JP3455891B2 - Conductive substances and their synthesis - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention has excellent heat resistance,
N, which is soluble in water or organic solvent, can control depolarization degree, electrochemical redox potential, shows clear color change by chemical / electrochemical redox, and is conductive by itself -Oxidized poly (nitrogen-containing condensed heterocycle) polymer, its production method and use.

[0002]

2. Description of the Related Art Poly (arylene) having a structure in which aromatic rings are continuously bonded, particularly poly (arylene) having a π-conjugated system continuous along a main chain [eg, poly (p-phenylene), poly ( 2,5-thienylene), poly (1,
4-naphthalenediyl)] generally has excellent heat resistance. In addition, the adducts of these poly (arylene) with electron acceptors (AsF ₅ etc.) and electron donors (lithium, sodium etc.) are electrically conductive and undergo reversible color change by electrochemical redox. Yes (electrochromic)
It is known to have properties that can be used as a display material [eg, "Polymer", Vol. 38, page 1080 (1989)]. Further, a group having a continuous π-conjugated system along the main chain and comprising a hetero six-membered ring unit, for example, 2,
A conductive substance produced by reducing a polymer having a 5-pyridinediyl group as a repeating constitutional unit is disclosed in JP-A-1-210420.
No., poly (quinolinediyl) consisting of fused heterocyclic units
And poly (isoquinolinediyl) polymer
70565, and quaternized poly (quinolinediyl) and poly (isoquinolinediyl) polymers are disclosed in JP-A-6-5.
6972. However, most of the poly (arylene) s proposed hitherto have low solubility in water or an organic solvent and are often infusible, so that their usages are limited, and they are useful for extracting their characteristic functions. It is a problem. Further, regarding the above-mentioned poly (arylene), by devising the molecular structure, development of a substance having characteristics not found in conventional poly (arylene) is desired. For example, conventional poly (arylene)
If it is possible to obtain poly (arylene) having an oxidation / reduction potential different from or exhibiting a different color change (electrochromic phenomenon), a conventional electrochromic display material [eg, “applied physics”,
56, 1433 (1987)], and an electrochromic display which uses a conventional polymer battery [eg, "electrochemistry and industrial physical chemistry" 54, 30 as an active material or electrode material].
6 (1986)], a polymer battery having characteristics different from the above is obtained. Further, in order to express the conductivity of poly (arylene) s, it is usually necessary to perform oxidation (p doping) or reduction (n doping) of poly (arylene) s in a neutral state (“applied physics” described above). See the text in "Electrochemistry and Industrial Physical Chemistry"). For this oxidation / reduction, a corrosive oxidant such as iodine is used, the process is complicated, or a chemical reaction of poly (arylene) in which a dopant such as I ⁻ , ClO ₄ ⁻ or NR ₄ ⁺ is made conductive. ,
It has a defect that it may cause physical instability. Therefore, it has been desired to develop a material which does not have such a dopant and whose poly (arylene) or its derivative itself exhibits conductivity.

[0003]

Under these circumstances, the present invention is directed to poly (arylene) having a novel molecular structure.
It was completed as a result of earnest research to search for. The object of the present invention is to have excellent heat resistance, be soluble in water or an organic solvent, control the degree of depolarization, and control the electrochemical redox potential, and by chemical / electrochemical redox. Another object of the present invention is to provide a poly (arylene), which exhibits a clear color change and is electrically conductive by itself, and particularly an N-oxidized (nitrogen-containing condensed heterocycle) polymer. Another object of the present invention is to provide such a novel N-oxidized poly (nitrogen-containing condensed heterocycle) polymer with a molded product such as fiber, film, electrochromic device, active material or electrode of battery, semiconductor, n.
Type semiconductor, etc.

[0004]

The above-mentioned object is achieved by the following formula (1):

[Chemical 11] (In the formula, any two of a, b, c, d, e, f, g and h are carbon atoms involved in the bond between repeating units,
At least one represents an N → O group, the rest independently represent a CH group or a nitrogen atom, and the maximum total number of N → O groups contained in a, b, c, d is 2, and a nitrogen atom The maximum total number of N is 0, the maximum total number of N → O groups contained in e, f, g, and h is 2, the maximum total number of nitrogen atoms is 3, and the degree of polymerization n is at least Represents 5. ) An N-oxidized poly (nitrogen-containing condensed heterocycle) polymer containing a polymer chain represented by the following formula, and the following formula (2):

[Chemical 12] (In the formula, any two of a, b, c, d, e, f, g and h are carbon atoms involved in the bond between repeating units,
At least one represents an N → O group, the rest independently represent a CH group or a nitrogen atom, and the maximum total number of N → O groups contained in a, b, c, d is 2, and a nitrogen atom The maximum total number of N is 0, the maximum total number of N → O groups contained in e, f, g, and h is 2, the maximum total number of nitrogen atoms is 3, and o , P, q, r, s, t, u and v, any two of them represent a carbon atom involved in a bond between repeating units, and the rest each independently represent a CH group or a nitrogen atom, o , P, q, r, the maximum total number of nitrogen atoms contained is 3, and the maximum total number of nitrogen atoms contained in s, t, u, v is 3, and the degree of polymerization l + m is at least 5. Represent )) N-oxidized poly (nitrogen-containing condensed heterocycle) polymer containing a polymer chain represented by The polymer of the above formula (1) is a polymer mainly containing a repeating unit in which the nitrogen atom of the nitrogen-containing condensed heterocycle is oxidized, and the polymer of the formula (2) is a polymer containing the nitrogen-containing condensed heterocycle. A copolymer comprising a repeating unit in which a nitrogen atom is oxidized and a repeating unit in which a nitrogen atom of a nitrogen-containing condensed heterocycle is not oxidized, and these polymers further include a third repeating unit, For example, a repeating unit conventionally known as a repeating unit forming a π-conjugated polymer such as a (thiophene 2,5-diyl) unit can be introduced. In the copolymer of the formula (2), the repeating unit in which the nitrogen atom of the nitrogen-containing condensed heterocycle is oxidized and the repeating unit in which the nitrogen atom of the nitrogen-containing condensed heterocycle is not oxidized are randomly copolymerized. It is polymerized.

As a subgroup of the N-oxidized poly (nitrogen-containing condensed heterocycle) polymer represented by the above formula (1), the formula (1) is represented by the following formulas (1a), (1b-1), (1b
-2), (1c-1) or (1c-2):

[Chemical 13] (Wherein the degrees of polymerization n ₁ , n ₂ , n ₃ , n ₄ and n ₅ represent at least 5), N-oxidized poly (quinolinediyl), poly (quinoxalinediyl) or poly (naphthyridinediyl) There is coalescence. Further, as a subgroup of the N-oxidized poly (nitrogen-containing condensed heterocyclic) polymer represented by the above formula (2), the formula (2) is represented by the following formulas (2a), (2b-1), ( 2b-2), (2c-1)
Or (2c-2):

[Chemical 14] (In the formula, the degree of polymerization l ₁ + m ₁ , l ₂ + m ₂ , l ₃ + m ₃ ,
l ₄ + m ₄ and l ₅ + m ₅ represent at least 5. )
Are N-oxidized poly (quinolinediyl), poly (quinoxalinediyl) or poly (naphthyridinediyl) copolymers.

The degree of polymerization of the polymers of the groups of the above formulas (1) and (2) is 5 to 1000, preferably 5 to 500,
Particularly preferably, it is 10 to 250. If the degree of polymerization is less than 5, the polymer cannot exhibit a sufficient function.

The above-mentioned polymer of the present invention has the following formula (3):

[Chemical 15] (In the formula, o, p, q, r, s, t, u and v have the same meanings as described above, and the degree of polymerization x represents at least 5.)
A poly (nitrogen-containing condensed heterocycle) polymer containing a divalent group represented by the formula (3), particularly the following formula (3a) and formula (3)
b) or formula (3c):

[Chemical 16] (In the formula, the degrees of polymerization x ₁ , x ₂ and x ₃ represent at least 5.) Poly (quinolinediyl) or poly (quinoxalinediyl) containing a divalent group represented by the formula
Alternatively, a poly (naphthyridinediyl) polymer is reacted with a suitable peroxide such as peracetic acid (hydrogen peroxide solution and glacial acetic acid), persulfuric acid, m-chloroperbenzoic acid to N-oxide the ring nitrogen atom. Is manufactured by In this reaction, the peroxide used is not limited to the above-mentioned examples, and the formula (1) of the compound of the present invention can be prepared by devising the type, equivalent weight or reaction conditions of the peroxide used.
And formula (2), or formula (1a) and formula (2a), formula (1b)
-1) and formula (2b-1), formula (1b-2) and formula (2b-
2), Formula (1c-1), Formula (2c-1), Formula (1c-
2) and the formula (2c-2) can be separately manufactured.

As another method for producing the polymer of the present invention, the following formula (4):

[Chemical 17] (In the formula, X and Y each represent a halogen atom,
Of a, b, c, d, e, f, g and h, any two are carbon atoms bonded to the halogen atom, at least one is an N → O group, and the rest are each independently, N represents a CH group or a nitrogen atom and is contained in a, b, c, d →
The maximum total number of O groups is 2, the maximum total number of nitrogen atoms is 3, and the maximum total number of N → O groups contained in e, f, g, and h is 2, and the maximum number of nitrogen atoms is 2. Represents a maximum total of 3. ), A quinoline oxide, quinoxaline oxide, quinoxaline dioxide, 1,5-naphthyridine oxide, or 1,5-naphthyridine dioxide represented by the formula (4a) in which any two hydrogen atoms are replaced by halogen atoms. ), Formula (4b-1), formula (4
b-2), formula (4c-1) or formula (4c-2):

[Chemical 18] (In the formula, X and Y each represent a halogen atom.)
The method of reacting the dihalide derivative represented by with a zero-valent nickel compound can be mentioned. That is, it is obtained by adding an equimolar amount or more of a zero-valent nickel compound to the above dihalide derivative in an organic solvent, reacting it, and dehalogenating. A suitable reaction temperature is from room temperature to about 80 ° C., and the reaction is completed in about 24 hours.
As the organic solvent, for example, N, N-dimethylformamide, acetonitrile, toluene, tetrahydrofuran or the like can be applied. A zero-valent nickel compound takes a halogen from a halogenated aromatic compound and causes a coupling reaction between aromatic groups [eg, "synthesis".
(Synthesis), page 736 (1984)]. This reaction can be represented by reaction formula (A).

[Chemical 19] (Here, Ar and Ar 'are aromatic groups, X is a halogen atom, L is a neutral ligand, and NiLm is a zero-valent nickel compound.) When an aromatic compound having a halogen atom, that is, the above dihalide derivative is reacted with an equimolar or more zero-valent nickel compound, a polymer is obtained by the dehalogenation reaction shown in the reaction formulas (B) and (C). .

[Chemical 20] (Here, Y-Ar ″ -X represents the above dihalide derivative.) In the above-mentioned reaction, the zero-valent nickel compound is in the reaction system (so-called in situ) immediately before the polymerization reaction.
The synthesized product can be used as it is, or the one synthesized and isolated in advance can be used. The zero-valent nickel compound is, for example, a nickel complex produced by a reduction reaction or a ligand exchange reaction in the presence of a neutral ligand, and the neutral ligand thereof is 1,5-cyclooctadiene, 2,2'-bipyridine, triphenylphosphine, etc. can be illustrated.

Further, the polymer of the present invention has the formula (4) in which any two hydrogen atoms of a nitrogen-containing condensed heterocyclic compound in which a nitrogen atom in the ring is N-oxidized is substituted with a halogen atom:

[Chemical 21] (In the formula, X and Y each represent a halogen atom,
Of a, b, c, d, e, f, g and h, any two are carbon atoms bonded to the halogen atom, at least one is an N → O group, and the rest are each independently, N represents a CH group or a nitrogen atom and is contained in a, b, c, d →
The maximum total number of O groups is 2, the maximum total number of nitrogen atoms is 3, and the maximum total number of N → O groups contained in e, f, g, and h is 2, and the maximum number of nitrogen atoms is 2. Represents a maximum total of 3. ), A quinoline oxide, quinoxaline oxide, quinoxaline dioxide, 1,5-naphthyridine oxide, or 1,5-naphthyridine dioxide represented by the formula (4a) in which any two hydrogen atoms are replaced by halogen atoms. ), Formula (4b-1), formula (4
b-2), formula (4c-1) or formula (4c-2):

[Chemical formula 22] (In the formula, X and Y each represent a halogen atom.)
It can also be produced by electrolytically reducing the dihalide derivative represented by: in the presence of a nickel compound.
That is, when the dihalide derivative is electrolytically reduced in the presence of a divalent nickel compound, an N-oxidized poly (nitrogen-containing condensed heterocycle) polymer can be obtained by the dehalogenation reaction. This reaction can be represented by reaction formula (D), reaction formula (E), reaction formula (F) and reaction formula (G).

[Chemical formula 23] (Here, Y-Ar "-X represents the above dihalide derivative.) If a divalent nickel compound is electrolytically reduced in an electrolytic cell, a zero-ized nickel compound is produced. Therefore, it has two halogen atoms in the molecule. When an aromatic compound, that is, the above dihalide derivative is electrolytically reduced in the presence of a divalent nickel compound, a polymer is obtained by the formation of a zero-valent nickel compound and the reaction involving Ni ⁰ Lm that is subsequently generated in the reaction system. Usually, it can be carried out under the following conditions: That is, for example, N, N-dimethylformamide or acetonitrile is used as a solvent, and tetraethylammonium perchlorate or tetraethylammonium tetrafluoroborate is dissolved as a supporting electrolyte to prepare an electrolytic solution. A platinum electrode, an ITO transparent electrode, or a graphite electrode is used for The dihalide derivative and the divalent nickel complex are dissolved in an electrolytic solution, and the reduction potential of the divalent nickel compound [for example, tris (2,2-bipyridine) nickel salt is -1.7 V (against Ag / Ag ⁺⁾ . )], The nickel compound may be one which is previously synthesized and isolated before carrying out the polymerization reaction, or one which is directly synthesized from nickel or a nickel compound in an electrolytic cell and used as it is. Examples of such nickel compounds include tris (2,2′-bipyridine) nickel bromide [Ni (bpy) ₃ Br ₂ ], dibromobis (triphenylphosphine) nickel [NiBr ₂ (P
Ph ₃ ) ₂ ] and the like.

Formula (1) or Formula (2) of the present invention:

[Chemical formula 24] (In the formula, a, b, c, d, e, f, g and h have the same meanings as described above, and the degree of polymerization n represents at least 5.)

[Chemical 25] (Where a, b, c, d, e, f, g, h, o, p,
q, r, s, t, u and v have the same meanings as described above, and the degree of polymerization 1 + m represents at least 5. ), The N-oxidized poly (nitrogen-containing condensed heterocycle) polymer is represented by formula (5) and formula (6):

[Chemical formula 26] (In the formula, a, b, c, d, e, f, g and h have the same meanings as described above.)

[Chemical 27] (Wherein, o, p, q, r, s, t, u and v have the same meanings as described above), but the present invention is not limited thereto. Formula (5):

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chemical 34]

[Chemical 35]

[Chemical 36]

[Chemical 37]

[Chemical 38]

[Chemical Formula 39]

[Chemical 40]

[Chemical 41]

[Chemical 42]

[Chemical 43]

[Chemical 44] Formula (6):

[Chemical formula 45]

[Chemical formula 46]

[Chemical 47]

[Chemical 48]

[Chemical 49]

[Chemical 50]

[Chemical 51]

[Chemical 52]

[Chemical 53]

The N-oxidized poly (nitrogen-containing condensed heterocycle) polymer, which is the compound of the present invention, has the formula (7) as an example.
And a structure having a resonance structure as shown by the formula (8) and a quinoid type bond is formed when the adjacent units are considered, and such a resonance structure spreads throughout the polymer along the π-conjugated system. It is thought that The change in the main chain structure generated by the quinoid structure is similar to the change in the structure during the doping reaction.

[Chemical 54]

The polymer of the present invention utilizes its excellent properties to make a fiber or film, an electrochromic device,
It can be used as an n-type semiconductor by being applied to a semiconductor, an active material of a battery or an electrode and exhibiting conductivity itself, and further reducing the compound of the present invention by a reducing agent or electrochemical doping. In addition, a compound such as a heat stabilizer, a light stabilizer, a filler or a reinforcing agent can be appropriately added to the polymer of the present invention when forming a fiber, film or other molded article.

[0013]

EXAMPLES The present invention will now be described more specifically and in detail using examples, but the present invention is not limited to these. Example 1 Synthesis of poly (quinoline-2,6-diyl) polymer Under a nitrogen atmosphere, 30 ml of N, N-dimethylformamide was added to 0.67 g (2.43 mmol) of bis (1,5-cyclooctadiene) nickel. Further, 0.35 ml of 1,5-cyclooctadiene, 0.30 g (1.92 mmol) of 2,2′-bipyridine and 0.32 g (1.59 mmol) of 2,6-dichloroquinoline were added, and 60
The mixture was heated and stirred at 48 ° C for 48 hours. The generated polymer is treated twice with aqueous ammonia, three times with an aqueous solution of ethylenediaminetetraacetic acid,
It was washed twice with aqueous ammonia, once with water and once with methanol, and dried under reduced pressure. Formula (3a-A):

[Chemical 55] (In the formula, x ₁ a represents the degree of polymerization.) The molecular weight (M
A yellow poly (quinoline-2,6-diyl) polymer having a w) of 15,000 and a degree of polymerization of 118 was obtained in a yield of 99%. Poly (quinoline-1-oxide-2,6-diyl) polymerization
Synthesis of Body 100 mg of poly (quinoline-2,6-diyl) polymer was suspended in 20 ml of glacial acetic acid, 8 ml of 30% aqueous hydrogen peroxide was added dropwise at room temperature, and the mixture was stirred at 60 ° C. for 3 days. After cooling, the orange solid formed was filtered under reduced pressure, and the solid obtained was washed successively with aqueous sodium hydroxide solution, aqueous hydrochloric acid solution, and then with water, and dried under reduced pressure to give an ocher powder. The yield of the poly (quinoline-1-oxide-2,6-diyl) polymer represented by the following formula (1a-A) is 21%.
Got with. It is considered that the reason for the low yield is that part of the yield was lost during the washing process when the polymer was purified due to the improvement in solubility described later.

[Chemical 56] (In the formula, n ₁ a represents the degree of polymerization.) The elemental analysis value of the polymer represented by the formula (1a-A) is carbon 7
1.0%, 3.7% hydrogen, 9.2% nitrogen, and the following formula containing 0.49 molecule of water per monomer unit:

[Chemical 57] A polymer having a structural unit of (calculated value: carbon 71.1%, hydrogen 4.0%, nitrogen 9.2%, oxygen 15.7%),
It was shown that N-oxidation progressed almost 100%. The degree of polymerization of the polymer is 118. Formula (1a-A)
The infrared absorption spectrum (IR spectrum, KBr pellet method) and the ultraviolet-visible absorption spectrum (UV spectrum, in a formic acid solution) of the compound are shown in comparison with the formula (3a-A).
Absorption by the quinoline skeleton at 00 cm ^-1 became slightly broad, and the absorption intensity also changed. Moreover, absorption derived from N- oxides in the vicinity of 1240 cm ^-1 is broad absorption due to water which is added to the polymer in the vicinity of 1650 cm ^-1 were observed respectively. On the other hand, in the UV spectrum, the formula (1
The maximum absorption wavelength indicated by a-A) is observed at 407 nm,
When this value was compared with the maximum absorption wavelength represented by the formula (3a-A), the maximum absorption wavelength was shifted to the shorter wavelength side by about 30 nm due to N-oxidation. Solubility of the polymer represented by the formula (1a-A) in various solvents was determined as follows: polymer 1 mg, solvent 1
When studied at room temperature using ml, the polymer was found to be water, aqueous sodium hydroxide solution, formic acid, sulfuric acid, N, N-dimethylformamide (DMF), N-methylpyrrolidone (NM
P), a polymer represented by the formula (3a-A), which is soluble in dimethylsulfoxide (DMSO) and the like (which is soluble in formic acid and sulfuric acid, but is a common organic solvent such as DMF, NMP and DMSO). The solubility was improved as compared with (insoluble).

Example 2 Synthesis of poly (naphthyridine-2,6-diyl) polymer N, N-dimethylformamide was added to 0.18 g (0.65 mmol) of bis (1,5-cyclooctadiene) nickel under a nitrogen atmosphere. 12 ml was added, and 0.14 ml of 1,5-cyclooctadiene, 0.11 g (0.72 mmol) of 2,2′-bipyridine and 0.11 g (0.53 mmo) of 2,6-dichloro-1,5-naphthyridine.
1) was added, and the mixture was heated with stirring at 60 ° C. for 48 hours. The polymer produced was washed in the same manner as in Example 1. The following formula (3c
-A):

[Chemical 58] A yellow poly (naphthyridine-2,6-diyl) polymer represented by the formula (wherein x ₃ a represents the degree of polymerization) was obtained at a yield of 97%. According to halogen analysis (0.3%), the polymer has a molecular weight of 23,700 and a degree of polymerization of 185. Poly (naphthyridine-1,5-dioxide-2,6-di
Synthesis of poly (naphthylidine-2,6-diyl) polymer 70 mg
Was suspended in 20 ml of glacial acetic acid, 8 ml of 30% aqueous hydrogen peroxide was added dropwise at room temperature, and the mixture was stirred at 60 ° C. for 3 days. After standing to cool, the formed orange solid was filtered under reduced pressure, and the solid obtained was washed successively with aqueous sodium hydroxide solution, aqueous hydrochloric acid solution, and then with water, and dried under reduced pressure to give a reddish brown powder. A poly (naphthyridine-1,5-dioxide-2,6-diyl) polymer represented by the formula (1c-2-A) was obtained in a yield of 33%.

[Chemical 59] (In the formula, n ₅ a represents the degree of polymerization.) Elemental analysis values of the polymer represented by the formula (1c-2-A) are as follows: carbon 56.3%, hydrogen 2.9%, nitrogen 16.4%. Represents
The following formula containing 0.41 molecule of water per monomer unit:

[Chemical 60] (Calculated value: carbon 57.4%, hydrogen 2.9%, nitrogen 16.7%, oxygen 23.0%) having N as a constitutional unit, and N-oxidation progresses almost 100%. I showed that. The degree of polymerization of the polymer is 185. Formula (1c-
2-A) infrared absorption spectrum (IR spectrum, KB
(r-pellet method) and the characteristics in the ultraviolet-visible absorption spectrum (UV spectrum, in formic acid solution) are represented by formula (3c-A).
When compared with, the IR spectrum shows 1400.
Absorption by the 1,5-naphthyridine skeleton at -1600 cm ^-1 became slightly broad, and the absorption intensity also changed. Also,
Absorption derived from N-oxide near 1237 cm ^-1
Broad absorption due to water added to the polymer was observed around 1600-1700 cm ^-1 . On the other hand, U
In the V spectrum, the maximum absorption wavelength represented by the formula (1c-2-A) is observed at 404 nm, and this value is calculated by the formula (3c-A).
Compared with the maximum absorption wavelength indicated by A), the maximum absorption wavelength was shifted to the shorter wavelength side by about 35 nm due to N-oxidation.

Example 3 The electrical conductivity of the poly (quinoline-1-oxide-2,6-diyl) polymer represented by the formula (1a-A) obtained in Example 1 was measured by applying pressure to the polymer. Pellets were satisfactorily pressure-molded by a molding machine, and then cut into a rectangle, and fixed between two platinum electrodes with a carbon paste as shown in FIG. 1 and measured (two-terminal method). The lengths of a, b, c (cm) in FIG. 1 were measured, the resistance value R (Ω) was measured, and the electric conductivity was calculated by the following formula. σ [Scm ⁻¹ ] = c / (abR) As a result, the polymer shows an electrical conductivity of 2.3 × 10 ⁻⁶ σ / Scm ⁻¹ , and is a polymer represented by the formula (3a-A). In comparison with the electric conductivity (4.0 × 10 ^-10 σ / Scm ^-1 ), the electric conductivity was increased by about 4 digits. Moreover, the cyclic voltagram (CV) of the formula (1a-A) cast on a platinum electrode with formic acid was measured (FIG. 2). The peak potential due to cation doping- _dedoping is E _Pc =
-2.31V, E _Pa = -2.00V (Ag / A for both
relative to g ⁺ ). The doping changed the color of the polymer from yellow to purple.

Example 4 The electric conductivity of the poly (naphthyridine-1,5-dioxide-2,6-diyl) polymer represented by the formula (1c-2-A) obtained in Example 2 was measured. The measurement was performed in the same manner as in 3. As a result, the polymer was 3.2 × 10 ⁻⁶ σ / Scm.
^-1 shows an electric conductivity of ^-1 , which is about 3 digits in comparison with the electric conductivity (1.1 × 10 ^-9 σ / Scm ^-1 ) of the polymer represented by the formula (3c-A). Rose.

[0017]

INDUSTRIAL APPLICABILITY The novel N-oxidized poly (nitrogen-containing condensed heterocyclic) polymer of the present invention, particularly N-oxidized poly (quinolinediyl), poly (quinoxalinediyl) or poly (naphthyridinediyl) polymer is Since it has heat resistance and is soluble in water or organic solvents, its fields of use
The use is expanded, and dry molding into a fiber, a membrane, etc. is possible by using a solution obtained by dissolving them in these appropriate solvents.
In addition, it has excellent properties that conventional polyarylene does not have, such as the degree of depolarization and the electrochemical redox potential that can be controlled by its structure. Further, according to the method of the present invention, it is possible to synthesize a polymer in which the charge generated by N-oxidation is delocalized along the π-conjugated system. And, it was found that the polymer of the present invention exhibits conductivity by itself.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a two-terminal method resistance measuring device used in Examples 3 and 4.

2 is a cyclic voltagram in Example 3. FIG.

[Explanation of symbols]

a Vertical width of test piece (cm) b Height of test piece (cm) c Width of test piece (cm) d Platinum electrode

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI H01L 51/00 H01M 4/60 H01M 4/60 H01L 29/28 (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 61/12

Claims (15)

(57) [Claims] 1. The following formula (1): (In the formula, any two of a, b, c, d, e, f, g and h are carbon atoms involved in the bond between repeating units,
At least one represents an N → O group, the rest independently represent a CH group or a nitrogen atom, and the maximum total number of N → O groups contained in a, b, c, d is 2, and a nitrogen atom The maximum total number of N is 0, the maximum total number of N → O groups contained in e, f, g, and h is 2, the maximum total number of nitrogen atoms is 3, and the degree of polymerization n is at least Represents 5. ) An N-oxidized poly (nitrogen-containing condensed heterocycle) polymer containing a polymer chain represented by 2. The following formula (2): (In the formula, any two of a, b, c, d, e, f, g and h are carbon atoms involved in the bond between repeating units,
At least one represents an N → O group, the rest independently represent a CH group or a nitrogen atom, and the maximum total number of N → O groups contained in a, b, c, d is 2, and a nitrogen atom The maximum total number of N is 0, the maximum total number of N → O groups contained in e, f, g, and h is 2, the maximum total number of nitrogen atoms is 3, and o , P, q, r, s, t, u and v, any two of them represent a carbon atom involved in a bond between repeating units, and the rest each independently represent a CH group or a nitrogen atom, o , P, q, r, the maximum total number of nitrogen atoms contained is 3, and the maximum total number of nitrogen atoms contained in s, t, u, v is 3, and the degree of polymerization l + m is at least 5. Represent ) An N-oxidized poly (nitrogen-containing condensed heterocycle) polymer containing a polymer chain represented by 3. The formula (1) is expressed by the following formulas (1a) and (1b-
1), (1b-2), (1c-1) or (1c-
2): The N-oxidized poly (nitrogen-containing condensed heterocycle) polymer according to claim ₁ , wherein the degree of polymerization n ₁ , n ₂ , n ₃ , n ₄ and n ₅ is at least 5. 4. The formula (2) is expressed by the following formulas (2a) and (2b-
1), (2b-2), (2c-1) or (2c-
2): (In the formula, the degree of polymerization l ₁ + m ₁ , l ₂ + m ₂ , l ₃ + m ₃ ,
l ₄ + m ₄ and l ₅ + m ₅ represent at least 5. )
The N-oxidized poly (nitrogen-containing condensed heterocycle) polymer according to claim 2. 5. The following formula (3): (In the formula, o, p, q, r, s, t, u and v have the same meanings as described above, and the degree of polymerization x represents at least 5.)
5. A poly (nitrogen-containing condensed heterocycle) polymer containing a polymer chain represented by: is reacted with a peroxide to N-oxidize a nitrogen atom in the ring. N-oxidized poly (nitrogen-containing condensed heterocycle)
Polymer production method. 6. The following formula (4): (In the formula, X and Y each represent a halogen atom,
Of a, b, c, d, e, f, g and h, any two are carbon atoms bonded to the halogen atom, at least one is an N → O group, and the rest are each independently, N represents a CH group or a nitrogen atom and is contained in a, b, c, d →
The maximum total number of O groups is 2, the maximum total number of nitrogen atoms is 3, and the maximum total number of N → O groups contained in e, f, g, and h is 2, and the maximum number of nitrogen atoms is 2. Represents a maximum total of 3. 5. The method for producing an N-oxidized poly (nitrogen-containing condensed heterocycle) polymer according to any one of claims 1 to 4, wherein the dihalide derivative represented by the formula (4) is reacted with a nickel-zero compound. . 7. The following formula (4): (In the formula, X and Y each represent a halogen atom,
Of a, b, c, d, e, f, g and h, any two are carbon atoms bonded to the halogen atom, at least one is an N → O group, and the rest are each independently, N represents a CH group or a nitrogen atom and is contained in a, b, c, d →
The maximum total number of O groups is 2, the maximum total number of nitrogen atoms is 3, and the maximum total number of N → O groups contained in e, f, g, and h is 2, and the maximum number of nitrogen atoms is 2. Represents a maximum total of 3. 5. The dihalide derivative represented by the formula (4) is electrolytically reduced in the presence of a nickel compound, to obtain the N-oxidized poly (nitrogen-containing condensed heterocycle) polymer according to any one of claims 1 to 4. Manufacturing method. 8. The formula (3) is represented by the following formula (3a), (3b) or (3c): The method for producing an N-oxidized poly (nitrogen-containing condensed heterocycle) polymer according to claim 5, wherein the degrees of polymerization x ₁ , x ₂ and x ₃ represent at least 5. 9. Formula (4) is expressed by the following formulas (4a) and (4b-
1), (4b-2), formula (4c-1) or (4c-
2): (In the formula, X and Y each represent a halogen atom.)
7. The method for producing an N-oxidized poly (nitrogen-containing condensed heterocycle) polymer according to claim 6. 10. The equation (4) is calculated by the following equations (4a) and (4b).
-1), formula (4b-2), formula (4c-1) or (4c
-2): (In the formula, X and Y each represent a halogen atom.)
The method for producing an N-oxidized poly (nitrogen-containing condensed heterocycle) polymer according to claim 7. 11. A fiber or film comprising the N-oxidized poly (nitrogen-containing condensed heterocycle) polymer according to any one of claims 1 to 4. 12. An electrochromic device comprising the N-oxidized poly (nitrogen-containing condensed heterocycle) polymer according to any one of claims 1 to 4. 13. A battery active material or electrode comprising the N-oxidized poly (nitrogen-containing condensed heterocycle) polymer according to any one of claims 1 to 4. 14. A semiconductor comprising the N-oxidized poly (nitrogen-containing condensed heterocycle) polymer according to any one of claims 1 to 4. 15. An n-type semiconductor obtained by reducing the N-oxidized poly (nitrogen-containing condensed heterocycle) polymer according to any one of claims 1 to 4 by a reducing agent or electrochemical doping.