JPS6411207B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel conductive polymer that is extremely stable and exhibits extremely high conductivity through doping.

[Formula] and/or

[Formula] (In the formula, R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, X ^- represents an electrolyte ion, and y represents the proportion of anions per mole of monomer. n is a number from 0.01 to 1 representing the degree of polymerization, and n is a number from 5 to 500 representing the degree of polymerization). The polymers can be used in the electrical and electronic industry as electrodes, electrochromic display elements, solar cell production, electrical connections, electromagnetic radiation fixing and converting devices and reversible redox systems. Conventional Technology In recent years, there has been remarkable progress in reducing the weight, thickness, and size of electrical and electronic equipment, and there is a strong desire to make the various conductive material elements used in these devices lighter, thinner, and smaller. Not only are there things;
There are strong expectations for the emergence of new and better materials. In order to meet these demands or expectations, new conductive polymers are being actively developed. For example, polyacetylene exhibits a high electrical conductivity of 10 ² to ^{10 3} s/cm by doping with iodine or arsenic pentafluoride (for example, Synthetic Metals, Vol. 1, No. 2, p. 101 (1979/1980 It is not only being considered as an electrode material for secondary batteries due to its excellent charging and discharging characteristics (see 2010), but also as a material for solar cells because its light absorption characteristics are similar to those of sunlight. However, polyacetylene itself has the disadvantage of being easily oxidized, and doped polyacetylene is extremely sensitive to moisture.On the other hand, polythiophene has a conjugated structure similar to cis-type polyacetylene, and has a sulfur atom. Because of its unique electronic structure, it is being considered not only as a conductive material or a battery electrode material, but also as an electrochromic material that utilizes discoloration in a doped state. - AMDruy et al. used the fact that when 2,2'-bitinyl is electrochemically polymerized, the polymer changes color from blue to red in the oxidized state to the reduced state, and that this is reversible. It has been reported that it is useful as an electrochromic material (J. de Physics).
Physique) Vol. 44, No. 6, p. C3-595 (1983)). Purpose of the Invention As a result of intensive studies in view of the above points, the present inventors found that a polymer having an isothianaphthene structure is an extremely stable compound even in the air, and that it can be oxidized or reduced sufficiently stably to enable repeated use. The present invention has been achieved by discovering that the polymer is a novel polymer that can reversibly change color under certain conditions and has an electrical conductivity higher than 10 ^-2 s/cm that can easily be used with conventional doping agents. Structure and operation of the invention That is, the polymer according to the present invention has the general formula

[Formula] and/or

[Formula] (In the formula, R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, X ^- represents an anion of the electrolyte, and y represents the amount of anion per mole of monomer. It is a number from 0.01 to 1 that represents the ratio, and n
is a number from 5 to 500 representing the degree of polymerization), preferably an isothianaphthene structural unit represented by
It is a polymer containing 0.1 to 100 mol%. The polymer according to the present invention can be easily synthesized by various polymerization methods. For example, the following general formula The desired polymer can be obtained by reacting 1,3-dihydroisothianaphthene-2-oxide represented by the formula or its derivative in a solvent having dehydrating and oxidizing effects, such as concentrated sulfuric acid. Furthermore, for example, the general formula obtained by dehydrating and sublimating a compound represented by general formula a on alumina (1) Electrochemically polymerizing isothianaphthene or its derivative represented by (1) in the presence of an electrolyte in an aprotic solvent; (2) polymerizing a compound represented by general formula b in the presence or absence of a solvent; The desired polymer can be obtained by cationic polymerization and dehydrogenation by exposing the resulting dihydro polymer to an oxidizing agent, or (3) oxidative polymerization of a compound represented by general formula b. can. When copolymerizing both of these, a polymer containing any proportion (for example, 0.1 to 99.9 mol%) can be obtained. The solvent used in the polymerization of the monomers can be appropriately selected depending on the respective polymerization method, and is not particularly limited. Generally speaking, when the isothianaphthene represented by the general formula b or its derivative is electrochemically polymerized in the presence of an electrolyte, an aprotic solvent such as acetonitrile,
Examples include benzonitrile, propionitrile, dioxane, tetrahydrofuran, sulfolane, and propylene carbonate. In addition, in the case of cationic polymerization of isothianaphthene or its derivative represented by general formula b, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrafluorethane, nitromethane,
Solvents such as nitroethane, nitrobenzene, carbon disulfide, etc. may be mentioned. Furthermore, dihydroisothianaphthene-2- represented by general formula a
When dehydrating and polymerizing oxides or derivatives thereof, solvents such as concentrated sulfuric acid and polyphosphoric acid can be used. Further, when carrying out oxidative addition polymerization of the isothianaphthene represented by the general formula b or its derivative, a combination of a solvent used in cationic polymerization and a Friedel-Crafts type catalyst may be used. Furthermore, the polymerization temperature used in polymerizing the monomers is determined by each polymerization method and is not particularly determined, but is generally between -80℃ and +200℃.
Preferably, the polymerization is carried out in the temperature range of .degree. The polymerization time is determined by the polymerization method, polymerization temperature, monomer structure, etc., but it is usually desirable to polymerize for 0.25 to 200 hours. The monomer compounds represented by the above general formulas a and b can be synthesized by known methods, for example, by the Journal of American Chemical Society (J.Am.Chem. Soc.) Vol. 81, p. 4266 (1959) and Journal of Organic Chemistry (J.Org.), also published by M.P. Kyaba et al.
Chem.) Vol. 36, No. 25, p. 3932 (1971). Furthermore, in order to increase the yield of the intermediate 1,3-dihydroisothianaphthene, a method using solubilized lithium sulfide obtained by reacting lithium triethyl boron hydride with sulfur has been proposed by JA Gradysz and others. It is proposed in Tetrahadron Letters, Vol. 35, p. 2329 (1979). Effects of the Invention The thus obtained polymer according to the present invention has a completely new structure, and not only exhibits extremely high conductivity through doping, but also undergoes repeated oxidation-reduction electrochemically. and has a unique color in each state.
The poly(isothianaphthenes) of the present invention are also very interesting polymers in that they do not lose their transparency even under fully oxidized conditions. Therefore, the polymer having an isothianaphthene structure according to the present invention can be used in the electrical and electronic industries as electrodes, electrochromic display elements, solar cells, electrical connections, electromagnetic radiation fixing and converting devices, and reversible It is extremely useful as a redox system. EXAMPLES The present invention will be explained in more detail with reference to Examples below, but it goes without saying that the technical scope of the present invention is not limited by these Examples.
In addition, in the following example, the NMR spectrum is
Varian EM-360A with TMS as internal standard
¹ H-NMR was measured using a spectrometer, and infrared absorption spectra were measured using a model 281 device manufactured by PerkinElmer. Example 1 Production of polyisothianaphthene by treating 1,3-dihydroisothianaphthene-2-oxide in concentrated sulfuric acid (a) Synthesis of 1,3-dihydroisothianaphthene-2-oxide Lithium triethylboron Hydride 1
3.21 g (0.1 mol) of powdered sulfur in a Schulenk flask at room temperature was added to 200 ml of the mol/solution under a nitrogen stream. A reaction occurred immediately, the sulfur powder dissolved and a yellow suspension was obtained. When this solution was exposed to a small amount of air, it turned into a pale yellow transparent solution. Separately, 26.4 g of o-xylylene dibromide was placed in a 2-four-necked flask equipped with a dropping funnel, stirrer, thermometer, and nitrogen inlet under a nitrogen atmosphere.
(0.1 mol) was dissolved in 1 mol of anhydrous tetrahydrofuran, and while stirring, 1.5 mol of the above tetrahydrofuran solution of lithium sulfide was added at room temperature.
It dripped over time. Thereafter, tetrahydrofuran was distilled off under reduced pressure, and the residue was further distilled to obtain 10.9 g (yield: 80%) of colorless 1,3-dihydroisothianaphthene having a temperature of 74 to 76°C/3 mmHg.
The infrared absorption spectrum of this product is 3060, 3026,
Absorption based on phenyl group at 1582, 1485 cm ^-1 ,
Absorption based on methylene group at 2910, 2840, and 1450 cm ^-1 , in-plane bending absorption of 1,2-substituted phenyl at 1195 cm ^-1 , absorption of o-substituted phenyl at 760 cm ^-1 ,
Absorption of sulfide was observed at 740 cm ^-1 . Also
The results of nuclear magnetic resonance spectrum ( ¹ H-NMR) analysis in deuterated chloroform using TMS as an internal standard were as follows. 4.22 (S, 4H), 7.20 (m, 4H) This compound was extremely unstable and changed from yellow to black even when stored in a tightly closed container protected from light. Next, the obtained 1,3-dihydroisothianaphthene was mixed with sodium metaiodate prepared in advance.
It was added to 450 ml of 50% methanol aqueous solution in which 18.6 g (0.086 mol) was dissolved, and stirred at room temperature for 12 hours.
The generated precipitate was filtered off, and the residue was washed with 50 ml of methanol and combined with the mother liquor. The filtrate was concentrated under reduced pressure, and the resulting yellow-white solid was recrystallized from ethyl acetate/cyclohexane to obtain slightly yellowish crystals. The melting point of this crystal was 87-89°C. When the obtained crystals were further recrystallized from ethyl acetate/cyclohexane, they showed a melting point of 90-91°C. In the infrared absorption spectrum of this crystal, in addition to the absorption of isothianaphthene, strong absorption of sulfoxide was observed at 1035 cm ^-1 , and the absorption of sulfoxide at 740 cm ^-1 disappeared. In addition, ¹ H− in deuterated chloroform with TMS as standard.
The NMR spectrum was as follows. 4.11 (d, 2H), 4.30 (d, 2H), 7.20 (m,
4H) The results of elemental analysis of the above crystal were as follows. Actual value C: 63.08% H: 5.15% S: 20.87% Calculated value (as C ₈ H ₈ SO) C: 63.16% H: 5.26% S: 21.05% (b) 1,3-dihydroisothianaphthene-2- Synthesis of polyisothianaphthene from oxide (R ¹ = R ² = H in formula a above) When 500 mg (3.29 mmol) of 1,3-dihydroisothianaphthene-2-oxide was added to 1 ml of concentrated sulfuric acid, a reaction system was formed. immediately turned dark red. Leave the almost solidified system at room temperature for 70 hours.
Pour into 400 ml of methanol, centrifuge the resulting brown precipitate, then wash well with water and incubate for 60 ml.
It was vacuum dried at ℃ overnight. The polymer was placed in a Soxhlet extractor and Soxhlet extracted with methylene chloride and then with chlorobenzene for 12 hours to obtain 203 mg of chlorobenzene insoluble portion. The infrared absorption spectrum of this polymer was as shown in FIG. Elemental analysis results are C: 67.26%, H: 3.12%,
S: 23.95%, and the repeating unit has the following structural formula The calculated value when estimated (C: 67.19%, H:
3.32%, S: 23.54%). The electrical conductivity (σ _RT ) of this polymer at room temperature was measured using a 4-terminal conductivity meter and found to be σ _RT =2×10 ⁻² s/cm. Example 2 Production of polyisothianaphthene by oxidizing polydihydroisothianaphthene obtained by cationic polymerization of isothianaphthene using an oxidizing agent (a) Isothianaphthene (R ¹ = R ² in general formula b) =
Synthesis of H) 300 mg of 1,3-dihydroisothianaphthene-2-oxide synthesized based on Example 1(a)
(1.97 mmol) and 450 mg (4.41 mmol) of neutral alumina were thoroughly ground and mixed in a mortar, placed in a sublimator, and heated under reduced pressure on an oil bath. 110℃/
At 20 mmHg, 250 mg (1.87 mmol) of white needle-like crystals of isothianaphthene were obtained at the bottom of the sublimator cooling section. (b) Production of polydihydroisothianaphthene This monomer was immediately dissolved in 5 ml of purified and degassed methylene chloride, 10 mg of trifluoroacetic acid was added at room temperature, and the mixture was left overnight. When the reaction solution was poured into 50 ml of methanol, a white precipitate was obtained.
This polymer contains chloroform, chlorobenzene,
It was soluble in tetrahydrofuran and N,N-dimethylformamide. The infrared absorption spectrum of the polymer is shown in Figure 2, and ^{the 1} H-NMR spectrum is shown in Figure 3. Furthermore, gel permeation chromatography (Varian 5000) of a solution of this polymer in tetrahydrofuran confirmed that the molecular weight was 2000 in terms of polystyrene. When the conductivity at room temperature was measured in the same manner as in Example 1, it was found to be σ _RT =10 ⁻⁸ s/cm or less. The results of elemental analysis were as follows. Actual value C: 71.27% H: 4.54% S: 23.96% Calculated value ((C ₈ H ₆ S) n) C: 71.64% H: 4.48% S: 23.88% In the above method, methane was used instead of trifluoroacetic acid. A polymer was similarly obtained when sulfonic acid was used as a polymerization initiator, and its infrared absorption spectrum completely matched that shown in FIG. When these polymers were dissolved in 5 ml of chlorobenzene and treated with twice the molar amount of chloranil, a black precipitate was formed. The conductivity σ _RT of this polymer at room temperature was 9×10 ⁻² s/cm, and the conductivity of the polymer doped with iodine was σ _RT 9×10 ⁻¹ s/cm. The infrared absorption spectrum of this product was as shown in FIG. Even when the doped polymer was left in the air at room temperature for one week, there was no change in its electrical conductivity. When 1.1 times the amount of N-chlorosuccinimide was used instead of chloranil and 5 ml of chloroform was used, a black precipitate was obtained that showed exactly the same infrared absorption spectrum as shown in FIG. 4. The electrical conductivity σ _RT of this polymer was 2.6×10 ⁻¹ s/cm. Example 3 One-step polymerization of polyisothianaphthene by oxidative polymerization of isothianaphthene Isothianaphthene was synthesized by the method described in Example 2(a) above. Isothianaphthene 250mg, anhydrous methylene chloride 5ml, anhydrous aluminum chloride 134mg
When 134 mg of anhydrous cupric chloride were reacted at a temperature of 35 to 37° C. for 1 hour, a black precipitate was generated. After maintaining this temperature for 12 hours, the precipitate was treated with an acidic methanol solution of hydrochloric acid, thoroughly washed with water, and dried. The dried polymer was extracted with hot methanol, hot methylene chloride, and then hot chlorobenzene to give 205 mg.
A black polymer was obtained. Its infrared absorption spectrum completely matched that shown in FIG. Also, the conductivity σ _RT is 2.8×
It was 10 ^-2 s/cm. Example 4 Polymerization of polyisothianaphthene by electrochemical polymerization of isothianaphthene The electrolyte shown in Table 1 below and isothianaphthene dissolved in a polar solvent at predetermined concentrations were used as the electrolyte, and the platinum plate was used as the sample electrode. Using an Al plate as a counter electrode and Li/Li ⁺ as a reference electrode, electrochemical polymerization was performed at room temperature for a predetermined time at a constant current density of 0.75 mA/cm ² , and a polyisothianaphthene film was formed on the platinum plate as the positive electrode. generated. The solution used had been deoxidized by bubbling with dry argon for at least 30 minutes. The maximum voltage during polymerization was 4.5V (vsLi/
Li ⁺ ). The produced film was thoroughly washed with acetonitrile and then methylene chloride, dried in vacuum, and its electrical performance was measured. The results obtained were as shown in Table 1 below.

[Electrochromic material experiment]

In Example 4-2, a conductive glass on which indium oxide was vapor-deposited was used as the positive electrode instead of the platinum plate.
The polymer was electrochemically deposited on conductive glass. Using a conductive glass coated with this polymer as a negative electrode, a platinum wire as a positive electrode, and a standard calomel electrode as a reference electrode, a polarographic analyzer (EG&G Co., Ltd.) was used in an acetonitrile solution containing 292 mmol of tetrabutylammonium perchlorate at room temperature. Cyclic voltam was measured using Model 174A). Applied voltage sweep speed is 20mV/
sec, the sweep range was +1.0V to -0.7V (vs. standard calomel electrode). The results obtained were as shown in FIG. As shown in Figure 5, the oxidation peak is +0.58V, the reduction peak is -0.5V, and the range from -0.7V to +0.6V is dark blue, and the range from +0.6 to +1.0V is extremely transparent. It turned a light green color. This shows that the deep blue state is the neutral state of the polymer, and the highly transparent green state in the oxidized doped state. [Battery experiment] The film obtained in Example 4-1 was 1 cm wide and 3 cm long.
One end was glued to a platinum wire using a conductive adhesive, and placed on both sides of a lithium foil of the same size through a 1 mm thick porous polypropylene diaphragm so that the electrolyte could be sufficiently impregnated. It was immersed to a depth of 2 cm in a propylene carbonate solution of mol/l lithium perchlorate. Using the thus prepared battery with poly(isothianaphthene) as the positive electrode and lithium foil as the negative electrode, charging was performed at 2.0 mA/cm ² for 30 minutes in an argon atmosphere. Immediately after charging, discharge at 2.0mA/cm ² until the battery voltage reaches
When the voltage reaches 1V, charge again under the same conditions as above. When we conducted a repeated charge-discharge test, we found that the number of charge-discharge cycles required for the charge-discharge efficiency to drop to 50% was 590. Furthermore, the charging/discharging efficiency after the fifth repetition was 99%. Furthermore, the self-discharge rate after 48 hours while remaining charged is 3.2
It was %. Example 6 Poly(dihydroisothianaphthene) “Tetrahedron” by electrochemical polymerization
1979, Vol. 35, p. 2239, J.A. Gladysz et al.; Journal of American Chemical Society (J.Amer.Chem.
MPCava et al.; Journal of Organic Chemistry (J.Org.Chem.) 1971, 36
The isothianaphthene monomer was prepared by the procedure described in M.P. Carba et al., Vol. 3932, and used immediately. This monomer was electrochemically oxidized in a two-electrode, compartment electrolytic cell to yield a poly(dihydroisothianaphthene) polymer. A platinum plate was used as an anode and graphite oxide was used as a cathode. The solution used for polymerization is colorless and transparent, and contains 0.23M isothianaphthene in acetonitrile as an electrolyte.
It was contained together with Bu ₄ NPF ₆ 0.30M.
Acetonitrile (purchased from Mallinckrodt) was used directly without further purification. A series 1.5V battery was used as the power source. All experiments were performed under dry _N2 . As soon as 4.5V was connected to this electrolytic cell, a large amount of white powder appeared near the anode. I turned off the battery after 10 minutes. The white powder, poly(dihydroisothianaphthene), was isolated by suction filtration, washed with acetonitrile and diethyl ether, and dried under vacuum. The generated solid is diluted with tetrahydrofuran.
It was purified by reprecipitation from H ₂ O and subjected to elemental analysis. A freshly prepared sample of isothianaphthene was
When electrolyzed in the anode chamber of an H-type electrolytic cell using Bu ₄ NClO ₄ or Bu ₄ NBF ₄ as the supporting electrolyte and tin oxide coated glass (TOG) as the anode,
The anode chamber was filled with a large amount of white precipitate (WP). Careful observation revealed that the anode was first coated (momentarily) with a very thin blue film, and shortly after that WP formation began. W.P.
The appearance was not related to electrode material, solvent or temperature. Isolation, characterization (infrared, elemental analysis) and chemical manipulation (see below) demonstrated that WP is a poly(dihydroisothianaphthene). Thiophene becomes a partially oxidized (doped) polymer film under the above conditions, while isothianaphthene forms a poly( It should be noted that it is converted to dihydroisothianaphthene). The only rational explanation for this surprising observation was that poly(isothianaphthene) acts as an initiator for the cationic polymerization of isothianaphthene. To test this hypothesis, we exposed freshly prepared solutions of isothianaphthenes to common cationic initiation catalysts (Brensted and Lewis acids) and found that all polymerized the isothianaphthenes to varying degrees. . However, by far the most interesting result was for sulfuric acid in methylene chloride. Under these conditions, isothianaphthene forms a dark blue powder of poly(isothianaphthene) doped with hydrated sulfuric acid.
was converted into. It is clear that the acid acted not only as a catalyst but also as an oxidizing agent. A "convergent" test solidifying about the above assumption showed that the product of chloranil dehydrogenation was poly(dihydroisothianaphthene) and that the product of H ₂ SO ₄ polymerization showed the same infrared spectrum. It was hot. The only reasonable explanation for this observation is that the infrared spectrum of doped poly(isothianaphthene) is dominated by absorption by conduction electrons, and absorption by intramolecular vibrations becomes a weak feature in the spectrum. be. Without additional control experiments, it is difficult to make detailed mechanistic inferences to explain this electrolyte effect. H ₂ SO ₄ directly converts dihydroisothianaphthene-S-oxide into poly(isothianaphthene).
It was discovered that (H ₂ SO ₄ ) can be converted to (H ₂ O)y. Solid dihydroisothianaphthene-S
- Oxide added to 98% H ₂ SO ₄ , in fact the desired partially doped poly(isothianaphthene)
(see illustration below). Additionally, 7,7,8,8-tetracyanoquinodimethane can be used as a catalyst for cationic polymerization. However, the product did not exhibit higher conductivity than any of the other doped poly(isothianaphthene) compounds. This probably indicates that the receptor is not included in the conductivity of the solid. Two reasons can be given for that observation: the acceptor molecules are probably not integrated into small crystalline regions and/or there is complete charge transfer. Although the above results explain the nature of the production method of poly(dihydroisothianaphthenes) and make it possible to find the correct procedure to chemically synthesize poly(isothianaphthenes), the electrochemistry of isothianaphthenes is still unclear. It does not interfere with the polymerization. This required finding a way to prevent the catalysis of poly(dihydroisothianaphthene) formation by "nascent" doped poly(isothianaphthenes). It has been found that if the reaction medium contains species that are more nucleophilic than the isothianaphthenes, the growth step is hindered. Test experiments in which iodide was added to the anode chamber prior to electrolysis were ineffective as iodide was easily oxidized under electrolysis conditions. However, in electrolysis with LiBr, Bu ₄ NBr or preferably Ph ₄ AsCl, platinum or
Produced excellent film on TOG. The only reasonable explanation for this observation is that the infrared spectrum of doped poly(isothianaphthene) is dominated by absorption by conduction electrons, and absorption by intramolecular vibrations is a weak feature in the spectrum. be. In the absence of additional control experiments,
It is difficult to speculate on a detailed mechanism to explain this electrolyte effect. Analysis, as (C ₈ H ₆ S) Calculated: C, 71.60; H, 4.51; S, 23.89 Actual: C, 71.27; H, 4.54; S, 23.96 For this reaction, LiBF ₄ and Bu ₄ NClO ₄ are used as electrolytes. It can be used as According to the present invention, metastable isothianaphthenes can be polymerized into highly conductive polymers exhibiting favorable properties by at least three different procedures; one of these Includes an electrochemical process for the polymerization of isothianaphthenes in the presence of nuclear anions. It has also been found that poly(isothianaphthene) is a better conductor than polythiophene. Example 7 Poly(dihydroisothianaphthene) by chemical cationic polymerization Isothianaphthene monomer (396 _mg , 2.96 mmol) in 10 ml of methylene chloride previously dried with _P2O5
was dissolved. One drop of methanesulfonic acid was added to this solution and the reaction mixture immediately changed from colorless to red. The color turned violet after 90 minutes. After removing the methylene chloride by evaporation,
The residue was dissolved in tetrahydrofuran. This solution was then poured into methanol, and the poly(dihydroisothianaphthene) polymer precipitated from the solution. This was separated by centrifugation and dried under vacuum. The infrared spectrum was the same as that of the poly(dihydroisothianaphthene) polymer described above. The following examples illustrate successful implementation of the invention and are not intended to limit the invention. Example 8 Doped Poly(isothianaphthene) by Electrochemical Polymerization The polymerization procedure was essentially the same as that previously described in Example 6 for poly(dihydroisothianaphthene) polymer. The most important point was electrolytes. When lithium bromide was used as the electrolyte, a blue film of doped poly(isothianaphthene) polymer was formed on the anode (conductive glass) upon connection to a 1.5V battery. Also,
Bu ₄ NBr and Ph ₄ AsCl can also be used as electrolytes for this reaction. Example 9 Doped poly(isothianaphthene) by chemical cationic oxidative polymerization using sulfuric acid.
mg, 2.96 mmol). The color of the monomer immediately changed from white to black with a hint of red. After pouring the reaction mixture into 400 ml of methanol and stirring overnight, a brown powder, the doped poly(isothianaphthene) polymer, precipitated from the solution. This was separated by centrifugation and extracted with methylene chloride and chlorobenzene using a Soxhlet extractor and then dried under vacuum. This reaction can also be carried out with a suspension of sulfuric acid in methylene chloride. Example 10 Doped poly(isothianaphthene) by chemical cationic oxidative polymerization using TCNQ (7,7,8,8-tetracyanoquinodimethane) Isothianaphthene monomer (238 mg, 1.77 mmol) was chlorinated Dissolved in 5 ml of methylene. In this solution
After adding a few mg of TCNQ, the color of the solution changed very slowly to red. After stirring overnight, the color turned blue-black. Next, 2 molar amounts of isothianaphthene monomer are added to this solution.
Double amount of TCNQ was added. This was heated to 110°C and held at this temperature for 1 hour. The reaction mixture was poured into methanol, and a greenish-black powder precipitated from the solution. This was washed with methanol and chlorobenzene using a Soxhlet extractor and then dried under vacuum. Example 11 Poly(isothianaphthene) from poly(dihydroisothianaphthene) Poly(dihydroisothianaphthene) polymer was made by electrochemical polymerization and dissolved in hot chlorobenzene. This was a light brown solution. Tetra-chloro-p-benzoquinone (chloranil) was added to this solution. The color of the solution quickly changed to dark green. When the solution was cooled, a powder precipitated. This was separated off by suction filtration, washed with methanol and dried under vacuum. Example 7~
All the substances described in 11 showed the same infrared spectra. From the above, the present invention provides poly(isothianaphthene)
provides three alternative routes to: 1. Electrochemical polymerization of isothianaphthenes in the presence of nucleophilic anions; 2. Chemical polymerization of isothianaphthenes or dihydroisothianaphthene-S-oxides in the presence of cationic polymerization catalysts. ;3 Dehydrogenation of poly(dihydroisothianaphthene). The predicted results of conductivity measurements are summarized in the table. The band edge of poly(isothianaphthene) was estimated to be ~1 eV (1.1 μ) (from the transmission through thin films at low doping levels). this is,
It is about 1 eV lower than the band edge of polythiophene (~2 eV, 620 nm).

【table】

Table Example 11a 2-probe compression measurements Figure 6 shows reversible electrochemical doping of poly(isothianaphthene). From this, aluminum is used as one electrode (in the case of the standard calomel reference electrode) and poly(isothianaphthene)
It can be seen that the polymer of the present invention is useful as a battery electrode by using lithium fluoroborate as the other electrode and a propylene carbonate solution of lithium fluoroborate as the electrolyte. The experiment of FIG. 6 further demonstrates the electrochromic properties of the novel polymers of the present invention.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the polymer produced in Example 1. FIG. 2 is an infrared absorption spectrum diagram of the polymer produced in Example 2, and FIG. 3 is an NMR spectrum diagram of the polymer produced in Example 2. FIG. 4 is an infrared absorption spectrum diagram of the first polymer produced in Example 2 after being treated with chloranil. FIG. 5 is a chart showing the results of polarographic analysis of the polymer obtained in the electrochromic material test of Example 5.
Figure 6 shows the electrochemical reversibility of poly(isothianaphthene) films recorded against a standard calomel electrode (SCE): +0.6V = yellow, transparent; -0.4V = dark blue, opaque; Electrolyte: Li + BF ₄ ^- in propylene carbonate. The oxidized polymer in this example contains BF ₄ as a doping agent.

Claims (1)

[Claims] 1 General formula [Formula] and/or [Formula] (In the formula, R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, and X ^- represents the electrolyte. (represents an anion, y is a number from 0.01 to 1 indicating the proportion of anion per mole of monomer, and n is a number from 5 to 500 indicating the degree of polymerization). Combined. 2 The electrolyte anion X ^- of the isothianaphthene structure represented by the general formula (b) is Cl ^- , Br ^- , I ^- ,
ClO ₄ , BF ₄ ^- , PF ₆ ^- , AsFb ₆ ^- , SbF ₆ ^- , AlCl ₄ ^- ,
A polymer according to claim 1, which is selected from AlBr ₃ Cl ⁻ , FeCl ₄ ⁻ , SnCl ₃ ⁻ and CF ₃ SO ₃ ⁻ .