JP2019206676A - Polymer compound, polymer compound production method, and applications thereof - Google Patents

Abstract

To provide: a method of producing a polymer compound allowing efficient production of the polymer compound; the polymer compound; and an organic electronics material, an ink composition, an organic electronics element, an organic EL element, a lighting device and a display device that employ the polymer compound.SOLUTION: The method of producing the polymer compound comprises reacting a compound represented by the specified formula (1) with a compound represented by the specified formula (2) in the presence of a transition metal catalyst obtained by reacting a reductant with a transition metal salt or a hydrate thereof or with a complex of the transition metal salt or hydrate thereof. In the formulas (1) and (2), X represents a divalent linking group, and Rand Reach independently represent a hydrogen atom or substituent.SELECTED DRAWING: None

Description

  Embodiments of the present invention include a polymer compound, a method for producing the polymer compound, an organic electronics material, an ink composition, an organic electronics element, an organic electroluminescence element (hereinafter also referred to as an organic EL element), a lighting device, and The present invention relates to a display device.

  A polymerization reaction using a cycloaddition trimerization reaction of alkyne as a bond formation reaction is expected as a useful polymer synthesis method for forming a branched polymer.

So far, cycloaddition trimerization polymerization of diyne compounds catalyzed by CpCo (CO) ₂ or TaCl ₅ -Ph ₄ Sn has been reported, but the polymer produced has many solvent-insoluble components and is solvent-soluble. It has been pointed out that only a part of such a polymer can be obtained (Non-patent Documents 1 and 2). This is due to gelation due to the formation of a hyperbranched polymer and a crosslinking reaction between the produced polymers.
Furthermore, by using a CpCo (CO) ₂ catalyst or TaCl ₅ -Ph ₄ Sn catalyst and adding an appropriate amount of a terminal monoalkyne-type comonomer to the diyne monomer, polymerization is performed, thereby yielding a solvent-soluble polymer. It has been reported that it can be synthesized well (Non-Patent Documents 2 to 4 and Patent Document 1).

US Patent Application Publication No. 2003/0225232

K. Xu et al., Chinese Journal of Polymer Science, 1999, 17, pp.397-402. M. Haeussler et al., C. R. Chimie, 2003, 6, pp.833-842. H. Peng et al., Macromolecules 2002, 35, pp.5349-5351. K. Xu et al., Macromolecules 2002, 35, pp.5821-5834.

  In the method of adding a terminal monoalkyne-type comonomer to the diyne monomer, there is a problem due to the progress of self-consumption due to the self-cyclization trimerization of the terminal monoalkyne-type monomer. That is, in the method of adding a terminal monoalkyne-type comonomer to the diyne monomer, the terminal monoalkyne-type comonomer is easily consumed during the polymerization reaction by a self-cycloaddition trimerization reaction that is not related to the polymerization reaction. For this reason, the produced polymer always tends to leave a terminal alkyne portion, and there is a concern that a cross-linking reaction between undesirable polymers that produce a solvent-insoluble component may progress depending on a long-time reaction. Therefore, for efficient polymer synthesis, it is necessary to strictly control the amount of terminal monoalkyne-type comonomer charged, the amount or concentration of catalyst, and the reaction time for each monomer combination. That is, depending on the combination of monomers, there is a problem in that it is necessary to add a large amount of terminal monoalkyne-type comonomer to the diyne monomer, to use a high concentration catalyst, and to control the reaction time. These become a big problem especially when mass synthesis is performed.

  In view of the above-described problems, embodiments of the present invention provide a method for producing a polymer compound that can efficiently produce a polymer compound, a polymer compound, an organic electronic material using the polymer compound, and an ink composition. An object of the present invention is to provide an organic electronics element, an organic EL element, a lighting device and a display device.

式（１）及び（２）中、Ｘは２価の連結基を表し、Ｒ^１及びＲ^２はそれぞれ独立に水素原子又は置換基を表す。 In an embodiment of the present invention, a compound represented by the following formula (1) and a compound represented by the following formula (2) are converted into a transition metal salt or a hydrate thereof, or a transition metal salt or a hydrate thereof. It is related with the manufacturing method of a high molecular compound including reacting in the presence of the transition metal catalyst obtained by making the complex of (1) react with a reducing agent.

In formulas (1) and (2), X represents a divalent linking group, and R ¹ and R ² each independently represent a hydrogen atom or a substituent.

式（３）〜（５）中、Ｘはそれぞれ独立に２価の連結基を表し、Ｒ^１及びＲ^２はそれぞれ独立に水素原子又は置換基を表し、「＊」は、他の構造単位との結合部位を表す。 Another embodiment of the present invention is a polymer compound comprising a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a structural unit represented by the following formula (5) About.

In formulas (3) to (5), X independently represents a divalent linking group, R ¹ and R ² each independently represent a hydrogen atom or a substituent, and “*” represents other structural units Represents the binding site.

Another embodiment of the present invention relates to an organic electronic material containing the polymer compound.
Another embodiment of the present invention relates to an ink composition comprising the organic electronic material and a solvent.
Other embodiment of this invention is related with the organic electronics element which has the organic layer formed using the said organic electronics material or the said ink composition.
Other embodiment of this invention is related with the organic electroluminescent element which has an organic layer formed using the said organic electronics material or the said ink composition.
Other embodiment of this invention is related with the display element provided with the said organic electroluminescent element.
Other embodiment of this invention is related with the illuminating device provided with the said organic electroluminescent element.
Other embodiment of this invention is related with the display apparatus provided with the said illuminating device and the liquid crystal element as a display means.

  According to embodiments of the present invention, a method for producing a polymer compound capable of efficiently producing a polymer compound, a polymer compound, an organic electronic material using the polymer compound, an ink composition, and an organic electronics element An organic EL element, a lighting device, and a display device can be provided.

It is a schematic diagram which shows an example of the organic EL element which is embodiment of this invention.

  An embodiment of the present invention will be described. The present invention is not limited to the following embodiments.

In the following description, “aromatic hydrocarbon” and “aromatic heterocycle” (hereinafter, “aromatic hydrocarbon” and “aromatic heterocycle” may be referred to as “aromatic ring”) indicate aromaticity. It is a ring to show. The aromatic ring may be a single ring such as benzene, or may be a condensed ring in which the rings are condensed with each other, such as naphthalene. The aromatic ring may have a structure in which two or more selected from independent single rings and condensed rings are bonded, such as biphenyl, terphenyl, and triphenylbenzene. Examples of aromatic hydrocarbons include benzene, naphthalene, anthracene, tetracene, fluorene, phenanthrene, biphenyl, terphenyl, triphenylbenzene, and the like. Examples of aromatic heterocycles include pyridine, pyrazine, quinoline, isoquinoline, acridine, phenanthroline, furan, pyrrole, thiophene, carbazole, oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzoxiadiazole, benzothiadiazole, Examples include benzotriazole and benzothiophene.
The aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. A heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocyclic ring. An arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. A heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic heterocycle.

<Method for producing polymer compound>
In the method for producing a polymer compound according to an embodiment of the present invention, a compound represented by the following formula (1) and a compound represented by the following formula (2) are converted into a transition metal salt or a hydrate thereof, or a transition. A method for producing a polymer compound comprising reacting a complex of a metal salt or a hydrate thereof with a reducing agent in the presence of a transition metal catalyst.

In formulas (1) and (2), X represents a divalent linking group, and R ¹ and R ² each independently represent a hydrogen atom or a substituent.

In the method of this embodiment, it is possible to carry out [2 + 2 + 2] type cycloaddition polymerization of a diyne monomer and a monoalkyne type comonomer, whereby a branched polymer compound can be synthesized.
In this method for producing a polymer compound, an internal alkyne-type monoalkyne-type comonomer that hardly undergoes self-cyclization and trimerization can be used by reacting in the presence of a specific catalyst.
Further, in this method for producing a polymer compound, various polymerizable functional groups that can be used for the crosslinking reaction can be introduced into the polymer compound.

In the formula (1), X represents a divalent linking group. Examples of the divalent linking group include a divalent organic group.
The divalent organic group is not particularly limited as long as it is a divalent group having one or more carbon atoms. For example, the divalent organic group includes a substituted or unsubstituted aromatic hydrocarbon structure and / or an aromatic heterocyclic structure. Valent groups and the like.
X may have an ethynyl group (—C≡CH), but the compound of formula (1) is a compound having two ethynyl groups (a compound in which X does not have an ethynyl group). Also good.

  When the obtained polymer compound is used for an organic electronic material or the like, X is preferably a divalent group containing a substituted or unsubstituted aromatic hydrocarbon structure and / or an aromatic heterocyclic structure. The divalent group containing a substituted or unsubstituted aromatic hydrocarbon structure and / or aromatic heterocyclic structure is particularly preferably a divalent group containing an aromatic hydrocarbon structure and / or aromatic heterocyclic structure. Without limitation, a divalent group containing a substituted or unsubstituted aromatic amine structure, a divalent group containing a substituted or unsubstituted benzene structure, a divalent group containing a substituted or unsubstituted fluorene structure, substituted or A divalent group containing an unsubstituted carbazole structure, a divalent group containing a substituted or unsubstituted biphenyl structure, and the like are preferable.

  As the aromatic amine structure, a tertiary aromatic amine structure is preferable, and a triarylamine structure is more preferable. In the aromatic amine structure, the aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and still more preferably 6 carbon atoms. As the triarylamine structure, a triphenylamine structure is more preferable.

  Examples of X include, for example, a divalent group represented by the following formula (X-1) and a divalent group represented by the following formula (X-2). The group is not limited to the group represented by the following formula.

In formulas (X-1) and (X-2), Ar ¹ is independently a substituted or unsubstituted arylene group or heteroarylene group. As the arylene group or heteroarylene group, an arylene group or heteroarylene group having 2 to 30 carbon atoms (more preferably 2 to 20, more preferably 6 to 14, more preferably 6 to 10) is preferable, A phenylene group is more preferred. Ar ² is a substituted or unsubstituted aryl group or heteroaryl group. The aryl group or heteroaryl group is preferably an aryl group or heteroaryl group having 2 to 30 carbon atoms (more preferably 2 to 20, more preferably 6 to 14, more preferably 6 to 10), A phenyl group is more preferred. As the substituent when the arylene group, heteroarylene group, aryl group, or heteroaryl group of Ar ¹ and Ar ² has a substituent, for example, an alkyl group (for example, having 1 to 22 carbon atoms, preferably 1 carbon atom) To 10 alkyl groups), an aryl group or a heteroaryl group (for example, an aryl group or heteroaryl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms), a hydroxyl group, an alkoxy group (for example, 1 carbon atom) -22, preferably an alkoxy group having 1 to 10 carbon atoms), a halogen atom, an amino group, a group containing a carboxylic ester bond, a group containing a borate ester bond, a nitro group, a group containing an amide bond, Examples thereof include groups containing a polymerizable functional group described later. Y ¹ is a single bond or a divalent linking group, and is preferably a single bond, O, a carbonyl group, S, SiR ₂ , a sulfinyl group, a sulfonyl group, or the like. Y ² is a trivalent linking group, preferably N, P, SiR or the like. R of SiR ₂ and SiR are each independently a substituent or H, and preferably each independently an alkyl group (for example, an alkyl group having 1 to 22 carbon atoms, preferably 1 to 10 carbon atoms), An aryl group or heteroaryl group (for example, an aryl group or heteroaryl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms), or H. )

Examples of the divalent group represented by the formula (X-1) include a divalent group represented by the following formula (1-1). Examples of the divalent group represented by the formula (X-2) include a divalent group represented by the following formula (1-2). For example, the following formula (1-1) is an example in which Y ¹ is O in the formula (X-1), but X is, for example, in the following formula (1-1): Y ¹ in X-1) may be changed to a single bond, a carbonyl group, S, or SiR ₂ , a sulfinyl group, a sulfonyl group, or the like. Similarly, the following formula (1-2) is an example in which Y ² is N in the formula (X-2), but X is a formula (X) in the following formula (1-2). -2) Y ² may be changed to P or SiR, for example.

In formulas (1-1) and (1-2), R ^a is each independently a substituent, and preferably each independently an alkyl group (for example, having 1 to 22 carbon atoms, preferably 1 to 10 carbon atoms). Alkyl groups), aryl groups or heteroaryl groups (for example, aryl groups or heteroaryl groups having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms), hydroxyl groups, alkoxy groups (for example, 1 to 22 carbon atoms). , Preferably an alkoxy group having 1 to 10 carbon atoms), a halogen atom, an amino group, a group containing a carboxylic ester bond, a group containing a borate ester bond, a nitro group, a group containing an amide bond, or A group containing a polymerizable functional group. l, n, o, and p are each independently an integer of 0 to 4, and m is an integer of 0 to 5.

  Preferable examples of X include the following divalent groups, but X is not limited to the following groups.

In Formula (2), R ¹ and R ² each independently represent a hydrogen atom or a substituent. For example, R ¹ and R ² may be independently selected from a hydrogen atom, a sulfo group, an amino group, an N-sulfonylamino group, a monovalent organic group, and the like. The monovalent organic group is not particularly limited as long as it is a monovalent group having one or more carbon atoms.

From the viewpoint of reducing the self-cyclization trimerization of the compound represented by (Formula 2), R ¹ and R ² are preferably each independently a substituent, and are each independently a monovalent organic group. It is more preferable.

When the obtained polymer compound is used for an organic electronic material or the like, at least one of R ¹ and R ² is a monovalent containing a substituted or unsubstituted aromatic hydrocarbon structure and / or an aromatic heterocyclic structure. It is preferably a group. The monovalent group containing an aromatic hydrocarbon structure and / or an aromatic heterocyclic structure is not particularly limited as long as it is a monovalent group containing an aromatic hydrocarbon structure and / or an aromatic heterocyclic structure. For example, a substituted or unsubstituted benzene structure, a substituted or unsubstituted furan structure, a substituted or unsubstituted thiophene structure, a substituted or unsubstituted pyridine structure, a substituted or unsubstituted aromatic amine structure (for example, a triarylamine structure) , And the like. In addition, the monovalent group including a substituted or unsubstituted aromatic hydrocarbon structure and / or an aromatic heterocyclic structure includes, for example, a substituted or unsubstituted aryl group or heteroaryl group, or an aromatic hydrocarbon structure and It may also be a monovalent group containing a group containing an aromatic heterocyclic structure (for example, an aryl group or heteroaryl group) as a substituent.

In one embodiment, it is preferable that at least one of R ¹ and R ² has a polymerizable functional group described below. For example, it may have only one polymerizable functional group R ¹ and R ^2, may have a polymerizable functional group at each of R ¹ and R ^2. For example, ^one of R ¹ and R ² may have a polymerizable functional group, and the other may be a hydrogen atom.

Examples of the monovalent organic group include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or heteroaryl group, —SO ₂ R ^b , an alkoxy group (for example, having 1 to 22 carbon atoms, preferably carbon Number 1 to 10 alkoxy groups), N-alkoxycarbonylamino groups, and the like. R ^b is a substituted or unsubstituted aryl group or heteroaryl group.

As an alkyl group, any of a linear, cyclic, or branched alkyl group may be sufficient, for example, C1-C22, Preferably a C1-C10 alkyl group is mentioned, for example. As the substituent when the alkyl group has a substituent, for example, an aryl group or a heteroaryl group (for example, an aryl group or heteroaryl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms), —OR ^c , and a group containing a polymerizable functional group. R ^c is a hydrogen atom, an alkyl group (for example, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, more preferably 1 to 10 carbon atoms), an aryl group or a heteroaryl group (for example, carbon number) 2-30, more preferably 2-20 aryl groups or heteroaryl groups).

The aryl group or heteroaryl group is preferably, for example, an aryl group or heteroaryl group having 2 to 30 carbon atoms (more preferably an aryl group or heteroaryl group having 2 to 20 carbon atoms), such as a phenyl group, a furan-yl group, or a thiophen-yl group. , A pyridinyl group, and the like. Examples of the substituent when the aryl group or heteroaryl has a substituent include, for example, —R ^d , —OR ^e , —COOR ^f , —N (R ^g ) ^2, and a group containing a polymerizable functional group. Is mentioned. R ^d represents an alkyl group (for example, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, more preferably 1 to 10 carbon atoms), or an aryl group or a heteroaryl group (for example, 2 to 2 carbon atoms). 30, more preferably 2 to 20 aryl groups or heteroaryl groups). R ^e , R ^f and R ^g are each independently a hydrogen atom, an alkyl group (for example, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, more preferably 1 to 10 carbon atoms), or An aryl group or a heteroaryl group (for example, an aryl group or heteroaryl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms) is represented. The same applies to the aryl group or heteroaryl group of R ^b and the substituent in the case where they have a substituent.

  Examples of the compound represented by the formula (2) include the following compounds, but the compound represented by the formula (2) is not limited to the following compounds. Examples of combinations are also included in the following, but there are no limitations on combinations when two or more compounds represented by formula (2) are used. For example, the compounds may be arbitrarily selected from the following compounds and used. Good.

  The “polymerizable functional group” refers to a functional group that can form a bond with each other by applying heat and / or light.

  When a polymer compound is used as a material, curing by a crosslinking reaction after forming a film or the like is an important factor. In order to achieve a crosslinking / curing reaction of a film or the like using a polymer compound as a material, it is an effective means to introduce a polymerizable functional group active in the crosslinking reaction into the monomer. Such a polymerizable functional group is preferably stable under the polymerization conditions and steady conditions of the monomer, and can be reacted under milder conditions in the crosslinking reaction.

  As the polymerizable functional group, a group having a carbon-carbon double bond (for example, vinyl group, allyl group, butenyl group, acryloyl group, acrylate group (acryloyloxy group), acryloylamino group, methacryloyl group, methacrylate group (methacryloyl) Oxy group), methacryloylamino group, vinyloxy group, vinylamino group and the like, groups having a small ring (for example, cyclic alkyl groups such as cyclopropyl group and cyclobutyl group; epoxy group (oxiranyl group), oxetane group (oxetanyl group) ), Etc .; diketene groups; episulfide groups; lactone groups; lactam groups, etc.), heterocyclic groups (for example, furan-yl groups, pyrrole-yl groups, thiophene-yl groups, silole-yl groups) and the like. It is done. The polymerizable functional group may have a substituent such as a methyl group or an ethyl group.

  Preferable polymerizable functional groups include oxetanyl group, oxiranyl group, vinyl group, acryloyloxy group, methacryloyloxy group and the like.

  From the viewpoint of increasing the degree of freedom of the polymerizable functional group and facilitating the polymerization reaction, it is preferable that the main skeleton of the obtained polymer compound and the polymerizable functional group are connected by an alkylene chain. For example, when the obtained polymer compound is used in an organic electronic material, for example, from the viewpoint of improving the affinity with the hydrophilic electrode, the main skeleton and the polymerizable functional group of the obtained polymer compound are ethylene. It is preferable to connect with hydrophilic chains, such as a glycol chain and a diethylene glycol chain. Further, from the viewpoint of facilitating the preparation of the monomer used for introducing the polymerizable functional group, the end part of the alkylene chain and / or the hydrophilic chain, that is, the linking of these chain and the polymerizable functional group. An ether bond or an ester bond may be present in the part and / or in the part serving as a connecting part between the chain and the skeleton of the obtained polymer compound. The above-mentioned “group containing a polymerizable functional group” means a polymerizable functional group itself or a group obtained by combining a polymerizable functional group with an alkylene chain or the like. As the group containing a polymerizable functional group, for example, a group exemplified in International Publication No. WO2010 / 140553 can be suitably used.

In the method for producing a polymer compound of the present embodiment, the compound represented by the formula (1) may be used alone or in combination of two or more. As for the compound represented by Formula (2), only 1 type may be used and 2 or more types may be used.
The ratio (molar ratio) between the compound represented by formula (1) and the compound represented by formula (2) (compound represented by formula (1): compound represented by formula (2)) is 1 : 0.1 to 10 is preferable, 1: 0.2 to 5 is more preferable, and 1: 0.5 to 2 is more preferable.

Examples of combinations of the compound represented by the formula (1) and the compound represented by the formula (2) are shown below, but the compound represented by the formula (1) and the compound represented by the formula (2) The combination is not limited to the following.

Examples of the combination of the compound represented by the formula (1) and the compound represented by the formula (2) include, for example, at least one compound selected from the compounds represented by the following formula (1), The combination with the at least 1 compound selected from the compound represented by following formula (2) is also mentioned.

In the method for producing a polymer compound of the present embodiment, a compound represented by the formula (1) and a compound represented by the formula (2) are converted into a transition metal salt or a hydrate thereof, or a transition metal salt or a compound thereof. Reacting in the presence of a transition metal catalyst obtained by reacting a hydrate complex with a reducing agent. A transition metal salt or a hydrate thereof or a complex of a transition metal salt or a hydrate thereof is reacted with a reducing agent to reduce the transition metal and generate a catalytically active species.
Hereinafter, a transition metal salt obtained by reacting a transition metal salt or a hydrate thereof or a complex of the transition metal salt or a hydrate with a reducing agent may be referred to as “transition metal catalyst (a)”.

The transition metal catalyst (a) is a transition metal catalyst obtained by reacting a transition metal salt or a hydrate thereof or a transition metal salt or a complex of the hydrate with a reducing agent. The hydrate complex may be obtained, for example, from a transition metal salt or a mixture of hydrates thereof. In this case, for example, a transition metal complex which is a complex of a transition metal salt or a hydrate thereof and a ligand is obtained by reacting a mixture of the transition metal salt or a hydrate thereof and a ligand with a reducing agent. The transition metal catalyst (a) is obtained by reacting with a reducing agent.
The transition metal catalyst (a) may be produced in the reaction system when the compound represented by the formula (1) and the compound represented by the formula (2) are reacted, or the transition metal obtained in advance The catalyst (a) may be added to the reaction system. When the transition metal catalyst (a) is produced in the reaction system, the compound represented by the formula (1), the compound represented by the formula (2), the material of the transition metal catalyst (a) (transition metal salt or water thereof) The order of addition and mixing of the reducing agent and the transition metal salt or its hydrate complex, transition metal salt or its hydrate-ligand mixture, etc.) and the reducing agent is not particularly limited. For example, the transition metal catalyst (a) is mixed with a reducing agent, and the transition metal salt or hydrate thereof, or the transition metal salt or complex of the hydrate is reacted with the reducing agent to thereby transition metal catalyst (a). Then, a compound represented by the formula (1) and a compound represented by the formula (2) are added, and the compound represented by the formula (1) and the formula (2) are represented. You may react with the compound. Further, for example, the transition metal catalyst (a) is formed by mixing the material of the transition metal catalyst (a), the reducing agent, the compound represented by the formula (1), the compound represented by the formula (2), and the like. And the reaction of the compound represented by the formula (1) and the compound represented by the formula (2) may be performed almost simultaneously.

The transition metal salt or hydrate thereof preferably includes a transition metal salt represented by MQ _n or a hydrate thereof. M is Ti, Nb, Ta, Fe, Ru, Co, Rh, Ir or the like, and Ti, Co, or Rh is preferable. Q is a cyclopentadienyl group, a halogen atom, an OAc group (Ac represents an acetyl group), an acetylacetonate group, an alkoxy group, or the like. Examples of the halogen atom include I, Br, Cl, and F, and I, Br, and Cl are preferable. n is a number corresponding to the valence of M. In MQ _n , two or more different types of Q may be included.

The complex of transition metal salt or hydrate thereof preferably includes a complex of transition metal salt represented by MQ _n or hydrate thereof and ligand L, and complex represented by MQ _n -L _m Is also preferable. MQ _n is as described above. Ligand L is 2- (2,6-diisopropylphenyl) iminomethylpyridine (dipimp), triphenylphosphine (PPh ₃ ), 1,2-bis (diphenylphosphino) ethane (dppe), 2,6- Bis (2,6-diisopropylphenyliminomethyl) pyridine or cyclooctadienyl (cod). m is an integer.

More specifically, as the transition metal salt, Ti (Oi-Pr) _4, CpTi (Oi-Pr) ₃ , CpTiCl ₃ , NbCl ₅ , TaCl ₅ , FeCl ₂ , FeCl ₃ , FeBr ₂ , FeBr ₃ , FeI ₂ , FeI ₃ , Fe (OAc) ₂ , Fe (OAc) ₃ , Fe (acac) ₂ , Fe (acac) ₃ , CoCl ₂ , CoCl ₃ , CoBr ₂ , CoBr ₃ , CoI ₂ , CoI ₃ , Co (OAc) ₂ , Co (OAc) ₃ , Co (acac) ₂ , Co (acac) ₃ , RhCl ₃ , RuCl ₃ , IrCl ₃ etc. are mentioned. i-Pr represents an isopropyl group, and acac represents an acetylacetonate group.

Examples of the transition metal catalyst (a) include Ti (Oi-Pr) _4, CpTi (Oi-Pr) ₃ , CpTiCl ₃ , NbCl ₅ , TaCl ₅ , FeCl ₂ , FeCl ₃ , FeBr ₂ , FeBr ₃ , FeI ₂ , FeI ₃ , Fe (OAc) ₂ , Fe (OAc) ₃ , Fe (acac) ₂ , Fe (acac) ₃ , CoCl ₂ , CoCl ₃ , CoBr ₂ , CoBr ₃ , CoI ₂ , CoI ₃ , Co (OAc) ₂ , Co (OAc) ₃ , Co (acac) ₂ , Co (acac) ₃ , RhCl ₃ , RuCl ₃ , IrCl A transition metal salt selected from the group consisting of ₃ or a hydrate thereof, or a complex of these transition metal salt or a hydrate thereof (for example, a complex with the above-described ligand L) is reduced with a reducing agent (for example, A catalyst obtained by reacting with a reducing agent such as a metal, an organic metal, a metal hydride, or an alkylamine described later) is preferable.

As the transition metal salt, ^a salt represented by CoQ ^a ₂ (Q ^a represents ^a cyclopentadienyl group, a halogen atom, an OAc group, or an acetylacetonate group) is also preferable. The transition metal catalyst (a), transition metal salt or a hydrate thereof represented by CoQ ^a _2, or transition metal salts or complexes of hydrate represented by CoQ ^a ₂ (e.g., the above coordination A catalyst obtained by reacting a complex with a child L) with a reducing agent (for example, a reducing agent such as a metal, organic metal, metal hydride, or alkylamine described later) is also preferable.

Examples of the reducing agent include metals (eg, Zn, Mn, Al, Mg, etc.), organic metals (eg, Grignard reagent, organolithium, etc.), metal hydrides (eg, NaBH ₄ , LiAlH ₄ etc.), alkylamines (eg, And trialkylamines such as triethylamine). The metal such as Zn, Mn, Al and Mg is preferably powder.

The following are mentioned as an example of the combination of a transition metal salt or its hydrate, and a reducing agent, and the combination of a transition metal salt or its hydrate, a ligand, and a reducing agent. In the combination of a transition metal salt or a hydrate thereof and a ligand and a reducing agent, the transition metal salt or a complex of the hydrate and the ligand may be reacted with a reducing agent. A mixture of hydrate and ligand may be reacted with a reducing agent.
Combination of CpTi (Oi-Pr) ₃ and Mg Combination of CpTiCl ₃ and Mg Combination of FeCl ₂ , dipimp and Zn Combination of FeCl ₃ , dipimp and Zn CoCl ₂ , combination of dipimp and Zn CoCl ₂ -6H ₂ O, dipimp and Zn combination CoCl ₃ dipip and Zn combination CoCl ₃ -4H ₂ O dipimp and Zn combination CoCl ₂ , PPh ₃ and Zn combination CoI ₂ , PPh ₃ and Mn combination of a combination RhCl ₃ and PPh ₃ and combinations RuCl ₃ of Zn and PPh ₃ in combination RuCl ₃ and combinations RhCl ₃ and triethylamine and Zn with triethylamine

As an example of a combination of a transition metal salt or a hydrate thereof and a reducing agent, and a combination of a transition metal salt or a hydrate thereof, a ligand and a reducing agent, more preferably, CpTi (O-i-Pr ) ₃ and Mg, CpTiCl ₃ and Mg, CoCl ₂ -6H ₂ O, dipimp and Zn, CoCl ₃ -4H ₂ O, dipimp and Zn, CoCl ₂ and PPh ₃ combination of Zn, a combination of a CoI ₂ and PPh ₃ and Mn, more preferably, a combination of CoCl ₂ -6H ₂ O and dipimp and Zn.

In the case of the combination of CoCl ₂ -6H ₂ O, dipimp and Zn powder, the catalyst activator is preferably 1.0 to 6.0 molar equivalents, more preferably 1.0 to CoCl ₂ -6H ₂ O. Up to 3.0 molar equivalents of diester additive can be added. Specific diester additives include dimethyl phthalate, diethyl phthalate, dimethyl glutarate, diethyl glutarate, dimethyl adipate, emethyl adipate, ethane-1,2-diyldibenzoate, ethane-1,2-diyldi Examples include acetate, hexamethylbenzene-1,2,3,4,5,6-hexacarboxylate and the like.

As the transition metal catalyst (a), a complex such as Q ^c Co (PPh ₃ ) ₃ (Q ^c is Cl, Br or I), ClRh (PPh ₃ ) ₃ , CpRuCl (cod) is preferable. ^c Co (PPh ₃ ) ₃ (Q ^c is Cl, Br or I), ClRh (PPh ₃ ) ₃ is more preferable.

In the production method of the present embodiment, the reaction between the compound represented by the formula (1) and the compound represented by the following formula (2) may be performed in the presence of a solvent. Examples of the solvent that can be used include N-methylpyrrolidone, tetrahydrofuran (THF), ethanol (EtOH), dimethylacetamide (DMA), 1,2-dimethoxyethane (DME), N, N-dimethylformamide (DMF), CH ₂ Cl ₂ , diethyl ether and the like and mixed solvents thereof can be exemplified.

  The manufacturing method of this embodiment can be performed under normal pressure or under pressure. Moreover, it is preferable to carry out in inert gas atmosphere, such as nitrogen and argon. Moreover, 0 to 130 degreeC is preferable and reaction temperature has preferable 20 to 60 degreeC. The reaction time is preferably 1 hour to 48 hours, and more preferably 3 hours to 24 hours. After completion of the reaction, the intended polymer compound can be obtained by treatment by a conventional method.

  By the production method of the present embodiment, a polymer compound containing a structural unit represented by formula (3), a structural unit represented by formula (4), and a structural unit represented by formula (5), which will be described later, is obtained. Can be manufactured.

  As an example of the manufacturing method of this embodiment, the following compound A is used as a compound represented by Formula (1), and the following compound B is used as a compound represented by Formula (2), for example. . Thereby, the high molecular compound which has the following partial structure C can be obtained.

The polymer compound of the embodiment of the present invention includes a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a structural unit represented by the following formula (5).

In formulas (3) to (5), X independently represents a divalent linking group, R ¹ and R ² each independently represent a hydrogen atom or a substituent, and “*” represents other structural units Represents the binding site.
This polymer compound can be produced by the polymer compound production method described above.

X, ^{R 1} and ^{R 2} are the same X in formula (1) and (2), and ^{R 1} and ^{R 2,} and preferred ranges are also the same. However, in the formulas (3) to (5), it is preferable that X, R ¹ and R ² each do not contain an ethynyl group (—C≡CH).

“*” Represents a binding site with another structural unit.
For example, the structural unit represented by the formula (3) and the structural unit represented by the formula (4) include a binding site shown on the right side of the formula (3) and a binding site shown on the left side of the formula (4). And the structural unit represented by the formula (4) and the structural unit represented by the formula (5) include a binding site shown on the right side of the formula (4) and a binding site shown in the formula (5). You may combine with.

In the polymer compound, the structural unit represented by the formula (3), the structural unit represented by the formula (4), and the structural unit represented by the formula (5) each include only one type or two or more types. It may be. The polymer compound may contain other structural units.
The polymer compound may be an alternating, random, block, or graft copolymer.

The polymer compound preferably has a polymerizable functional group.
From the viewpoint of contributing to a change in solubility, the polymerizable functional group is preferably contained in a large amount in the polymer compound. On the other hand, from the viewpoint of not hindering the charge transport property, it is preferable that the amount contained in the polymer compound is small. The content of the polymerizable functional group can be appropriately set in consideration of these.

  For example, the number of polymerizable functional groups per molecule of the polymer compound is preferably 2 or more, more preferably 3 or more from the viewpoint of obtaining a sufficient solubility change.

  The polymer compound of the present embodiment is preferably used as a charge transport material. A charge transporting material is a compound having the ability to transport charges. The polymer compound preferably has the ability to transport holes. The hole transporting material can be used, for example, in a hole injection layer and / or a hole transport layer of an organic EL element. Moreover, if it is an electron transport material, it can use for an electron carrying layer and / or an electron injection layer, for example. In addition, any compound having the ability to transport both holes and electrons can be used as a material for the light emitting layer, for example.

  The polymer compound of this embodiment includes at least a benzene structure, but when used as a charge transporting material, it preferably includes an atomic group having the ability to transport charges. Examples of the atomic group having the ability to transport charges include, for example, a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, phenoxazine structure, benzene structure, biphenyl structure, terphenyl structure, and naphthalene structure. , Anthracene structure, tetracene structure, phenanthrene structure, dihydrophenanthrene structure, pyridine structure, pyrazine structure, quinoline structure, isoquinoline structure, quinoxaline structure, acridine structure, diazaphenanthrene structure, furan structure, pyrrole structure, oxazole structure, oxadiazole structure , Thiazole structure, thiadiazole structure, triazole structure, benzothiophene structure, benzoxazole structure, benzooxadiazole structure, benzothiazole structure, benzothiadiazole structure, Zotoriazoru structure and, a structure that comprises one or more of these. Examples of the structure containing two or more of these, for example, bithiophene structure.

(Number average molecular weight)
The number average molecular weight of the polymer compound can be appropriately adjusted in consideration of solubility in a solvent, film formability, and the like. The number average molecular weight is preferably 500 or more, more preferably 1,000 or more, and still more preferably 2,000 or more. The number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
(Weight average molecular weight)
The weight average molecular weight of the polymer compound can be appropriately adjusted in consideration of solubility in a solvent, film formability, and the like. The weight average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, and still more preferably 10,000 or more. The weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, and still more preferably 400,000 or less.
The number average molecular weight and the weight average molecular weight can be measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.

<Organic electronics materials>
The organic electronic material which is embodiment of this invention contains the above-mentioned high molecular compound.

[Dopant]
The organic electronic material may further contain a dopant. The dopant is not particularly limited as long as it is a compound that can be added to the organic electronic material to develop a doping effect and improve the charge transport property. Doping includes p-type doping and n-type doping. In p-type doping, a substance serving as an electron acceptor is used as a dopant, and in n-type doping, a substance serving as an electron donor is used as a dopant. It is preferable to perform p-type doping for improving hole transportability and n-type doping for improving electron transportability. The dopant used in the organic electronic material may be a dopant that exhibits any effect of p-type doping or n-type doping. Further, one kind of dopant may be added alone, or plural kinds of dopants may be mixed and added.

The dopant used for p-type doping is an electron-accepting compound, and examples thereof include Lewis acids, proton acids, transition metal compounds, ionic compounds, halogen compounds, and π-conjugated compounds. Specifically, as the Lewis acid, FeCl ₃ , PF ₅ , AsF ₅ , SbF ₅ , BF ₅ , BCl ₃ , BBr _{3 and the} like; as the protonic acid, HF, HCl, HBr, HNO ₅ , H ₂ SO ₄ , HClO _{4 and} other inorganic acids, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, polyvinylsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, 1-butanesulfonic acid, vinylphenylsulfonic acid Organic acids such as camphorsulfonic acid; transition metal compounds include FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , AlCl ₃ , NbCl ₅ , TaCl ₅ , MoF ₅ ; Phenyl) borate ion, tris (trifluoro) Methanesulfonyl) Mechidoion, bis (trifluoromethanesulfonyl) imide ion, hexafluoroantimonate ion, AsF ₆ ^- (hexafluoro arsenic acid ions), BF ₄ ^- (tetrafluoroborate), PF ₆ ^- (hexafluorophosphate) A salt having a perfluoroanion such as a salt, a salt having a conjugate base of the protonic acid as an anion; halogen compounds such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr and IF; π-conjugated compounds Examples thereof include TCNE (tetracyanoethylene), TCNQ (tetracyanoquinodimethane) and the like. Moreover, it is also possible to use the electron-accepting compounds described in JP 2000-36390 A, JP 2005-75948 A, JP 2003-213002 A, and the like. Preferred are Lewis acids, ionic compounds, π-conjugated compounds and the like. Of these, onium salts are particularly preferably used.

  An onium salt is a compound containing an onium ion. Examples of the onium salt include salts containing onium ions such as ammonium, phosphonium, oxonium, sulfonium, iodonium and the like. For example, an onium salt can be selected from the examples of the ionic compound and used.

The dopant used for n-type doping is an electron donating compound, for example, alkali metals such as Li and Cs; alkaline earth metals such as Mg and Ca; alkali metals such as LiF and Cs ₂ CO ₃ and / or Examples include alkaline earth metal salts; metal complexes; electron-donating organic compounds.

  In order to easily change the solubility of the organic layer, it is preferable to use a compound that can act as a polymerization initiator for the polymerizable functional group as a dopant. Examples of the substance having both a function as a dopant and a function as a polymerization initiator include the onium salts.

[Polymerization initiator]
When the polymer compound has a polymerizable functional group, the organic electronic material preferably contains a polymerization initiator. As the polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators and the like can be used. From the viewpoint of easily preparing the ink composition, it is preferable to use a substance that has both a function as a dopant and a function as a polymerization initiator. Examples of the polymerization initiator having a function as a dopant include the onium salts. Examples of onium include salts having the perfluoroanion, and specific examples include salts of perfluoroanion with iodonium ions or ammonium ions. Examples of these are given below.

[Other optional ingredients]
The organic electronic material may further contain other charge transporting materials (charge transporting polymer and / or charge transporting low molecular weight compound) and the like.

[Content]
The content of the polymer compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more based on the total mass of the organic electronic material from the viewpoint of obtaining good charge transportability. . It may be 100% by mass.

  When the dopant is contained, the content is preferably 0.01% by mass or more, and 0.1% by mass or more with respect to the total mass of the organic electronic material from the viewpoint of improving the charge transport property of the organic electronic material. More preferred is 0.5% by mass or more. Moreover, from a viewpoint of maintaining favorable film formability, 50 mass% or less is preferable with respect to the total mass of the organic electronic material, 30 mass% or less is more preferable, and 20 mass% or less is still more preferable.

  In the case of containing a polymerization initiator, the content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on the total mass of the organic electronic material, from the viewpoint of improving the curability of the polymer compound. Is more preferable, and 0.5 mass% or more is still more preferable. Moreover, from a viewpoint of keeping charge transportability favorable, 50 mass% or less is preferable with respect to the total mass of organic electronics material, 30 mass% or less is more preferable, and 20 mass% or less is still more preferable.

<Ink composition>
The organic electronic material is preferably used as an ink composition containing the organic electronic material of the above embodiment and a solvent capable of dissolving or dispersing the material. By using the ink composition, the organic layer can be easily formed by a simple method such as a coating method.

[solvent]
As the solvent, water, an organic solvent, or a mixed solvent thereof can be used. Organic solvents include alcohols such as methanol, ethanol and isopropyl alcohol; alkanes such as pentane, hexane and octane; cyclic alkanes such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin and diphenylmethane; ethylene glycol Aliphatic ethers such as dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, Aromatic ethers such as 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole; ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate Aliphatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate; N, N-dimethylformamide, N, N-dimethylacetamide, etc. Amide solvents; dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, methylene chloride and the like can be mentioned. Aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, aromatic ethers and the like are preferable, and aromatic hydrocarbons are more preferable.

[Additive]
The ink composition may further contain an additive as an optional component. Examples of additives include polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, antioxidants, oxidizing agents, reducing agents, surface modifiers, emulsifiers, antifoaming agents, Examples thereof include a dispersant and a surfactant.

[Content]
The content of the solvent in the ink composition can be determined in consideration of application to various coating methods. For example, the content of the solvent is preferably such that the ratio of the polymer compound to the solvent is 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.5% by mass or more. Is more preferred. Further, the content of the solvent is preferably such that the ratio of the polymer compound to the solvent is 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.

<Organic layer>
The organic electronics element and the organic EL element which are embodiments of the present invention include an organic layer formed using the organic electronics material or ink composition of the embodiment. By using the ink composition, the organic layer can be favorably formed by a coating method. Examples of the coating method include spin coating method; casting method; dipping method; letterpress printing, intaglio printing, offset printing, planographic printing, letterpress inversion offset printing, screen printing, gravure printing and other plate printing methods; ink jet method, etc. A known method such as a plateless printing method may be used. When the organic layer is formed by a coating method, the organic layer (coating layer) obtained after the coating may be dried using a hot plate or an oven to remove the solvent.

  When the polymer compound has a polymerizable functional group, the polymerization reaction of the polymer compound may be advanced by light irradiation, heat treatment, or the like to change the solubility of the organic layer. By laminating organic layers with different solubility, it is possible to easily increase the number of organic electronics elements. For the method of forming the organic layer, for example, the description of International Publication No. WO2010 / 140553 can be referred to.

  From the viewpoint of improving the efficiency of charge transport, the thickness of the organic layer after drying or curing is preferably 0.1 nm or more, more preferably 1 nm or more, and further preferably 3 nm or more. In addition, the thickness of the organic layer is preferably 300 nm or less, more preferably 200 nm or less, and still more preferably 100 nm or less, from the viewpoint of reducing electrical resistance.

<Organic electronics elements>
The organic electronics element which is embodiment of this invention has the organic layer of the said embodiment at least. Examples of the organic electronics element include an organic EL element, an organic photoelectric conversion element, and an organic transistor. The organic electronic element preferably has a structure in which an organic layer is disposed between at least a pair of electrodes.

<Organic EL device>
The organic EL element which is embodiment of this invention has an organic layer of the said embodiment at least. The organic EL element usually includes a light emitting layer, an anode, a cathode, and a substrate, and other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer are provided as necessary. I have. Each layer may be formed by a vapor deposition method or a coating method. The organic EL element preferably has an organic layer as a light emitting layer or other functional layer, more preferably as a functional layer, and still more preferably as at least one of a hole injection layer and a hole transport layer.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of an organic EL element. The organic EL element in FIG. 1 is an element having a multilayer structure, and includes a substrate 8, an anode 2, a hole injection layer 3, a hole transport layer 6, a light emitting layer 1, an electron transport layer 7, which are organic layers of the above-described embodiment. The electron injection layer 5 and the cathode 4 are provided in this order. Hereinafter, each layer will be described.

  In FIG. 1, the hole injection layer 3 is an organic layer formed using the organic electronic material of the above embodiment, but the organic EL element of the embodiment of the present invention is not limited to such a structure, The organic layer may be an organic layer formed using the organic electronic material of the embodiment.

[Light emitting layer]
As a material used for the light emitting layer, a light emitting material such as a low molecular compound, a polymer, or a dendrimer can be used. A polymer is preferable because it has high solubility in a solvent and is suitable for a coating method. Examples of the light emitting material include a fluorescent material, a phosphorescent material, a thermally activated delayed fluorescent material (TADF), and the like.

  Fluorescent materials such as perylene, coumarin, rubrene, quinacdrine, stilbene, dyes for dye lasers, aluminum complexes, and derivatives thereof; polyfluorene, polyphenylene, polyphenylene vinylene, polyvinyl carbazole, fluorene-benzothiadiazole copolymer , Fluorene-triphenylamine copolymers, polymers thereof such as derivatives thereof; mixtures thereof and the like.

As the phosphorescent material, a metal complex containing a metal such as Ir or Pt can be used. Examples of the Ir complex include FIr (pic) that emits blue light (iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate), Ir (ppy) ₃ that emits green light. (Factris (2-phenylpyridine) iridium), which emits red light (btp) ₂ Ir (acac) (bis [2- (2′-benzo [4,5-α] thienyl) pyridinate-N, C ³ ] Iridium (acetyl-acetonate)), Ir (piq) ₃ (tris (1-phenylisoquinoline) iridium) and the like. Examples of the Pt complex include PtOEP (2, 3, 7, 8, 12, 13, 17, 18-octaethyl-21H, 23H-formin platinum) that emits red light.

  When the light emitting layer includes a phosphorescent material, it is preferable that a host material is further included in addition to the phosphorescent material. As the host material, a low molecular compound, a polymer, or a dendrimer can be used. Examples of the low molecular weight compound include CBP (4,4′-bis (9H-carbazol-9-yl) biphenyl), mCP (1,3-bis (9-carbazolyl) benzene), CDBP (4,4′- Bis (carbazol-9-yl) -2,2′-dimethylbiphenyl), derivatives thereof, and the like are exemplified by the organic electronic materials, polyvinyl carbazole, polyphenylene, polyfluorene, derivatives thereof, and the like of the embodiment. It is done.

  Examples of thermally activated delayed fluorescent materials include Adv. Mater., 21, 4802-4906 (2009); Appl. Phys. Lett., 98, 083302 (2011); Chem. Comm., 48, 9580 (2012). Appl. Phys. Lett., 101, 093306 (2012); J. Am. Chem. Soc., 134, 14706 (2012); Chem. Comm., 48, 11392 (2012); Nature, 492, 234 (2012 ); Adv. Mater., 25, 3319 (2013); J. Phys. Chem. A, 117, 5607 (2013); Phys. Chem. Chem. Phys., 15, 15850 (2013); Chem. Comm., 49, 10385 (2013); Chem. Lett., 43, 319 (2014) and the like.

[Hole transport layer, hole injection layer]
In FIG. 1, the hole injection layer 3 is an organic layer formed using the organic electronic material of the above embodiment, but the organic EL element is not limited to such a structure, and other organic layers are the above embodiment. The organic layer may be formed using any organic electronics material. It is preferably used as at least one of a hole transport layer and a hole injection layer formed using the organic electronic material of the embodiment, and more preferably used as at least a hole injection layer. For example, when the organic EL element has a layer formed using the organic electronic material of the embodiment as a hole injection layer and further has a hole transport layer, a known material is used for the hole transport layer. it can. In addition, for example, when the organic EL element has a layer formed using the organic electronic material of the embodiment as a hole transport layer and further has a hole injection layer, a known material is used for the hole injection layer. Can be used.

  Examples of materials that can be used for the hole injection layer and the hole transport layer include aromatic amine compounds (for example, N, N′-di (naphthalen-1-yl) -N, N′-diphenyl-benzidine ( Aromatic diamines such as α-NPD), phthalocyanine compounds, thiophene compounds (for example, poly (3,4-ethylenedioxythiophene): poly (4-styrenesulfonate) (PEDOT: PSS), etc. System conductive polymer).

[Electron transport layer, electron injection layer]
Examples of materials used for the electron transport layer and the electron injection layer include phenanthroline derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, condensed ring tetracarboxylic anhydrides such as naphthalene and perylene, and carbodiimides. , Fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives (e.g. 2,2 ', 2 "-(1,3,5-benzenetriyl) tris ( 1-phenyl-1H-benzimidazole) (TPBi)), quinoxaline derivatives, aluminum complexes (for example, bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum (BAlq)) and the like. Ma The organic electronic material of the embodiment can also be used.

[cathode]
As the cathode material, for example, a metal or a metal alloy such as Li, Ca, Mg, Al, In, Cs, Ba, Mg / Ag, LiF, and CsF is used.

[anode]
As the anode material, for example, a metal (for example, Au) or another material having conductivity is used. Examples of other materials include oxides (for example, ITO: indium oxide / tin oxide) and conductive polymers (for example, polythiophene-polystyrene sulfonic acid mixture (PEDOT: PSS)).

[substrate]
As the substrate, glass, plastic or the like can be used. The substrate is preferably transparent and preferably has flexibility. Quartz glass, light transmissive resin film, and the like are preferably used.

  Examples of the resin film include films made of polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate, and the like. Can be mentioned.

  When using a resin film, in order to suppress permeation | transmission of water vapor | steam, oxygen, etc., you may coat and use inorganic substances, such as a silicon oxide and a silicon nitride, on a resin film.

[Luminescent color]
The emission color of the organic EL element is not particularly limited. The white organic EL element is preferable because it can be used for various lighting devices such as home lighting, interior lighting, a clock, or a liquid crystal backlight.

  As a method of forming a white organic EL element, a method of simultaneously emitting light of a plurality of emission colors using a plurality of light emitting materials and mixing the colors can be used. A combination of a plurality of emission colors is not particularly limited, but a combination containing three emission maximum wavelengths of blue, green and red, a combination containing two emission maximum wavelengths of blue and yellow, yellow green and orange, etc. Is mentioned. The emission color can be controlled by adjusting the type and amount of the light emitting material.

<Display element, lighting device, display device>
The display element which is embodiment of this invention is equipped with the organic EL element of the said embodiment. For example, a color display element can be obtained by using an organic EL element as an element corresponding to each pixel of red, green, and blue (RGB). Image forming methods include a simple matrix type in which individual organic EL elements arranged in a panel are directly driven by electrodes arranged in a matrix, and an active matrix type in which thin film transistors are arranged in each element and driven.

  Moreover, the illuminating device which is embodiment of this invention is equipped with the organic EL element of embodiment of this invention. Furthermore, the display apparatus which is embodiment of this invention is equipped with the illuminating device and the liquid crystal element as a display means. For example, the display device may be a display device using a known liquid crystal element as a display unit, that is, a liquid crystal display device, using the illumination device according to the embodiment of the present invention as a backlight.

（式（１）及び（２）中、Ｘは２価の連結基を表し、Ｒ^１及びＲ^２はそれぞれ独立に水素原子又は置換基を表す。）
＜２＞ Ｘが、置換又は非置換の、芳香族炭化水素構造及び芳香族複素環構造からなる群から選択される少なくとも１つを含む、＜１＞に記載の高分子化合物の製造方法。
＜３＞ 前記遷移金属塩又はその水和物は、ＭＱ_ｎで表される遷移金属塩又はその水和物を含み、前記遷移金属塩又はその水和物の錯体は、ＭＱ_ｎで表される遷移金属塩又はその水和物と配位子Ｌとの錯体を含み、Ｍは、Ｔｉ、Ｎｂ、Ｔａ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ又はＩｒであり、Ｑは、シクロペンタジエニル基、ハロゲン原子、ＯＡｃ基、アセチルアセトナート基、又はアルコキシ基であり、Ａｃはアセチル基であり、ｎはＭの価数に対応する数であり、Ｌは、２−（２，６−ジイソプロピルフェニル）イミノメチルピリジン、トリフェニルホスフィン、１，２−ビス(ジフェニルホスフィノ)エタン、又はシクロオクタジエニルである、＜１＞又は＜２＞に記載の高分子化合物の製造方法。
＜４＞ ＭはＴｉ、Ｃｏ又はＲｈである、＜３＞に記載の高分子化合物の製造方法。
＜５＞ 前記還元剤は、金属、有機金属、金属ヒドリド、又はアルキルアミンを含む、＜１＞〜＜４＞のいずれか１項に記載の製造方法。
＜６＞ 下記式（３）で表される構造単位と下記式（４）で表される構造単位と下記式（５）で表される構造単位とを含む高分子化合物。

（式（３）〜（５）中、Ｘはそれぞれ独立に２価の連結基を表し、Ｒ^１及びＲ^２はそれぞれ独立に水素原子又は置換基を表し、「＊」は、他の構造単位との結合部位を表す。）
＜７＞ Ｘが、置換又は非置換の、芳香族炭化水素構造及び芳香族複素環構造からなる群から選択される少なくとも１つを含む、＜６＞に記載の高分子化合物。
＜８＞ Ｘが、置換又は非置換の芳香族アミン構造を含む、＜７＞に記載の高分子化合物。
＜９＞ Ｒ^１及びＲ^２がそれぞれ独立に置換基である、＜６＞〜＜８＞のいずれか１項に記載の高分子化合物。
＜１０＞ Ｒ^１及びＲ^２からなる群から選択される少なくとも１つが、重合性官能基を含む、＜６＞〜＜９＞のいずれか１項に記載の高分子化合物。
＜１１＞ ＜６＞〜＜１０＞のいずれか１項に記載の高分子化合物を含む、有機エレクトロニクス材料。
＜１２＞ ドーパントをさらに含む、＜１１＞に記載の有機エレクトロニクス材料。
＜１３＞ ＜１１＞又は＜１２＞に記載の有機エレクトロニクス材料と、溶媒とを含む、インク組成物。
＜１４＞ ＜１１＞又は＜１２＞に記載の有機エレクトロニクス材料、又は＜１３＞に記載のインク組成物を用いて形成された有機層を有する、有機エレクトロニクス素子。
＜１５＞ ＜１１＞又は＜１２＞に記載の有機エレクトロニクス材料、又は＜１３＞に記載のインク組成物を用いて形成された有機層を有する、有機エレクトロルミネセンス素子。
＜１６＞ フレキシブル基板をさらに有する、＜１５＞に記載の有機エレクトロルミネセンス素子。
＜１７＞ 前記フレキシブル基板が樹脂フィルムを含む、＜１６＞に記載の有機エレクトロルミネセンス素子。
＜１８＞ ＜１５＞〜＜１７＞のいずれか１項に記載の有機エレクトロルミネセンス素子を備えた表示素子。
＜１９＞ ＜１５＞〜＜１７＞のいずれか１項に記載の有機エレクトロルミネセンス素子を備えた照明装置。
＜２０＞
＜１９＞に記載の照明装置と、表示手段として液晶素子とを備えた表示装置。 Embodiments of the present invention include the following. The present invention is not limited to the following embodiment.
<1> A compound represented by the following formula (1) and a compound represented by the following formula (2) are reduced to a transition metal salt or a hydrate thereof, or a transition metal salt or a complex of the hydrate. The manufacturing method of a high molecular compound including making it react in presence of the transition metal catalyst obtained by making it react with an agent.

(In formulas (1) and (2), X represents a divalent linking group, and R ¹ and R ² each independently represents a hydrogen atom or a substituent.)
<2> The method for producing a polymer compound according to <1>, wherein X includes at least one selected from the group consisting of a substituted or unsubstituted aromatic hydrocarbon structure and aromatic heterocyclic structure.
<3> The transition metal salt or a hydrate thereof includes a transition metal salt or a hydrate thereof represented by MQ _n, complex of the transition metal salt or a hydrate thereof is expressed by MQ _n Including a complex of a transition metal salt or a hydrate thereof and a ligand L, wherein M is Ti, Nb, Ta, Fe, Ru, Co, Rh or Ir, Q is a cyclopentadienyl group, halogen An atom, an OAc group, an acetylacetonate group, or an alkoxy group, Ac is an acetyl group, n is a number corresponding to the valence of M, and L is 2- (2,6-diisopropylphenyl) imino The method for producing a polymer compound according to <1> or <2>, which is methylpyridine, triphenylphosphine, 1,2-bis (diphenylphosphino) ethane, or cyclooctadienyl.
<4> The method for producing a polymer compound according to <3>, wherein M is Ti, Co, or Rh.
<5> The production method according to any one of <1> to <4>, wherein the reducing agent includes a metal, an organic metal, a metal hydride, or an alkylamine.
<6> A polymer compound comprising a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a structural unit represented by the following formula (5).

(In formulas (3) to (5), each X independently represents a divalent linking group, each of R ¹ and R ² independently represents a hydrogen atom or a substituent, and “*” represents another structural unit. Represents the binding site.
<7> The polymer compound according to <6>, wherein X includes at least one selected from the group consisting of a substituted or unsubstituted aromatic hydrocarbon structure and aromatic heterocyclic structure.
<8> The polymer compound according to <7>, wherein X includes a substituted or unsubstituted aromatic amine structure.
<9> The polymer compound according to any one of <6> to <8>, wherein R ¹ and R ² are each independently a substituent.
<10> The polymer compound according to any one of <6> to <9>, wherein at least one selected from the group consisting of R ¹ and R ² includes a polymerizable functional group.
<11> Organic electronic material containing the high molecular compound of any one of <6>-<10>.
<12> The organic electronic material according to <11>, further including a dopant.
<13> An ink composition comprising the organic electronic material according to <11> or <12> and a solvent.
<14> An organic electronics element having an organic layer formed using the organic electronics material according to <11> or <12> or the ink composition according to <13>.
<15> An organic electroluminescence device having an organic layer formed using the organic electronic material according to <11> or <12> or the ink composition according to <13>.
<16> The organic electroluminescent element according to <15>, further comprising a flexible substrate.
<17> The organic electroluminescent element according to <16>, wherein the flexible substrate includes a resin film.
<18> The display element provided with the organic electroluminescent element of any one of <15>-<17>.
<19> An illumination device comprising the organic electroluminescent element according to any one of <15> to <17>.
<20>
<19> The display apparatus provided with the illuminating device and liquid crystal element as a display means.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Monomer>
As described below, monomers A1 to A3, which are compounds represented by the formula (1), were obtained.

(Monomer A1)

Under an argon atmosphere, 4,4′-oxybis (bromobenzene) (3.28 g, 10.0 mmol), bistriphenylphosphine palladium (II) dichloride (210 mg, 0.30 mmol), copper (I) iodide (57 mg, 0.30 mmol) ), Triphenylphosphine (53 mg, 0.20 mmol) and triethylamine (10 mL) in THF (30 mL) were added trimethylsilylacetylene (4.14 mL, 30 mmol) at room temperature, and the mixture was added at 70 ° C for 12 ° C. Stir for hours. After cooling to room temperature, saturated aqueous ammonium chloride solution was added. The mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was dissolved in a mixture of THF (30 mL) and ethanol (30 mL). To this, potassium carbonate (about 0.5 g) was added and stirred vigorously at room temperature for 12 hours. Water (50 mL) was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain 4,4′-oxybis (ethynylbenzene) (monomer A1) (1.52 g) in a yield of 78%. .
¹ H-NMR measurement of the product (monomer A1) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.48 (d, J = 7.0 Hz, 4H, Ar), 6.95 (d, J = 7.0 Hz, 4H, Ar), 3.05 (s, 2H, CCH). ¹³ CNMR (125 MHz, CDCl ₃ ) δ 156.85, 133.77, 118.77, 117.20, 82.94, 76.92.

(Monomer A2)

Under an argon atmosphere, bis (4-bromophenyl) methanone (3.35 g, 9.84 mmol), bistriphenylphosphine palladium (II) dichloride (210 mg, 0.30 mmol), copper (I) iodide (57 mg, 0.30 mmol), Trimethylsilylacetylene (4.14 mL, 30 mmol) was added to a THF (30 mL) solution of triphenylphosphine (53 mg, 0.20 mmol) and triethylamine (10 mL) at room temperature, and then the mixture was stirred at 70 ° C. for 12 hours. did. After cooling to room temperature, saturated aqueous ammonium chloride solution was added. The mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was dissolved in a mixture of THF (30 mL) and ethanol (30 mL). To this, potassium carbonate (about 0.5 g) was added and stirred vigorously at room temperature for 12 hours. Water (50 mL) was added, the mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain bis (4-ethynylphenyl) methanone (1.79 g) (monomer A2) in a yield of 79%.
¹ H-NMR measurement of the product (monomer A2) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.75 (d, J = 7.0 Hz, 4H, Ar), 7.60 (d, J = 6.5 Hz, 4H, Ar), 3.26 (s, 4H, CCH).

(Monomer A3)

Under an argon atmosphere, 4-bromo-N- (4-bromophenyl) -N-phenylaniline (8.06 g, 20.0 mmol), bistriphenylphosphine palladium (II) dichloride (420 mg, 0.60 mmol), copper iodide (I ) (114 mg, 0.60 mmol), triphenylphosphine (106 mg, 0.40 mmol) and triethylamine (20 mL) in THF (60 mL) was added trimethylsilylacetylene (8.28 mL, 60 mmol) at room temperature, The mixture was stirred at 70 ° C. for 12 hours. After cooling to room temperature, saturated aqueous ammonium chloride solution was added. The mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was dissolved in a mixture of THF (60 mL) and ethanol (60 mL). To this was added potassium carbonate (about 1 g), and the mixture was vigorously stirred at room temperature for 12 hours. Water (100 mL) was added, the mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain 4-ethynyl-N- (4-ethynylphenyl) -N-phenylaniline (monomer A3) (5.43 g). Obtained at a rate of 92%.
¹ H-NMR measurement of the product (monomer A3) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.26-7.39 (m, 6H, Ar), 6.94-7.15 (m, 7H, Ar), 3.04 (s, 2H, CCH).

  As described below, monomers B1 to B17, which are compounds represented by the formula (2), were obtained.

(Monomer B1)

Under an argon atmosphere, n-butyllithium (21.9 mL, 1.6 hexane solution, 36.0 mmol) was added dropwise to a THF (50 mL) solution of ethynylbenzene (3.30 mL, 30.0 mmol) at −78 ° C., and the mixture was stirred for about 1 hour. . Paraformaldehyde (2.16 g, 72.0 mmol) was added thereto, and then the temperature was slowly raised to room temperature. A saturated aqueous ammonium chloride solution was added, and the mixture was extracted with diethyl ether. The organic image was dried over anhydrous MgSO ₄ and filtered, and then the filtrate was concentrated. The residue was purified by silica gel column chromatography to obtain 3-phenylprop-2-in-1-ol (monomer B1) (4.8 g).
¹ H-NMR measurement of the product (monomer B1) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.43-7.46 (m, 2H, Ph), 7.28-7.33 (m, 3H, Ph), 4.50 (d, J = 5.0 Hz, 2H, CH ₂ ), 3.65 ( br t, J = 5.0 Hz, 1H, OH).

(Monomer B2)

Under argon atmosphere, 3-((4-bromophenoxy) methyl) -3-ethyloxetane (1.36 g, 5.0 mmol), bistriphenylphosphine palladium (II) dichloride (140 mg, 0.20 mmol), copper (I) iodide (38 mg, 0.20 mmol), triphenylphosphine (110 mg, 0.40 mmol) and triethylamine (8 mL) in THF (17 mL) were added trimethylsilylacetylene (2.08 mL, 15 mmol) at room temperature and mixed. The solution was stirred at 70 ° C. for 12 hours. After cooling to room temperature, saturated aqueous ammonium chloride solution was added. The mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was dissolved in a mixture of THF (16 mL) and ethanol (16 mL). To this was added potassium carbonate (about 1 g), and the mixture was vigorously stirred at room temperature for 12 hours. Water was added, the mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was directly used in the next reaction. N-Butyllithium (3.2 mL, 1.55 hexane solution, 5.0 mmol) at -78 ° C in THF (10 mL) solution of 3-ethyl-3-((4-ethynylphenoxy) methyl) oxetane obtained under argon atmosphere Was added dropwise and stirred for 2 hours, and then paraformaldehyde (180 mg, 6.0 mmol) was added. The temperature was slowly raised to room temperature and stirred for 2 hours. Saturated aqueous ammonium chloride solution was added. The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to give 3- (4-((3-ethyloxetane-3-yl) methoxy) phenyl) -2-propyne-1- All (monomer B2) (0.98 g) was obtained with a yield of 80%.
¹ H-NMR measurement of the product (monomer B2) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.38 (d, J = 7.0 Hz, 2H, Ar), 6.87 (d, J = 7.5 Hz, 2H, Ar), 4.57 (d, J = 5.5 Hz, 2H, oxetane CH ₂ ), 4.49 (d, J = 5.5 Hz, 2H, oxetane CH ₂ ), 4.47 (s, 2H, CCCH ₂ O), 4.07 (s, 2H, ArOC H ₂ ), 1.88 (q, J = 6.3 Hz, 2H, C H ₂ CH ₃ ), 0.93 (t, J = 6.3 Hz, 3H, CH ₃ ).
HR-MS: m / z = calcd. For C ₁₅ H ₁₈ NaO ₃ [M + Na] ⁺ : 269.1154, found 269.1144.

(Monomer B3)

A solution of phenylpropiolic acid (0.77 g, 5.3 mmol) and sulfuric acid (0.36 g, 3.7 mmol) in methanol (10 mL) was stirred at reflux for 12 hours. Concentrated, diluted with ethyl acetate, neutralized with saturated aqueous sodium hydrogen carbonate solution, extracted with ethyl acetate, the organic layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtration, methyl phenylpropiolate (monomer B3) (0.85 g) obtained by concentrating the filtrate could be obtained quantitatively.
¹ H-NMR measurement of the product (monomer B3) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.59 (d, J = 8.5 Hz, Ph), 7.46 (t, J = 7.5 Hz, 1H, Ph), 7.38 (t, J = 7.0 Hz, 2H, Ph) , 3.84 (s, 3H, OCH ₃ ).

(Monomer B4)

Triethylamine (60 mL) solution of iodobenzene (2.04 g, 10.0 mmol), bistriphenylphosphine palladium (II) dichloride (140 mg, 0.20 mmol) and copper iodide (I) (18 mg, 0.01 mmol) under an argon atmosphere 3-butyn-1-ol (0.90 mL, 12.0 mmol) was added thereto at room temperature, and the mixture was stirred at 60 degrees for 12 hours. A saturated aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, and then dried over anhydrous sodium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain 4-phenylbut-3-in-1-ol (monomer B4) (0.98 g) in a yield of 67%. .
¹ H-NMR measurement of the product (monomer B4) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.39-7.44 (m, 2H, Ph), 7.27-7.34 (m, 3H, Ph), 3.82 (dt, J = 6.0, 6.5 Hz, 2H, CH ₂ O) , 2.70 (t, J = 6.0 Hz, CCCH ₂ ), 1.80 (br s, 1H, OH).

(Monomer B5)

Under an argon atmosphere, n-butyllithium (7.3 mL, 1.64 M hexane solution, 12.0 mmol) was added dropwise at −20 ° C. to a THF (17 mL) solution of ethynylbenzene (1.02 g, 10.0 mmol). After heating to 0 ° C., acetaldehyde (0.33 g, 11.0 mmol) was added and stirred for 2 hours. Saturated aqueous ammonium chloride solution was added and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain 4-phenyl-3-butyn-2-ol (monomer B5) (2.63 g) in a yield of 90%.
¹ H-NMR measurement of the product (monomer B5) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.42-7.44 (m, 2H, Ph), 7.28-7.33 (m, 3H, Ph), 4.76 (dq, J = 6.0, 6.5 Hz, 1H, CH), 1.90 (br s, 1H, OH), 1.56 (d, J = 6.5 Hz, 3H, CH ₃ ).

(Monomer B6)

Under an argon atmosphere, n-butyllithium (11.0 mL, 1.64 M hexane solution, 18.0 mmol) was added dropwise at −20 ° C. to a THF (25 mL) solution of ethynylbenzene (1.53 g, 15.0 mmol). After heating to 0 ° C., acetaldehyde (0.50 g, 16.5 mmol) was added and stirred for 2 hours. Saturated aqueous ammonium chloride solution was added and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. After filtration, the residue obtained by concentrating the filtrate was directly used in the next reaction. 4-Phenyl-3-butyn-2ol was added dropwise to a mixture of pyridinium chlorocolomate (PCC, 4.85 g, 22.5 mmol) and celite (2 g) in methylene chloride (75 mL) and stirred at room temperature for 2 hours. did. The mixture was filtered through celite, and the filtrate was concentrated. Hexane was added to the residue, filtered through Celite, the filtrate was concentrated, and the resulting residue was purified by silica gel column chromatography to obtain 4-phenyl-3-butyn-2-one (monomer B6) (0.44 g) was obtained with a yield of 20%.
¹ H-NMR measurement of the product (monomer B6) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.56-7.59 (m, 2H, Ph), 7.43-7.48 (m, 1H, Ph), 7.37-7.40 (m, 2H, Ph), 2.45 (s, 3H, CH ₃ ).

(Monomer B7)

1-bromohexane (6.6 g, 40 mmol) was stirred at 60 ° C. for 12 hours in a solution of 4-bromophenol (3.46 g, 20 mmol) and potassium carbonate (5.52 g, 40 mmol) in acetone (40). After cooling to room temperature, the mixture was filtered, concentrated, and diluted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated, and the resulting residue was used as such for the next reaction. Under an argon atmosphere, 4-hexyloxybromobenzene, bistriphenylphosphine palladium (II) dichloride (701 mg, 1.0 mmol), triphenylphosphine (524 mg, 2.0 mmol), copper iodide (I) (190 mg, 1.0 mmol) ) In THF (71 mL) was added triethylamine (29 mL), followed by 2-propyn-1-ol (2.40 g, 40.0 mmol) at room temperature, and the mixture was stirred at 60 ° C. for 12 hours. After cooling to room temperature, a saturated aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, and then dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to collect 3- (4-hexyloxyphenyl) -2-propyn-1-ol (monomer B7) (0.48 g). Obtained at a rate of 10%.
¹ H-NMR measurement of the product (monomer B7) was performed.
¹ H NMR (500 MHz; CDCl ₃ ) δ 7.36 (d, J = 9.0 Hz, 2H, Ar), 6.82 (d, J = 8.5 Hz, 2H, Ar), 4.48 (d, J = 6.0 Hz, 2H, CCCH ₂ ), 3.95 (t, J = 6.0 Hz, 2H, OCH ₂ ), 1.77 (m, 2H, CH ₂ ), 1.60 (t, J = 6.0 Hz, 1H, OH), 1.32-1.347 (m, 6H , CH ₂ ), 0.90 (t, J = 7.5 Hz, 3H, CH ₃ ).

(Monomer B8)

To a solution of 4-bromophenol (1.70 g, 10.0 mmol) and 1-bromo-2-ethylhexane (3.43 mL, 20.0 mmol) in acetone (20 mL) was added anhydrous potassium carbonate (2.80 g, 20.0 mmol) for 12 hours. Heated to reflux. After cooling to room temperature, the mixture was filtered through Celite, and the filtrate was concentrated. Saturated brine was added and the mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was directly used in the next reaction. 1-bromo-4- (2-ethylhexyloxy) benzene, bistriphenylphosphine palladium (II) dichloride (350 mg, 0.50 mmol), triphenylphosphine (262 mg, 1.0 mmol), iodinated under argon atmosphere To a solution of copper (I) (95 mg, 0.5 mmol) in THF (35 mL) was added triethylamine (15 mL), followed by 2-propyn-1-ol (2.40 g, 40.0 mmol) at room temperature and mixed. The solution was stirred at 50 ° C. for 12 hours. After cooling to room temperature, saturated aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, and dried over anhydrous sodium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain 3- (4- (2-ethylhexyloxy) phenyl) -2-propyn-1-ol (monomer B8) (0.220). g) was obtained with a yield of 8%.
¹ H-NMR measurement of the product (monomer B8) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.36 (d, J = 8.5 Hz, 2H, Ar), 6.83 (d, J = 8.0 Hz, 2H, Ar), 4.48 (s, 2H, CCCH ₂ ), 3.83 (br d, J = 5.5 Hz, 2H, ArOC H ₂ ), 1.68-1.74 (m, 1H, CH), 1.28-1.64 (m, 9H, CH ₂ and OH), 0.92 (t, J = 7.5 Hz, 3H, CH ₃ ), 0.90 (t, J = 6.5 Hz, 3H, CH ₃ ).

(Monomer B9)

Under an argon atmosphere, 4-bromoanisole (1.87 g, 10.0 mmol), bistriphenylphosphine palladium (II) dichloride (350 mg, 0.50 mmol), triphenylphosphine (262 mg, 1.0 mmol), copper (I) iodide ( To a solution of 95 mg, 0.5 mmol) in THF (35 mL) was added triethylamine (15 mL), followed by 2-propyn-1-ol (1.12 g, 20.0 mmol) at room temperature. Stir for 12 hours. After cooling to room temperature, a saturated aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, and then dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to yield 3- (4-methoxyphenyl) -2-propyn-1-ol (monomer B9) (0.24 g). Obtained at 14.8%.
¹ H-NMR measurement of the product (monomer B9) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.38 (J = 7.0 Hz, 2H, Ar), 6.84 (d, J = 6.5 Hz, 2H, Ar), 4.48 (d, J = 5.0 Hz, 2H, CH ₂ O), 3.81 (s, 3H, CH ₃ ), 1.60 (br s, 1H, OH).

(Monomer B10)

Under an argon atmosphere, 2-bromothiophene (1.63 g, 10.0 mmol), bistriphenylphosphine palladium (II) dichloride (280 mg, 0.40 mmol), copper (I) iodide (76 mg, 0.40 mmol), triphenylphosphine ( To a solution of 209 mg, 0.80 mmol) and triethylamine (15 mL) in THF (35 mL) was added 1-hexyne (2.3 mL, 20.0 mmol) at room temperature, and the mixture was stirred at 60 ° C. for 12 hours. After cooling to room temperature, saturated aqueous ammonium chloride solution was added. The mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to quantitatively obtain 2- (1-hexyn-1-yl) thiophene (monomer B10) (1.64 g).
¹ H-NMR measurement of the product (monomer B10) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.16 (dd, J = 1.5, 5.0 Hz, 1H, Ar), 7.11 (dd, J = 1.0, 3.5 Hz, 1H, Ar), 6.93 (dd, J = 3.5 , 5.0 Hz, 1H, Ar), 2.43 (t, J = 7.3 Hz, 2H, ArC H ₂ ), 1.55-1.61 (m, 2H, CH ₂ ), 1.44-1.51 (m, 2H, CH ₂ ), 0.94 (t, J = 7.0 Hz, 3H, CH ₃ ).

(Monomer B11)

Under an argon atmosphere, 2-bromopyridine (0.97 mL, 10.0 mmol), bistriphenylphosphine palladium (II) dichloride (280 mg, 0.40 mmol), copper (I) iodide (76 mg, 0.40 mmol), triphenylphosphine ( To a solution of 210 mg, 0.80 mmol) and triethylamine (15 mL) in THF (35 mL) was added 1-hexyne (1.37 mL, 12.0 mmol) at room temperature, and the mixture was stirred at 60 ° C. for 12 hours. After cooling to room temperature, saturated aqueous ammonium chloride solution was added. The mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain 2- (1-hexyn-1-yl) pyridine (monomer B11) (1.59 g) in a yield of 69%. It was.
¹ H-NMR measurement of the product (monomer B11) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 8.52-8.56 (m, 1H, Ar), 7.60 (dt, J = 2.0, 8.0 Hz, 1H, Ar), 7.37 (d, J = 8.0 Hz, 1H, Ar ), 7.15-7.19 (m, 1H Ar), 2.45 (t, J = 7.0 Hz, ArCH ₂ ), 1.58-1.65 (m, 2H, CH ₂ ), 1.41-1.55 (m, 2H, CH ₂ ), 0.94 (t, J = 7.5 Hz, 3H, CH ₃ ).

(Monomer B12)

Under an argon atmosphere, 2-bromofuran, bistriphenylphosphine palladium (II) dichloride (560 mg, 0.80 mmol), copper (I) iodide (156 mg, 0.40 mmol), triphenylphosphine (420 mg, 0.4 mmol) and triethylamine ( 1-hexyne (2.76 mL, 24.0 mmol) was added to a solution of 30 mL) in THF (80 mL) at room temperature, and the mixture was stirred at 60 ° C. for 12 hours. After cooling to room temperature, saturated aqueous ammonium chloride solution was added. The mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain 2- (1-hexyn-1-yl) furan (monomer B12) (0.68 g) in a yield of 42%. It was.
¹ H-NMR measurement of the product (monomer B12) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.30-7.33 (m, 1H, Ar), 6.46 (d, J = 3.0 Hz, 1H, Ar), 6.34 (dd, J = 2.0, 3.5 Hz, 1H, Ar ), 2.43 (t, J = 7.0 Hz, ArC H ₂ ), 1.54-1.62 (m, 2H, CH ₂ ), 1.42-1.51 (m, 2H, CH ₂ ), 0.94 (t, J = 7.5 Hz, 3H , CH ₃ ).

(Monomer B13)

After adding n-butyllithium (7.7 mL, 1.55 M hexane solution, 12.0 mmol) to a THF (40 mL) solution of 1-hexyne (1.37 mL, 12.0 mmol) at −78 ° C. in an argon atmosphere, di-p -Tolyl disulfide (2.96 g, 12.0 mmol) was added. After warming to room temperature, the mixture was stirred for 2 hours. A saturated aqueous ammonium chloride solution was added, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, and then dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain 1-hexyn-1-yl (p-tolyl) sulfane. To a solution of the obtained 1-hexyn-1-yl (p-tolyl) sulfane in methylene chloride (30 mL), m-chloroperbenzoic acid (5.30 g, 24 mmol) in methylene chloride (60 mL) was added. Added at ° C. The mixture was warmed to room temperature and stirred for 3 hours. A saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with methylene chloride. The organic layer was washed with saturated brine, and then dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to collect 1- (1-hexyn-1-ylsulfonyl) -4-methylbenzene (monomer B13) (0.59 g). Obtained at a rate of 25%.
¹ H-NMR measurement of the product (monomer B13) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.88 (d, J = 8.0 Hz, 2H, Ar), 7.36 (d, J = 8.5 Hz, 2H, Ar), 2.46 (s, 3H, ArC H ₃ ), 2.35 (t, J = 7.5 Hz, 2H, SO ₂ CH ₂ ), 1.50-1.57 (m, 2H, CH ₂ ), 1.32-1.40 (m, 2H, CH ₂ ), 0.88 (t, J = 7.5 Hz, 3H, CH ₃ ).

(Monomer B14)

Under argon atmosphere, NaH (0.38 g, 63 wt% in oil, 10.0 mmol), 3-phenyl-2-propyn-1-ol (0.62 g, 5.0 mmol) and THF (6.25 mL) in iodomethane at 0 ° C (0.63 mL, 10.0 mmol) was added, followed by stirring at room temperature for 2 hours. A saturated aqueous ammonium chloride solution was added, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, and then dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain (3-methoxy-2-prop-1-ynyl) benzene (monomer B14) (0.34 g) in a yield of 47%. Got in.
¹ H-NMR measurement of the product (monomer B14) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.40-7.47 (m, 2H, Ph), 7.30-7.33 (m, 3H, Ph), 4.33 (s, 2H, CH ₂ ), 3.46 (s, 3H, CH ₃ ).

(Monomer B15)

Under an argon atmosphere, add NaH (0.38 g, 63 wt% in oil, 10.0 mmol), 3-phenyl-2-propyn-1-ol (0.62 g, 5.0 mmol) and THF (6.25 mL) at 0 ° C. -Bromohexane (1.10 mL, 10.0 mmol) was added, followed by stirring at room temperature for 12 hours. A saturated aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, and then dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain (3-hexyloxy-2-prop-1-ynyl) benzene (monomer B15) (0.51 g) in a yield of 44. %.
¹ H-NMR measurement of the product (monomer B15) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.40-7.47 (m, 2H, Ph), 7.28-7.33 (m, 3H, Ph), 4.36 (s, 2H, CCCH ₂ ), 3.58 (t, J = 6.0 Hz, 2H, OC H ₂ CH ₂ ), 1.60-1.66 (m, 2H, CH ₂ ), 1.26-1.42 (m, 6H, CH ₂ ), 0.89 (t, J = 5.5 Hz, 3H, CH ₃ ).

(Monomer B16)

Under an argon atmosphere, 2-iodoanisole (1.37 mL, 10.0 mmol), bistriphenylphosphine palladium (II) dichloride (280 mg, 0.40 mmol), copper (I) iodide (76 mg, 0.40 mmol), triphenylphosphine ( To a solution of 210 mg, 0.80 mmol) and triethylamine (15 mL) in THF (35 mL) was added 1-hexyne (1.37 mL, 12.0 mmol) at room temperature, and the mixture was stirred at 60 ° C. for 12 hours. After cooling to room temperature, saturated aqueous ammonium chloride solution was added. The mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to yield 1- (1-hexyn-1-yl) -2-methoxybenzene (monomer B16) (1.59 g). Obtained at 85%.
¹ H-NMR measurement of the product (monomer B16) was performed.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.37 (dd, J = 1.5, 6.0 Hz, 1H, Ar), 7.24 (t, J = 5.5 Hz, 1H, Ar), 6.88 (t, J = 6.0 Hz, 1H, Ar), 6.85 (d, J = 6.5 Hz, 1H, Ar), 3.87 (s, 3H, OCH ₃ ), 2.47 (t, J = 6.0 Hz, 2H, ArC H ₂ ), 1.59-1.65 (m , 2H, CH ₂ ), 1.46-1.52 (m, 2H, CH ₂ ), 0.95 (t, J = 6.0 Hz, 3H, CH ₃ ).

(Monomer B17)

Under an argon atmosphere, 1-bromo-4-phenoxybenzene (2.49 g, 10.0 mmol), bistriphenylphosphine palladium (II) dichloride (280 mg, 0.40 mmol), copper (I) iodide (76 mg, 0.40 mmol), Trimethylsilylacetylene (2.07 mL, 15 mmol) was added to a solution of triphenylphosphine (210 mg, 0.80 mmol) and triethylamine (15 mL) in THF (35 mL) at room temperature, and then the mixture was stirred at 70 ° C. for 12 hours. did. After cooling to room temperature, saturated aqueous ammonium chloride solution was added. The mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was dissolved in a mixture of THF (20 mL) and ethanol (20 mL). To this, potassium carbonate (about 0.5 g) was added and stirred vigorously at room temperature for 12 hours. Water (40 mL) was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate. After filtration, the residue obtained by concentrating the filtrate was purified by silica gel column chromatography to obtain 1-ethynyl-4-phenoxybenzene (monomer B17) (1.52 g) in a yield of 78%.
¹ H-NMR measurement of the product (monomer B17) was performed.
¹ H NMR (500 MHz; CDCl3) δ 7.45 (d, J = 9.0 Hz, 2H, Ar), 7.36 (t, J = 8.5 Hz, 2H, Ar), 7.14 (t, J = 7.5 Hz, 1H, Ar ), 7.03 (d, J = 7.5 Hz, 2H, Ar), 6.95 (d, J = 11.5 Hz, 2H, Ar), 3.03 (s, 1H, CCH).

<Synthesis of polymer compounds>
Polymer compounds 1 to 22 were obtained as follows. Hereinafter, the compound represented by the formula (1) may be referred to as “Dyne”. Further, the compound represented by the formula (2) may be referred to as “Monoyne”.

In the following, the number average molecular weight and the weight average molecular weight were measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. The measurement conditions are as follows.
Liquid feed pump: L-6050 Hitachi High-Technologies UV-Vis detector: L-3000 Hitachi High-Technologies columns: Gelpack (registered trademark) GL-A160S / GL-A150S Hitachi Chemical Co., Ltd.
Eluent: THF (for HPLC, without stabilizer) Wako Pure Chemical Industries, Ltd.
Flow rate: 1 mL / min
Column temperature: Room temperature Molecular weight Standard: Standard polystyrene

(Polymer compounds 1-1 and 1-2)

  1,4-Dimethoxybut-2-yne (0.060 mL, 0.50 mmol or 0.12 mL, 1.0 mmol), 4,4'-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and zinc at room temperature under argon atmosphere Cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) imino were mixed with powder (6.5 mg, 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) A solution of methylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the desired polymer compounds (polymer compounds 1-1 and 1-2).

The number average molecular weight M _n , weight average molecular weight M _w , M _w / M _n , and the degree of branching of the obtained polymer compound are shown below.
Polymer compound 1-1 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 5,914, M _w = 24,375, M _w / M _n = 4.12 (GPC analysis with THF, PSt standard).
The degree of branching: 0.85 (calculated by 1H NMR analysis).
Polymer compound 1-2 (Diyne (1.0 equiv.) + Monoyne (2.0 equiv.)): M _n = 3,116, M _w = 9,318, M _w / M _n = 2.99 (GPC analysis with THF, PSt standard).
The degree of branching: 0.71 (calculated by 1H NMR analysis).

¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.10-8.30 (m, Ar), 3.82-4.90 (m, CH ₂ ), 2.90-3.75 (m, CH ₃ ).

(Polymer compounds 2-1 and 2-2)

  3-phenylprop-2-yn-1-ol (66 mg, 0.50 mmol or 132 mg, 1.0 mmol), 4,4'-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) at room temperature under argon atmosphere And zinc powder (6.5 mg, 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) ) A solution of iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the desired polymer compounds (polymer compounds 2-1 and 2-1).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 2-1 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 5,806, M _w = 25,138, M _w / M _n = 4.33 (GPC analysis with with THF, PSt standard).
Polymer compound 2-2 (Diyne (1.0 equiv.) + Monoyne (2.0 equiv.)): M _n = 2,438, M _w = 5,428, M _w / M _n = 2.22 (GPC analysis containing with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.70-7.80 (m, Ar), 4.25-4.75 (m, CH ₂ ).

(Polymer Compound 3)

  2- (1-Hexin-1-yl) furan (74 mg, 0.5 mmol), 4,4'-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and zinc powder (6.5 mg) at room temperature under argon atmosphere , 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethylpyridine (dipimp , 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 3).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 3 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 3,727, M _w = 14,434, M _w / M _n = 3.87 (GPC analysis with with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 5.80-7.90 (m, Ar), 2.30-3.20 (m, benzylic CH ₂ ), 0.60-1.75 (m. CH ₂ and CH ₃ ).

(Polymer Compound 4)

  2- (1-Hexin-1-yl) thiophene (82 mg, 0.5 mmol), 4,4'-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and zinc powder (6.5 mg) at room temperature under argon atmosphere , 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethylpyridine (dipimp , 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 4).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 4 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 3,945, M _w = 22,980, M _w / M _n = 5.83 (GPC analysis containing with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 5.80-7.80 (m, Ar), 2.30-3.10 (m, benzylic CH ₂ ), 0.60-1.70 (m, CH ₂ and CH ₃ ).

(Polymer Compound 5)

  1,4-dimethoxybut-2-yne (0.24 mL, 2.0 mmol), bis (4-ethynylphenyl) methanone (115 mg, 0.50 mmol) and zinc powder (6.5 mg, 0.10 mmol) at room temperature under argon atmosphere Of 2-methyl-2-pyrrolidone (NMP, 1.5 mL) in cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 5).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 5 (Diyne (1.0 equiv.) + Monoyne (4.0 equiv.)): M _n = 5,859, M _w = 15,944, M _w / M _n = 2.71 (GPC analysis with with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.20-8.30 (m, Ar), 4.05-4.77 (m, CH ₂ O), 3.93 (br s, CCH), 3.22-3.61 (m, OCH ₃ ).

(Polymer compounds 6-1 and 6-2)

  1,4-dimethoxybut-2-yne (0.060 mL, 0.50 mmol or 0.12 mL, 1.0 mmol), 4-ethynyl-N- (4-ethynylphenyl) -N-phenylaniline (147 mg, 0.50 mmol) and zinc powder (6.5 mg, 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2 , 6-Diisopropylphenyl) iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the desired polymer compounds (polymer compounds 6-1 and 6-2).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 6-1 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 6,452, M _w = 19,568, M _w / M _n = 3.03 (GPC analysis containing with THF, PSt standard).
Polymer compound 6-2 (Diyne (1.0 equiv.) + Monoyne (2.0 equiv.)): M _n = 4,387, M _w = 8,241, M _w / M _n = 1.88 (GPC analysis using with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.70-7.95 (m, Ar), 4.05-4.75 (m, CH ₂ O), 3.25-3.65 (m, OCH ₃ ).

(Polymer compounds 7-1 and 7-2)

  At room temperature under an argon atmosphere, 3-phenyl-2-propyn-1-ol (62 mg, 0.50 mmol or 124 mg, 1.0 mmol), 4-ethynyl-N- (4-ethynylphenyl) -N-phenylaniline ( 147 mg, 0.50 mmol) and zinc powder (6.5 mg, 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- ( A solution of 2,6-diisopropylphenyl) iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 12-24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in THF, and methanol was added to precipitate the polymer compound. The purified solid was collected by filtration to obtain the target polymer compounds (polymer compounds 7-1 and 7-2).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 7-1 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 4,716, M _w = 19,856, M _w / M _n = 4.21 (GPC analysis with THF, PSt standard).
Polymer compound 7-2 (Diyne (1.0 equiv.) + Monoyne (2.0 equiv.)): M _n = 3,616, M _w = 6,707, M _w / M _n = 1.85 (GPC analysis with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.60-8.20 (m, Ar), 4.15-4.70 (m, CH ₂ O).
¹ H NMR (THF-d ₈ , 600 MHz) δ 6.39-8.15 (m, Ar), 3.79-4.64 (m, CH ₂ O).

(Polymer Compound 8)

  3- (4-((3-Ethyloxetane-3-yl) methoxy) phenyl) -2-propin-1-ol (124 mg, 0.5 mmol), (4-ethynyl-N--) at room temperature under argon atmosphere Cobalt chloride hexahydrate in a mixture of (4-ethynylphenyl) -N-phenylaniline (146 mg, 0.50 mmol) and zinc powder (6.5 mg, 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) Product (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) were added. The mixture was stirred for 24 hours at -50 ° C. After cooling to room temperature, the mixture was poured into water, and the purified solid was collected by filtration, and the resulting solid was dissolved in THF, and methanol was added to precipitate the polymer compound. The purified solid was collected by filtration to obtain the target polymer compound (polymer compound 8).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 8 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 7,007, M _w = 26,300, M _w / M _n = 3.75 (GPC analysis with with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.20-8.20 (m, Ar), 3.80-4.35 (m, CH ₂ O), 1.80-2.05 (m, C H ₂ CH ₃ ), 0.70-1.30 (m, CH ₃ ).

(Polymer compounds 9-1 and 9-2)

  3-phenyl-2-propyn-1-ol (31 mg, 0.25 mmol or 59 mg, 0.45 mmol) and 3- (4-((3-ethyloxetane-3-yl) methoxy) at room temperature under argon atmosphere Phenyl) -2-propyn-1-ol (62 mg, 0.25 mmol or 12 mg, 0.05 mmol), (4-ethynyl-N- (4-ethynylphenyl) -N-phenylaniline (146 mg, 0.50 mmol) and Cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture of zinc powder (6.5 mg, 0.10 mmol) A solution of iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added and the resulting mixture was stirred for 24 hours at 45 ° C. to 50 ° C. After cooling to room temperature, the mixture was poured into water. The purified solid was collected by filtration, dissolved in THF, methanol was added to precipitate the polymer compound, and the purified solid was collected by filtration. Compound (polymer compound 9-1 and 9-2) were obtained.

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 9-1 (Diyne (1.0 equiv.) + 3-phenyl-2-propyn-1-ol (0.9 equiv.) + Oxetane monomer (0.1 equiv.)): M _n = 4,618, M _w = 9,592, M _w / M _n = 2.08 (GPC analysis contained with THF, PSt standard).
Polymer compound 9-2 (Diyne (1.0 equiv.) + 3-phenyl-2-propyn-1-ol (0.5 equiv.) + Oxetane monomer (0.5 equiv.)): M _n = 3,215, M _w = 3,933, M _w / M _n = 1.22 (GPC analysis possibly with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (THF ₆ , 500 MHz) δ 6.30-8.10 (m, Ar), 3.85-4.60 (m, CH ₂ O), 1.70-2.30 (m, C H ₂ CH ₃ ), 0.75-1.25 (m, CH ₃ ).

(Polymer compounds 10-1, 10-2, 10-3 and 10-4)

  1-ethynyl-4-phenoxybenzene (97 mg, 0.5 mmol or 194 mg, 1.0 mmol), 1,4-dimethoxybut-2-yne (0.060 mL, 0.50 mmol or 0.12 mL, 1.0) at room temperature under an argon atmosphere mmol), 4,4'-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and zinc powder (6.5 mg, 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) A solution of hydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 12-24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the desired polymer compounds (polymer compounds 10-1, 10-2, 10-3 and 10-4).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 10-1 (Diyne (1.0 equiv.) + Terminal alkyne (1.0 equiv.) + 1,4-dimethoxybut-2-yne (1.0 equiv.)): M _n = 5,288, M _w = 14,511, M _w / M _n = 2.74 (GPC analysis registered with THF, PSt standard).
Polymer compound 10-2 (Diyne (1.0 equiv.) + Terminal alkyne (0.5 equiv.) + 1,4-dimethoxybut-2-yne (0.5 equiv.)): M _n = 4,504, M _w = 18,470, M _w / M _n = 4.10 (GPC analysis registered with THF, PSt standard).
Polymer compound 10-3 (Diyne (1.0 equiv.) + Terminal alkyne (2.0 equiv.) + 1,4-dimethoxybut-2-yne (1.0 equiv.)): M _n = 2,833, M _w = 4,736, M _w / M _n = 1.67 (GPC analysis registered with THF, PSt standard).
Polymer compound 10-4 (Diyne (1.0 equiv.) + Terminal alkyne (1.0 equiv.) + 1,4-dimethoxybut-2-yne (2.0 equiv.): M _n = 3,652, M _w = 6,052, M _w / M _n = 1.66 (GPC analysis registered with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.05-8.31 (m, Ar), 3.80-4.90 (m, CH ₂ ), 2.90-3.80 (m, CH ₃ ),

(Polymer Compound 11)

  3- (4-Hexyloxyphenyl) -2-propyn-1-ol (116 mg, 0.50 mmol), 4,4′-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and at room temperature under an argon atmosphere Cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture of zinc powder (6.5 mg, 0.10 mmol) A solution of iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 11).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 11 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 3,907, M _w = 11,458, M _w / M _n = 2.93 (GPC analysis using with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.30-7.75 (m, Ar), 4.20-4.72 (m, C [H] ₂ OH), 3.70-4.05 (m, C [H] ₂ OAr), 1.10- 1.85 (m, CH ₂ ), 0.75-0.98 (m, CH ₃ ).

(Polymer Compound 12)

  3- (4- (2-Ethylhexyloxy) phenyl) -2-propyn-1-ol (144 mg, 0.50 mmol), 4,4′-oxybis (ethynylbenzene) (109 mg, at room temperature under argon atmosphere) 0.50 mmol) and zinc powder (6.5 mg, 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixed with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6 A solution of -diisopropylphenyl) iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 12).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 12 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 5,164, M _w = 23,715, M _w / M _n = 4.59 (GPC analysis containing with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.40-7.80 (m, Ar), 4.05-4.50 (m, C [H] ₂ OH), 3.60-3.95 (m, C [H] ₂ OAr), 1.10- 2.35 (m, CH ₂ and CH), 0.80-0.98 (m, CH ₃ ).

(Polymer Compound 13)

  (3-hexyloxy-2-prop-1-ynyl) benzene (108 mg, 0.50 mmol), 4,4'-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and zinc powder at room temperature under argon atmosphere (6.5 mg, 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethyl A solution of pyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 13).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 13 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 6,447, M _w = 31,239, M _w / M _n = 4,85 (GPC analysis using with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.20-8.60 (m, Ar), 3.35-4.40 (m, CH ₂ O), 1.10-2.00 (m, CH ₂ ), 0.75-0.90 (m, CH ₃ ) .

(Polymer Compound 14)

  4-phenyl-3-butyn-2ol (146 mg, 1.0 mmol), 4,4′-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and zinc powder (6.5 mg, 0.10) at room temperature under argon atmosphere mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixed with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate the polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 14).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 14 (Diyne (1.0 equiv.) + Monoyne (2.0 equiv.)): M _n = 7,234, M _w = 19,683, M _w / M _n = 2.72 (GPC analysis with with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.60-7.90 (m, Ar), 4.35-4.95 (m, CHO), 1.05-1.65 (m, CH ₃ ).

(Polymer Compound 15)

  At room temperature under an argon atmosphere, 4-phenyl-3-butyn-2-one (71 mg, 0.5 mmol), 4,4′-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and zinc powder (6.5 mg, 0.10 mmol) 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 15).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 15 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 2,754, M _w = 4,089, M _w / M _n = 1.49 (GPC analysis with with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.55-8.00 (m, Ar), 1.80-2.20 (m, CH ₃ ).

(Polymer Compound 16)

  At room temperature under an argon atmosphere, 4-phenylbut-3-in-1-ol (292 mg, 2.0 mmol), 4,4′-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and zinc powder (6.5 mg, 0.10 mmol) 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 16).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 16 (Diyne (1.0 equiv.) + Monoyne (4.0 equiv.)): M _n = 3,421, M _w = 13,879, M _w / M _n = 3.69 (GPC analysis with with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.70-7.75 (m, Ar), 3.30-3.95 (m, CH ₂ O), 2.75-3.05 (m, ArC [H] ₂ ).

(Polymer Compound 17)

  Under argon atmosphere at room temperature, (3-methoxy-2-prop-1-ynyl) benzene (73 mg, 0.5 mmol), 4,4′-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and zinc powder ( 6.5 mg, 0.10 mmol) of 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixed with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethylpyridine A solution of NMP (1.0 mL) in (dipimp, 8.0 mg, 0.03 mmol) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 17).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 17 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 5,941, M _w = 23,715, M _w / M _n = 4.59 (GPC analysis containing with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.50-7.90 (m, Ar), 3.80-4.45 (m, CH ₂ ), 2.90-3.60 (m, CH ₃ ).

(Polymer Compound 18)

  2-methylpropionate (80 mg, 0.5 mmol), 4,4'-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and zinc powder (6.5 mg, 0.10 mmol) 2- Cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in a mixture of methyl-2-pyrrolidone (NMP, 1.5 mL) Of NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer polymer, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 18).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 18 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 3719, M _w = 29926, M _w / M _n = 8.05 (GPC analysis containing with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.70-8.30 (m, Ar), 3.20-3.90 (m, CH ₃ ).

(Polymer Compound 19)

  1- (1-hexyn-1-ylsulfonyl) -4-methylbenzene (118 mg, 0.5 mmol), 4,4′-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and at room temperature under an argon atmosphere Cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture of zinc powder (6.5 mg, 0.10 mmol) A solution of iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 19).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 19 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)): M _n = 3,759, M _w = 13,879, M _w / M _n = 3.69 (GPC analysis using with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.70-7.75 (m, Ar), 2.80-3.60 (m, C [H] ₂ Ar and C [H] ₃ Ar), 1.05-1.80 (m, CH ₂ ) , 0.75-0.95 (m, CH ₃ ).

(Polymer Compound 20)

  2- (1-Hexin-1-yl) pyridine (318 mg, 2.0 mmol), 4,4'-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and zinc powder (6.5 mg) at room temperature under an argon atmosphere , 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethylpyridine (dipimp , 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 20).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 20 (Diyne (1.0 equiv.) + Monoyne (4.0 equiv.)): M _n = 3,693, M _w = 8,288, M _w / M _n = 2.24 (GPC analysis with THF, PSt standard).

(Polymer Compound 21)

  3-4- (methoxyphenyl) prop-2-yn-1-ol (324 mg, 2.0 mmol), 4,4′-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and at room temperature under an argon atmosphere Cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture of zinc powder (6.5 mg, 0.10 mmol) A solution of iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 21).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 21 (Diyne (1.0 equiv.) + Monoyne (4.0 equiv.)): M _n = 8,144, M _w = 19,489, M _w / M _n = 2.39 (GPC analysis with THF, PSt standard).

(Polymer Compound 22)

  4-octyne (0.073 mL, 0.50 mmol), 4,4'-oxybis (ethynylbenzene) (109 mg, 0.50 mmol), phthalic acid dimethyl ester (15 mg, 0.075 mmol) and zinc powder at room temperature under argon atmosphere (6.5 mg, 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethyl A solution of pyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 22).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 22 (Diyne (1.0 equiv.) + Monoyne (1.0 equiv.)) In the presence of 15 mol% of dimethyl phthalate: M _n = 4,500, M _w = 9,300, M _w / M _n = 2.06 (GPC analysis represented with THF, PSt standard).

(Polymer Compound 30)

  3- (4-methoxyphenyl) prop-2-yn-1-ol (162 mg, 1.0 mmol), 4,4′-oxybis (ethynylbenzene) (109 mg, 0.50 mmol) and at room temperature under an argon atmosphere Cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture of zinc powder (6.5 mg, 0.10 mmol) A solution of iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 30).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer compound 30: M _n = 4,390, M _w = 16,333, M _w / M _n = 3.72 (GPC analysis containing with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.55-7.75 (m, Ar), 4.10-4.65 (m, CH ₂ ), 3.55-3.80 (m, CH ₃ ).

(Polymer Compound 31)

  2- (hex-1-yne) furan (148 mg, 1.0 mmol), 4-ethynyl-N- (4-ethynylphenyl) -N-phenylaniline (147 mg, 0.50 mmol) and at room temperature under an argon atmosphere Cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture of zinc powder (6.5 mg, 0.10 mmol) A solution of iminomethylpyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 12-24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in THF, and methanol was added to precipitate the polymer compound. The purified solid was collected by filtration to obtain the target polymer compound (polymer compound 31).

The number average molecular weight M _n , weight average molecular weight M _w , and M _w / M _n of the obtained polymer compound are shown below.
Polymer Compound 31: M _n = 2,838, M _w = 6,083, M _w / M _n = 2.14 (GPC analysis registered with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 6.60-7.95 (m, Ar), 2.90-3.15 (m, C [H] ₂ Ar) .1.20-2.20 (m, CH ₂ ), 0.75-0.92 (m, CH ₃ ).

(Polymer Compound 32)

  1,4-Dimethoxybut-2-yne (0.24 mL, 2.0 mmol), 2,7-diethynyl-9,9-dihexyl-9H-fluorene (191 mg, 0.50 mmol) and zinc powder at room temperature under argon atmosphere (6.5 mg, 0.10 mmol) in 2-methyl-2-pyrrolidone (NMP, 1.5 mL) mixture with cobalt chloride hexahydrate (6.0 mg, 0.025 mmol) and 2- (2,6-diisopropylphenyl) iminomethyl A solution of pyridine (dipimp, 8.0 mg, 0.03 mmol) in NMP (1.0 mL) was added. The resulting mixture was stirred at 45-50 ° C. for 24 hours. After cooling to room temperature, the mixture was poured into water and the purified solid was collected by filtration. The obtained solid was dissolved in tetrahydrofuran (THF) and then filtered. Methanol was added to the filtrate to precipitate a polymer compound, and the solid was collected by filtration to obtain the target polymer compound (polymer compound 32).

Polymer compound 32: M _n = 11,351, M _w = 69,379, M _w / M _n = 4.13 (GPC analysis registered with THF, PSt standard).
¹ H-NMR measurement results are as follows.
¹ H NMR (CDCl ₃ , 500 MHz) δ 7.25-8.20 (m, Ar), 4.10-4.75 (m, CH ₂ O), 3.25-3.75 (m, CH ₃ O), 0.95-2.20 (m, CH ₂ ), 0.70-0.90 (m, CH ₃ ).

<Production of organic EL element>
The polymer compound 9-1 (10.0 mg) was dissolved in toluene (455 μL) to obtain a polymer solution. The following onium salt 1 (10.0 mg) was dissolved in toluene (1000 μL) to obtain an onium salt solution. The obtained polymer solution and an onium salt solution (111 μL) were mixed to prepare ink composition 1 containing charge transporting polymer 1. The ink composition ¹ was spin-coated at 3,000 min ⁻¹ on a glass substrate patterned with ITO to a width of 1.6 mm in the atmosphere, and then heated on a hot plate at 200 ° C. for 30 minutes to form a hole injection layer (80 nm) was formed.

Thereafter, the glass substrate was transferred into a vacuum deposition machine, α-NPD (20 nm) as a hole transport layer was formed on the hole injection layer, and CBP: Ir (ppy) ₃ (94: 6, 30 nm), BAlq (10 nm), Alq ₃ (30 nm), LiF (0.8 nm), and Al (100 nm) in this order, the film was formed by vapor deposition, sealing treatment was performed, and the organic EL device of Example 1 Was made.

<Evaluation of organic EL element>
When voltage was applied to the organic EL device of Example 1 obtained above, green light emission was confirmed. For each element, emission luminance 1,000 cd / ^{m 2} at the drive voltage and luminous efficiency, as well as to measure the light emission life at an initial luminance 5,000 cd / ^{m 2} (luminance half-life). The measurement results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 Light emitting layer 2 Anode 3 Hole injection layer 4 Cathode 5 Electron injection layer 6 Hole transport layer 7 Electron transport layer 8 Substrate

Claims (20)

A compound represented by the following formula (1) and a compound represented by the following formula (2) are reacted with a transition metal salt or a hydrate thereof, or a transition metal salt or a complex of the hydrate with a reducing agent. A process for producing a polymer compound comprising reacting in the presence of a transition metal catalyst obtained by the reaction.

(In formulas (1) and (2), X represents a divalent linking group, and R ¹ and R ² each independently represents a hydrogen atom or a substituent.)   The method for producing a polymer compound according to claim 1, wherein X comprises at least one selected from the group consisting of a substituted or unsubstituted aromatic hydrocarbon structure and aromatic heterocyclic structure. The transition metal salt or a hydrate thereof includes a transition metal salt or a hydrate thereof represented by MQ _n, complex of the transition metal salt or a hydrate thereof, the transition metal salt represented by MQ _n Or a complex of a hydrate thereof and a ligand L, wherein M is Ti, Nb, Ta, Fe, Ru, Co, Rh or Ir, and Q is a cyclopentadienyl group, a halogen atom, OAc A acetylacetonate group or an alkoxy group, Ac is an acetyl group, n is a number corresponding to the valence of M, L is 2- (2,6-diisopropylphenyl) iminomethylpyridine, The method for producing a polymer compound according to claim 1 or 2, which is triphenylphosphine, 1,2-bis (diphenylphosphino) ethane, or cyclooctadienyl.   The manufacturing method of the high molecular compound of Claim 3 whose M is Ti, Co, or Rh.   The said reducing agent is a manufacturing method of any one of Claims 1-4 containing a metal, an organic metal, a metal hydride, or an alkylamine. A polymer compound comprising a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a structural unit represented by the following formula (5).

(In formulas (3) to (5), each X independently represents a divalent linking group, each of R ¹ and R ² independently represents a hydrogen atom or a substituent, and “*” represents another structural unit. Represents the binding site.   The polymer compound according to claim 6, wherein X comprises at least one selected from the group consisting of a substituted or unsubstituted aromatic hydrocarbon structure and aromatic heterocyclic structure.   The polymer compound according to claim 7, wherein X contains a substituted or unsubstituted aromatic amine structure. The polymer compound according to any one of claims 6 to 8, wherein R ¹ and R ² are each independently a substituent. At least one selected from the group consisting of R ¹ and R ^2, but including a polymerizable functional group, the polymer compound according to any one of claims 6-9.   Organic electronic material containing the high molecular compound of any one of Claims 6-10.   The organic electronic material of claim 11, further comprising a dopant.   An ink composition comprising the organic electronic material according to claim 11 or 12, and a solvent.   An organic electronic device having an organic layer formed using the organic electronic material according to claim 11 or 12, or the ink composition according to claim 13.   The organic electroluminescent element which has an organic layer formed using the organic electronics material of Claim 11 or 12, or the ink composition of Claim 13.   The organic electroluminescent element according to claim 15, further comprising a flexible substrate.   The organic electroluminescent element according to claim 16, wherein the flexible substrate includes a resin film.   The display element provided with the organic electroluminescent element of any one of Claims 15-17.   The illuminating device provided with the organic electroluminescent element of any one of Claims 15-17.   A display device comprising the illumination device according to claim 19 and a liquid crystal element as display means.

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