JPS63317507A - Novel polymer and electrically active polymer derived therefrom - Google Patents

Abstract

PURPOSE:To obtain a novel substantially linear copolymer, having specific recurring units and high polymerization degree and capable of simultaneously exhibiting excellent electrochemical characteristics, mechanical strength and moldability and providing an electrically active polymer by doping with an electron acceptor. CONSTITUTION:A novel copolymer expressed by formula I (R is H, 1-20C hydrocarbon group, furyl, pyridyl or methoxyphenyl; n is 1-50; x is 2-1,000). The above-mentioned copolymer is obtained by, e.g. polycondensing a compound having a 3,10-phenoxazinediyl structure expressed by formula II as recurring units with an aldehyde expressed by the formula RCHO or polymer thereof in an organic solvent, such as ethyl ether or chloroform, at 0-200 deg.C using a catalyst, such as sulfuric acid. The copolymer expressed by formula I is doped with an electron acceptor, e.g. iodine or nitric acid, to afford an electrically active polymer capable of exhibiting high electrical activity and carrying out oxidative and reductive reaction with excellent repeatability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel polymer, and particularly to a novel conductive polymer and its precursor.

[Conventional technology]

As polymers used to form conductive polymers,
Polyacetylene, polyparaphenylene, polythiophene, polypyrrole, etc. are known. These polymers can be used as conductive polymers by doping them with certain compounds, but they have the disadvantage that they are easily degraded in the air and their electrical properties change. In addition, these conductive polymers have problems such as extremely poor processability due to poor meltability and solubility, which is a major obstacle in practical use. For example, as an application field of conductive polymers, it has been proposed to use the reversible redox properties of conductive polymers in electrodes for secondary batteries, but in most cases, the electrolyte solution of secondary batteries is However, they are physically or chemically unstable, and therefore cannot be expected to have stable repeated charging and discharging characteristics (cyclability), which is the basic performance required of secondary batteries. Furthermore, since the polymer skeleton of conductive polymers is composed of a rigid π-electron conjugated system, they are insoluble and infusible, which is a major obstacle to practical application. As a method to solve these problems, in US Pat. No. 4,505,844, λ1
An electroactive polymer obtained by doping an electron acceptor into a polymer having an 0-phenoxazinediyl structure kn repeating unit has been proposed.

[Problems that the invention attempts to solve]

However, the above-mentioned phenoxazine polymer is an oligomer with a low degree of polymerization, and lacks the mechanical strength and moldability that a polymer compound should have. When used as an electrode material, there is a problem that soluble components are eluted during repeated charging and discharging, and cyclability cannot be expected. In addition, in order to give the above-mentioned phenoxazine polymer good electrochemical properties as well as mechanical strength and moldability, it is necessary to obtain a polymer with a higher degree of polymerization (high polymer). It is difficult to obtain high molecular weight polymers by methods such as Grignard coupling, oxidative coupling, Friedel-Krach reaction, and electrolytic oxidative polymerization, which are commonly used as synthesis methods for aromatic compounds and polyheteroaromatics. Even if the reaction conditions are made more severe, it will not only induce dissimilar bonds and crosslinking reactions, making it impossible to obtain a polymer compound, but it will also lose its processability, which is one of the advantages and disadvantages of polymer compounds, and become insoluble and infusible. The problem is that the polymer becomes inert.

[Means for solving problems]

The purpose of the invention is to solve the problems of the prior art.

That is, the present invention is based on the general formula l (wherein R is a hydrocarbon residue having 1 to 20 H1 carbon atoms, a furyl group, a pyridyl group, or a methoxyphenyl π, and n is 1 to 20 carbon atoms).
50° preferably from 2 to 30, X is from 2 to 1000,
Preferably #'i represents an integer from 2 to 500. ) and an electroactive polymer obtained by doping the copolymer with an electron acceptor.

The copolymer represented by the general formula (1) of the present invention comprises a compound having a 3,10-phenoxazinediyl structure represented by the general formula (II) as a repeating unit, and an aldehyde represented by the general formula (2) or It can be obtained by polycondensing the polymer.

RCHO song) As the compound represented by the general formula (n), a polymer having phenoxazine or a λ10-phenoxazinediyl structure as a repeating unit is used.

A polymer having a λ10-phenoxazinediyl structure represented by the general formula (It) as a repeating unit can be used, for example, by oxidation of permanganate, dichromate, etc. in acetone, pyridine, benzene, water, or a mixed solvent thereof. It can be synthesized using an agent. In addition, together with these oxidizing agents (iiiIt acid hydrogen tetraalkylammonium salt,
Phase transfer catalysts such as crown ethers may also be used.

As the aldehyde represented by the general formula, compounds in which R is hydrogen, a hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, or a furyl group, a pyridyl group, or a methoxyphenyl group are used; As a hydrogen residue,
Methyl group, ethyl group, n-propyl group, 1-propyl group, n-butyl group, l-butyl group, n-hexyl group or allyl group, and various aryl groups such as phenyl group, tolyl group, ethylphenyl group , aralkyl groups and derivatives thereof, etc. can be used. Representative examples of these aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, acrylaldehyde, cinnamaldehyde, anisaldehyde, nicotinaldehyde, and furfural.

In addition, a single polymer of aldehyde refers to a polymer obtained by self-condensing an aldehyde represented by the general formula (g) in a concentrated solution or condensing it in the presence of an acid catalyst. It represents a compound that is easily hydrolyzed to produce an aldehyde monomer under the reaction conditions used to synthesize the copolymer of the invention. Typical examples include paraformaldehyde, which is a polymer of formaldehyde, and paraaldehyde, which is a trimer of acetaldehyde.

Polycondensation of the compound represented by the general formula (10) and the aldehyde represented by the general formula (to) or its polymer is carried out using an acid or alkali catalyst at a temperature of 0°C to 200°C in an organic solvent in which both are soluble. Examples of acid catalysts include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as acidic acid, acetic acid, and propionic acid. Examples of preferable organic solvents include ethyl Ethers, ethers such as tetrahydrofuran and dioxane, chloroform,
Halogenated hydrocarbons such as dichloromethane and chlorobenzene, nitro compounds such as nitrobenzene, acetonitrile, propylene carbonate, dimethylformamide,
Examples include N-methylpyrrolidone. The reaction time is 1
The time can be appropriately selected from the range of minutes to 100 hours, preferably 5 minutes to 24 hours.

Through the above reaction, a substantially linear copolymer of the present invention having a high degree of polymerization can be obtained. The copolymer of the present invention includes dimethylformamide, N-methylpyrrolidone, nitrobenzene,
It is a thermoplastic resin that is soluble in solvents such as sulfuric acid, but insoluble in alcohol, chloroform, hydrocarbons, acetonitrile and propylene carbonate used in organic electrolyte batteries, and can be melted by heating. It has excellent processability and can be made into various molded bodies of arbitrary shapes.

When the copolymer of the present invention is doped with an electron acceptor as a dopant, it exhibits high electroactivity and can perform redox reactions with good repeatability. 1. In particular, even if the number of repetitions (cycles) of charging and discharging is significantly increased, elution occurs and cyclability decreases, as seen in the case of phenoxazine polymers. Extremely stable characteristics can be obtained without any

Examples of electron-accepting dopants include halogen compounds such as iodine, bromine, and hydrogen iodide, arsenic pentafluoride, phosphorus pentachloride, phosphorus pentafluoride, antimony pentafluoride, silicon tetrafluoride, aluminum chloride, and aluminum bromide. , metal halides such as aluminum fluoride, ferric chloride, protic acids such as sulfuric acid, nitric acid, chlorosulfonic acid, oxidizing agents such as sulfur trioxide, difluorosulfonyl peroxide, and tetracyanoquinodimethane. Examples include organic substances.

In addition, dopants that can be electrochemically doped include:
Halide anions of elements of the Va group such as PF, "', SbF, -1AsF@-, l1l such as BF4-
halide anion of an element of group a, 1-(Is)
, anion such as Br-1CI-, ClO
Examples include anions such as perchlorate anions such as 4-.

Furthermore, the copolymer of the present invention has the property that when doped with anions, the nitrogen atoms in the polymer become positively charged and stable, so it is stable against repeated oxidation-reduction and processing. It is used to construct various functional electrodes such as batteries by taking advantage of its good properties. That is, the copolymer of the present invention can be molded by dissolving it in a solvent, it can be molded by heating and melting it, or it can be molded by pressure using the copolymer as the main component, or by using a binder. The electrode can be formed into any shape. Examples of the binder include polytetrafluoroethylene, polyvinylidene heptadide, polyvinyl chloride, polyethylene, etc., but are not necessarily limited to these.

〔Effect of the invention〕

Since the copolymer of the present invention is linear, it has excellent processability and can be easily produced into various molded products. In addition, by doping this copolymer with an electron acceptor, it can exhibit high conductivity.Moreover, the doping is reversible and it has extremely high cyclability, making it highly conductive. Excellent as a polymer.

[Examples]' Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

Example 1° (Synthesis of phenoxazine oligomer) 3 equipped with a stirrer, dropping funnel and reflux condenser
Acetone 150- and phenoxazine 5.1f were placed in a 00-Mitsuro flask and stirred to dissolve the phenoxazine, and then cooled on ice. Then, a saturated acetone solution of potassium permanganate was added dropwise. After adding 10.52 tubes of potassium permanganate, the reaction was terminated, and the precipitate was filtered and washed with acetone. After air drying, the mixture was stirred in hot toluene, and insoluble manganese dioxide was separated by filtration. A gray crude phenoxazine oligomer powder was obtained by removing toluene from the filtrate under reduced pressure. The crude phenoxazine oligomer powder was dissolved in toluene again and purified by reprecipitation with methanol to obtain a purified phenoxazine oligomer of 3.3f.

The yield was 65 cm.

(Polycondensation of phenoxazine oligomer and formaldehyde) Add 0 of the above phenoxazine oligomer to a 50-trilo flask.
．． 30ff: and dissolved in 51ml/g of 1,4-dioxane. Several drops of concentrated sulfuric acid were added thereto, and 40 ml of a 371s formaldehyde aqueous solution was added dropwise, followed by heating and stirring at 80° C. for 1 hour to cause a reaction.

After the reaction, the reaction precipitate was filtered, washed with methanol, and then dried to obtain a green polymer 0.319. The obtained polymer was soluble in N-methylpyrrolidone and nitrobenzene, but insoluble in acetonitrile, propylene carbonate, dichloromethane, and hydrocarbons.

The results of measuring the infrared absorption spectrum are shown in FIG.

800 an-” and 870 cm-’1.2.4-
Absorption derived from trisubstituted benzene and absorption derived from 1,2-disubstituted benzene of 750crIM-1 were observed, and the other absorption positions matched the infrared absorption spectrum of phenoxazine oligomer, indicating that aldehyde It was found that polycondensation with the phenoxazine oligomer occurred at the 3-position of the terminal end of the phenoxazine oligomer.

Reference Example 1゜The copolymer obtained in Example 1 was crimped onto a platinum mesh to prepare a measurement electrode. 0.07 mol/1 n as electrolyte
-C4H@NClO4 solution in acetonitrile, a platinum plate as a counter electrode, and Ag/AgN0 as a reference electrode. Cyclic voltammetry of the above electrode was measured in a dry nitrogen atmosphere using the electrode. Sweep speed is 50 mV/see
was used. The results obtained are shown in FIG. .

There was no change even after dozens of redox cycles, indicating reversible and extremely stable redox behavior. The redox potential is 0.
46VVS-Ag/AgNOs fc.

Example λ A reaction was carried out in the same manner as in Example 1, except that the phenoxazine oligomer and the above phenoxazine were used. phenoxazine 0.70f,
37% formaldehyde aqueous solution, 0.70f, 1.4-
Dioxane 15- was used and the reaction was carried out at room temperature for 30 minutes. After purification, a polycondensation reaction product with a concentration of 0.759 was obtained.

Reference Example 2 Cyclic voltammetry was performed in the same manner as in Reference Example 1, except that the copolymer obtained in Example 2 was used as the polycondensation reaction product of phenoxazine oligomer and formaldehyde in Reference Example 1. Measurements were made. The results obtained are shown in FIG. It showed reversible and extremely stable redox behavior.

Redox potential is 0.36 V VS Ag/Ag
It was NOs.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the copolymer obtained in Example 1, and FIGS. 2 and 3 show the results of cyclic voltammetry of the electrodes in Reference Examples 1 and 2, respectively.

Claims (1)

[Claims] 1. General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R represents H, a hydrocarbon residue having 1 to 20 carbon atoms, a furyl group, a pyridyl group, or a methoxyphenyl group. ,n
represents an integer of 1 to 50, and x represents an integer of 2 to 1000. )
A copolymer represented by 2. General formulas ▲ Numerical formulas, chemical formulas, tables, etc.
An integer of 50, x represents an integer of 2 to 1000. ) An electroactive polymer obtained by doping a copolymer represented by the formula with an electron acceptor.