WO2018207699A1 - Polymer having graphite- or graphene-like lamellar structure - Google Patents

Abstract

A polymer or a reduced form thereof is disclosed, the polymer comprising, as constituent units, optionally substituted benzoquinone and either an optionally substituted heterocyclic aromatic compound or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as substituents, the benzoquinone and the aromatic compound or hydrocarbon undergoing an addition cyclization reaction with each other.

Description

Polymer having a layered structure like graphite or graphene

The present invention relates to a polymer having a graphite or graphene-like layered structure, a sheet containing the polymer, nanoflakes containing the polymer, a method for producing the polymer, and a coating or electrode material for the polymer. Regarding use.

The production and application of inorganic nanosheets by peeling off layered inorganic compounds has been actively studied, and nanosheets have properties different from bulk, such as formation of two-dimensional anisotropic shapes, high specific surface area, and quantum size effects. It has been reported to show.

On the other hand, the production of nanosheets of layered organic compounds requires complicated molecular design and synthesis, so there are few reports. For example, Non-Patent Document 1 describes oxidative synthesis and coating of a copolymer from the gas phase by the o-CVD method and the VPP method. Non-Patent Document 2 describes the synthesis of a layered organic compound (two-dimensional polymer nanostructure) using a bis-acylurea derivative or the like.

In the synthesis of the copolymer of Non-Patent Document 1, high temperature or vacuum conditions are required as synthesis conditions. Moreover, since it is necessary to apply an oxidizing agent to a target substrate in advance, there is a problem that the types of substrates or base materials to be coated are limited.

For the synthesis of the polymer of Non-Patent Document 2, the designed molecule and the interaction between molecules (non-covalent bond such as complex formation including hydrogen bond) are utilized. A polymer using a bond and its laminated structure cannot be synthesized.

An object of the present invention is to provide a polymer having a graphite or graphene-like covalent bond that can be synthesized even under a mild environment of 100 ° C. or lower and normal pressure.

The inventors have surprisingly found that benzoquinone or a monocyclic aromatic hydrocarbon having an electron-withdrawing substituent, a heterocyclic aromatic compound optionally having a substituent, or a plurality of alkenyl groups. Is reacted with a monocyclic aromatic hydrocarbon having an electron-withdrawing substituent and a heterocyclic aromatic compound or a plurality of alkenyl groups. It has been found that a polymer having a layered structure similar to graphite or graphene can be synthesized by forming a condensed ring with a monocyclic aromatic hydrocarbon having a substituent, and the present invention has been completed.

According to the present invention, the following aspects are provided.
[1] A benzoquinone which may have a substituent which causes a cycloaddition reaction with each other, or a monocyclic aromatic hydrocarbon which has an electron-withdrawing substituent, and a heterocyclic which may have a substituent A polymer comprising an aromatic compound or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as substituents, or a reduced product thereof.
[2] A benzoquinone which may have a substituent, or a group having at least one of carbons at the 2nd and 3rd positions and the 5th and 6th positions having an electron withdrawing substituent Consists of a monocyclic aromatic hydrocarbon in which carbon is not substituted and a heterocyclic aromatic compound which may have a substituent or a monocyclic aromatic hydrocarbon having an alkenyl group as a substituent at the para position. A polymer or a reduced form thereof as a unit.
[3] The heterocyclic aromatic compound which may have the substituent or the monocyclic aromatic hydrocarbon which has a plurality of alkenyl groups as substituents may have the heterocyclic aromatic which may have the substituent A compound in which the benzoquinone or the monocyclic aromatic hydrocarbon having an electron-withdrawing substituent and the heterocyclic aromatic compound are carbon-carbon bonded, and two molecules of the benzoquinone or The polymer according to [1] or [2], which has a moiety in which a monocyclic aromatic hydrocarbon having an electron-withdrawing substituent and one molecule of the heterocyclic aromatic compound form a condensed ring. Or its reduced form.
[4] The heterocyclic aromatic compound which may have a substituent or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as a substituent is an azole, pyridine or pyrimidine which may have a substituent Or the polymer or the reduced product thereof according to any one of [1] to [3], which is pyridazine.
[5] The heterocyclic aromatic compound which may have a substituent or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as a substituent is pyrrole, pyridine, pyridazine or thiazole. [4] The polymer or the reduced product thereof according to any one of [4].
[6] The polymer according to any one of [1] to [5], including any part represented by the following formulas (i) to (iv):

(In the formula, Cy1 is a 5-membered nitrogen-containing heterocycle,
Cy2 is a monocyclic aromatic hydrocarbon,
Cy3 is a 6-membered nitrogen-containing heterocycle,
A is an electron-withdrawing substituent selected from vinyl group, acyl group, cyano group, halogen group, nitro group, hydroxy group; alkenyl substituted by halogen group, cyano group, nitro group, or hydroxy group: Yes,
The bond between A and Cy is a single bond or a double bond. )
[7] The polymer according to any one of [1] to [6], which includes a moiety represented by the following formula (I) or formula (II).

[8] The polymer according to [7], including a moiety represented by the following formula (III) or (IV).

(Where
R ₁ and R ₂ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, alkyl group, or pyrrolyl group, or R ₁ and R ₂ are both an adjacent pyrrole group and an adjacent benzoquinolyl group. Forming a condensed ring with the group,
R ₃ and R ₄ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, alkyl group, or pyrrolyl group, or R ₃ and R ₄ together are an adjacent pyrrole group and an adjacent benzoquinolyl group. Forming a condensed ring with the group,
However, when R ₁ and R ₂ , or R ₃ and R ₄ form a condensed ring, either one of them forms a condensed ring,
R ₅ , R ₆ and R ₇ are each independently hydrogen, halogen, hydroxy, an alkyl group, or a benzoquinolyl group. )

(Where
R ₁ and R ₂ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, alkyl group, or thiazolyl group, or R ₁ and R ₂ are both adjacent thiazolyl groups and adjacent benzoquinolyl groups. Forming a condensed ring with the group,
R ₃ and R ₄ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, alkyl group, or thiazolyl group, or R ₃ and R ₄ are both adjacent thiazolyl groups and adjacent benzoquinolyl groups. Forming a condensed ring with the group,
However, when R ₁ and R ₂ , or R ₃ and R ₄ form a condensed ring, either one of them forms a condensed ring,
R ₆ is hydrogen, halogen, hydroxy, an alkyl group, or a benzoquinolyl group. )
[9] The polymer or a reduced product thereof according to any one of [1] to [8], including a moiety represented by the following formula (IX).

(Where
R ₁₅ , R ₁₇ , and R ₁₈ are each independently a hydrogen, halogen, nitro, amide, thiol, hydroxy, or alkyl group;
R ₁₆ , R ₁₉ and R ₂₀ are each independently a hydrogen, halogen, hydroxy or alkyl group;
R ₂₁ and R ₂₂ are each independently a hydrogen, halogen, hydroxy or alkyl group;
k is an integer greater than or equal to 1,
x is a real number from 0 to 100. )
[10] The polymer or a reduced product thereof according to any one of [1] to [8], including a moiety represented by the following formula (X).

(Where
R ₁₅ , R ₁₇ , and R ₁₈ are each independently a hydrogen, halogen, nitro, amide, thiol, hydroxy, or alkyl group;
R ₁₆ , R ₁₉ and R ₂₀ are each independently a hydrogen, halogen, hydroxy or alkyl group;
R ₂₁ and R ₂₂ are each independently a hydrogen, halogen, hydroxy or alkyl group;
R ₂₃ , R ₂₅ , and R ₂₆ are each independently a hydrogen, halogen, nitro, amide, thiol, hydroxy, or alkyl group;
R ₂₄ , R ₂₇ and R ₃₀ are each independently a hydrogen, halogen, hydroxy or alkyl group;
R ₂₈ and R ₂₉ are each independently a hydrogen, halogen, hydroxy or alkyl group,
m and n are each an integer of 1 or more,
x is a real number from 0 to 100. )
[11] A polymer containing a moiety represented by the formula (XI).

(Where
R ₁₅ , R ₁₇ , and R ₁₈ are each independently a hydrogen, halogen, nitro, amide, thiol, hydroxy, or alkyl group;
R ₁₆ , R ₁₉ and R ₂₀ are each independently a hydrogen, halogen, hydroxy or alkyl group;
R ₂₁ and R ₂₂ are each independently a hydrogen, halogen, hydroxy or alkyl group;
n is an integer of 1 or more,
x is a real number from 0 to 20. )
[12] The heterocyclic aromatic compound optionally having a substituent or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as a substituent is a monocyclic aroma having a plurality of alkenyl groups as a substituent. The polymer according to [1] or [2], which is a group hydrocarbon and has a moiety in which the benzoquinone and the monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as a substituent form a condensed ring, or Its reductant.
[13] The heterocyclic aromatic compound which may have a substituent or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as a substituent is divinylbenzene [1], [2] or [12 Or a reduced product thereof.
[14] The polymer according to [1], [2], [12], or [13], which contains a moiety represented by at least one of formulas (XII) to (XVII).

[15] A sheet having a thickness of 0.2 nm to 2.0 nm having the polymer according to any one of [1] to [14] extending in a planar shape.
[16] A laminate in which a plurality of sheets according to [15] are laminated with an interlayer spacing of 0.2 nm to 2.0 nm.
[17] Nanoflakes having a length of 1 to 1000 nm and a thickness of 1 to 100 nm comprising the polymer according to any one of claims 1 to 14.
[18] Monocyclic aroma having a benzoquinone which may have a substituent and a heterocyclic aromatic compound which may have a substituent or a plurality of alkenyl groups as a substituent, causing a cycloaddition reaction with each other A method for producing a polymer, comprising polymerizing an aromatic hydrocarbon.
[19] A method of using the polymer according to any one of [1] to [14] as a coating.
[20] An electrode material comprising the polymer according to any one of [1] to [14].
[21] The electrode material according to [20], which is an electrode active material or an electrode catalyst.

According to the present invention, a two-dimensional or planar polymer in which a monomer is incorporated by a covalent bond can be obtained under milder conditions than before. In addition, the coating containing the polymer of the present invention can be applied to any substrate or substrate. Further, a laminate in which a plurality of planar polymers of the present invention are laminated can be peeled in various liquid phases, and an improvement in specific surface area, an improvement in reactivity, and the like due to peeling are expected.

1 is a schematic diagram illustrating a reaction system for synthesizing a BQ / Py polymer by a gas phase method. IR spectra of BQ / Py polymer, BQ standard, HQ standard, and PPy standard. The graph of the mass reduction | decrease rate of the BQ / Py polymer, BQ standard sample, BQ / HQ charge-transfer complex, and PPy sample measured with the thermogravimetry apparatus. Estimated structural formula consisting of oxidant, reductant and water molecule in BQ / Py polymer. (A) XRD data of BQ / Py polymer. (B) BQ / Py polymer molecular model in the interlayer direction, (C) BQ / Py polymer in the surface model. (A) to (F) SEM images of BQ / Py polymers. (A) to (C) are particles having a smooth surface, and (D) to (F) are particles having a rough surface. Model diagram of polymer BQ / Py. A portion surrounded by a dotted line indicates a portion where the bond extends upward or downward with respect to the plane in which the polymer extends. IR spectra of BQ / Py soot polymer and two reductants. (A) to (D) TEM images of BQ / Py nanosheets after peeling of BQ / Py soot polymer. (A) AFM image of the BQ / Py nanosheet of FIG. (B) A graph in which BQ / Py15 mg is released by dispersing in 20 mL of pure water, the dispersion is cast on a single crystal silicon substrate, and the thickness of the sheet is measured. (A) Cyclic voltammogram of benzoquinone (BQ) sample and anthraquinone (AQ) sample, (B) Cyclic voltammogram of polymer BQ / Py, (C) Oxidation and reduction states of benzoquinone (BQ) (D) Structural formula of BQ-like site (I) and AQ-like site (II). Cyclic voltammogram before and after peeling of polymer BQ / Py. Theoretical capacity: 317.2 mA h g ^-1 .   Linear Sweep Voltammetry (LSV) graph. The vertical axis represents the reaction current value, and the horizontal axis represents the potential. IR spectra of BQ / Th polymer and BQ / Py polymer. The graph of the mass decreasing rate of BQ / Py polymer, BQ / Th polymer, and BQ / Pyr polymer measured with the thermogravimetry apparatus. Partial structural formula of BQ / Th polymer. IR spectra of BQ / DVB polymer, BQ and DVB. The graph of the mass decreasing rate of BQ and BQ / DVB polymer measured with the thermogravimetry apparatus. The graph which shows the result of the XRD measurement of a BQ / DVB polymer. The graph which shows the result of mass spectrometry of a BQ / DVB polymer. Schematic diagram of molecular model of BQ / DVB polymer. TEM image of BQ / DVB nanoflakes ((a), (b)) and length histogram (c)). AFM image (A) and thickness graph (B) of BQ / DVB nanoflakes. Cyclic voltammogram of BQ / DVB polymer and BQ / DVB nanoflakes. Cycle rate characteristics (a) and charge / discharge curve (b) of BQ / DVB nanoflakes. IR spectrum of TCNQ / DVB polymer. The graph of the mass decreasing rate of the TCNQ / DVB polymer measured with the thermogravimetry apparatus. Some presumed structural formulas of TCNQ / DVB polymer.

1. Polymer The polymer of the present invention causes a cycloaddition reaction with each other. The benzoquinone which may have a substituent (hereinafter sometimes simply referred to as benzoquinone) or the monocyclic which has an electron withdrawing substituent Aromatic hydrocarbon and optionally substituted heterocyclic aromatic compound (hereinafter sometimes referred to simply as “heteroaromatic compound”) or monocyclic aroma having a plurality of alkenyl groups as substituents Group hydrocarbon (B) as a structural unit. That is, the polymer of the present invention has a benzoquinone which may have a substituent as a monomer component or a monocyclic aromatic hydrocarbon having an electron withdrawing substituent and a substituent as a monomer component. It is a polymer obtained by polymerizing a heterocyclic aromatic compound which may be substituted or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as substituents. The monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as substituents is preferably a monocyclic aromatic hydrocarbon having an alkenyl group as a substituent at the para position.

The cycloaddition reaction is one of the pericyclic reactions (a reaction in which a plurality of bonds including a π-electron system are simultaneously formed and cleaved without forming a reaction intermediate through a cyclic transition state) It refers to a reaction in which an unsaturated molecule loses two π bonds and is linked by two new σ bonds to form a cyclic compound. Cycloaddition reactions include Diels-Alder reaction in which a six-membered ring is formed from a conjugated diene and an alkene (double bond), and two new σ bonds, each of which loses a π bond. Reactions that produce linked cyclic compounds are included.

In the present invention, the cycloaddition reaction is preferably a Diels-Alder reaction between a benzene ring of a benzoquinone which may have a substituent and a heterocycle of a heterocyclic aromatic compound which may have a substituent. Or a Diels-Alder reaction between a benzene ring of benzoquinone which may have a substituent and an alkenyl group of a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as substituents, or an electron This is a cycloaddition reaction between an electron withdrawing property of a monocyclic aromatic hydrocarbon having an attractive substituent and an alkenyl group of a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as substituents.

The present invention includes a reduced form of such a polymer. That is, a monocyclic aromatic hydrocarbon (A) having a benzoquinone or an electron-withdrawing substituent and a monocyclic aromatic hydrocarbon (B) having a heterocyclic aromatic compound or a plurality of alkenyl groups as a substituent And the like, which are reduced with hydrogen after the polymerization reaction. For example, the present invention includes a polymer obtained by reducing the polymer after the polymerization reaction using benzoquinone (A) and reducing the oxygen atom of benzoquinone (A) with a hydrogen atom to hydroquinone.

In the present invention, the monocyclic aromatic hydrocarbon (A) having a benzoquinone or an electron-withdrawing substituent has carbon at the 2nd and 3rd positions, and 5 At least one of the carbons at the 6th and 6th positions is not substituted. In one embodiment, the 2-position, 3-position, 5-position and 6-position of the benzoquinone or monocyclic aromatic hydrocarbon (A) having an electron-withdrawing substituent are all hydrogen.

Since the monocyclic aromatic hydrocarbon (A) having a benzoquinone or an electron-withdrawing substituent has an electron-withdrawing substituent, the carbon adjacent to the carbon to which the substituent is bonded becomes deficient in electrons. Become. On the other hand, the heterocyclic aromatic compound (B) has a hetero atom (O, S, N) on the aromatic ring. For this reason, benzoquinone or an electron withdrawing substitution is performed by an electrophilic substitution reaction between a monocyclic aromatic hydrocarbon (A) having an electron withdrawing substituent and a heterocyclic aromatic compound (B). A carbon-carbon bond is newly formed between the monocyclic aromatic hydrocarbon (A) having a group and the heterocyclic aromatic compound (B).

In addition, benzoquinone or a monocyclic aromatic hydrocarbon (A) having an electron-withdrawing substituent and a monocyclic aromatic hydrocarbon (B) having a heterocyclic aromatic compound or a plurality of alkenyl groups as a substituent And has a π-conjugated skeleton of an aromatic ring, so that the 2-position and 3-position and / or 5-position and 6-position of the monocyclic aromatic hydrocarbon (A) having a benzoquinone or an electron-withdrawing substituent Monocyclic aromatic hydrocarbon having a benzoquinone or electron-withdrawing substituent (A) and a heterocyclic aromatic compound or a plurality of alkenyl groups as substituents at the position A cycloaddition reaction (Diels-Alder reaction or a cycloaddition reaction between a triple bond and a double bond) occurs between (B) and a condensed ring is formed. In the present invention, since the monocyclic aromatic hydrocarbon (B) has a plurality of alkylene groups as substituents, each alkylene group reacts with a different benzoquinone (A) to achieve high polymerization of the polymer. ing.

When benzoquinone (A) or a monocyclic aromatic hydrocarbon having an electron withdrawing substituent is reacted with a heterocyclic aromatic compound such as azole or pyridine, two molecules of benzoquinone or electron withdrawing Cycloaddition reaction between a monocyclic aromatic hydrocarbon (A) having a substituent and one molecule of a heteroaromatic compound (B) (Diels-Alder reaction or between a triple bond and a double bond) Of the resulting cycloaddition reaction, and a condensed ring is formed.

When a benzoquinone (A) or a monocyclic aromatic hydrocarbon having an electron-withdrawing substituent is reacted with a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as substituents, one molecule of benzoquinone ( Cycloaddition reaction (Diels-Alder reaction or cycloaddition reaction between triple bond and double bond) occurs between A) and one or two molecules of monocyclic aromatic hydrocarbon (B). A condensed ring is formed.

Thus, a benzoquinone which may have a substituent or a monocyclic aromatic hydrocarbon (A) having an electron-withdrawing substituent and a heterocyclic aromatic compound which may have a substituent or Monocyclic aromatic hydrocarbons (B) having a plurality of alkenyl groups as substituents are polymerized using the monomer component as a monomer component, thereby obtaining monocyclic aromatic hydrocarbons having a benzoquinone or electron-withdrawing substituent ( A carbon-carbon bond between A) and a heterocyclic aromatic compound or a monocyclic aromatic hydrocarbon (B) having a plurality of alkenyl groups as substituents and condensed ring formation occur, and the polymer is in a plane. Alternatively, a layered structure similar to graphite or graphene can be synthesized.

In the field of dye synthesis, a new carbon-carbon bond is formed between these molecules by electrophilic substitution of 1,4-naphthoquinone and 1-methylpyrrole (Heterocycl. Chem. 2000, 37 , 1635), and the diels-alder reaction of naphthoquinone and indole formed a condensed ring between these molecules (Tetrahedron Lett. 1974,15,1361), although individually known, polycyclic Due to the fact that it is a compound, it has not been possible to obtain a layered polymer by polymerization in any document. In the polymer of the present invention, a monocyclic aromatic hydrocarbon (A) having a benzoquinone or an electron withdrawing substituent and a heterocyclic aromatic compound which may have a substituent or a plurality of alkenyl groups are substituted. It was found that these two reactions occur by selecting the monocyclic aromatic hydrocarbon (B) as a group.

The average molecular weight of the polymer is not particularly limited, but is preferably 1000 to 10000000, and preferably 10000 to 1000000.

Benzoquinone (A) may be unsubstituted or substituted. When substituted, examples of the substituent include hydrogen, halogen, nitro, amide, thiol, hydroxy and the like.

Examples of the aromatic ring of the monocyclic aromatic hydrocarbon (A) having an electron withdrawing substituent include a benzene ring, cyclohexadiene, cyclopentadiene and the like.

The electron-withdrawing substituent of the monocyclic aromatic hydrocarbon (A) having an electron-withdrawing substituent is not particularly limited, but a vinyl group, an acyl group, a cyano group, a halogen group, a nitro group, A hydroxy group; a halogen group, a cyano group, a nitro group, or an alkenyl group substituted by a hydroxy group; and the like, and a vinyl group is preferred. The carbon chain of the alkenyl group is preferably 2-5.

The number of electron-withdrawing substituents may be one, two, or three or more, but two is preferable for forming a layered polymer. When there are two electron-withdrawing substituents, the substituent can take an ortho position, a meta position, or a para position, but is preferably a para position.

Preferred examples of benzoquinone (A) include 1,2-benzoquinone and 1,4-benzoquinone. Examples of the monocyclic aromatic hydrocarbon (A) having a preferable electron-withdrawing substituent include divinylbenzene. After polymerizing 1,4-benzoquinone and a heterocyclic aromatic compound which may have a substituent or a monocyclic aromatic hydrocarbon (B) having a plurality of alkenyl groups as substituents, a polymer is obtained. A reduced product of a polymer which is reduced to hydrogen by adding hydrogen to the oxygen of the carbonyl group of 1,4-benzoquinone is also encompassed in the present invention.

The heterocyclic aromatic compound (B) having a plurality of alkenyl groups as substituents is a compound having a hetero atom on the aromatic ring. The heterocyclic aromatic compound is preferably a nitrogen-containing heterocyclic aromatic compound. In order to produce the polymer of the present invention, the nitrogen-containing heterocyclic aromatic compound needs to have a carbon-carbon double bond in the nitrogen heterocyclic ring. The heterocyclic ring can be a 3- to 10-membered ring, is preferably a monocyclic compound, more preferably a 5-membered ring or a 6-membered ring, and a 5-membered or 6-membered nitrogen-containing heterocyclic ring The aromatic compound is more preferably an aromatic compound, and the 5-membered nitrogen-containing heterocyclic aromatic compound is preferably an azole.

An azole refers to a heterocyclic 5-membered compound containing one or more nitrogens, and includes pyrrole (also referred to as 1H-azole), 2H-pyrrole (also referred to as 2H-azole), imidazole (1,3-diazole), pyrazole (1, 2-diazole), thiazole, isothiazole (1,3-thiazole), oxazole, isoxazole (1,3-oxazole), furazane (1,2,5-oxadiazole), 1,2,5-thiadiazole, Examples include 1,2,3-thiadiazole and 1,2,3-triazole, and pyrrole and thiazole are preferable.

The 6-membered nitrogen-containing heterocyclic aromatic compound is preferably pyridine, pyrimidine, pyridazine or the like.

Examples of the aromatic ring of the monocyclic aromatic hydrocarbon (B) having a plurality of alkenyl groups as substituents include a benzene ring, cyclohexadiene, cyclopentadiene and the like.

Examples of the alkenyl group of the monocyclic aromatic hydrocarbon (B) having a plurality of alkenyl groups as substituents include a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, and a cyclopropenyl group. , Cyclobutenyl group, cyclopentenyl group, cyclohexenyl group and the like. The alkenyl group may further have a substituent, such as an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group; a pyridyl group, a thienyl group, a furyl group, a pyrrolyl group, an imidazolyl group, Heteroaromatic groups such as pyrazinyl group, oxazolyl group, thiazolyl group, pyrazolyl group, benzothiazolyl group, benzoimidazolyl group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert- Alkoxy groups such as butoxy group, pentyloxy group, isopentyloxy group, neopentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group; methylthio group, ethyl Alkylthio groups such as thio group, propylthio group and butylthio group; arylthio groups such as phenylthio group and naphthylthio group; trisubstituted silyloxy groups such as tert-butyldimethylsilyloxy group and tert-butyldiphenylsilyloxy group; methylsulfinyl group and ethyl Alkylsulfinyl groups such as sulfinyl groups; arylsulfinyl groups such as phenylsulfinyl groups; sulfonic acid ester groups such as methylsulfonyloxy group, ethylsulfonyloxy group, phenylsulfonyloxy group, methoxysulfonyl group, ethoxysulfonyl group, and phenyloxysulfonyl group Cyano group; nitro group and the like.

The plurality of alkenyl groups of the monocyclic aromatic hydrocarbon (B) can be the same or different, but are preferably the same from the viewpoint of production. The number of alkenyl groups in the monocyclic aromatic hydrocarbon (B) is preferably 2 to 4, and more preferably 2. The position of the two alkenyl groups may be ortho, meta or para, but is preferably para. An example of a preferred monocyclic aromatic hydrocarbon (B) is divinylbenzene. Note that the monocyclic aromatic hydrocarbon (B) having a plurality of alkenyl groups as substituents has a different structure from the monocyclic aromatic hydrocarbon (A) having an electron-withdrawing substituent.

In one embodiment, the polymer of the present invention contains 1,4-benzoquinone which may have a substituent or 1,4-hydroquinone which may have a substituent, and an azole which may have a substituent. Or pyridine as a structural unit, a portion where 1,4-benzoquinone or 1,4-hydroquinone and azole or pyridine are carbon-carbon-carbon bonded, and 1,4-benzoquinone or 1,4-hydroquinone The azole or pyridine has a moiety that forms a condensed ring.

In another embodiment, the polymer of the present invention may have 1,4-benzoquinone which may have a substituent or 1,4-hydroquinone which may have a substituent, and a substituent. A part containing 1,4-benzoquinone or 1,4-hydroquinone and pyrrole or thiazole in a carbon-carbon-carbon bond, and 1,4-benzoquinone or 1,4-hydroquinone And pyrrole or thiazole have a portion forming a condensed ring.

In still another embodiment, the polymer of the present invention has 1,4-benzoquinone which may have a substituent or 1,4-hydroquinone which may have a substituent, and an alkenyl group substituted at the para position. It contains a monocyclic aromatic hydrocarbon as a group as a structural unit, and 1,4-benzoquinone or 1,4-hydroquinone and a monocyclic aromatic hydrocarbon have a portion that forms a condensed ring.

In particular, 1,4-benzoquinone as benzoquinone (A), azole (especially pyrrole, thiazole, etc.) as a heterocyclic aromatic compound or monocyclic aromatic hydrocarbon (B) having a plurality of alkenyl groups as substituents Alternatively, when divinylbenzene is used, the benzoquinone that acts as a reactive organic oxidant and the monomer liquid azole or divinylbenzene are simply sealed in a single sealed container at a low temperature (100 ° C. or lower) and normal pressure. Therefore, the polymer having a layered structure similar to graphite or graphene can be synthesized even in a mild environment, which is advantageous as compared with the conventional method.

Because of the above-described configuration, the polymer of the present invention (including the reduced form thereof) can extend into a planar shape, that is, a two-dimensional sheet shape, and further, a plurality of sheet-like polymers are laminated to form a tertiary layer. An original laminate can be formed. By using a sheet structure, it is expected that the specific surface area of the laminate is improved and the reactivity is improved.

Furthermore, the polymer of the present invention (including the reduced form thereof) is dispersed in water or an organic solvent such as benzyl alcohol, ethanol, toluene, chloroform, hexane, etc., and subjected to ultrasonic treatment to obtain a dispersion liquid. It can also be made into flakes. Nanoflakes refer to a flaky material in which at least one of the length and thickness dimensions is in the range of 1 to 1000 nm, and the length dimension is larger than the thickness dimension. By adjusting the temperature and length of sonication, the dimensions of the nanoflakes can be changed. The dimensions of the nanoflakes are not particularly limited, but are preferably 1 to 1000 nm in length and 1 to 100 nm in thickness. The length of the nanoflakes refers to the maximum length viewed from the vertical direction of the surface when the nanoflakes are placed on a horizontal surface. The thickness of the nanoflakes refers to the thickness of the nanoflakes in the direction perpendicular to the surface. When there are a plurality of nanoflakes, the average length is preferably 1 to 1000 nm and the average thickness is preferably 1 to 100 nm. When there are 10 or more nanoflakes, the average length and thickness of 10 may be measured.

</ RTI> By converting the polymer of the present invention into nanoflakes, the overvoltage is reduced and the capacitance is increased, so that the charge storage ability can be improved.

In another embodiment, the polymer of the present invention includes a moiety represented by any of the following formulas (i) to (iv).

(In the formula, Cy1 is a 5-membered nitrogen-containing heterocycle,
Cy2 is a monocyclic aromatic hydrocarbon,
Cy3 is a 6-membered nitrogen-containing heterocycle,
A is an electron-withdrawing substituent selected from vinyl group, acyl group, cyano group, halogen group, nitro group, hydroxy group; alkenyl substituted by halogen group, cyano group, nitro group, or hydroxy group: Yes,
The bond between A and Cy is a single bond or a double bond. )
Cy1 is preferably pyrrole (also called 1H-azole), 2H-pyrrole (also called 2H-azole), imidazole (1,3-diazole), pyrazole (1,2-diazole), thiazole, isothiazole (1,3 -Thiazole), oxazole, isoxazole (1,3-oxazole), furazane (1,2,5-oxadiazole), 1,2,5-thiadiazole, 1,2,3-thiadiazole, or 1,2, 3-triazole.

Cy2 is preferably a benzene ring, cyclohexadiene, or cyclopentadiene.

Cy3 is preferably pyridine, pyrimidine, or pyridazine.

In another embodiment, the polymer of the present invention includes a moiety represented by the following formula (I) or formula (II).

In one embodiment, the polymer includes a moiety represented by the following formula (III) or (IV).

(Where
R ₁ and R ₂ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, alkyl group, or pyrrolyl group, or R ₁ and R ₂ are both an adjacent pyrrole group and an adjacent benzoquinolyl group. Forming a condensed ring with the group,
R ₃ and R ₄ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, alkyl group, or pyrrolyl group, or R ₃ and R ₄ together are an adjacent pyrrole group and an adjacent benzoquinolyl group. Forming a condensed ring with the group,
However, when R ₁ and R ₂ , or R ₃ and R ₄ form a condensed ring, either one of them forms a condensed ring,
R ₅ , R ₆ and R ₇ are each independently hydrogen, halogen, hydroxy, an alkyl group, or a benzoquinolyl group. )

(Where
R ₁ and R ₂ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, alkyl group, or thiazolyl group, or R ₁ and R ₂ are both adjacent thiazolyl groups and adjacent benzoquinolyl groups. Forming a condensed ring with the group,
R ₃ and R ₄ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, alkyl group, or thiazolyl group, or R ₃ and R ₄ are both adjacent thiazolyl groups and adjacent benzoquinolyl groups. Forming a condensed ring with the group,
However, when R ₁ and R ₂ , or R ₃ and R ₄ form a condensed ring, either one of them forms a condensed ring,
R ₆ is hydrogen, halogen, hydroxy, an alkyl group, or a benzoquinolyl group. )
When R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are alkyl groups, it is preferably independently a C1-C6 alkyl group. Examples of the C1-C6 alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, Examples thereof include 1,1-dimethylbutyl group and 1,3-dimethylbutyl group.

In one embodiment, the benzoquinolyl group that forms a condensed ring with R ₁ and R ₂ and the benzoquinolyl group that forms a condensed ring with R ₃ and R ₄ are represented by formula (V).

In a particular embodiment, the benzoquinolyl group that forms a condensed ring with R ₁ and R ₂ and the benzoquinolyl group that forms a condensed ring with R ₃ and R ₄ are represented by formula (VI).

R ₈ and R ₉ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, or an alkyl group. Preferably, R ₈ and R ₉ are each independently hydrogen, halogen, hydroxy or an alkyl group.

R ₁₀ is hydrogen, halogen, hydroxy or an alkyl group.

In one embodiment, the benzoquinolyl group that is R ₅ , R ₆ and R ₇ is represented by formula (VII).

In certain embodiments, the benzoquinolyl group represented by formula (VII) is a benzoquinolyl group represented by formula (VIII).

R ₁₁ and R ₁₂ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, or an alkyl group. Preferably, R ₁₁ and R ₁₂ are each independently hydrogen, halogen, hydroxy or an alkyl group.

R ₁₃ is hydrogen, halogen, hydroxy or an alkyl group.
Formula (V) and formula (VII) may be the same or different, but are preferably the same in terms of production efficiency. The group of formula (VI) and the group of formula (VIII) can be the same or different, but are preferably the same in terms of production efficiency.

In one embodiment, the polymer of the present invention includes a polymer containing a moiety represented by the following formula (IX) or a reduced form thereof.

Where
R ₁₅ , R ₁₇ , and R ₁₈ are each independently a hydrogen, halogen, nitro, amide, thiol, hydroxy, or alkyl group;
R ₁₆ , R ₁₉ and R ₂₀ are each independently a hydrogen, halogen, hydroxy or alkyl group;
R ₂₁ and R ₂₂ are each independently a hydrogen, halogen, hydroxy or alkyl group;
k is an integer greater than or equal to 1,
x is a real number from 0 to 100.

K is preferably 1 to 1000, more preferably 5 to 40.

When R ₁₅ , R ₁₆ , R ₁₇ , R _18, R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ are alkyl groups, it is preferably independently a C1-C6 alkyl group. Examples of the C1-C6 alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, Examples thereof include 1,1-dimethylbutyl group and 1,3-dimethylbutyl group.
In particular, R ₁₅ , R ₁₆ , R ₁₇ , R _18, R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ are all hydrogen.

In another embodiment, the polymer of the present invention includes a polymer containing a moiety represented by the following formula (X) or a reduced form thereof.

Where
R ₁₅ , R ₁₇ , and R ₁₈ are each independently a hydrogen, halogen, nitro, amide, thiol, hydroxy, or alkyl group;
R ₁₆ , R ₁₉ and R ₂₀ are each independently a hydrogen, halogen, hydroxy or alkyl group;
R ₂₁ and R ₂₂ are each independently a hydrogen, halogen, hydroxy or alkyl group;
R ₂₃ , R ₂₅ , and R ₂₆ are each independently a hydrogen, halogen, nitro, amide, thiol, hydroxy, or alkyl group;
R ₂₄ , R ₂₇ and R ₃₀ are each independently a hydrogen, halogen, hydroxy or alkyl group;
R ₂₈ and R ₂₉ are each independently a hydrogen, halogen, hydroxy or alkyl group,
m and n are each an integer of 1 or more,
x is a real number from 0 to 100.

m and n are each preferably 1 to 1000, and more preferably 5 to 40. In the formula, R ₁₅ , R ₁₆ , R ₁₇ , R _18, R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ When is an alkyl group, it is preferably each independently a C1-C6 alkyl group. Examples of the C1-C6 alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, Examples thereof include 1,1-dimethylbutyl group and 1,3-dimethylbutyl group.

In particular, R ₁₅ , R ₁₆ , R ₁₇ , R _18, R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ Are both hydrogen.

In a further embodiment, the polymer of the present invention includes a polymer comprising a moiety represented by formula (XI).

(Where
R ₁₅ , R ₁₇ , and R ₁₈ are each independently a hydrogen, halogen, nitro, amide, thiol, hydroxy, or alkyl group;
R ₁₆ , R ₁₉ and R ₂₀ are each independently a hydrogen, halogen, hydroxy or alkyl group;
R ₂₁ and R ₂₂ are each independently a hydrogen, halogen, hydroxy or alkyl group;
n is an integer of 1 or more,
x is a real number between 0 and 20)
In one embodiment, the polymer of the present invention includes a polymer containing a moiety represented by the following formulas (XII) to (XVII).

In a specific embodiment, the polymer of the present invention includes a polymer comprising a moiety represented by formulas (XII), (XIII), (XIV), and (XV) and hydrated water.

The present invention includes a functional nanosheet containing the polymer of the present invention. That is, the sheet of the present invention is a sheet having a thickness of 0.2 nm to 2.0 nm containing the above-described polymer of the present invention extending in a planar shape. The present invention further includes a laminate in which a plurality of the above sheets are laminated. The interlayer distance of the sheet is 0.2 nm to 2.0 nm. The thickness of the laminated body is not limited, and may be, for example, 5 nm to 10000 nm. This laminated structure can be peeled to a desired thickness in various liquid phases. The peeling is expected to improve the specific surface area and the reactivity of the laminate.

2. Production method of polymer, sheet and laminate The polymer of the present invention causes a cycloaddition reaction with each other, and may have a substituent as a monomer component, or a monocycle having an electron-withdrawing substituent. And a monocyclic aromatic hydrocarbon (B) having a heterocyclic aromatic compound which may have a substituent as a monomer component or a plurality of alkenyl groups as a substituent. Manufactured by polymerization. These two monomer components are benzoquinone or monocyclic aromatic hydrocarbon (A) having an electron withdrawing substituent and a heterocyclic aromatic compound or a monocyclic aromatic having a plurality of alkenyl groups as substituents. By polymerizing the hydrocarbon group (B) to form a carbon-carbon bond to form a condensed ring, a polymer extending in a two-dimensional shape, a planar shape, or a steric shape is obtained.

About monocyclic aromatic hydrocarbons (B) having benzoquinone or electron-withdrawing substituents (A) and heterocyclic aromatic compounds or plural alkenyl groups as substituents As described in “1. Polymer”.

A monocyclic aromatic hydrocarbon (A) having a benzoquinone or an electron-withdrawing substituent, and a monocyclic aromatic hydrocarbon (B) having a heterocyclic aromatic compound or a plurality of alkenyl groups as a substituent. Each may optionally be dissolved in a solvent, methyl isobutyl ketone, methyl ethyl ketone, ethanol, N-methyl-2-pyrrolidone, 2, N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphamide These may be used, and these may be used alone or in combination of two or more. In one embodiment, a monocyclic aromatic hydrocarbon (A) having a benzoquinone or an electron withdrawing substituent and a monocyclic aromatic hydrocarbon having a heterocyclic aromatic compound or a plurality of alkenyl groups as a substituent (B) is polymerized without dissolving in the solvent.

The temperature of the polymerization reaction is preferably low temperature, that is, 100 ° C. or lower in order to prevent the product from volatilizing. The lower limit of the temperature is preferably 0 ° C. or higher, and preferably 20 ° C. or higher. In order to accelerate the reaction, it may be 60 ° C. or higher. Among monocyclic aromatic hydrocarbons (B) having a benzoquinone or an electron-withdrawing substituent (A) and a heterocyclic aromatic compound or a plurality of alkenyl groups as substituents In particular, in order to bring the heterocyclic aromatic compound or the monocyclic aromatic hydrocarbon (B) having a plurality of alkenyl groups as substituents into a liquid state, the polymerization reaction temperature is the heterocyclic aromatic The temperature is preferably higher than the melting point of the compound or the monocyclic aromatic hydrocarbon (B) having a plurality of alkenyl groups as substituents.

The polymerization time is not particularly limited, but is preferably 0.5 minutes to 120 hours, and more preferably 15 minutes to 72 hours. When the polymerization time is increased, the polymer extends in a planar shape to form a sheet, and a plurality of sheet structures extending in the planar shape are further laminated to form a laminated structure. The obtained polymer has a layered structure similar to graphite or graphene having excellent conductivity.

The thickness of the above-mentioned sheet and laminate can be adjusted by adjusting the polymerization reaction time, and can also be adjusted by peeling the laminate made of the polymer to a desired thickness in various solvents. it can. As examples of such solvents, known solvents can be used; low polarity solvents such as hexane and toluene; medium polarity solvents such as chloroform, dichloromethane, diethyl ether, tetrahydrofuran (THF), ethyl acetate, acetone, and acetonitrile. , Water, a highly polar solvent such as methanol, ethanol or the like, or an aqueous solution containing additional molecules such as various ionic surfactants and organic ions, but is not limited thereto.

The polymerization pressure is not particularly limited and is usually normal pressure (also referred to as standard pressure, 1.01325 × 10 ⁵ Pa), but may be performed at a pressure lower than normal pressure in order to promote the reaction.

The polymerization reaction is usually performed in an air atmosphere, but is not limited thereto.

Examples of the synthesis method include (i) synthesis by a gas phase method, (ii) synthesis by a liquid phase method, or (iii) synthesis by direct mixing. In the synthesis by the gas phase method of (i), benzoquinone or a monocyclic aromatic hydrocarbon (A) having an electron-withdrawing substituent and a heterocyclic aromatic compound or a single group having a plurality of alkenyl groups as substituents. The cyclic aromatic hydrocarbon (B) can be put in another container, and these two containers can be sealed in one sealed container. When the monocyclic aromatic hydrocarbon (A) having a benzoquinone or an electron-withdrawing substituent has volatility, the reaction can proceed spontaneously. The reaction product can be washed with a solvent and optionally dried. In the synthesis by the liquid phase method of (ii), a benzoquinone or an electron withdrawing substituent is added to a container and a monocyclic aromatic hydrocarbon (A) having an electron withdrawing substituent and a solvent are added to the container. After dissolving the monocyclic aromatic hydrocarbon (A) in the solvent, the monocyclic aromatic hydrocarbon (B) having a heterocyclic aromatic compound or a plurality of alkenyl groups as substituents is further added, and the temperature is constant. The solution after the reaction is washed with a solvent and optionally dried. In the synthesis by direct mixing of (iii), benzoquinone or a monocyclic aromatic hydrocarbon (A) having an electron withdrawing substituent and a heterocyclic aromatic compound or a monocyclic having a plurality of alkenyl groups as substituents The aromatic hydrocarbon (B) can be placed in the same glass container, sealed in a sealed container, and allowed to stand at a constant temperature for a certain time. The reaction product can be washed with a solvent and optionally dried.

Furthermore, by arranging various substrates or base materials in a sealed container before the start of the polymerization reaction, a coating made of a polymer can be directly applied to the substrate or the base material.

The state of the substrate or base material is not limited, and it may be liquid or solid. Alternatively, the type of the substrate or base material is not limited, and examples thereof include, but are not limited to, metal, glass, ceramics, plastic, wood, fiber, and composite materials thereof.

In this way, since the coating of the polymer of the present invention can be applied to a substrate or base material of any material and state placed in the reaction vessel, the polymer of the present invention is applicable as a coating material. Is wide. Such coatings can be used, for example, for electrode deposition and electronic circuit interconnection.

Furthermore, the polymer of the present invention and the flakes produced from the polymer undergo charge / discharge reactions associated with redox of the quinone moiety of benzoquinone or the electron-withdrawing substituent of monocyclic aromatic hydrocarbons, resulting in a high capacity. As shown, the present invention can be applied to charge storage using electrode materials such as supercapacitors. For example, the polymer of the present invention and the flakes produced from the polymer can be used as an electrode active material.

Furthermore, since the polymer of the present invention has a small hydrogen generation overvoltage, it can serve as an excellent hydrogen generation electrode catalyst. The polymer of the present invention can be applied to the field of renewable energy because it can save hydrogen with high efficiency and save energy.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Experimental procedure Structural analysis by Fourier transform infrared spectroscopy (FTIR) A Fourier transform infrared spectrometer (FT / IR-4200typeA, JASCO) was used to confirm the polymerization of the sample. The sample was molded into a disk shape by KBr method, the measuring range 4000-400 ^-1, resolution 4 cm ^-1, was measured by setting the number of integration 128 times.
2. Measurement of mass loss by thermogravimetry (TG-DTA) TG-DTA (TG / DTA7200, EXSTER) was used for confirmation of sample polymerization. The temperature range was set from 25 ° C to 1000 ° C and measurements were taken. The TG of BQ / Py polymer, BQ sample, quinhydrone, which is an electrolytic transfer complex of BQ and hydroxyquinone (HQ), and polypyrrole (Ppy) sample were measured.
3. Elemental analysis Elemental analysis was performed at Keio University Faculty of Science and Technology Central Laboratory to measure the elemental ratio of samples.
4). Analysis of layered structure by X-ray diffractometer (XRD) An X-ray diffractometer (Mini Flex and Bruker D8 Advance, Rigaku) was used to analyze the interlayer distance of BQ / Py polymer samples. The powder sample was pressure-bonded to a sample holder and measured by a continuous scanning method using CuKα rays, with a scanning speed of 5 degree min ^-1 and a scanning range of 3 to 80 degree.
The distance between layers was calculated using the following Bragg equation.
2dsinθ = nλ (n = 1)
d is the crystal plane spacing (nm), λ is the X-ray wavelength (λ = 0.1542 nm), and θ is the diffraction angle.
5). Mass spectrometry (MALDI-TOFMS)
For confirmation of molecular weight, measurement was performed using a mass spectrometer (MALDI-7090: SHIMADZU). A sample and a matrix (2,5-dihydroxybenzonic acid) were dispersed in NMP, cast on a plate, dried, and measured with an m / z value of 1-5000 and an integration count of 50 times.
6). Molecular mechanics method (MM2)
The simulation of the most stable state of the molecular model of the synthesized sample was performed using ChemBioProfessional. A molecular model was created from the software using ChemBio3D, stacked vertically, and the most stable state of energy was simulated using the Molecular Mechanics (MM2) program.
7). Observation by Scanning Electron Microscope (SEM) SEM (VE-9800, KEYENCE) was used to observe the shape of the BQ / Py polymer sample before peeling. For observation, the sample was fixed to an aluminum table with conductive tape. Each sample after fixation was observed after OSMIUM COATER (HPC-1S, Vacuum Device Co., Ltd.) was used to coat the surface with an osmium coating of about 5 nm to ensure conductivity.
8). Observation by Transmission Electron Microscope (TEM) FE-TEM (Tecnai F20, FEI) and TEM-120 (TecnaiSpirit, FEI) were used for shape observation of the peeled sheet (sample of Example 3 below).
9. Observation by Atomic Force Microscope (AFM) An atomic force microscope (SPM9600, Shimadzu Corporation) was used to measure the thickness of the peeled sheet (sample of Example 3 below). The silicon substrate was immersed in methanol / hydrochloric acid (1: 1 (volume ratio)) and concentrated sulfuric acid for 30 minutes.
The substrate was taken out, washed with water, and dried by blowing argon gas. The cleaned substrate was heated to 100 ° C. on a hot plate, and the dispersion was dropped and observed.
10. Cyclic voltammetry Cyclic voltammetry (VerasSTAT / PARSTAT, Princeton Applied Research) was used to examine the electrochemical activity of the obtained samples. In the aqueous measurement, a silver-silver chloride electrode was used as the reference electrode, a Pt substrate as the counter electrode, and 1 mol cm ^-3 H ₂ SO4 as the electrolyte. Measurements were taken with a scanning range of -0.5 to 1.2 V (vs. Ag / AgCl) and a scanning speed of 1 mV S- ¹ .
11. Charging / discharging measurement It measured using the charging / discharging apparatus (HJ1001SD8: HOKUTO). The same measurement cell as in the cyclic voltammetry measurement was used. Similarly, a current was passed at a constant potential of −0.3 V for 30 minutes, and then charge / discharge measurement was performed.
12 Contact angle measurement A contact angle measuring device (DMe-201, Kyowa Interface Chemical Co., Ltd.) was used to measure the wettability of the glass substrate before and after coating. The contact angle between water and the glass substrate was measured by a liquid suitability method.

Example 1 Synthesis of BQ / Py polymer (synthesis method)
1,4-benzoquinone (BQ) powder (purity 98.0%, Tokyo Chemical Industry Co., Ltd.) and pyrrole (Py) liquid (purity 99,0%, Tokyo Chemical Industry Co., Ltd.) are separated as shown in FIG. They were placed in containers 1 and 2 and placed in a sealed container 3 in an air atmosphere and allowed to stand for 48 hours. The crude product was recovered from container 1 that contained BQ. Suction filtration was used to remove unreacted monomer molecules from the crude product and washed with acetone. Next, in order to remove molecules with low polymerization degree, add 25 cm ³ of N-methyl-2-pyrrolidone (NMP) (purity 99.0%, Wako Pure Chemical Industries, Ltd.) and recovered material to a Teflon (registered trademark) centrifuge tube. Centrifugation was performed at 13500 rpm for 15 minutes to collect the precipitate. Thereafter, in order to remove the remaining NMP, it was washed with acetone using suction filtration. Further, in order to remove hydroquinone and NMP remaining between the layers of the sample, vacuum drying was performed at 190 ° C. for 16 hours to obtain a copolymer composed of 1,4-benzoquinone and pyrrole (hereinafter referred to as BQ / Py polymer). . Further, this was dispersed in water to obtain a nanosheet dispersion medium.

The polymer was produced with a sample in which the ratio of BQ and Py was changed from 10 nmol: 50 nmol to 50 nmol: 10 nmol, but the composition of the product did not change (data not shown). In order to make the supply amount of Py sufficient, the ratio of BQ to Py was set to 30 nmol: 30 nmol.

(result)
Structural Analysis by Fourier Transform Infrared Spectroscopy (FTIR) First, IR spectra of BQ / Py polymer, BQ sample, HQ sample, and PPy sample measured with a Fourier transform infrared spectrometer are shown in Fig. 2. . From comparison of each spectrum, the peak of (1) can be attributed to NH stretching, the peak of (2) can be attributed to OH stretching, and the peak of (3) can be attributed to C = O stretching. In addition, the peak of (4) is aromatic CH 3 stretch, and it was confirmed that the BQ / Py polymer greatly decreased.

It was suggested that the BQ / Py polymer has a polymerized structure containing BQ and Py. In addition, by comparing with the HQ standard, it was thought that part of the structure was a reduced form and the presence of water molecules.

Measurement of mass reduction by thermogravimetry (TG-DTA) Next, as shown in Fig. 3, from the comparison of TG graphs, the mass reduction start temperature of BQ / Py polymer is about 400 ° C, and this value is Since it is much higher than the mass reduction temperature of PPy samples and BQ / HQ charge transfer complexes, it was confirmed that the polymer was polymerized together with IR results.

Elemental analysis Next, as shown in Table 1, the results of elemental analysis of BQ / Py polymer are as follows: C = 67.02 wt%, H = 2.79 wt%, N = 6.22 wt%, O = 23.97 wt% Met. As for the weight ratio of O 2, the calculated value obtained when assuming that the obtained product contains only C, H, N, and O 2 is described. When the weight ratio of each atom obtained from the result is compared with the weight ratio of the atom calculated from the structure estimated based on the previous result, as shown in Table 1, the oxidized form, the reduced form, and the water A structure composed of Japanese water was estimated.

Also, from the results of TG, there was little error in the experimental values and calculated values when it was assumed that the mass loss up to 200 ° C was due to water evaporation, so the consistency of the estimated structure was confirmed.

In the BQ / Py polymer, as shown in Fig. 4, it is considered that a two-dimensional polymerization reaction that spreads in the plane direction occurs due to the carbon-carbon-carbon bond between BQ and Py and the ring-condensation reaction between BQ and Py. It is done.

Analysis of layered structure by X-ray diffractometer (XRD) Next, FIG. 5A shows the XRD results of the BQ / Py polymer. In addition, FIG. 5B shows a molecular model in ChemBio3D after MM2 calculation in the interlayer direction of the BQ / Py polymer, and FIG. 5C shows a molecular model in ChemBio3D after MM2 calculation in the surface direction of the BQ / Py polymer. The d value at the peak (1) in FIG. 5A was calculated to be 0.37 nm (FIGS. 5A and 5B), and the d value at the peak (2) in FIG. 5B was calculated to be 0.21 nm (FIGS. 5A and 5C). The values of these periods and the shape of the diffraction pattern were found to be similar to those when graphene formed a turbulent layer structure. From this, it is considered that the polymer has a two-dimensional polymer forming a turbulent layer structure.

Observation by Scanning Electron Microscope (SEM) Next, SEM images of the BQ / Py polymer are shown in FIGS. In the macro, particles having a size of about 100 to 500 μm were observed. When the surface of one particle was magnified and observed, a very smooth surface without irregularities and a rough surface with small particles gathered were observed. The size of one particle on the rough surface was about 100 nm, and it was confirmed that they gathered to form secondary particles.

Example 2 Elemental analysis of BQ / Py polymer and construction of model The BQ / Py polymer obtained in Example 1 was subjected to elemental analysis. As a result, as shown in Table 2, the calculated value of the CHN element ratio agreed with the measured value within 0.5%.

Further, when the obtained BQ / Py polymer was represented by a model by ChemBio3D, as shown in FIG. 7, the BQ / Py polymer had a structure spreading in a two-dimensional plane, and the vertical direction with respect to the plane. It has been found that it has a portion where the connection extends.

Example 3 Reduction of BQ / Py polymer (experimental method)
5 mg of the BQ / Py polymer obtained by the gas phase method and 15 cm ³ of a hydrazine solution having a predetermined concentration were placed in a glass container and stirred for a predetermined time in an air atmosphere. The stirring time was set to 10 minutes for hydrazine / pure water (1: 1 (volume ratio)) and 24 hours for hydrazine stock solution. Next, the sample was washed with pure water using suction filtration, and then hydrazine was removed by vacuum drying at 60 ° C. for 12 hours.

(result)
Structural analysis by Fourier transform infrared spectroscopy (FTIR) A BQ / Py polymer was added to a solution in which a hydrazine solution and water were mixed at a volume ratio of 1: 1, and the reductant obtained after stirring for 10 minutes (hereinafter referred to as reduction) It was considered that the reduction reaction proceeded because it was visually confirmed that gas was generated during the reaction. Further, from the IR spectrum shown in FIG. 8, a large OH stretching peak can be confirmed in the vicinity of 3400 cm ⁻¹ , indicating that the reduction reaction at the C = O portion derived from quinone proceeds. However, it was found that the reduction reaction did not proceed sufficiently because there was also a peak derived from C = O near 1650 cm- ¹ .

Next, since it was confirmed in the same manner as in the previous experiment that a gas was generated even when the product was added to the hydrazine stock solution and stirred for 24 hours, a reduced form (hereinafter referred to as reduced form 2) was obtained. It was confirmed that the reduction reaction was progressing. However, the IR spectrum results in FIG. 8 show that the peak derived from C = O stretching near 1650 cm ^-1 disappears, but no sharp peak near 3400 cm ^-1 is observed. A peak similar to the peak was observed.

Elemental analysis Also, as shown in Table 3, it was confirmed from the results of elemental analysis that the ratio of N in the reductant was greatly increased.

From the change in IR spectrum from reductant 1 to reductant 2 in Fig. 8, compared with IR of BQ / Py polymer before reduction, the C = O portion in reductant 1 is partially reduced by hydrazine to C-OH. However, in the reductant 2, the peak of OH stretching disappears, and it can be seen that NH stretching is greatly confirmed. From this, it was considered that the reaction with hydrazine was progressing other than the reduction of the C = O part to C-OH.

From the results of the above elemental analysis, it was considered that an addition reaction accompanied by an increase in nitrogen atoms in the polymer progressed.

Here, in the reaction of 1,4-dicarbonyl compound with hydrazine, the oxygen atom as shown in Fig. 5-2a is replaced with a nitrogen atom, and pyridazine is newly synthesized (Tetrahedron Lett., 1974, 15, 1361), assuming that all 1,4-dicarbonyl sites have been changed to pyridazine, and applying this to the presumed structure of BQ / Py polymer, the reaction shown in the following scheme (I) is considered to occur. .

From here, assuming that there is a water molecule having a molar ratio x to the n-dimer of the molecule of the estimated structure as shown in the following formula (VI), the weight ratio of the atoms is as shown in Table 4.

From this, the structure of the compound obtained when the BQ / Py polymer is reduced with hydrazine is closest to the result of elemental analysis of the reductant 2 with x = 17 compared to n = 5. It was thought that it contained much more than the BQ / Py soot polymer. The presence of the 1,4-dicarbonyl moiety confirmed the consistency with the predicted structure in the BQ / Py polymer.

Example 4 Nanosheet Formation from BQ / Py Polymer (Experimental Method)
The BQ / Py polymer 15 mg obtained in Example 1 and 20 mL of pure water were placed in a glass container, subjected to ultrasonic waves for 2 hours, and then stirred at room temperature for 16 hours to peel off the sample. The obtained dispersion was freeze-dried to remove pure water, and the peeled sample was collected.
It was observed whether the nanosheet of the sample was formed.

(result)
Observation by Scanning Electron Microscope (SEM) Observation of the SEM image of Example 1 confirmed that the polymer particles before the peeling operation were large particles of 100 μm or more.

Observation by transmission electron microscope (TEM) and atomic force microscope (AFM) On the other hand, as shown in the TEM image of the product after peeling (hereinafter referred to as BQ / Py nanosheet) in FIG. Then, the presence of the nanosheet was confirmed by performing a peeling operation. Next, as shown in the AFM image of the BQ / Py nanosheet in FIG. 10, the thickness of one sheet was found to be about 5 nm.

Cyclic voltammetry Next, the results of the evaluation of electrochemical characteristics performed for confirmation of the oxidation-reduction reaction in the aqueous electrolyte are shown in FIGS.

Since the redox peak was confirmed as shown in FIG. 11B, it was confirmed that the BQ / Py polymer had a redox ability derived from the quinone moiety (FIGS. 11B and 11C). In addition, by comparing the shape of the BQ / Py polymer with the BQ standard and AQ standard, it was confirmed that the polymer had a BQ-like part near 0.5V and an AQ-like part near 0V. (FIGS. 11A and 11B). From this, it is considered that the BQ / Py polymer has a BQ site (i) corresponding to benzoquinone and an AQ site (ii) corresponding to anthraquinone as shown in FIG. 11D. The presumption that the structure has a structure in which 1,4-benzoquinone and pyrrole have a carbon-carbon bond and a structure in which 1,4-benzoquinone and pyrrole form a condensed ring was supported.

In the BQ / Py polymer, the incorporated quinone moiety is electrochemically active and is considered to be applicable to efficient charge storage.

FIG. 12 shows a cyclic voltammogram before and after peeling of the BQ / Py polymer. Capacity before peeling Whereas a 50.1mA h g ^-1, volume after peeling was increased to 152.5 mA h g ^-1. In the BQ / Py copolymer laminated by peeling, an increase in the reaction interface due to nanosheet formation was confirmed.

Example 5 Coating of BQ / Py copolymer on substrate (experimental method)
The substrate to be coated was fixed to the lid of the closed container of the reaction system in which BQ and Py of Example 1 were reacted by the vapor phase method so as to be positioned above the glass bottle containing BQ. After completion of the reaction, the surface of the substrate was washed with acetone. A glass substrate, ITO glass substrate, KBr substrate, Ti substrate, Cu mesh, or Ti mesh was selected as the substrate.

(result)
In any case, it was confirmed that the surface of the substrate was coated brown.

Contact angle measurement Further , when the contact angle of the substrate before and after the coating was measured for the glass substrate (n = 10), as shown in Table 5, the coated glass substrate (coated plate) had a glass substrate (before coating) ( An increase in the contact angle was confirmed as compared with the glass plate.

Example 6 Characteristic evaluation of polymer as a hydrogen generating electrode catalyst Experimental method After casting a dispersion medium of BQ / Py copolymer on a glassy carbon electrode (GC electrode) and drying in a 60 ° C constant temperature bath. Evaluation was performed by Linear Sweep Voltammetry (LSV). At this time, 1 mg of BQ / Py copolymer was dispersed in 200 μL of 2-propanol as a dispersion medium. The GC electrode used was a CPE carbon paste electrode manufactured by BAS with a diameter of 3 mm. LSV measurement is performed at a scanning range of -0.19 to -0.8 V (vs. Ag / AgCl), that is, 0 to -0.61 V (vs. SHE), at a scanning speed of 5 mV / s, and the electrolyte is 0.5M H ₂ SO ₄ . The reference electrode was Ag / AgCl, and the counter electrode was Pt.

Experimental Results In the graph shown in FIG. 13, the intercept on the horizontal axis corresponds to the overvoltage required for hydrogen generation. From the results of this LSV, it was found that the BQ / Py copolymer having 3 casts has an excellent hydrogen generation ability by performing a reduction operation. Moreover, it turned out that it has very high activity compared with the graphene of the commercial powder cast on the same conditions.

Example 7 Synthesis of BQ / Th polymer (synthesis method)
In Example 1, a copolymer consisting of 1,4-benzoquinone and thiazole (hereinafter referred to as BQ / Th polymer) was used under the same conditions except that pyrrole (Py) was replaced with thiazole (Th) having the same substance amount. Got. The ratio of BQ to Th was 30 nmol: 30 nmol.

The obtained BQ / Th polymer was subjected to “1. Structural analysis by Fourier transform infrared spectroscopy (FTIR)” to “3. Elemental analysis” in the experimental procedure.

(result)
Structural Analysis by Fourier Transform Infrared Spectroscopy (FTIR) First, IR spectra of BQ / Th polymer and BQ / Py polymer measured with a Fourier transform infrared spectrometer are shown in FIG. From comparison of each spectrum, it was confirmed that the peak of (1) was C = O stretching, the peak of (2) was C = S stretching, and the peak of (3) was C = S stretching. It was suggested that the BQ / Th polymer has a polymerized structure containing BQ and Th.

Measurement of mass reduction by thermogravimetry (TG-DTA) Next, as shown in FIG. 15, according to the TG graph, the mass reduction start temperature of the BQ / Th polymer is higher than 400 ° C. of the BQ / Py polymer. Although it is low, it exceeds 300 ° C., and the graph of BQ / Th polymer is similar to that of BQ / Py polymer. By combining the results of TG and IR, it was confirmed that the BQ / Th polymer was polymerized. FIG. 16 shows a partial structural formula of the BQ / Th polymer.

Elemental analysisNext , the results of elemental analysis of BQ / Th polymer were as follows: C = 62 wt%, H = 2.98 wt%, N = 2.27 wt%, S = 4.894 wt%, O = 27.856 wt%. there were. The presence of S and N is also confirmed from the results of elemental analysis. It can be seen from the results of TG that the polymer is polymerized. On the other hand, since the weight of S is small compared to the estimated structure assuming only the Diels-Alder reaction and the formation of CC bond, not only the bond of Th and BQ but also the polymer that includes the bond between BQs Can be considered.

Example 8 Synthesis of BQ / Pyr polymer (synthesis method)
In Example 1, a copolymer consisting of 1,4-benzoquinone and pyridine (hereinafter referred to as BQ / Pyr polymer) was used under the same conditions except that pyrrole (Py) was replaced with pyridine (Pyr) having the same substance amount. Got. The ratio of BQ to Pyr was 30 nmol: 30 nmol.

The obtained BQ / Pyr polymer was subjected to “2. Measurement of mass reduction by thermogravimetry (TG-DTA)” and “3. Elemental analysis” in the experimental procedure.

(result)
Measurement of mass reduction by thermogravimetry (TG-DTA) As shown in FIG. 15, according to the TG graph, the mass reduction start temperature of the BQ / Pyr polymer is lower than 400 ° C. of the BQ / Py polymer, Above 300 ° C, the graph of BQ / Pyr polymer is similar to BQ / Py polymer. From the results of this TG, it was confirmed that the BQ / Pyr polymer was polymerized.

Elemental Analysis Next, the results of elemental analysis of the BQ / Pyr polymer were C = 65.76 wt%, H = 3.506 wt%, N = 0.974 wt%, and O = 29.76 wt% in weight ratio. The presence of N is confirmed from the results of elemental analysis, and it is understood that the structure incorporates pyridine. It can be seen from the results of TG that the polymer is polymerized. On the other hand, since the weight of N is smaller than when assuming only the Diels-Alder reaction and the formation of CC bond, it is considered to polymerize not only the bond of Pyr and BQ but also the bond between BQs. It is done.

Example 9 Synthesis of BQ / DVB polymer
(Synthesis method)
1,4-benzoquinone (BQ) powder (purity 98.0%, Tokyo Chemical Industry Co., Ltd.) 4.32 g and 1,4-divinylbenzene (DVB) liquid (purity> 50%, Tokyo Chemical Industry Co., Ltd.) 1.14 cm ³ Were placed in a sealed container and left in a 110 ° C. constant temperature bath for 48 hours to recover the crude product. Suction filtration was used to remove unreacted monomer molecules from the crude product and washed with acetone. Next, in order to remove molecules with low polymerization degree, add 25 cm ³ of N-methyl-2-pyrrolidone (NMP) (purity 99.0%, Wako Pure Chemical Industries, Ltd.) and recovered material to a Teflon (registered trademark) centrifuge tube. Centrifugation was carried out at 13500 rpm for 10 minutes to collect the precipitate. Thereafter, in order to remove residual NMP, it was vacuum-dried at 210 ° C. for 16 hours to obtain a copolymer composed of 1,4-benzoquinone and 1,4-divinylbenzene (hereinafter referred to as BQ / DVB polymer).

(result)
Structural Analysis by Fourier Transform Infrared Spectroscopy (FTIR) FIG. 17 shows the IR measurement result of the purified BQ / DVB polymer. The peak near 3400 cm ^{-1 in} (1) is OH stretching vibration, the peak near 1600 cm ^{-1 in} (2) is C = O stretching vibration, and the peak near 1400 cm ^{-1 in} (3) is carbon aromatic ring stretching. Attributed to vibration.

Since the peaks of C = O stretching vibration and carbon aromatic ring stretching vibration were confirmed, the copolymer is considered to have a molecular structure in which a quinone moiety is incorporated.

From the result of changing the ratio of BQ and DVB during polymerization (not shown), in the subsequent experiments, the ratio of BQ / DVB polymer was 5 nmol: 1 nmol.

Measurement of mass reduction by thermogravimetry (TG-DTA) As shown in FIG. 18, according to the TG graph, the mass reduction start temperature of the BQ / DVB polymer is 400 ° C., which is higher than that of the BQ standard. It was found that mass reduction began at temperature. From this, it was confirmed that the BQ / DVB polymer was polymerized.

The results of elemental analysis of the elemental analysis BQ / DVB polymer were C = 74.32 wt%, H = 3.87 wt%, N = 0.00 wt%, and O = 21.81 wt% in weight ratio. The weight ratio of O is described as a calculated value when it is assumed that the obtained product contains only C, H, N, and O. From this, when the molecular structure is estimated as the following formula (XIX), the ratio of the molecular structure of p: q: r: s: t: u is 2: 6: 2: 2: 0: 0, As a structure containing 3H ₂ O.

Analysis of layered structure and mass spectrometry using X-ray diffractometer (XRD) FIG. 19 shows the results of XRD measurement, and FIG. 20 shows the results of mass spectrometry.

From this, it was found that the molecular weight of the BQ / DVB polymer is about 700 to 4000. A molecular model was prepared from the molecular structure and molecular weight. The model is shown in FIG. From this model, it is considered that the BQ / DVB polymer molecules have a linear and branched structure.

Example 10 Synthesis of BQ / DVB nanoflakes (synthesis method)
30 mg of the BQ / DVB polymer obtained in Example 9 was placed in 20 cm ³ of benzyl alcohol, sonicated for 90 minutes, and then stirred at 60 ° C. for 48 hours to obtain a dispersion. . This dispersion was used as a BQ / DVB nanoflakes suspension.

(result)
Observation by Transmission Electron Microscope (TEM) and Atomic Force Microscope (AFM) FIG. 22 shows TEM images of BQ / DVB nanoflakes ( FIGS. 22A and 22B). When the average length of the nanoflakes observed by TEM was measured (FIG. 22 (c)), it was about 50 nm.

Fig. 23 shows an AFM image of BQ / DVB nanoflakes. The average thickness of BQ / DVB nanoflakes was about 15 nm.

Cyclic Voltammetry Next, FIG. 24 shows the results of cyclic voltammetry of BQ / DVB polymer and BQ / DVB nanoflakes.

From this, the oxidation peak of the BQ / DVB polymer was around 0.8 V, and the oxidation peak of the BQ / DVB nanoflakes was around 0.6 V, indicating a decrease in overvoltage. In addition, the capacitance of BQ / DVB nanoflakes was improved to 209.0 mA h g ^-1 compared to the capacitance of BQ / DVB polymer of 70.0 mA h g ^-1 .

Charge / Discharge Measurement FIG. 25 shows the results of charge / discharge measurement of BQ / DVB nanoflakes. This showed a capacitance of 162 mA h g ^-1 at 0.2 A g ^-1 . In addition, a plateau derived from the quinone site was observed in the vicinity of 0.2 to 0.6 V from the charge / discharge curve, which was consistent with the cyclic voltammetry results of FIG.

Example 11 Synthesis of TCNQ / DVB Polymer (Synthesis Method)
In Example 1, the same conditions were used except that 1,4-benzoquinone (BQ) was replaced with 7, 7, 8, 8-tetracyanoquinodimethane (TCNQ), and 7, 7, 8, 8-tetracyanoquino was used. A copolymer composed of dimethane and 1,4-divinylbenzene (hereinafter referred to as TCNQ / DVB polymer) was obtained. The ratio of TCNQ to DVB was 5 mmol: 1 mmol.

The obtained TCNQ / DVB polymer was subjected to the experimental procedures “1. Structural analysis by Fourier transform infrared spectroscopy (FTIR)” to “3. Elemental analysis”.

(result)
Structural Analysis by Fourier Transform Infrared Spectroscopy (FTIR) First, the IR spectrum of the TCNQ / DVB polymer measured with a Fourier transform infrared spectrometer is shown in FIG. From the comparison of each spectrum, the peak of (1) was confirmed to be NH stretching and the peak of (2) was confirmed to be NH deflection. It was suggested that the TCNQ / DVB polymer has a polymerized structure incorporating TCNQ and DVB. In addition, it is considered that the peak of the CN triple bond disappeared because the cyano group participated in the cycloaddition reaction.

Measurement of weight loss by thermogravimetric measuring apparatus (TG-DTA) Next, as shown in FIG. 27, according to the TG graph, weight loss initiation temperature of the TCNQ / DVB polymers, TCNQ single weight loss initiation temperature 300 ° C. Is over. Combining the results of TG and IR, it was confirmed that the TCNQ / DVB polymer was polymerized. FIG. 28 shows a partial structural formula of the TCNQ / DVB polymer.
Elemental Analysis Next, the results of elemental analysis of the TCNQ / DVB polymer were C = 74.4 wt%, H = 4.99 wt%, N = 11.1 wt%, and O = 9.15 wt% in weight ratio. The presence of N is also confirmed from the results of elemental analysis. It can be seen from the results of TG that the polymer is polymerized.

Claims (21)

1. A benzoquinone which may have a substituent or a monocyclic aromatic hydrocarbon which has an electron-withdrawing substituent and a heterocyclic aromatic compound which may have a substituent, causing a cycloaddition reaction with each other Alternatively, a polymer containing a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as substituents as a structural unit or a reduced product thereof.
2. A benzoquinone which may have a substituent, or an electron-withdrawing substituent which is substituted with at least one of the carbons at the 2nd and 3rd positions, and the carbon at the 5th and 6th positions And a monocyclic aromatic hydrocarbon which may have a substituent and a monocyclic aromatic hydrocarbon having an alkenyl group as a substituent at the para position as a structural unit A polymer or a reduced form thereof.
3. The heterocyclic aromatic compound which may have the substituent or the monocyclic aromatic hydrocarbon which has a plurality of alkenyl groups as a substituent is a heterocyclic aromatic compound which may have the substituent. A portion in which the monocyclic aromatic hydrocarbon having the benzoquinone or electron-withdrawing substituent and the heterocyclic aromatic compound are carbon-carbon bonded, and two molecules of the benzoquinone or electron-withdrawing group. The polymer according to claim 1 or 2, or a reduced product thereof, having a moiety in which a monocyclic aromatic hydrocarbon having a functional substituent and one molecule of the heterocyclic aromatic compound form a condensed ring.
4. The heterocyclic aromatic compound which may have a substituent or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as a substituent is an azole, pyridine, pyrimidine or pyridazine which may have a substituent The polymer according to any one of claims 1 to 4, or a reduced product thereof.
5. The heterocyclic aromatic compound which may have a substituent or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as a substituent is pyrrole, pyridine, pyridazine or thiazole. The polymer according to claim 1, or a reduced product thereof.
6. The polymer according to any one of claims 1 to 5, comprising any part represented by the following formulas (i) to (iv):
   

   

   (In the formula, Cy1 is a 5-membered nitrogen-containing heterocycle,
   Cy2 is a monocyclic aromatic hydrocarbon,
   Cy3 is a 6-membered nitrogen-containing heterocycle,
   A is an electron-withdrawing substituent selected from vinyl group, acyl group, cyano group, halogen group, nitro group, hydroxy group; alkenyl substituted by halogen group, cyano group, nitro group, or hydroxy group: Yes,
   The bond between A and Cy is a single bond or a double bond. )
7. The polymer according to any one of claims 1 to 6, comprising a moiety represented by the following formula (I) or formula (II).
   

   

   
8. The polymer of Claim 7 containing the part represented by following formula (III) or (IV).
   

   

   (Where
   R ₁ and R ₂ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, alkyl group, or pyrrolyl group, or R ₁ and R ₂ are both an adjacent pyrrole group and an adjacent benzoquinolyl group. Forming a condensed ring with the group,
   R ₃ and R ₄ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, alkyl group, or pyrrolyl group, or R ₃ and R ₄ together are an adjacent pyrrole group and an adjacent benzoquinolyl group. Forming a condensed ring with the group,
   However, when R ₁ and R ₂ , or R ₃ and R ₄ form a condensed ring, either one of them forms a condensed ring,
   R ₅ , R ₆ and R ₇ are each independently hydrogen, halogen, hydroxy, an alkyl group, or a benzoquinolyl group. )
   

   

   (Where
   R ₁ and R ₂ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, alkyl group, or thiazolyl group, or R ₁ and R ₂ are both adjacent thiazolyl groups and adjacent benzoquinolyl groups. Forming a condensed ring with the group,
   R ₃ and R ₄ are each independently hydrogen, halogen, nitro, amide, thiol, hydroxy, alkyl group, or thiazolyl group, or R ₃ and R ₄ are both adjacent thiazolyl groups and adjacent benzoquinolyl groups. Forming a condensed ring with the group,
   However, when R ₁ and R ₂ , or R ₃ and R ₄ form a condensed ring, either one of them forms a condensed ring,
   R ₆ is hydrogen, halogen, hydroxy, an alkyl group, or a benzoquinolyl group. )
9. The polymer or reduced product thereof according to any one of claims 1 to 8, which comprises a moiety represented by the following formula (IX).
   

   

   (Where
   R ₁₅ , R ₁₇ , and R ₁₈ are each independently a hydrogen, halogen, nitro, amide, thiol, hydroxy, or alkyl group;
   R ₁₆ , R ₁₉ and R ₂₀ are each independently a hydrogen, halogen, hydroxy or alkyl group;
   R ₂₁ and R ₂₂ are each independently a hydrogen, halogen, hydroxy or alkyl group;
   k is an integer greater than or equal to 1,
   x is a real number from 0 to 100. )
10. The polymer or the reduced product thereof according to any one of claims 1 to 8, which comprises a moiety represented by the following formula (X).
    

    

    (Where
    R ₁₅ , R ₁₇ , and R ₁₈ are each independently a hydrogen, halogen, nitro, amide, thiol, hydroxy, or alkyl group;
    R ₁₆ , R ₁₉ and R ₂₀ are each independently a hydrogen, halogen, hydroxy or alkyl group;
    R ₂₁ and R ₂₂ are each independently a hydrogen, halogen, hydroxy or alkyl group;
    R ₂₃ , R ₂₅ , and R ₂₆ are each independently a hydrogen, halogen, nitro, amide, thiol, hydroxy, or alkyl group;
    R ₂₄ , R ₂₇ and R ₃₀ are each independently a hydrogen, halogen, hydroxy or alkyl group;
    R ₂₈ and R ₂₉ are each independently a hydrogen, halogen, hydroxy or alkyl group,
    m and n are each an integer of 1 or more,
    x is a real number from 0 to 100. )
11. A polymer containing a moiety represented by the formula (XI).
    

    

    (Where
    R ₁₅ , R ₁₇ , and R ₁₈ are each independently a hydrogen, halogen, nitro, amide, thiol, hydroxy, or alkyl group;
    R ₁₆ , R ₁₉ and R ₂₀ are each independently a hydrogen, halogen, hydroxy or alkyl group;
    R ₂₁ and R ₂₂ are each independently a hydrogen, halogen, hydroxy or alkyl group;
    n is an integer of 1 or more,
    x is a real number between 0 and 20)
12. The heterocyclic aromatic compound that may have a substituent or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as a substituent is a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as a substituent And
    The polymer or reduced product thereof according to claim 1 or 2, wherein the benzoquinone and the monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as substituents form a condensed ring.
13. The polymer according to claim 1, 2, or 12, wherein the heterocyclic aromatic compound which may have a substituent or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as a substituent is divinylbenzene. Its reductant.
14. The polymer according to claim 1, 2, 12, or 13, comprising a moiety represented by at least one of formulas (XII) to (XVII).
    

    
15. A sheet having a thickness of 0.2 nm to 2.0 nm comprising the polymer according to claim 1 extending in a planar shape.
16. A laminate in which a plurality of sheets according to claim 15 are laminated at an interlayer spacing of 0.2 nm to 2.0 nm.
17. A nanoflakes having a length of 1 to 1000 nm and a thickness of 1 to 100 nm comprising the polymer according to any one of claims 1 to 14.
18. A heteroaromatic compound having a substituent or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as a substituent, and a heterocycle having a substituent A method for producing a polymer, comprising polymerizing a cyclic aromatic compound or a monocyclic aromatic hydrocarbon having a plurality of alkenyl groups as substituents.
19. Use of the polymer according to any one of claims 1 to 14 as a coating material.
20. An electrode material comprising the polymer according to any one of claims 1 to 14.
21. The electrode material according to claim 20, which is an electrode active material or an electrode catalyst.

Images