JP4136204B2 - Poly (diene-arylene) and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process 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.
[0002]
[Prior art]
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.
[0003]
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.
[0004]
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.
[0005]
Conventionally, methods for producing poly (diene-arylene) and the like have been limited. As a related polyphenylene production method, for example, oxidative cationic polymerization called a Cobasic method is known as a condensation polymerization method using benzene as a monomer. As described in P. Kovacic, et al., Chem. Rev., 1987, 87, 357-379, using an oxidizing agent such as cupric chloride and a Lewis acid catalyst such as aluminum chloride, In general, an indefinite structure of insoluble polyphenylene results. Polyphenylene produced by the oxidation of benzene is said to have a low molecular weight with a branched chain.
[0006]
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 alkali metal), Ullmann reaction (method of condensing diiodobenzene with metal copper), Grignard reaction called Yamamoto method (chlorinating a dihalogenobenzene glycinyl derivative) 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.
[0007]
[Problems to be solved by the invention]
However, a polymer in which the repeating unit is arylene-diene-arylene is not known. 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.
[0008]
For example, JP-A-9-309945 discloses a polyphenylene copolymer. In this publication, polyphenylene copolymers are synthesized using various monoarylenes as repeating units.
[0009]
[Means for Solving the Problems]
Therefore, an object of the present invention is to provide poly (diene-arylene) in which the repeating unit is diene-arylene.
[0010]
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).
[0011]
[Chemical 8]
[0012]
(Wherein 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 be arylene having 4 to 18 carbon atoms. ;
R ¹ And R ² Are each independently the same or different and each may have a hydrogen atom or a substituent, ₁ ~ C ₂₀ Hydrocarbon group, optionally having substituent, C ₁ ~ C ₂₀ Alkoxy group, optionally having substituent, C ₆ ~ C ₂₀ Aryloxy group, amine group, hydroxyl group or formula -Si (R ^Three ) (R ^Four ) (R ^Five ) (In the formula, R ^Three , R ^Four And R ^Five Are independently of each other, the same or different, C ₁ ~ C ₂₀ Alkyl group, C ₆ ~ C ₂₀ Arylalkyl group, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ An arylalkyloxy group; ) And
However, in the case of the repeating unit represented by the formula (I), R ¹ And R ² Each may be interrupted by an oxygen atom and may have a substituent. _Four ~ C ₂₀ May form a saturated or unsaturated ring;
A is a hydrogen atom; a halogen atom; an optionally substituted C; ₁ ~ C ₂₀ Hydrocarbon group; optionally substituted, C ₁ ~ C ₂₀ Alkoxy group; optionally substituted, C ₆ ~ C ₂₀ Aryloxy group; optionally substituted C ₆ ~ C ₂₀ An alkylaryloxy group; an optionally substituted alkoxycarbonyl group; an optionally substituted C ₆ ~ C ₂₀ Aryloxycarbonyl group; cyano group (—CN); carbamoyl group (—C (═O) NH ₂ A haloformyl group (—C (═O) —X, where X represents a halogen atom); a formyl group (—C (═O) —H);
n is an integer of 2 or more. )
In the present invention, Ar ¹ And Ar ² Are preferably phenylene groups which are independent of each other and may be the same or different and may have a substituent.
[0013]
And having a repeating unit represented by the above formula (I), and R ¹ And R ² Each may be interrupted by an oxygen atom and may have a substituent. _Four ~ C ₂₀ A saturated or unsaturated ring is preferably formed.
[0014]
In addition, C ₁ ~ C ₂₀ The hydrocarbon group is linear or branched C ₁ ~ C ₂₀ Alkyl group, linear or branched C ₂ ~ C ₂₀ Alkenyl groups, linear or branched C ₂ ~ C ₂₀ Alkynyl group, linear or branched C _Three ~ C ₂₀ Allyl group, linear or branched C _Four ~ C ₂₀ Alkyldienyl group, linear or branched C _Four ~ C ₂₀ Polyenyl group, C ₆ ~ C ₁₈ Aryl group, C ₆ ~ C ₂₀ Alkylaryl group, C ₆ ~ C ₂₀ Arylalkyl group, C _Four ~ C ₂₀ A cycloalkyl group or C _Four ~ C ₂₀ A cycloalkenyl group is preferred.
[0015]
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).
[0016]
[Chemical 9]
[0017]
(Wherein 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 be arylene having 4 to 18 carbon atoms. ;
R ¹ And R ² Are each independently the same or different and each may have a hydrogen atom or a substituent, ₁ ~ C ₂₀ Hydrocarbon group, optionally having substituent, C ₁ ~ C ₂₀ Alkoxy group, optionally having substituent, C ₆ ~ C ₂₀ Aryloxy group, amine group, hydroxyl group or formula -Si (R ^Three ) (R ^Four ) (R ^Five ) (In the formula, R ^Three , R ^Four And R ^Five Are independently of each other, the same or different, C ₁ ~ C ₂₀ Alkyl group, C ₆ ~ C ₂₀ Arylalkyl group, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ An arylalkyloxy group; ) And
However, in the case of the diene-aryl represented by the formula (III), R ¹ And R ² Each may be interrupted by an oxygen atom and may have a substituent. _Four ~ C ₂₀ May form a saturated or unsaturated ring;
A is a hydrogen atom; a halogen atom; an optionally substituted C; ₁ ~ C ₂₀ Hydrocarbon group; optionally substituted, C ₁ ~ C ₂₀ Alkoxy group; optionally substituted, C ₆ ~ C ₂₀ Aryloxy group; optionally substituted C ₆ ~ C ₂₀ Alkylaryloxy group; optionally substituted, C ₁ ~ C ₂₀ Alkoxycarbonyl group; optionally substituted, C ₆ ~ C ₂₀ Aryloxycarbonyl group; cyano group (—CN); carbamoyl group (—C (═O) NH ₂ A haloformyl group (—C (═O) —X, where X represents a halogen atom); a formyl group (—C (═O) —H);
X ¹ And X ² Are independent of each other and are 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):
[0018]
[Chemical Formula 10]
[0019]
(Wherein 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 be arylene having 4 to 18 carbon atoms. ;
R ¹ And R ² Are each independently the same or different and each may have a hydrogen atom or a substituent, ₁ ~ C ₂₀ Hydrocarbon group, optionally having substituent, C ₁ ~ C ₂₀ Alkoxy group, optionally having substituent, C ₆ ~ C ₂₀ Aryloxy group, amine group, hydroxyl group or formula -Si (R ^Three ) (R ^Four ) (R ^Five ) (In the formula, R ^Three , R ^Four And R ^Five Are independently of each other, the same or different, C ₁ ~ C ₂₀ Alkyl group, C ₆ ~ C ₂₀ Arylalkyl group, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ An arylalkyloxy group; ) And
However, in the case of the repeating unit represented by the formula (I), R ¹ And R ² Each may be interrupted by an oxygen atom and may have a substituent. _Four ~ C ₂₀ May form a saturated or unsaturated ring;
A is a hydrogen atom; a halogen atom; an optionally substituted C; ₁ ~ C ₂₀ Hydrocarbon group; optionally substituted, C ₁ ~ C ₂₀ Alkoxy group; optionally substituted, C ₆ ~ C ₂₀ Aryloxy group; optionally substituted C ₆ ~ C ₂₀ Alkylaryloxy group; optionally substituted, C ₁ ~ C ₂₀ Alkoxycarbonyl group; optionally substituted, C ₆ ~ C ₂₀ Aryloxycarbonyl group; cyano group (—CN); carbamoyl group (—C (═O) NH ₂ A haloformyl group (—C (═O) —X, where 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.
[0020]
Embedded image
[0021]
(Wherein Ar ¹ , Ar ² , R ¹ , R ² And A each have the above meaning,
X ¹ And X ² Are independent of each other and are 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:
[0022]
Embedded image
[0023]
(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 represents ¹ And L ² May be cross-linked,
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 be arylene having 4 to 18 carbon atoms. ;
R ¹ And R ² Are each independently the same or different and each may have a hydrogen atom or a substituent, ₁ ~ C ₂₀ Hydrocarbon group, optionally having substituent, C ₁ ~ C ₂₀ Alkoxy group, optionally having substituent, C ₆ ~ C ₂₀ Aryloxy group, amine group, hydroxyl group or formula -Si (R ^Three ) (R ^Four ) (R ^Five ) (In the formula, R ^Three , R ^Four And R ^Five Are independently of each other, the same or different, C ₁ ~ C ₂₀ Alkyl group, C ₆ ~ C ₂₀ Arylalkyl group, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ An arylalkyloxy group; ) And
However, in the case of the metallacyclopentadiene represented by the formula (V), R ¹ And R ² Each may be interrupted by an oxygen atom and may have a substituent. _Four ~ C ₂₀ May form a saturated or unsaturated ring;
X ¹ And X ² Are independent of each other and are the same or different and are leaving groups. )
Reaction with a compound represented by the following formula (VII)
[0024]
Embedded image
[0025]
(Where A ¹ Is a hydrogen atom; a halogen atom; an optionally substituted C _Three ~ C ₂₀ Allyl group; optionally substituted, C ₆ ~ C ₂₀ An arylmethyl group.
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.
[0026]
Embedded image
[0027]
(Wherein 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 a delocalized cyclic η ^Five -Coordination ligand, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ It is preferably an aryloxy group or a dialkylamide group.
[0028]
Also, the delocalized cyclic η ^Five The coordination ligand is preferably a cyclopentadienyl group, an indenyl group, a fluorenyl group, or an azulenyl group, which may be substituted.
[0029]
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.
[0030]
DETAILED DESCRIPTION OF THE INVENTION
In one aspect of the present invention, there is provided a poly (diene-arylene) represented by the above formula (I) or (II).
[0031]
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 be arylene having 4 to 18 carbon atoms. . Ar ¹ And Ar ² Is preferably a 5- to 18-membered ring, and more preferably a 6- to 14-membered ring. 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.
[0032]
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, 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. As the arylene, phenylene, naphthalenediyl and pyridinediyl which may have a substituent are preferable, and phenylene and naphthalenediyl which may have a substituent are more preferable.
[0033]
Ar ¹ And Ar ² Examples of the substituent for the arylene of C are, for example, C ₁ ~ C ₂₀ Hydrocarbon group, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ Aryloxy group, amine group, hydroxyl group or formula -Si (R ^Three ) (R ^Four ) (R ^Five ) (In the formula, R ^Three , R ^Four And R ^Five Are independently of each other, the same or different, C ₁ ~ C ₂₀ Alkyl group, C ₆ ~ C ₂₀ Arylalkyl group, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ An arylalkyloxy group; ).
[0034]
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, in particular, 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.
[0035]
R ¹ And R ² Are each independently the same or different and may have a substituent, ₁ ~ C ₂₀ Hydrocarbon group, optionally having substituent, C ₁ ~ C ₂₀ Alkoxy group, optionally having substituent, C ₆ ~ C ₂₀ Aryloxy group, amine group, hydroxyl group or formula -Si (R ^Three ) (R ^Four ) (R ^Five ) (In the formula, R ^Three , R ^Four And R ^Five Are independently of each other, the same or different, C ₁ ~ C ₂₀ Alkyl group, C ₆ ~ C ₂₀ Arylalkyl group, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ An arylalkyloxy group; ).
[0036]
In this specification, C ₁ ~ C ₂₀ The hydrocarbon group may be saturated or unsaturated acyclic, or may be saturated or unsaturated cyclic. C ₁ ~ C ₂₀ When the hydrocarbon group is acyclic, it may be linear or branched. C ₁ ~ C ₂₀ Hydrocarbon groups include C ₁ ~ C ₂₀ Alkyl group, C ₂ ~ C ₂₀ Alkenyl group, C ₂ ~ C ₂₀ Alkynyl group, C _Three ~ C ₂₀ Allyl group, C _Four ~ C ₂₀ Alkyldienyl group, C _Four ~ C ₂₀ Polyenyl group, C ₆ ~ C ₁₈ Aryl group, C ₆ ~ C ₂₀ Alkylaryl group, C ₆ ~ C ₂₀ Arylalkyl group, C _Four ~ C ₂₀ A cycloalkyl group, C _Four ~ C ₂₀ A cycloalkenyl group and the like are included.
[0037]
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.
[0038]
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.
[0039]
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.
[0040]
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.
[0041]
Formula -Si (R ^Three ) (R ^Four ) (R ^Five ) Group is not limited, but is not limited to trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenylmethylsilyl, triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, methyl There are methoxyphenyl and the like.
[0042]
C ₁ ~ C ₂₀ Hydrocarbon group, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ A substituent may be introduced into the aryloxy group, and examples of the substituent include a halogen atom, a hydroxyl group, and an amino group.
[0043]
However, in the case of the repeating unit represented by the formula (I), R ¹ And R ² Each may be interrupted by an oxygen atom and may have a substituent. _Four ~ C ₂₀ A saturated or unsaturated ring may be formed. It is preferably a 4-membered ring to a 16-membered ring, more preferably a 4-membered ring to a 12-membered ring. This ring contains C ₁ ~ C ₂₀ Hydrocarbon group, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ Aryloxy group, amine group, hydroxyl group or formula -Si (R ^Three ) (R ^Four ) (R ^Five ) (In the formula, R ^Three , R ^Four And R ^Five Are independently of each other, the same or different, C ₁ ~ C ₂₀ Alkyl group, C ₆ ~ C ₂₀ Arylalkyl group, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ An arylalkyloxy group; ) And the like may be introduced.
[0044]
A is independently of each other, the same or different, a hydrogen atom; optionally having a substituent, C ₁ ~ C ₂₀ Hydrocarbon group; optionally substituted, C ₁ ~ C ₂₀ Alkoxy group; optionally substituted, C ₆ ~ C ₂₀ Aryloxy group; optionally substituted C ₆ ~ C ₂₀ Alkylaryloxy group; optionally substituted, C ₁ ~ C ₂₀ Alkoxycarbonyl group; optionally substituted, C ₆ ~ C ₂₀ Aryloxycarbonyl group; 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 For aryloxy group and amino group, R ¹ , R ² It is the same.
[0045]
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.
[0046]
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.
[0047]
Note that the carbamoyl group (—C (═O) NH ₂ ), A haloformyl group (—C (═O) —X, wherein X represents a halogen atom), a formyl group (—C (═O) —H) and the like are mutually converted into a cyano group and an alkoxycarbonyl group. can do.
[0048]
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.
[0049]
Further, copolymers may be formed with ethylene, propylene, cycloolefin olefins; vinyl derivatives such as vinyl chloride and vinyl acetate.
Since unsaturated bonds are introduced into the poly (diene-arylene) of the present invention, these unsaturated bonds can be further reacted with a radical polymerization initiator, a 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.
[0050]
In another aspect of the invention, resin compositions, such as blends, are provided that contain 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.
[0051]
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.
[0052]
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 a reinforcing material such as glass fiber, carbon fiber, aramid fiber, and boron fiber.
[0053]
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.
[0054]
In another aspect of the present invention, there is provided a diene-aryl represented by the above formula (III) or (IV). Ar in the formula (III) or (IV) ¹ , Ar ² , R ¹ , R ² , A has the above meaning.
[0055]
X ¹ And X ² Are each independently, the same or different, 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.
[0056]
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.
[0057]
Embedded image
[0058]
(Wherein Ar ¹ , Ar ² , R ¹ , R ² , A, X ¹ And X ² Has the above meaning. )
[0059]
Embedded image
[0060]
(Wherein Ar ¹ , Ar ² , R ¹ , R ² , A, X ¹ And X ² Has the above meaning. )
The polymerization is carried out by a reducing agent with a leaving group X ¹ And X ² Is removed to couple the monomer. 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.
[0061]
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 monomers described above 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.
[0062]
That is, when mild reducing agents such as magnesium and zinc are used, bis (triphenylphosphine) dichloronickel, dichloro (2,2′-bipyridine) nickel, PdCl ₂ A catalyst of an organometallic complex such as (2,2′-bipyridine) 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.
[0063]
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.
[0064]
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.
[0065]
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.
[0066]
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.
[0067]
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.
[0068]
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.
[0069]
Embedded image
[0070]
(Wherein Ar ¹ , Ar ² , R ¹ , R ² , A ¹ , X ¹ , X ² And W have the above meanings. )
[0071]
Embedded image
[0072]
(Wherein Ar ¹ , Ar ² , R ¹ , R ² , A ¹ , X ¹ , X ² And W have the above 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. Examples of the metal compound include CuX and NiX. ₂ , BiX _Three A metal salt such as (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.
[0073]
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.
[0074]
A ¹ When a cyano group or an alkoxycarbonyl group is obtained, this substituent is converted into a carbamoyl group (—C (═O) NH by a well-known method. ₂ ), A haloformyl group (—C (═O) —X, where X represents a halogen atom), and a formyl group (—C (═O) —H).
[0075]
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).
[0076]
The metallacyclopentadiene represented by the above formula (V) or (VI) can be synthesized, for example, by the following reaction.
[0077]
Embedded image
[0078]
(Wherein Ar ¹ , R ¹ , A ¹ , X ¹ , L ¹ And L ² Has the above meaning. Z ¹ And Z ² Are the same or different and can be eliminated. )
[0079]
Embedded image
[0080]
(Wherein Ar ¹ , Ar ² , X ¹ , X ² , L ¹ And L ² Has the above meaning. B is a crosslinking group. Z ¹ And Z ² Are the same or different and can be eliminated. )
[0081]
Embedded image
[0082]
(Wherein Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , L ¹ And L ² Has the above meaning. Z ¹ And Z ² Are the same or different and can be eliminated. )
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.
[0083]
Z ¹ And Z ² Is not limited as long as it can be coordinated 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.
[0084]
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.
[0085]
M is preferably a metal complex containing a Group 4 or lanthanide series metal of the periodic table. Delocalized cyclic η ^Five Metal complexes containing a coordination ligand are also preferred.
L ¹ And L ² Is the delocalized cyclic η ^Five -It is preferable that it is a coordination type ligand. Delocalized cyclic η ^Five Examples of the coordination 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.
[0086]
Delocalized cyclic η ^Five In the coordination 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.
[0087]
Delocalized cyclic η ^Five -Coordination ligands, for example cyclopentadienyl groups, may be bridged with a central metal and one or more bridging ligands which may be cyclic. Examples of the bridging ligand include CH. ₂ , CH ₂ CH ₂ , CH (CH _Three ) CH ₂ , CH (C _Four H ₉ ) C (CH _Three ) ₂ , C (CH _Three ) ₂ , (CH _Three ) ₂ Si, (CH _Three ) ₂ Ge, (CH _Three ) ₂ Sn, (C ₆ H _Five ) ₂ Si, (C ₆ H _Five ) (CH _Three ) Si, (C ₆ H _Five ) ₂ Ge, (C ₆ H _Five ) ₂ Sn, (CH ₂ ) _Four Si, CH ₂ Si (CH _Three ) ₂ , O-C ₆ H _Four Or 2, 2 ′-(C ₆ H _Four ) ₂ Is mentioned.
[0088]
2 or more delocalized cyclic η ^Five -Coordination ligands, for example cyclopentadienyl groups, may be cross-linked by one or more cross-linking groups which may be cyclic to one another. Examples of the crosslinking group include CH. ₂ , CH ₂ CH ₂ , CH (CH _Three ) CH ₂ , CH (C _Four H ₉ ) C (CH _Three ) ₂ , C (CH _Three ) ₂ , (CH _Three ) ₂ Si, (CH _Three ) ₂ Ge, (CH _Three ) ₂ Sn, (C ₆ H _Five ) ₂ Si, (C ₆ H _Five ) (CH _Three ) Si, (C ₆ H _Five ) ₂ Ge, (C ₆ H _Five ) ₂ Sn, (CH ₂ ) _Four Si, CH ₂ Si (CH _Three ) ₂ , O-C ₆ H _Four Or 2, 2 ′-(C ₆ H _Four ) ₂ Is mentioned.
[0089]
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.
[0090]
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 produced 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.
[0091]
【Example】
Hereinafter, the present invention will be described based on examples. The present invention is not limited to the following examples.
[0092]
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.
[0093]
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 _Three ) _Four (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%.
[0094]
¹ H NMR (CDCl _Three , Me _Four 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 _Three , Me _Four 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
Screw (η ^Five -Cyclopentadienyl) dichlorozirconium (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. 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
The 2,5-bis (p-bromophenyl) -cyclohexa [c] -1-zirconacyclopenta-2,4-diene obtained in Reference Example 2 was used as it was 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%.
[0095]
¹ H NMR (C ₆ D ₆ , Me _Four 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 _Four Si) δ26.27 (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 value C ₂₀ H ₁₈ Br ₂ 415.9774; Found 415.9763. Example 2
1,2-bis ((p-bromophenyl) chloromethylidene) -cyclohexane
The 2,5-bis (p-bromophenyl) -cyclohexa [c] -1-zirconacyclopenta-2,4-diene obtained in Reference Example 2 was used as it was without separation. That is, 2,5-bis (p-bromophenyl) -cyclohexa [c] -1-zirconacyclopenta-2,4-diene (1.0 mmol) in THF (10 ml) was added to N-chloro at room temperature. 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%.
[0096]
¹ H NMR (CDCl _Three , Me _Four 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 _Three , Me _Four 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).
[0097]
High resolution mass spectrometry (HRMS): Calculated value C ₂₀ H ₁₆ Br ₂ Cl ₂ 483.8995; found 483.8998.
Example 3
1,2-bis (1 ′-(p-bromophenyl) -3′-butenylidene) -cyclohexane
The 2,5-bis (p-bromophenyl) -cyclohexa [c] -1-zirconacyclopenta-2,4-diene obtained in Reference Example 2 was used as it was 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%.
[0098]
¹ H NMR (CDCl _Three , Me _Four 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).
[0099]
¹³ C NMR (CDCl _Three , Me _Four 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).
[0100]
High resolution mass spectrometry (HRMS) calculation value for C ₂₆ H ₂₆ Br ₂ 496.0400, found 496.0417.
The reactions from Reference Example 1 to Example 3 are summarized below.
[0101]
Embedded image
[0102]
(Where A ¹ Are the hydrogen atom, chlorine atom and allyl group (CH═CH—CH in Examples 1, 2 and 3, respectively. ₂ -). )
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 changed. 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 Was used to synthesize the reaction time twice for 3 hours and 24 hours.
[0103]
The results of Examples 4 to 6 are shown in Table 1.
[0104]
[Table 1]
[0105]
Reference example 3
2,5-bis (p-bromophenyl) -cyclopenta [c] -1-zirconacyclopenta-2,4-diene
Screw (η ^Five -Cyclopentadienyl) dibutylzirconium (1.2 mmol) and THF (10 ml) are charged into a 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
Screw (η ^Five -Cyclopentadienyl) dibutylzirconium (1.2 mmol) and THF (10 ml) are charged into a 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 and then allowed to warm to room temperature and left for 1 hour to give the title compound.
[0106]
That is, the title compound is a kind of the compound represented by the above formula (V), and R ¹ And R ² Together, the formula —CH ₂ -CH ₂ -O-CH ₂ -CH ₂ The group shown by-is formed. 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.
[0107]
The reactions of Reference Examples 3 and 4 and Examples 7 and 8 are summarized in the following scheme.
[0108]
Embedded image
[0109]
(Where B ¹ Means an oxygen atom or a methylene group. A ¹ Is 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 Conacyclopenta-2,4-diene mixture
Screw (η ^Five -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.
[0110]
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 prepared in the same manner as in Examples 1 to 3, respectively, 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 and then by recrystallization.
[0111]
And it polymerizes like Example 4 and the corresponding poly (diene-arylene) is obtained.
[0112]
【The invention's effect】
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.

Claims (6)

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 of each other, the same or different, a hydrogen atom, a C _{1 to} C ₂₀ hydrocarbon group which may have a substituent, which may have a substituent, C ₁ -C ₂₀ alkoxy group which may have a substituent, C ₆ -C ₂₀ aryloxy group, an amine group, a hydroxyl group or the formula -Si (R ³⁾ ( Groups represented by 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 or a C ₆ -C ₂₀ aryl group). alkyl group, C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₂₀ arylalkyl group.), and
However, in the case of the repeating unit represented by the formula (I), R ¹ and R ² may be interrupted with each other by an oxygen atom, and may have a substituent, C _{4 to} C _20. May be 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; optionally having a C ₆ -C ₂₀ aryloxy group; optionally having a C ₆ -C ₂₀ alkyl aryloxy group; having a substituent An optionally substituted alkoxycarbonyl group; an optionally substituted 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); formyl group (—C (═O) —H); n is an integer of 2 or more. ) The poly (diene-arylene) according to claim ^1, wherein Ar ¹ and Ar ² are each independently a phenylene group which is the same or different and may have a substituent. C _{4 to} C ₂₀ having a repeating unit represented by the above formula (I), and R ¹ and R ² may be interrupted by an oxygen atom or may have a substituent. 3. A poly (diene-arylene) according to claim 1 or 2 forming a saturated or unsaturated ring. 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, a linear or branched C ₄ -C ₂₀ alkadienyl group, a linear or branched C ₄ -C ₂₀ polyenyl group, C ₆ -C ₁₈ aryl group, C ₆ -C ₂₀ alkylaryl group , poly according to C ₆ -C ₂₀ arylalkyl group, C ₄ -C ₂₀ cycloalkyl group or C ₄ -C ₂₀ claim 1, 2 or 3 is a cycloalkenyl group (diene - arylene).   A resin composition comprising the poly (diene-arylene) described in any one of claims 1 to 4 and a synthetic organic polymer. 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 of each other, the same or different, a hydrogen atom, a C _{1 to} C ₂₀ hydrocarbon group which may have a substituent, which may have a substituent, C ₁ -C ₂₀ alkoxy group which may have a substituent, C ₆ -C ₂₀ aryloxy group, an amine group, a hydroxyl group or the formula -Si (R ³⁾ ( Groups represented by 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 or a C ₆ -C ₂₀ aryl group). alkyl group, C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₂₀ arylalkyl group.), and
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 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; optionally having a C ₆ -C ₂₀ aryloxy group; optionally having a C ₆ -C ₂₀ alkyl aryloxy group; having a substituent An optionally substituted C ₁ -C ₂₀ alkoxycarbonyl group; an optionally substituted 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); n is an integer of 2 or more. ) Polymerizing a diene-aryl represented by the following formula (III) or (IV): A method for producing poly (diene-arylene).
(Wherein Ar ¹ , Ar ² , R ¹ , R ² , and A have the above-mentioned meanings, and X ¹ and X ² are each independently of each other, the same or different, and a leaving group .)