, C _{4 to} C _20. A saturated or unsaturated ring may be formed. It is preferably a 4-membered ring to a 16-membered ring, and more preferably a 4-membered ring to a 12-membered ring. This ring includes a C _{1 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ alkoxy group, a C _{6 to} C ₂₀ aryloxy group, an amine group, a hydroxyl group, or a formula —Si (R ³ ) (R ⁴ ) (R ⁵ (Wherein R ³ , R ⁴ and R ⁵ are each independently the same or different and are each a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ arylalkyl group, a C _1- A substituent such as a C ₂₀ alkoxy group or a C ₆ -C ₂₀ arylalkyloxy group) may be introduced.

A is independently of each other, the same or different, a hydrogen atom; an optionally substituted C _{1 to} C ₂₀ hydrocarbon group; an optionally substituted C _{1 to} C ₂₀ alkoxy group; which may have a substituent, C ₆ -C ₂₀ aryloxy group; which may have a substituent; may have a substituent group C ₆ -C ₂₀ alkylaryl group C ₁ -C ₂₀ alkoxycarbonyl group; C ₆ -C ₂₀ aryloxycarbonyl group optionally substituted; cyano group (—CN); carbamoyl group (—C (═O) NH ₂ ) A haloformyl group (—C (═O) —X, wherein X represents a halogen atom); a formyl group (—C (═O) —H). C ₁ -C ₂₀ hydrocarbon group; optionally substituted, C ₁ -C ₂₀ alkoxy group; optionally substituted, C ₆ -C ₂₀ aryloxy group, amino group , R ¹ and R ² are the same.

Examples of alkoxycarbonyl groups useful in the practice of the present invention include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, 2-methoxyethoxycarbonyl, t-butoxycarbonyl, and the like.
Examples of aryloxycarbonyl groups useful in the practice of the present invention include, but are not limited to, phenoxycarbonyl, naphthoxycarbonyl, phenylphenoxycarbonyl, 4-methylphenoxycarbonyl, and the like.
Note that a carbamoyl group (—C (═O) NH ₂ ), a haloformyl group (—C (═O) —X, where X represents a halogen atom), a formyl group (—C (═O) —H And the like can be converted to each other with a cyano group or an alkoxycarbonyl group.

The poly (diene-arylene) of the present invention may be a copolymer. For example, in addition to the above repeating unit composed of diene-aryl, one or more other repeating units may be contained. The other repeating unit may be arylene. Examples of arylene include phenylene (1,3- and 1,4-phenylene), 5-amino-1,3-phenylene, 4-benzoyl-1,3-phenylene, 5-benzoyl-1,3-phenylene, 2-benzoyl-1,4-phenylene, 4,4′-biphenyldiyl, 2-carboxy-methyl-1,4-phenylene, 4-carboxymethyl-1,3-phenylene, 5-carboxymethyl-1, 3-phenylene, 1,3-naphthalenediyl, 1,4-naphthalenediyl, 5-phenoxy-1,3-phenylene, 2-phenyl-1,3-phenylene, 4-phenyl-1,3-phenylene, 5- Phenyl-1,3-phenylene, 2-phenyl-1,4-phenylene, 2,6-pyridinediyl, 2,4-pyridinediyl, 3,5-pyridinediyl, There are 3,6-pyridinediyl, 5,8-quinolinediyl, 2,4-toluenediyl, 2,5-xylenediyl and the like. Examples of isomers not specifically listed other than the 1,3-position and 1,4-position of the above-described arylene include 2,4-quinolinediyl, 2,5-quinolinediyl, 2,6-quinolinediyl, and the like.
Further, copolymers may be formed with ethylene, propylene, cycloolefin olefins; vinyl derivatives such as vinyl chloride and vinyl acetate.
Since the unsaturated bond is introduced into the poly (diene-arylene) of the present invention, this unsaturated bond can be further reacted with a radical polymerization initiator, Ziegler-Natta catalyst or the like. For example, branches can be introduced into the main chain. Moreover, two or more main chains can be cross-linked with each other by adding a cross-linking agent such as sulfur.

  In another aspect of the invention, a resin composition, such as a blend, is provided that contains poly (diene-arylene) and a synthetic organic polymer. For example, a resin composition containing 1 to 99% by weight of poly (diene-arylene) and 99 to 1% by weight of a synthetic organic polymer is provided. Also provided is a resin composition containing 10-90 wt% poly (diene-arylene) and 90-10 wt% synthetic organic polymer.

Synthetic organic polymers include thermoplastic polymers, thermosetting polymers, engineering plastics, and the like. The synthetic organic polymer may be a copolymer. Thermoplastic polymers include, for example, polyolefins such as polyethylene, polypropylene, polycycloolefin, ethylene-propylene copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, polymethacrylic acid, polystyrene, polyamide, polyester, Polycarbonate and the like are included. Examples of the thermosetting polymer include phenol resin, urea resin, melamine resin, alkyd resin, unsaturated polyester resin, epoxy resin, silicon resin, and polyurethane resin. Engineering plastics include, for example, polyimide, polyphenylene oxide, polysulfone, and the like. The synthetic organic polymer may be a synthetic rubber such as styrene-butadiene, or a fluororesin such as polytetrafluoroethylene.
The resin composition may further contain various additives. Examples of the additive include a plasticizer, an antistatic agent, and a colorant. Furthermore, the resin composition may contain reinforcing materials such as glass fiber, carbon fiber, aramid fiber, and boron fiber.

  The poly (diene-arylene) or resin composition according to the present invention can be made into a fiber, film or sheet form using methods known to those skilled in the art, and is not limited thereto. , Melt spinning, spinning from solution, dry jet wet spinning, extrusion, casting, and molding. The fibers, films or sheets can be further processed by rolling, stamping, secondary forming or other methods known to those skilled in the art.

In another aspect of the present invention, there is provided a diene-aryl represented by the above formula (III) or (IV). In the formula (III) or (IV), Ar ¹ , Ar ² , R ¹ , R ² and A have the above-mentioned meanings.
X ¹ and X ² are each independently the same or different and are a leaving group. Examples of the leaving group include halogen atoms such as F, Cl, Br, and I, p-toluenesulfonyl group, and Br is particularly preferable.

In another aspect of the present invention, a method for producing a poly (diene-arylene) represented by the above formula (I) or (II) is provided. This reaction is shown in the following formula.
(In the formula, Ar ¹ , Ar ² , R ¹ , R ² , A, X ¹ , and X ² have the above-mentioned meanings.)
(In the formula, Ar ¹ , Ar ² , R ¹ , R ² , A, X ¹ , and X ² have the above-mentioned meanings.)

In the polymerization, the leaving groups X ¹ and X ² are eliminated by a reducing agent, and the monomer is coupled. As the reducing agent, for example, metals of Groups 1 to 14 of the periodic table can be widely used. Examples thereof include metals of Group 1 of the periodic table such as lithium and sodium, metals of Group 2 of the periodic table such as magnesium, metals of Group 11 of the periodic table such as copper, and metals of Group 12 of the periodic table such as zinc.
Also, nickel (0) compounds as described in T. Kanbara, T. Kushida, N. Saito, I. Kuwajima, K. Kubota, and T. Yamamoto, Chemistry Letters, 1992, pages 583 to 586 are used. The above monomers are polymerized by reductive coupling, or by nickel-catalyzed reductive coupling as described in US Pat. No. 5,227,457 or US Pat. No. 5,241,044. A polymer can be formed.
That is, when mild reducing agents such as magnesium and zinc are used, organometallic complexes such as bis (triphenylphosphine) dichloronickel, dichloro (2,2′-bipyridine) nickel, PdCl ₂ (2,2′-bipyridine), etc. These catalysts can be used. This is because the polymerization proceeds under relatively mild conditions. Further, a nitrogen-containing organic compound such as bipyridine and a phosphorus-containing organic compound such as phosphine may coexist as a promoter.

As an organometallic complex, a ligand such as a phosphine; an aromatic amine such as pyridine or bipyridine, or a ligand such as a halogen atom is coordinated to the central metal of Group 3 to 11 of the periodic table, preferably the central metal of Group 6 to 11 of the periodic table. What is doing is used preferably. The central metal is preferably so-called 4-6 coordination, and more preferably a metal of Group 10 of the periodic table. The phosphine is not limited, such as triphenylphosphine and methyldiphenylphosphine.
The polymerization reaction using magnesium as a reducing agent is described in T.W. Yamamoto et al. Bull. Chem. Soc. Jpn. 1978, 51, 2091, T .; Yamamoto, Prog. Polym. Sci. 1992, 17, 1155, M.M. Rehahan et. al. , Polymer, 1989, 30, 1054.
For example, T. Yamamoto et al., Macromol. Chem., 1989, 190,1649, M. Ueda et al., Macromolecules, 1990, 23, 926, I. Colon et al. ., J. Polym. Sci., Polym. Chem. Ed., 1990, 28, 367, M. Ueda et al, J. Polym. Sci., Chem. Ed., 1992, 30, 1567, V. Chaturvede et al., J. Chem. Soc., Chem. Commun., 1992, 1658.

The polymerization is preferably performed in a temperature range of -80 ° C to 300 ° C, particularly preferably in a temperature range of 0 ° C to 150 ° C. The pressure is in the range of 0.1 bar to 2500 bar, preferably in the range of 0.5 bar to 10 bar. The polymerization can be carried out continuously or batchwise, in one step or more, in solution, suspension, gas phase or supercritical medium.
As the solvent, an aliphatic or aromatic solvent is used, and a polar solvent is preferably used. Ether solvents such as halogenated hydrocarbons such as tetrahydrofuran or diethyl ether or methylene chloride, halogenated aromatic hydrocarbons such as o-dichlorobenzene, amides such as N, N-dimethylformamide, dimethyl sulfoxide, etc. Sulfoxide.

In another aspect of the present invention, a method for producing a diene-aryl represented by the above formula (IIIa) or (IVa) is provided. This reaction is shown in the following formula.
(In the formula, Ar ¹ , Ar ² , R ¹ , R ² , A ¹ , X ¹ , X ² and W have the above-mentioned meanings.)
(In the formula, Ar ¹ , Ar ² , R ¹ , R ² , A ¹ , X ¹ , X ² and W have the above-mentioned meanings.)

This reaction is preferably performed in the presence of a catalyst. As the catalyst, for example, a metal compound of Groups 4 to 15 of the periodic table, particularly a metal compound of Groups 8 to 15 of the periodic table is used. As the metal compound, for example, a metal salt such as CuX, NiX ₂ , BiX ₃ (wherein X represents a halogen atom such as a chlorine atom or a bromine atom) is used. Alternatively, the organometallic complex described in the polymerization, particularly a nickel complex, may be used.
Reaction of a metallacyclopentadiene such as zirconacyclopentadiene with an acetylene derivative in the presence of CuCl to form a benzene ring is described in T. Takahashi et al., J. Am. Chem. Soc. 1998, 120, 1672-1680.
When A ¹ is obtained as a cyano group or an alkoxycarbonyl group, this substituent can be converted to a carbamoyl group (—C (═O) NH ₂ ), a haloformyl group (—C (═O) —X by a known method. In the formula, X represents a halogen atom.) And a formyl group (—C (═O) —H).
The reaction is preferably carried out in the temperature range of −80 ° C. to 300 ° C., particularly preferably in the temperature range of −20 ° C. to 50 ° C. The pressure is in the range of 0.1 bar to 2500 bar, preferably in the range of 0.5 bar to 10 bar. The reaction is preferably allowed to proceed in situ without separating the metallacyclopentadiene represented by formula (V) or (VI).

The metallacyclopentadiene represented by the above formula (V) or (VI) can be synthesized, for example, by the following reaction.
(In the formula, Ar ¹ , R ¹ , A ¹ , X ¹ , L ¹ and L ² have the above-mentioned meanings. Z ¹ and Z ² are the same or different and can be eliminated. is there.)
(In the formula, Ar ¹ , Ar ² , X ¹ , X ² , L ¹ and L ² have the above-mentioned meanings. B is a bridging group. Z ¹ and Z ² are the same or different, respectively. , A detachable ligand.)
(In the formula, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , L ¹ and L ² have the above-mentioned meanings. Z ¹ and Z ² are the same or different, A detachable ligand.)

B is a bridging group, for example, a hydrocarbon group which may be interrupted by an oxygen atom, and particularly an alkylene group which may be interrupted by an oxygen atom.
Z ¹ and Z ² are not limited as long as they can coordinate to M. For example, olefins such as ethylene, alkyl groups such as n-butyl group, and the like are included.
The organometallic compound represented by the formula (IX) may be an ion, for example, an anion.
The above reaction is preferably carried out in the presence of a strong base such as alkyllithium in the temperature range of −120 ° C. to 50 ° C., more preferably −120 ° C. to 0 ° C. The production of metallacyclopentadiene is described, for example, in T. Takahashi et al. J. Org. Chem. 1995, 60, 4444.

M is preferably a metal complex containing a Group 4 or lanthanide series metal of the periodic table. A metal complex containing a delocalized cyclic η ⁵ -coordinated ligand is also preferred.
L ¹ and L ² are preferably delocalized cyclic η ⁵ -coordinate ligands. Examples of the delocalized cyclic η ⁵ -coordinated ligand are an unsubstituted cyclopentadienyl group and a substituted cyclopentadienyl group. This substituted cyclopentadienyl group includes, for example, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, t-butylcyclopentadienyl, dimethylcyclopentadienyl, diethylcyclopentadienyl, diisopropylcyclo Pentadienyl, di-t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl group, 2-methylindenyl group, 2-methyl-4-phenylindenyl group, tetrahydroindenyl group, benzoindenyl A group, a fluorenyl group, a benzofluorenyl group, a tetrahydrofluorenyl group and an octahydrofluorenyl group.

In the delocalized cyclic η ⁵ -coordinated ligand, one or more atoms of the delocalized cyclic π system may be substituted with a hetero atom. In addition to hydrogen, it can contain one or more heteroatoms such as elements of group 14 of the periodic table and / or elements of groups 15, 16 and 17 of the periodic table.
A delocalized cyclic η ⁵ -coordinated ligand, for example, a cyclopentadienyl group may be bridged by a central metal and one or more bridging ligands, which may be cyclic. Good. The bridging ligand, _{e.g., CH 2, CH 2 CH 2} , CH (CH 3) CH 2, CH (C 4 H 9) C (CH 3) 2, C (CH 3) 2, (CH 3) ₂ Si, (CH ₃ ) ₂ Ge, (CH ₃ ) ₂ Sn, (C ₆ H ₅ ) ₂ Si, (C ₆ H ₅ ) (CH ₃ ) Si, (C ₆ H ₅ ) ₂ Ge, (C ₆ H ₅ ) ₂ Sn, (CH ₂ ) ₄ Si, CH ₂ Si (CH ₃ ) ₂ , o-C ₆ H ₄ or 2, 2 ′-(C ₆ H ₄ ) ₂ .
Two or more delocalized cyclic η ⁵ -coordinating ligands, for example, cyclopentadienyl groups, may be cyclic to each other, and may be cross-linked by one or more cross-linking groups. . Examples of the bridging group include CH ₂ , CH ₂ CH ₂ , CH (CH ₃ ) CH ₂ , CH (C ₄ H ₉ ) C (CH ₃ ) ₂ , C (CH ₃ ) ₂ , (CH ₃ ) ₂ Si. , (CH ₃ ) ₂ Ge, (CH ₃ ) ₂ Sn, (C ₆ H ₅ ) ₂ Si, (C ₆ H ₅ ) (CH ₃ ) Si, (C ₆ H ₅ ) ₂ Ge, (C ₆ H ₅ ) ₂ Sn, (CH ₂ ) ₄ Si, CH ₂ Si (CH ₃ ) ₂ , o-C ₆ H ₄ or 2, 2 ′-(C ₆ H ₄ ) ₂ .

  The metallacyclopentadiene of the present invention also includes compounds having two or more metallacyclopentadiene moieties. Such compounds are known as polynuclear metallocenes. The polynuclear metallocene may have any substitution pattern and any bridge form. The independent metallocene portions of the polynuclear metallocene may be the same or different. Examples of the polynuclear metallocene are described in, for example, EP-A-632063, JP-A-4-80214, JP-A-4-85310, and EP-A-654476.

The metallacyclopentadiene of the present invention can be synthesized using, for example, the following metallocene.
Bis (indenyl) dichlorozirconium; bis (fluorenyl) dichlorozirconium; (indenyl) (fluorenyl) dichlorozirconium;
(Dimethylsilanediyl) bis (indenyl) dichlorozirconium; (dimethylsilanediyl) bis (tetrahydroindenyl) dichlorozirconium; (dimethylsilanediyl) (indenyl) dichlorozirconium; (dimethylsilane) (Diyl) bis (2-methylindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-ethylindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-methyl-4,5-benzoindenyl) dichlorozirconium (Dimethylsilanediyl) bis (2-ethyl-4,5-benzoindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-methyl-4-phenylindenyl) dichlorozirconium; For dichloro compounds such as (Lusilanediyl) bis (2-ethyl-4-phenylindenyl) dichlorozirconium; (Dimethylsilanediyl) bis (2-methyl-4,6-diisopropylindenyl) dichlorozirconium, alkali metals such as sodium Metallacyclopentadiene is formed after reduction with a strong base such as an alkaline earth metal such as magnesium or after conversion of the dichloro form to a dialkyl form.
Bis (cyclopentadienyl) dibutylzirconium;
Bis (indenyl) dibutylzirconium;
Bis (fluorenyl) dibutylzirconium;
(Indenyl) (fluorenyl) dibutylzirconium;
(3-methyl-5-naphthylindenyl) (2,7-di-tert-butylfluorenyl) dibutylzirconium;
(3-methyl-5-naphthylindenyl) (3,4,7-trimethoxyfluorenyl) dibutylzirconium;
(Pentamethylcyclopentadienyl) (tetrahydroindenyl) dibutylzirconium;
(Cyclopentadienyl) (1-octen-8-ylcyclopentadienyl) dibutylzirconium;
(Indenyl) (1-buten-4-ylcyclopentadienyl) dibutylzirconium;
[1,3-bis (trimethylsilyl) cyclopentadienyl] (3,4-benzofluorenyl) dibutylzirconium;
Bis (cyclopentadienyl) dibutyltitanium;
Dimethylsilanediylbis (indenyl) dibutylzirconium;
Dimethylsilanediylbis (tetrahydroindenyl) dibutylzirconium;
Dimethylsilanediyl (cyclopentadienyl) (indenyl) dibutylzirconium;
Dimethylsilanediylbis (2-methylindenyl) dibutylzirconium;
Dimethylsilanediylbis (2-ethylindenyl) dibutylzirconium;
Dimethylsilanediylbis (2-methyl-4,5-benzoindenyl) dibutylzirconium;
Dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) dibutylzirconium;
Dimethylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) dibutylzirconium;
Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) dibutylzirconium;
Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) dibutylzirconium;
Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) dibutylzirconium;
Dimethylsilanediyl (2-ethylindenyl) (2-ethyl-4-phenylnaphthyl) dibutylzirconium;
Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) dibutylzirconium;
Dimethylsilanediylbis (2-methyl-4-phenylindenyl) dibutylzirconium;
Dimethylsilanediylbis (2-ethyl-4-phenylindenyl) dibutylzirconium;
Dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium;
Dimethylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium;
Dimethylsilanediylbis (2-methyl-4-naphthylindenyl) dibutylzirconium;
Dimethylsilanediylbis (2-ethyl-4-naphthylindenyl) dibutylzirconium;
Methylphenylsilanediylbis (indenyl) dibutylzirconium;
Methylphenylsilanediyl (cyclopentadienyl) (indenyl) dibutylzirconium;
Methylphenylsilanediylbis (tetrahydroindenyl) dibutylzirconium;
Methylphenylsilanediylbis (2-methylindenyl) dibutylzirconium;
Methylphenylsilanediylbis (2-ethylindenyl) dibutylzirconium;
Methylphenylsilanediylbis (2-methyl-4,5-benzoindenyl) dibutylzirconium;
Methylphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) dibutylzirconium;
Methylphenylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) dibutylzirconium;
Methylphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) dibutylzirconium;
Methylphenylsilanediyl (2-ethylindenyl) (2-methyl-4-phenylindenyl) dibutylzirconium;
Methylphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) dibutylzirconium;
Methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-indenyl) dibutylzirconium;
Methylphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) dibutylzirconium;
Methylphenylsilanediylbis (2-methyl-4phenylindenyl) dibutylzirconium;
Methylphenylsilanediylbisdibutylzirconium;
Methylphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium;
Methylphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium;
Methylphenylsilanediylbis (4-naphthylindenyl) dibutylzirconium;
Methylphenylsilanediylbis (2-ethyl-4-naphthylindenyl) dibutylzirconium;
Diphenylsilanediylbis (indenyl) dibutylzirconium;
Diphenylsilanediylbis (2-methylindenyl) dibutylzirconium;
Diphenylsilanediylbis (2-ethylindenyl) dibutylzirconium;
Diphenylsilanediyl (cyclopentadienyl) (indenyl) dibutylzirconium;
Diphenylsilanediylbis (2-methyl-4,5-benzoindenyl) dibutylzirconium;
Diphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) dibutylzirconium;
Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4phenylindenyl) dibutylzirconium;
Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4phenylindenyl) dibutylzirconium;
Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4phenylindenyl) dibutylzirconium;
Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4naphthylindenyl) dibutylzirconium;
Diphenylsilanediyl (2-methylindenyl) (4phenylindenyl) dibutylzirconium;
Diphenylsilanediylbis (2-methyl-4phenylindenyl) dibutylzirconium;
Diphenylsilanediylbis (2-ethyl-4phenylindenyl) dibutylzirconium;
Diphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium;
Diphenylsilanediylbi; bis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium
Diphenylsilanediylbis (2-methyl-4-naphthylindenyl) dibutylzirconium;
Diphenylsilanediylbis (2-ethyl-4-naphthylindenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (indenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (2-methylindenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (2-ethylindenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (2-methyl-4,5-benzoindenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (2-ethyl-4,5-benzoindenyl) dibutylzirconium;
1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) dibutylzirconium;
1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) dibutylzirconium;
1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-ethyl-4-phenylindenyl) dibutylzirconium;
1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-ethyl-4-naphthylindenyl) dibutylzirconium;
1-silacyclopentane-1- (2-methylindenyl) -1- (4-phenylindenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (2-methyl-4-phenylindenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (2-ethyl-4-phenylindenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (2-methyl-4-naphthylindenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (2-ethyl-4-naphthylindenyl) dibutylzirconium;
Bis (cyclopentadienyl) dibutyltitanium;
Ethylene-1,2-bis (indenyl) dibutylzirconium;
Ethylene-1,2-bis (tetrahydroindenyl) dibutylzirconium;
Ethylene-1- (cyclopentadienyl) -2- (1-indenyl) dibutylzirconium;
Ethylene-1- (cyclopentadienyl) -2- (2-indenyl) dibutylzirconium;
Ethylene-1- (cyclopentadienyl) -2- (2-methyl-1-indenyl) dibutylzirconium;
Ethylene-1,2-bis (2-methylindenyl) dibutylzirconium;
Ethylene-1,2-bis (2-ethylindenyl) dibutylzirconium;
Ethylene-1,2-bis (2-methyl-4,5-benzoindenyl) dibutylzirconium;
Ethylene-1,2-bis (2-ethyl-4,5-benzoindenyl) dibutylzirconium;
Ethylene-1,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) dibutylzirconium;
Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) dibutylzirconium;
Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) dibutylzirconium;
Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) dibutylzirconium;
Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) dibutylzirconium;
Ethylene-1- (2-methylindenyl) -2- (4-phenylindenyl) dibutylzirconium;
Ethylene-1,2-bis (2-methyl-4-phenylindenyl) dibutylzirconium;
Ethylene-1,2-bis (2-ethyl-4-phenylindenyl) dibutylzirconium;
Ethylene-1,2-bis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium;
Ethylene-1,2-bis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium;
Ethylene-1,2-bis (2-methyl-4-naphthylindenyl) dibutylzirconium;
Ethylene-1,2-bis (2-ethyl-4-naphthylindenyl) dibutylzirconium;
Propylene-2,2-bis (indenyl) dibutylzirconium;
Propylene-2-cyclopentadienyl-2- (1-indenyl) dibutylzirconium;
Propylene-2-cyclopentadienyl-2- (4-phenyl-1-indenyl) dibutylzirconium;
Propylene-2-cyclopentadienyl-2- (9-fluorenyl) dibutylzirconium;
Propylene-2-cyclopentadienyl-2- (2,7-dimethoxy-9-fluorenyl) dibutylzirconium;
Propylene-2-cyclopentadienyl-2- (2,7-di-tert-butyl-9-fluorenyl) dibutylzirconium;
Propylene-2-cyclopentadienyl-2- (2,7-dibromo-9-fluorenyl) dibutylzirconium;
Propylene-2-cyclopentadienyl-2- (2,7-diphenyl-9-fluorenyl) dibutylzirconium;
Propylene-2-cyclopentadienyl-2- (2,7-dimethyl-9-fluorenyl) dibutylzirconium;
Propylene-2- (3-methylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) dibutylzirconium;
Propylene-2- (3-tert-butylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) dibutylzirconium;
Propylene-2- (3-trimethylsilylcyclopentadienyl) -2- (3,6-di-tert-butyl-9-fluorenyl) dibutylzirconium;
Propylene-2-cyclopentadienyl-2- [2,7-bis (3-buten-1-yl) -9-fluorenyl] dibutylzirconium;
Propylene-2-cyclopentadienyl-2- (3-tert-butyl-9-fluorenyl) dibutylzirconium;
Propylene-2,2-bis (tetrahydroindenyl) dibutylzirconium;
Propylene-2,2-bis (2-methylindenyl) dibutylzirconium;
Propylene-2,2-bis (2-ethylindenyl) dibutylzirconium;
Propylene-2,2-bis (2-methyl-4,5-benzoindenyl) dibutylzirconium;
Propylene-2,2-bis (2-ethyl-4,5-benzoindenyl) dibutylzirconium;
Propylene-2,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) dibutylzirconium;
Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) dibutylzirconium;
Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) dibutylzirconium;
Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) dibutylzirconium;
Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) dibutylzirconium;
Propylene-2- (2-methylindenyl) -2- (4-phenylindenyl) dibutylzirconium;
Propylene-2,2-bis (2-methyl-4-phenylindenyl) dibutylzirconium;
Propylene-2,2-bis (2-ethyl-4-phenylindenyl) dibutylzirconium;
Propylene-2,2-bis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium;
Propylene-2,2-bis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium;
Propylene-2,2-bis (2-methyl-4-naphthylindenyl) dibutylzirconium;
Propylene-2,2-bis (2-ethyl-4-naphthylindenyl) dibutylzirconium;
1,6-bis [methylsilylbis (2-methyl-4-phenylindenyl) dibutylzirconium] hexane;
1,6-bis [methylsilylbis (2-methyl-4,5-benzoindenyl) dibutylzirconium] hexane;
1,6-bis [methylsilylbis (2-ethyl-4-phenylindenyl) dibutylzirconium] hexane;
1,6-bis [methylsilylbis (2-methyl-4-naphthylindenyl) dibutylzirconium] hexane;
1,6-bis [methylsilylbis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium] hexane;
1,6-bis [methylsilyl (2-methyl-4phenylindenyl) (4,5-benzoindenyl) dibutylzirconium] hexane;
1- [methylsilylbis (tetrahydroindenyl) dibutylzirconium] -6- [ethylstannyl (cyclopentadienyl) (fluorenyl) dibutylzirconium] hexane;
1,6-disila-1,1,6,6-tetramethyl-1,6-bis [methylsilylbis (2-methyl-4phenylindenyl) dibutylzirconium] hexane;
1,4-disila 1,4-bis [methylsilylbis (2-methyl-4phenylindenyl) dibutylzirconium] cyclohexane;
[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (pentamethylcyclopentadienyldibutylzirconium);
[1,4-bis (9-fluorenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienyldibutylzirconium);
[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienyldibutylzirconium);
[1- (1-Indenyl) -6- (2-phenyl-1-indenyl) -1,1,6,6-tetraethyl-1,6-disila-4-oxahexane] bis (tert-butylcyclopentadi Enildibutylzirconium);
[1,10-bis (2,3-dimethyl-1-indenyl) -1,1,10,10-tetramethyl-1,10-digermadecane] bis (2-methyl-4-phenylindenyldibutylzirconium);
(1-methyl-3-tert-butylcyclopentadienyl) (1-phenyl-4-methoxy-7-chlorofluorenyl) dibutylzirconium;
(4,7-dichloroindenyl) (3,6-dimesitylfluorenyl) dibutylzirconium;
Bis (2,7-di-tert-butyl-9-cyclohexylfluorenyl) dibutylzirconium;
(2,7-dimesitylfluorenyl) [2,7-bis (1-naphthyl) fluorenyl] dibutylzirconium;
Dimethylsilylbis (fluorenyl) dibutylzirconium;
Dibutylstannylbis (2-methylfluorenyl) dibutylzirconium;
1,1,2,2-tetraethyldisilanediyl (2-methylindenyl) (4-phenylfluorenyl) dibutylzirconium;
Propylene-1- (2-indenyl) -2- (9-fluorenyl) dibutylzirconium;
1,1-dimethyl-1-silaethylenebis (fluorenyl) dibutylzirconium;
[4- (cyclopentadienyl) 4,7,7-trimethyl (tetrahydroindenyl) dibutylzirconium;
[4- (cyclopentadienyl) 4,7-dimethyl-7-phenyl (5,6-dimethyltetrahydroindenyl) dibutylzirconium;
[4- (cyclopentadienyl) -4,7-dimethyl-7- (1-naphthyl) (7-phenyltetrahydroindenyl)] dibutylzirconium;
[4- (cyclopentadienyl) -4,7-dimethyl-7-butyl (6,6-diethyltetrahydroindenyl)] dibutylzirconium;
[4- (3-tert-butylcyclopentadienyl) -4,7,7-trimethyl (tetrahydroindenyl)] dibutylzirconium;
[4- (1-indenyl) -4,7,7-trimethyl (tetrahydroindenyl)] dibutylzirconium;
Bis (cyclopentadienyl) dibutylhafnium;
Bis (indenyl) dibutyl vanadium;
Bis (fluorenyl) dibutyl scandium;
(Indenyl) (fluorenyl) dibutylniobium;
(2-methyl-7-naphthylindenyl) (2,6-di-tert-butylfluorenyl) dibutyltitanium;
(Pentamethylcyclopentadienyl) (tetrahydroindenyl) butyl hafnium bromide;
(Cyclopentadienyl) (1-octen-8-ylcyclopentadienyl) dibutylhafnium;
(Indenyl) (2-buten-4-ylcyclopentadienyl) dibutyltitanium;
[1,3-bis (trimethylsilyl) cyclopentadienyl] (3,4-benzofluorenyl) dibutyl niobium;
Bis (cyclopentadienyl) dibutyltitanium;
Dimethylsilanediylbis (indenyl) dibutyltitanium;
Dimethylsilanediylbis (tetrahydroindenyl) dibutylhafnium;
Dimethylsilanediyl (cyclopentadienyl) (indenyl) dibutyltitanium;
Dimethylsilanediylbis (2-methylindenyl) dibutylhafnium;
Dimethylsilanediylbis (2-ethylindenyl) methylscandium;
Dimethylsilanediylbis (2-butyl-4,5-benzoindenyl) dibutylniobium;
Dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) dibutyltitanium;
Dimethylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) dibutyltitanium;
Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) dibutyltitanium;
Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) dibutylhafnium;
Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) methylscandium;
Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) dibutyltitanium;
Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) dibutylhafnium;
Dimethylsilanediylbis (2-methyl-4-phenylindenyl) dibutylniobium;
Dimethylsilanediylbis (2-ethyl-4-phenylindenyl) dibutylvanadium;
Dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) dibutylhafnium;
Dimethylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) dibutylvanadium;
Dimethylsilanediylbis (2-methyl-4-naphthylindenyl) butyl hafnium bromide;
Dimethylsilanediylbis (2-ethyl-4-naphthylindenyl) dibutyltitanium;
Methylphenylsilanediylbis (indenyl) dibutyltitanium;
Methylphenylsilanediyl (cyclopentadienyl) (indenyl) hafnium;
Methylphenylsilanediylbis (tetrahydroindenyl) dibutylhafnium;
Methylphenylsilanediylbis (2-methylindenyl) dibutyltitanium;
Methylphenylsilanediylbis (2-ethylindenyl) dibutylhafnium;
Methylphenylsilanediylbis (2-methyl-4,5-benzoindenyl) dibutylhafnium;
Methylphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) dibutylvanadium;
Methylphenylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) dibutyltitanium;
Methylphenylsilanediylbis (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) butyltitanium bromide;
Methylphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) dibutyltitanium;
Methylphenylsilanediylbis (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) dibutylhafnium;
Methylphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) dibutylhafnium;
Methylphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) dibutyltitanium;
Methylphenylsilanediylbis (2-methyl-4-phenylindenyl) dibutylhafnium;
Methylphenylsilanediylbis (2-ethyl-4-phenylindenyl) dibutylvanadium;
Methylphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) dibutyltitanium;
Methylphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) dibutylhafnium;
Methylphenylsilanediylbis (2-methyl-4-naphthylindenyl) dibutylhafnium;
Methylphenylsilanediylbis (2-ethyl-4-naphthylindenyl) dibutyltitanium;
Diphenylsilanediylbis (indenyl) dibutyltitanium;
Diphenylsilanediylbis (2-methylindenyl) dibutylhafnium;
Diphenylsilanediylbis (2-ethylindenyl) dibutyltitanium;
Diphenylsilanediylbis (cyclopentadienyl) (indenyl) dibutylhafnium;
Diphenylsilanediylbis (2-methyl-4,5-benzoindenyl) dibutyltitanium;
Diphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) dibutylhafnium;
Diphenylsilanediyl (2-methyl-4 ,,-benzoindenyl) (2-methyl-4,5-phenylindenyl) dibutylhafnium;
Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4,5-phenylindenyl) dibutyltitanium;
Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4,5-phenylindenyl) dibutylhafnium;
Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4,5-phenylindenyl) dibutyltitanium;
Diphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) dibutyltitanium;
Diphenylsilanediylbis (2-methyl-4-phenylindenyl) dibutyltitanium;
Diphenylsilanediylbis (2-ethyl-4-phenylindenyl) dibutylhafnium;
Diphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) dibutylhafnium;
Diphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) dibutylhafnium;
Diphenylsilanediylbis (2-methyl-4-naphthylindenyl) dibutylhafnium;
Diphenylsilanediylbis (2-ethyl-4-naphthylindenyl) dibutyltitanium;
1-silacyclopentane-1,1-bis (indenyl) dibutylhafnium;
1-silacyclopentane-1,1-bis (2-methylindenyl) dibutylhafnium;
1-silacyclopentane-1,1-bis (2-ethylindenyl) dibutylhafnium;
1-silacyclopentane-1,1-bis (2-methyl-4,5-benzoindenyl) dibutyltitanium;
1-silacyclopentane-1,1-bis (2-ethyl-4,5-benzoindenyl) dibutylhafnium;
1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) methyl scandium;
1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) dibutylhafnium;
1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-ethyl-4-phenylindenyl) dibutyltitanium;
1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-ethyl-4-phenylindenyl) dibutylhafnium;
1-silacyclopentane-1- (2-methylindenyl) -1- (4-phenylindenyl) dibutylhafnium;
1-silacyclopentane-1,1-bis (2-methyl-4-phenylindenyl) dibutylhafnium;
1-silacyclopentane-1,1-bis (2-ethyl-4-phenylindenyl) dibutyltitanium bromide;
1-silacyclopentane-1,1-bis (2-methyl-4,6-diisopropylindenyl) dibutyltitanium;
1-silacyclopentane-1,1-bis (2-ethyl-4,6-diisopropylindenyl) dibutyltitanium;
1-silacyclopentane-1,1-bis (2-methyl-4-naphthylindenyl) methyl scandium;
1-silacyclopentane-1,1-bis (2-ethyl-4-naphthylindenyl) dibutylhafnium;
Bis (cyclopentadienyl) dibutyltitanium;
Ethylene-1,2-bis (indenyl) methyl scandium;
Ethylene-1,2-bis (tetrahydroindenyl) dibutyltitanium;
Ethylene-1- (cyclopentadienyl) -2- (1-indenyl) dibutylhafnium;
Ethylene-1-bromide-1- (cyclopentadienyl) -2- (2-indenyl) butyltitanium;
Ethylene-1- (cyclopentadienyl) -2- (2-methyl-1-indenyl) dibutylhafnium;
Ethylene-1,2-bis (2-methylindenyl) dibutylhafnium;
Ethylene-1,2-bis (2-ethylindenyl) dibutylhafnium;
Ethylene-1,2-bis (2-methyl-4,5-benzoindenyl) dibutylhafnium;
Ethylene-1,2-bis (2-ethyl-4,5-benzoindenyl) dibutyltitanium;
Ethylene-1,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) dibutyltitanium;
Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) dibutyltitanium;
Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) dibutyltitanium;
Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) methyl scandium;
Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) dibutylhafnium;
Ethylene-1- (2-methylindenyl) -2- (4-phenylindenyl) dibutyltitanium;
Ethylene-1,2-bis (2-methyl-4-phenylindenyl) dibutylhafnium;
Ethylene-1,2-bis (2-ethyl-4-phenylindenyl) dibutylhafnium;
Ethylene-1,2-bis (2-methyl-4,6-diisopropylindenyl) dibutylhafnium;
Ethylene-1,2-bis (2-ethyl-4,6-diisopropylindenyl) dibutyltitanium;
Ethylene-1,2-bis (2-methyl-4-naphthylindenyl) dibutyltitanium;
Ethylene-1,2-bis (2-ethyl-4-naphthylindenyl) dibutylhafnium;
Propylene-2,2-bis (indenyl) dibutylhafnium;
Propylene-2-cyclopentadienyl-2- (1-indenyl) dibutyltitanium;
Propylene-2-cyclopentadienyl-2- (4-phenyl-1-indenyl) dibutyltitanium;
Propylene-2-cyclopentadienyl-2- (9-fluorenyl) dibutylhafnium;
Propylene-2-cyclopentadienyl-2- (2,7-dimethoxy-9-fluorenyl) dibutylhafnium;
Propylene-2-cyclopentadienyl-2- (2,7-di-tert-butyl-9-fluorenyl) dibutylhafnium;
Propylene-2-cyclopentadienyl-2- (2,7-dibromo-9-fluorenyl) dibutyltitanium;
Propylene-2-cyclopentadienyl-2- (2,7-diphenyl-9-fluorenyl) dibutylhafnium;
Propylene-2-cyclopentadienyl-2- (2,7-dimethyl-9-fluorenyl) dibutyltitanium;
Propylene-2- (3-methylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) dibutylhafnium;
Propylene-2- (3-tert-butylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) dibutyltitanium;
Propylene-2- (3-trimethylsilylcyclopentadienyl) -2- (3,6-di-tert-butyl-9-fluorenyl) dibutyltitanium;
Propylene-2-cyclopentadienyl-2- [2,7-bis (3-buten-1-yl) -9-fluorenyl] dibutylhafnium;
Propylene-2-cyclopentadienyl-2- (3-tert-butyl-9-fluorenyl) dibutyltitanium;
Propylene-2,2-bis (tetrahydroindenyl) dibutylhafnium;
Propylene-2,2-bis (2-methylindenyl) dibutylhafnium;
Propylene-2,2-bis (2-ethylindenyl) dibutyltitanium;
Propylene-2,2-bis (2-methyl-4,5-benzoindenyl) dibutyltitanium;
Propylene-2,2-bis (2-ethyl-4,5-benzoindenyl) dibutylhafnium;
Propylene-2,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) dibutylhafnium;
Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) dibutylhafnium;
Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) dibutyltitanium;
Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) dibutylhafnium;
Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) dibutyltitanium;
Propylene-2- (2-methylindenyl) -2- (4-phenylindenyl) dibutylhafnium;
Propylene-2,2-bis (2-methyl-4-phenylindenyl) dibutyltitanium;
Propylene-2,2-bis (2-ethyl-4-phenylindenyl) dibutylhafnium;
Propylene-2,2-bis (2-methyl-4,6-diisopropylindenyl) dibutyltitanium;
Propylene-2,2-bis (2-ethyl-4,6-diisopropylindenyl) dibutylhafnium;
Propylene-2,2-bis (2-methyl-4-naphthylindenyl) dibutyltitanium;
Propylene-2,2-bis (2-ethyl-4-naphthylindenyl) dibutyltitanium;
1,6-bis [methylsilylbis (2-methyl-4-phenylindenyl) dibutylhafnium] hexane;
1,6-bis [methylsilylbis (2-methyl-4,5-benzoindenyl) dibutyltitanium] hexane;
1,6-bis [methylsilylbis (2-ethyl-4-phenylindenyl) dibutylhafnium] hexane;
1,6-bis [methylsilylbis (2-methyl-4-naphthylindenyl) dibutyltitanium] hexane;
1,6-bis [methylsilylbis (2-methyl-4,6-diisopropylindenyl) dibutylhafnium] hexane;
1,6-bis [methylsilyl (2-methyl-4phenylindenyl) (4,5-benzoindenyl) dibutyltitanium] hexane;
1- [methylsilylbis (tetrahydroindenyl) dibutylhafnium] -6- [ethylstannyl (cyclopentadienyl) (fluorenyl) dibutyltitanium] hexane;
1,6-disila-1,1,6,6-tetramethyl-1,6-bis [methylsilylbis (2-methyl-4phenylindenyl) dibutylhafnium] hexane;
1,4-disila 1,4-bis [methylsilylbis (2-methyl-4phenylindenyl) dibutylhafnium] cyclohexane;
[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (pentamethylcyclopentadienyldibutylhafnium);
[1,4-bis (9-fluorenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienyldibutylhafnium);
[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienyldibutyltitanium);
[1- (1-Indenyl) -6- (2-phenyl-1-indenyl) -1,1,6,6-tetraethyl-1,6-disila-4-oxahexane] bis (tert-butylcyclopentadi Enildibutyltitanium);
[1,10-bis (2,3-dimethyl-1-indenyl) -1,1,10,10-tetramethyl-1,10-digermadecane] bis (2-methyl-4-phenylindenyldibutylhafnium);
(1-methyl-3-tert-butylcyclopentadienyl) (1-phenyl-4-methoxy-7-chlorofluorenyl) dibutyltitanium;
(4,7-dichloroindenyl) (3,6-dimesitylfluorenyl) dibutyltitanium;
Bis (2,7-di-tert-butyl-9-cyclohexylfluorenyl) dibutylhafnium;
(2,7-dimesitylfluorenyl) [2,7-bis (1-naphthyl) fluorenyl] dibutylhafnium;
Dimethylsilylbis (fluorenyl) dibutyltitanium;
Dibutylstannylbis (2-methylfluorenyl) dibutylhafnium;
1,1,2,2-tetraethyldisilanediyl (2-methylindenyl) (4-phenylfluorenyl) dibutyltitanium;
Propylene-1- (2-indenyl) -2- (9-fluorenyl) dibutylhafnium;
1,1-dimethyl-1-silaethylenebis (fluorenyl) dibutyltitanium;
[4- (cyclopentadienyl) 4,7,7-trimethyl (tetrahydroindenyl) dibutyltitanium;
[4- (cyclopentadienyl) 4,7-dimethyl-7-phenyl (5,6-dimethyltetrahydroindenyl) dibutylhafnium;
[4- (cyclopentadienyl) -4,7-dimethyl-7- (1-naphthyl) (7-phenyltetrahydroindenyl)] dibutyltitanium;
[4- (cyclopentadienyl) -4,7-dimethyl-7-butyl (6,6-diethyltetrahydroindenyl)] dibutylhafnium;
[4- (3-tert-butylcyclopentadienyl) -4,7,7-trimethyl (tetrahydroindenyl)] dibutylhafnium;
[4- (1-indenyl) -4,7,7-trimethyl (tetrahydroindenyl)] dibutyltitanium;
Bis (cyclopentadienyl) dibutylhafnium;
Bis (cyclopentadienyl) dichlorozirconium;
Bis (indenyl) dichlorozirconium;
Bis (fluorenyl) dichlorozirconium;
(Indenyl) (fluorenyl) dichlorozirconium;
Bis (cyclopentadienyl) dichlorotitanium;
(Dimethylsilanediyl) bis (indenyl) dichlorozirconium;
(Dimethylsilanediyl) bis (tetrahydroindenyl) dichlorozirconium;
(Dimethylsilanediyl) (indenyl) dichlorozirconium;
(Dimethylsilanediyl) bis (2-methylindenyl) dichlorozirconium;
(Dimethylsilanediyl) bis (2-ethylindenyl) dichlorozirconium;
(Dimethylsilanediyl) bis (2-methyl-4,5-benzoindenyl) dichlorozirconium;
(Dimethylsilanediyl) bis (2-ethyl-4,5-benzoindenyl) dichlorozirconium;
(Dimethylsilanediyl) bis (2-methyl-4-phenylindenyl) dichlorozirconium;
(Dimethylsilanediyl) bis (2-ethyl-4-phenylindenyl) dichlorozirconium;
(Dimethylsilanediyl) bis (2-methyl-4,6-diisopropylindenyl) dichlorozirconium;
Bis (cyclopentadienyl) (η ^Four -Butadiene) zirconium;
Bis (methylcyclopentadienyl) (η ^Four -Butadiene) zirconium;
Bis (n-butylcyclopentadienyl) (η ^Four -Butadiene) zirconium;
Bisindenyl (η ^Four -Butadiene) zirconium;
(Tert-Butylamide) 痔 Methyl (tetramethyl-η ^Five -Cyclopentadienyl) silane (η ^Four -Butadiene) zirconium;
Bis (2-methylbenzoindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-indenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbisindenyl (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-indenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-4-naphthylindenyl) (η ^Four -Butadiene) zirconium;
Isopropylidene (cyclopentadienyl) (fluorenyl) (η ^Four -Butadiene) zirconium;
Isopropylidene (cyclopentadienyl) (indenyl) (η ^Four -Butadiene) zirconium;
(4-η ^Five -Cyclopentadienyl) -4,7,7-trimethyl- (η ^Five -4,5,6,7-tetrahydroindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-indenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbisindenyl (η ^Four -Butadiene) zirconium
Dimethylsilanediylbis (2-methylbenzoindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-indenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (2-methylbeindenyl) (4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbisindenyl (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methylbenzoindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (2-benzoindenyl) (4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-4-naphthylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbisindenyl (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methylbenzoindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (2-methylbenzoindenyl) (4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-methyl-4-naphthylindenyl) (η ^Four -Butadiene) zirconium;
Methylphenylmethylene (fluorenyl) (cyclopentadienyl) (η ^Four -Butadiene) zirconium;
Diphenylmethylene (fluorenyl) (cyclopentadienyl) (η ^Four -Butadiene) zirconium;
Isopropylidene (3-methylcyclopentadienyl) (fluorenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediyl (3-tert-butylcyclopentadienyl) (fluorenyl) (η ^Four -Butadiene) zirconium;
Diphenylsilanediyl (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) (η ^Four -Butadiene) zirconium;
Phenylmethylsilanediylbis (2-methylindenyl) (η ^Four -Butadiene) zirconium;
Phenylmethylsilanediylbisindenyl (η ^Four -Butadiene) zirconium;
Phenylmethylsilanediylbis (2-methyl-4,5-benzoindenyl) (η ^Four -Butadiene) zirconium;
Phenylmethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methylindenyl) (η ^Four -Butadiene) zirconium;
Phenylmethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Phenylmethylsilanediyl (2-methylindenyl) (4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Phenylmethylsilanediylbis (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Phenylmethylsilanediylbis (2-ethyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Phenylmethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) (η ^Four -Butadiene) zirconium;
Phenylmethylsilanediylbis (2-methyl-4-naphthyllindenyl) (η ^Four -Butadiene) zirconium;
Ethylenebis (2-methylindenyl) (η ^Four -Butadiene) zirconium;
Ethylene bisindenyl (η ^Four -Butadiene) zirconium;
Ethylenebis (2-methyl-4,5-benzoindenyl) (η ^Four -Butadiene) zirconium;
Ethylene (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Ethylene (2-methylindenyl) (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Ethylene (2-methylindenyl) (4-phenyl-indenyl) (η ^Four -Butadiene) zirconium;
Ethylenebis (2-methyl-4,5-benzoindenyl) (η ^Four -Butadiene) zirconium;
Ethylenebis (2-methyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Ethylenebis (2-methyl-4,6-diisopropylindenyl) (η ^Four -Butadiene) zirconium;
Ethylenebis (2-methyl-4-naphthylindenyl) (η ^Four -Butadiene) zirconium;
Ethylenebis (2-ethyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Ethylenebis (2-ethyl-4,6-diisopropylindenyl) (η ^Four -Butadiene) zirconium;
Ethylenebis (2-ethyl-4-naphthylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2-ethyl-4-phenylindenyl) (η ^Four -Butadiene) zirconium;
Dimethylsilanediylbis (2,3,5-trimethylcyclopentadienyl) (η ^Four -Butadiene) zirconium;
1,6- {bis [methylsilylbis (2-methyl-4-phenylindenyl (η ^Four -Butadiene) zirconium]} hexane;
1,6- {bis [methylsilylbis (2-ethyl-4-phenylindenyl (η ^Four -Butadiene) zirconium]} hexane;
1,6- {bis [methylsilylbis (2-methyl-4-naphthylindenyl (η ^Four -Butadiene) zirconium]} hexane;
1,6- {bis [methylsilylbis (2-methyl-4,5-benzoindenyl (η ^Four -Butadiene) zirconium]} hexane;
1,6- {bis [methylsilyl (2-methyl-4-phenylindenyl) (2-methylindenyl) (η ^Four -Butadiene) zirconium]} hexane;
1,2- {bis [methylsilylbis (2-methyl-4-phenylindenyl (η ^Four -Butadiene) zirconium]} ethane;
1,2- {bis [methylsilylbis (2-ethyl-4-phenylindenyl (η ^Four -Butadiene) zirconium]} ethane;
1,2- {bis [methylsilylbis (2-methyl-4-naphthylindenyl (η ^Four -Butadiene) zirconium]} ethane;
1,2- {bis [methylsilylbis (2-methyl-4,5-benzoindenyl (η ^Four Butadiene) zirconium)) ethane;
1,2- {bis [methylsilyl (2-methyl-4-phenylindenyl) (2-methylindenyl) (η ^Four -Butadiene) zirconium]} ethane.

Hereinafter, the present invention will be described based on examples. The present invention is not limited to the following examples.
The following reactions were performed using standard Schlenk techniques under an argon or nitrogen atmosphere. The solvent was used after refluxing in the presence of a suitable desiccant followed by distillation under a stream of argon or nitrogen.
In the following examples, the number average molecular weight (Mn) of the polymer was determined by gel permeation chromatography. On the other hand, the weight average molecular weight (Mw) was determined by elemental analysis.

Reference example 1
Synthesis of 1,8-bis (p-bromophenyl) -1,7-octadiyne p-bromoiodobenzene (10 ml), 1,7-octadiyne, Pd (PPh ₃ ) ₄ (0.05 mmol), CuI (0. 1 mmol) and tetrahydrofuran (hereinafter referred to as THF, 30 ml) were mixed inside a Schlenk tube (50 ml) to obtain a solution. Triethylamine was added to this solution and stirred at room temperature for 48 hours to allow the reaction to proceed. 3N hydrochloric acid was added to terminate the reaction. The organic phase was then extracted with diethyl ether and dried over magnesium sulfate anhydride. The solvent was removed under reduced pressure to obtain a solid. This solid was washed with hexene to obtain a yellowish green solid. The yield was 75%.
¹ H NMR (CDCl ₃ , Me ₄ Si) δ 1.75-1.78 (m, 4H), 2.44-2.47 (m, 4H), 7.23-7.26 (m, 4H), 7.39-7.42 (m, 4H);
¹³ C NMR (CDCl ₃ , Me ₄ Si) δ 19.01 (2C), 27.73 (2C), 79.98 (2C), 91.00 (2C), 121.65 (2C), 122.86 (2C), 131.40 (4C), 132.99 (4C) ).

Reference example 2
2,5-bis (p-bromophenyl) -cyclohexa [c] -1-zirconacyclopenta-2,4-diene bis (η ⁵ -cyclopentadienyl) dichlorozirconium (1.2 mmol) and THF (10 ml ) Was introduced into the Schlenk tube. The solution was cooled to −78 ° C. and then n-butyl lithium (2.4 mmol) was added. The solution was stirred at -78 ° C for 1 hour. Add 1,8-bis (p-bromophenyl) -1,7-octadiyne (1.0 mmol) to the reaction mixture at −78 ° C., then warm to room temperature and let stand for 1 hour to give the title compound Got.

Example 1
1,2-bis (4′-bromobenzylidene) -cyclohexane 2,5-bis (p-bromophenyl) -cyclohexa [c] -1-zirconacyclopenta-2,4-diene obtained in Reference Example 2 Was used as a solution without separation. That is, water was added to a solution of 2,5-bis (p-bromophenyl) -cyclohexa [c] -1-zirconacyclopenta-2,4-diene (1.0 mmol) in THF (10 ml) at room temperature. The reaction was terminated. Subsequently, it extracted with ether and dried with anhydrous magnesium sulfate. Column chromatography was performed using hexane with silica gel as the packing material to give the white title compound. The yield was 72%.
¹ H NMR (C ₆ D ₆ , Me ₄ Si) δ1.43 (m, 4H), 2.41 (m, 4H), 6.51 (s, 2H), 6.94 (d, J = 8.4 Hz, 4H), 7.33 ( d, J = 8.4 Hz, 4H);
¹³ C NMR (C ₆ D ₆ , Me ₄ Si) δ 26.27 (2C), 30.09 (2C), 120.79 (2C), 123.78 (2C), 131.37 (4C), 131.58 (4C), 136.96 (2C), 145.01 (2C)
High resolution mass spectrometry (HRMS): Calculated C ₂₀ H ₁₈ Br ₂ 415.9774; Found 415.9763.

Example 2
1,2-bis ((p-bromophenyl) chloromethylidene) -cyclohexane 2,5-bis (p-bromophenyl) -cyclohexa [c] -1-zirconacyclopenta-2,4 obtained in Reference Example 2 -The diene was used in solution without separation. That is, 2,5-bis (p-bromophenyl) -cyclohexa [c] -1-zirconacyclopenta-2,4-diene (1.0 mmol) in THF (10 ml) solution at room temperature with N-chloro Succinimide (NCS) (3.0 mmol) was added and stirred for 12 hours. 3N hydrochloric acid was added to the solution to terminate the reaction. Subsequently, it extracted with ether and dried with anhydrous magnesium sulfate. Column chromatography was performed using hexane with silica gel as the packing material to give the white title compound. The yield was 75%.
¹ H NMR (CDCl ₃ , Me ₄ Si) δ 1.42-1.47 (m, 2H), 1.80-1.82 (m, 2H), 2.07-2.14 (m, 2H), 2.58-2.61 (m, 2H), 7.28- 7.30 (m, 4H), 7.49-7.52 (m, 4H).
¹³ C NMR (CDCl ₃ , Me ₄ Si) δ 28.14 (2C), 33.63 (2C), 122.51 (2C), 124.59 (2C), 130.81 (4C), 131.51 (4C), 137.36 (2C), 137.80 (2C) ).
High resolution mass spectrometry (HRMS): Calculated C ₂₀ H ₁₆ Br ₂ Cl ₂ 483.8995; found 483.8998.

Example 3
1,2-bis (1 ′-(p-bromophenyl) -3′-butenylidene) -cyclohexane 2,5-bis (p-bromophenyl) -cyclohexa [c] -1-zyl obtained in Reference Example 2 Conacyclopenta-2,4-diene was used as a solution without separation. Specifically, 2,5-bis (p-bromophenyl) -cyclohexa [c] -1-zirconacyclopenta-2,4-diene (1.0 mmol) in THF (10 ml) was added to 3-chloro at room temperature. -1-Propene (2.5 mmol) and CuCl (2.5 mmol) were added and stirred for 12 hours. 3N hydrochloric acid was added to the solution to terminate the reaction. Subsequently, it extracted with ether and dried with anhydrous magnesium sulfate. Column chromatography was performed using hexane with silica gel as the packing material to give the white title compound. The yield was 60%.
¹ H NMR (CDCl ₃ , Me ₄ Si) δ 1.38-1.46 (m, 2H), 1.73-1.87 (m, 4H), 2.41-2.45 (m, 2H), 2.97 (dd, J = 14.6, 7 Hz, 2H), 3.35 (dd, J = 14.6, 7 Hz, 2H), 4.83-4.94 (m, 4H), 5.59-5.69 (m, 2H), 7.03-7.09 (m, 4H), 7.44-7.49 (m, 4H).
¹³ C NMR (CDCl ₃ , Me ₄ Si) δ 29.26 (2C), 34.55 (2C), 39.47 (2C), 116.05 (2C), 120.24 (2C), 130.14 (2C), 130.60 (4C), 131.16 (4C ), 135.71 (2C), 139,19 (2C), 140.18 (2C).
High resolution mass spectrometry (HRMS) calculated for C ₂₆ H ₂₆ Br ₂ 496.0400, found 496.0417.

The reactions from Reference Example 1 to Example 3 are summarized below.
(In the formula, A ¹ represents a hydrogen atom, a chlorine atom, or an allyl group (CH═CH—CH ₂ —) in Examples 1, 2, and 3, respectively.)

Example 4
In a 20 ml Schlenk tube, bistriphenylphosphine dichloronickel (II) (0.05 mmol), bipyridine (0.05 mmol), metallic zinc (1.5 mmol) and 1,2-bis (4 ′) obtained in Example 1 were used. -Bromobenzylidene) -cyclohexane was charged. Dry dimethylformamide (5 ml) was then added and then stirred at 80 ° C. for 3 hours. A large excess of 3N hydrochloric acid and methanol mixture was added to the resulting mixture to terminate the reaction. The solid in the solution was filtered, washed with methanol, diethyl ether and methanol, and vacuum dried at 80 ° C. for 12 hours. The polymer was obtained as a yellow-green solid. The yield was 75%.

Example 5
The same operation as in Example 4 was performed. However, instead of 1,2-bis (4′-bromobenzylidene) -cyclohexane obtained in Example 1, 1,2-bis ((p-bromophenyl) chloromethylidene) -cyclopropane was used, and the reaction time was Synthesized twice for 3 hours and 24 hours.

Example 6
The same operation as in Example 4 was performed. However, instead of 1,2-bis (4′-bromobenzylidene) -cyclohexane obtained in Example 1, 1,2-bis (1 ′-(p-bromophenyl) -3′-butenylidene) -cyclohexane The reaction time was synthesized twice for 3 hours and 24 hours.

The results of Examples 4 to 6 are shown in Table 1.

Reference example 3
2,5-bis (p-bromophenyl) -cyclopenta [c] -1-zirconacyclopenta-2,4-diene bis (η ⁵ -cyclopentadienyl) dibutylzirconium (1.2 mmol) and THF (10 ml ) Into the Schlenk tube. The solution is cooled to −78 ° C. and then n-butyl lithium (2.4 mmol) is added. The solution was stirred at -78 ° C for 1 hour. Add 1,7-bis (p-bromophenyl) -1,6-heptadiine (1.0 mmol) to the reaction mixture at −78 ° C., then warm to room temperature and let stand for 1 hour to give the title compound Got.

Reference example 4
2,5-bis (p-bromophenyl) -cyclofurana [c] -1-zirconacyclopenta-2,4-diene bis (η ⁵ -cyclopentadienyl) dibutylzirconium (1.2 mmol) and THF (10 ml ) Into the Schlenk tube. The solution is cooled to −78 ° C. and then n-butyl lithium (2.4 mmol) is added. The solution was stirred at -78 ° C for 1 hour. At −78 ° C., the reaction mixture was subjected to 1,7-bis (p-bromophenyl) -4-oxa-1,6-heptadiyne, ie di (3- (p-bromophenyl) -2-propynyl) ether (1 0.0 mmol) was then added, then warmed to room temperature and left for 1 hour to give the title compound.
That is, the title compound is a kind of the compound represented by the above formula (V), and R ¹ and R ² together are represented by the formula —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —. Forming a group. And the 5-membered ring interrupted by the oxygen atom is condensed with zirconacyclopentadiene.

Example 7
The zirconacyclopenta-2,4-diene derivative obtained in Reference Example 3 was reacted with water, N-chlorosuccinimide, and 3-chloro-1-propene, respectively, as in Examples 1-3. Thus, a monomer can be obtained. And it polymerizes like Example 4 and the corresponding poly (diene-arylene) is obtained.

Example 8
The zirconacyclopenta-2,4-diene derivative obtained in Reference Example 4 was reacted with water, N-chlorosuccinimide, and 3-chloro-1-propene, respectively, as in Examples 1-3. Thus, a monomer can be obtained. And it polymerizes like Example 4 and the corresponding poly (diene-arylene) is obtained.
The reactions of Reference Examples 3 and 4 and Examples 7 and 8 are summarized in the following scheme.
(In the formula, B ¹ represents an oxygen atom or a methylene group. A ¹ represents a hydrogen atom, a chlorine atom, or an allyl group (CH═CH—CH ₂ —).)

Reference Example 5
2,4-bis (p-bromophenyl) -3,5-dibutylcyclohexa [c] -1-zirconacyclopenta-2,4-diene, 2,5-bis (p-bromophenyl) -3, 4-dibutylcyclohexa [c] -1-zirconacyclopenta-2,4-diene and 3,4-bis (p-bromophenyl) -2,5-dibutylcyclohexa [c] -1-zyl Mixture of Konacyclopenta-2,4-diene Bis (η ⁵ -cyclopentadienyl) dibutylzirconium (1.2 mmol) and THF (10 ml) were charged into a Schlenk tube. The solution was cooled to −78 ° C. and then n-butyl lithium (2.4 mmol) was added. The solution was stirred at -78 ° C for 1 hour. At −78 ° C., 1- (p-bromophenyl) -1-hexyne (1.0 mmol) was added to the reaction mixture, then warmed to room temperature and left for 1 hour to give 2,4-bis (p -Bromophenyl) -3,5-dibutylcyclohexa [c] -1-zirconacyclopenta-2,4-diene (5 parts by weight), 2,5-bis (p-bromophenyl) -3,4- Dibutylcyclohexa [c] -1-zirconacyclopenta-2,4-diene (1 part by weight) and 3,4-bis (p-bromophenyl) -2,5-dibutylcyclohexa [c]- A mixture of 1-zirconacyclopenta-2,4-diene (1 part by weight) was obtained.
In this example, the three isomers of the zirconacyclopenta-2,4-diene derivative are not separated. However, these derivatives can be separated by chromatography and, if desired, subsequent recrystallization. In particular, 2,4-bis (p-bromophenyl) -cyclohexa [c] -1-zirconacyclopenta-2,4-diene produced preferentially can be easily isolated.

Example 9
A mixture of three kinds of isomers of the zirconacyclopenta-2,4-diene derivative obtained in Reference Example 5 was respectively treated with water, N-chlorosuccinimide, 3- By reacting with chloro-1-propene, a mixture of three isomers can be obtained. From these mixtures, the meta form can be obtained by chromatography followed by recrystallization.
And it polymerizes like Example 4 and the corresponding poly (diene-arylene) is obtained.

Claims (5)

A diene-aryl represented by the following formula (III) or (IV):

(In formula, Ar < ¹ > and Ar < ² > are respectively mutually independent, and are the same or different, may have a substituent, may have 1-5 nitrogen atoms, and may be 4-18. R ¹ and R ² are each independently of each other, the same or different, and each may be a C _{1 to} C ₂₀ hydrocarbon group, a substituent. C _{1 to} C ₂₀ alkoxy group which may have, C _{6 to} C ₂₀ aryloxy group which may have a substituent, amine group, hydroxyl group or formula —Si (R ³ ) (R ⁴ ) A group represented by (R ⁵ ) (wherein R ³ , R ⁴ and R ⁵ are each independently the same or different and represent a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ arylalkyl group, A C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₂₀ arylalkyloxy group).
However, in the case of diene-aryl represented by the formula (III), R ¹ and R ² may be interrupted by an oxygen atom, and may have a substituent, C _{4 to} C ₂₀ may form a saturated or unsaturated ring; A is a hydrogen atom; a halogen atom; an optionally substituted C _{1 to} C ₂₀ hydrocarbon group; an optionally substituted group , C ₁ -C ₂₀ alkoxy group; a substituent; may have a substituent, C ₆ -C ₂₀ aryloxy group; which may have a substituent group C ₆ -C ₂₀ alkylaryl group which may have, C ₁ -C ₂₀ alkoxycarbonyl group; which may have a substituent, C ₆ -C ₂₀ aryloxycarbonyl group; a cyano group (-CN); a carbamoyl group (-C (= O) NH ₂ ); haloformyl group (—C (═O) —X, wherein X represents a halogen atom A formyl group (—C (═O) —H); X ¹ and X ² are each independently the same or different and are a leaving group. ) A metallacyclopentadiene represented by the following formula (V) or (VI):

(In the formula, M represents a group 3 to group 5 or a lanthanide series metal of the periodic table, and L ¹ and L ² are independent of each other and are the same or different and represent an anionic ligand, provided that , L ¹ and L ² may be cross-linked, and Ar ¹ and Ar ² are each independently the same or different and may have a substituent, and 1 to 5 nitrogen atoms R ¹ and R ² are each independently of each other, the same or different, and optionally having a substituent, which is an arylene having 4 to 18 carbon atoms. _{1 to} C ₂₀ hydrocarbon group, optionally having a substituent, C _{1 to} C ₂₀ alkoxy group, optionally having a substituent, C _{6 to} C ₂₀ aryloxy group, amine group, hydroxyl group or group (wherein the formula ^{-Si (R 3) (R 4} ) (R 5), R 3, R 4 and R ⁵ are each Independently of one another, identical or different, are C ₁ -C ₂₀ alkyl group, C ₆ -C ₂₀ arylalkyl group, C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₂₀ arylalkyl group.)
However, in the case of the metallacyclopentadiene represented by the formula (V), R ¹ and R ² may be interrupted by an oxygen atom, or may have a substituent, C ₄ -C ₂₀ saturated or unsaturated rings may be formed; X ¹ and X ² are each independently of one another, the same or different and a leaving group. ) Reaction with a compound represented by the following formula (VII):

(In the formula, A ¹ is a hydrogen atom; a halogen atom; an optionally substituted C _{3 to} C ₂₀ allyl group; an optionally substituted C _{6 to} C ₂₀ arylmethyl group. W is a leaving group.)
A method for producing a diene-aryl, which comprises producing a diene-aryl represented by the following formula (IIIa) or (IVa):

(In the formula, Ar ¹ , Ar ² , R ¹ , R ² , A ¹ , X ¹ and X ² each have the above-mentioned meaning.) M is a Group 4 or lanthanide series metal, and the anionic ligand is a delocalized cyclic η ⁵ -coordinated ligand, a C ₁ -C ₂₀ alkoxy group, a C _6- is a C ₂₀ aryloxy group or a dialkylamide group, diene according to claim 2 - the manufacturing method aryl. The diene-aryl group according to claim 3, wherein the delocalized cyclic η ⁵ -coordinated ligand is a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, which may be substituted. Production method. The method for producing a diene-aryl according to any one of claims 2 to 4, wherein the reaction is allowed to proceed in the presence of a compound containing a metal of Groups 9 to 15 of the periodic table.