JPH0859830A - Water-soluble self-doping conductive polymer and its production - Google Patents

Abstract

PURPOSE: To provide a water-sol. self-doping conductive polymer which comprises a pluraility of kinds of monomer units having Broensted acid groups and has a π-conjugation along the main chain and to obtain a quick doping response by using the polymer as an electrode of a cell. CONSTITUTION: This polymer comprises 0.01-100mol% structural units of formula I (wherein Y2 , y3 , and Y4 are each H or R2 XM2 ; Rz is a single bond, a 1-10C alkylene, an ether or an ester group; X is a group of formula II or III; and M2 is H, Li, Na, or K) and other kinds of monomer units. The main chain of the polymer is exemplified by polypyrrole and polyanilne and pref. has repeating units of formula IV or V (wherein Ht is hetero; Y is H or R1 XM1 ; M1 is a cation-generating group; X is a Broensted acid anion; and Ru is an 1-10C alkylene etc.). The synthesis of the polymer is pref. conducted in such a manner that an amphoion type is obtd. by an electrochemical process and then it is converted into a doping-free type electrochemically or with a reducing agent. The polymer exhibits high charging and discharging speeds as an electrode of an electrochemical cell.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates generally to the field of conductive polymers. More specifically, the present invention relates to a water-soluble self-doped conductive polymer having a Bronsted acid group covalently bonded to the main chain of the polymer and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION The requirements for conductive polymers for use in the electronics and other industries are becoming ever more stringent. Also,
There is an increasing demand for materials that can be made smaller and lighter in weight and have long-term stability and excellent performance.

In order to satisfy such requirements, new conductive polymers or polymer materials have been actively developed in recent years, and many proposals have been made for uses of such polymer compounds. ing. For example, PJ Nigrey et al., Chemical Communication (Chem.Comm), 1979,
The use of polyacetylene as a secondary battery electrode is disclosed after page 591. Also, the Journal of Electrochemical Society (J. Electrochem. So
c.), 1981, p. 1651 and thereafter, JP-A-56-13
6469, 57-12168, and 59-387.
0, 59-3872, 59-3873, 5
9-196566, 59-196573, 59
Nos. 203,368 and 59-203369 are polyacetylene, quinazone polymers having Schiff base, polyarylenequinones, poly-para-phenylene, poly-.
It teaches that polymeric compounds such as 2,5-thienylene can be used as electrode materials for secondary batteries.

In addition, as a proposal for other uses of polymer compounds, polyaniline [Journal of Electroanalytical Chemistry, Vol. 111,
111 pages (1980), A.F.D.Az et al. Or Vol. 161, 419 (1984), Yoneyama et al.], Polypyrrole [Journal of Electroanalytical Chemistry, 149, 101 (1983).
), A / F Diaz, etc.], polythiophene [Journal de Fijique, Vol. 44, June issue, C3-
595 (1983), M.A.Dry, etc., or Japan Journal of Applied Physics, Vol. 22, No. 7, L412 (1983), Kanto et al.] For use in electrochromic materials. To be

These highly conductive polymers known in the art are typically rendered conductive by an acceptor or donor doping process. Acceptor doping oxidizes the main chain of the acceptor-doped polymer, thereby introducing a positive charge into the polymer chain. Similarly, donor doping reduces the polymer, thereby introducing a negative charge into the polymer chain. It is these mobile positive or negative charges introduced into the polymer chain from the outside that induce the conductivity of the doped polymer.
In addition, such "p-type" (oxidation) or "n-type"
-Type "(reduction) doping induces substantially all changes in electronic structure after doping, including changes in optical and infrared absorption spectra.

That is, in all of the conventional doping methods, counter ions are derived from an external acceptor or donor function. During the electrochemical cycle between neutral and ionic states, counterions must enter and exit the polymer body. This solid-state diffusion of counterions introduced from the outside is often the rate-determining step in the circulation process. Therefore, it is desirable to overcome this limitation in electrochemical or electrochromic doping and dedoping operations, thereby reducing the response time. It has been found that the response time can be shortened if the time required for the movement of counterions can be shortened. The present invention is based on this finding. Heretofore, a water-soluble conductive polymer or a self-doped conductive polymer has not been known.

[0007]

SUMMARY OF THE INVENTION The present invention is a water soluble self-doping conductive material that can be rapidly doped and undoped and that maintains a stable doping state for a long period of time as compared with the conductive polymer of the prior art. And a method for producing the same are provided. The superior properties of the polymers of the present invention result from the finding that conducting polymers can be made in a "self-doping" state, that is, a counterion imparting conductivity can be covalently attached to the polymer itself. Thus, in contrast to prior art polymers, the need for externally introducing counterions is eliminated, as is the rate limiting diffusion step described above.

The polymers of this invention have at least about 1 S / cm.
It can exhibit a degree of conductivity. Self-doped polymers are used as electrodes in electrochemical cells, as conductive layers in electrochromic displays, field effect transistors, Schottky diodes, etc., or in many applications where highly conductive polymers with rapid doping kinetics are desired. be able to.

The invention, in its broadest aspect, comprises a plurality of monomeric units, about 0.01 to 100 mol% of said units covalently bound to at least one Bronsted acid group, along a backbone. The present invention is directed to a conductive self-doped polymer having a π-electron conjugated system and a method for producing the same. The present invention also includes zwitterionic forms of the polymers.
Polymer chains that can form the backbone skeleton of the self-doping polymers of the present invention include, for example, polypyrrole, polythiophene, polyisothianaphthene, polyaniline, poly-p-phenylene and copolymers thereof.

In a preferred embodiment, the above-mentioned self-doping conductive polymer has a repeating structure selected from the following structures (I) and (II), and a method for producing them is provided:

Embedded image

[Chemical 9] Here, in the formula I, Ht is a hetero group, Y ₁ is hydrogen or —R ₁ —X—M ₁ ; M ₁ is an atom or group that produces a monovalent cation when oxidized; X is Bronsted acid anion; R ₁ is a linear or branched alkylene, ether, ester or amide component having 1 to 10 carbon atoms. In formula II, Y ₂ , Y ₃ and Y ₄ are independently selected from the group consisting of hydrogen and —R ₂ —X—M ₂ .
R ₂ is absent or is a linear or branched alkylene, ether, ester or amide component having 1 to 10 carbon atoms and M ₂ is an atom or group which produces a monovalent cation when oxidized.

In yet another preferred embodiment of the invention, there are provided water-soluble self-doping conductive polymers having a repeating zwitterionic structure according to (Ia) or (IIa) below and a process for their preparation:

[Chemical 10]

[Chemical 11] (In the formulae, Ht, R ₁ , R ₂ and X are as defined above). The present invention is further directed to monomers useful in making the above-described self-doping polymers, methods of synthesizing the polymers, and apparatus using the polymers.

The term "conductive" refers to the ability to transfer charge by passing ionized atoms or electrons. "Conductive" compounds include compounds that contain or add mobile ions or electrons, as well as compounds that can be oxidized to contain or add mobile ions or electrons. The term "self-doped" means that the material can be made conductive without the external introduction of ions by conventional doping techniques. In the self-doped polymers disclosed herein, those that can be counterions are covalently attached to the polymer backbone. The term “Bronsted acid” is used to refer to a chemical species that can act as one or more proton sources, ie, proton-donors. See, for example, McGraw-Hill's Dictionary of Chemistry and Technical Term (3rd Edition, 1984), page 220.
Thus, examples of Bronsted acids include carboxylic acids, sulfonic acids, phosphoric acids.

The term "Bronsted acid group" as used herein refers to Bronsted acids, Bronsted acid anions (ie, when the protons are removed), Bronsted acid anions, as defined above. By a salt of Bronsted acid associated with a monovalent cationic counterion. "Monomer unit" as used herein refers to a repeating structural unit of a polymer. The individual monomer units of a particular polymer may be the same, as in a homopolymer, or different, as in a copolymer.

The water soluble self-doping polymer of the present invention may be a copolymer or a homopolymer,
It has a main chain structure that gives a π-electron conjugated system. Examples of such polymer backbones include, but are not limited to, polypyrrole, polythiophene, polyisothianaphthene, polyaniline, poly-p-phenylene and copolymers thereof.
The above-described polymers of the present invention include one or more "-
R ₁ -X-M ₁ "or" -R ₂ -X-M ₂ "may be composed of substituted monomer units from about 0.01 to about 100 mole% with a substituent. For applications requiring high conductivity,
The self-doping polymer of the present invention is preferably composed of at least about 10 mol% of the monomer unit having the substituent, typically about 50 to 100 mol%. In semiconductor applications, the monomer unit containing the group is about 10 mol%
Smaller amounts are common, but sometimes as low as about 0.1 to about 0.01 mol%.

The polyheterocycle monomer units represented by formulas I and Ia include monomer units that are either mono- or di-substituted by the --R ₁ --X--M ₁ substituent. Similarly, the polyaniline monomer unit represented by the formulas II and IIa has a “—R ₂ —X—M ₂ ” substituent group 1,
It contains monomer units substituted with 2, 3 or 4 units. The self-doping polymers of the present invention likewise contemplate copolymers containing these different types of substituted monomer units. In both the self-doped homopolymers and copolymers of the present invention, about 0.01 to 100 mol% of the polymer should have Bronsted acid groups.

In a preferred embodiment, the self-doping polymers of the present invention include the electrically neutral polymers given by Formula I or II above. In order to render the polymer conductive, the polymer is oxidized to at least one M ₁ or M
A polymer containing _two components and repeating zwitterionic structure according to Ia or IIa must be produced. In a preferred embodiment, for example, Ht is NH, S,
It is preferred to select from the group consisting of O, Se and Te; M ₁ is independently Na, Li or K; M ₂
Are each independently H, Na, Li or K; X is preferably CO ₂ , SO ₃ or HPO ₃ ;
R ₁ is a linear alkylene or ether group [that is,-
(CH _{2) X} - or _{- (CH 2) y O (} CH 2) Z -
(Where x and (y + 2) are from 1 to about 10)], and when R ₂ is present, it is a divalent group similar to the above R ₁ . In a particularly preferred embodiment, Ht is NH or S; M ₁ is Li or Na; M ₂ is H, Li or Na; X is CO ₂ or SO ₃ ; R ₁ And R ₂ is a linear alkyl having 2 to about 4 carbon atoms; the substituted monomer units in the polymer are —R ₁ —X—M ₁ groups or —
Monosubstituted or disubstituted with R ₂ -X-M ₂ group.

To "undop" the zwitterionic form of the polymer, the charge may be provided in the opposite direction to that used in the doping (alternatively, a mild reducing agent may be used as discussed above). Good). M ₁ or M ₂ is transferred into the polymer to neutralize the X ⁻ anion. Thus, the undoping process is as fast as the doping process.

Schemes I and II represent the oxidation and reduction of the above polymers (which are mono-substituted examples), ie the transition between an electrically neutral and a conductive zwitterionic form:

[Chemical 12]

[Chemical 13] When X is CO ₂ , the above electrochemical transition is pH 1
It strongly depends on pH in the range of ˜6 (pKa is about 5 for X = CO ₂ and M ₁ ═H in formula I). On the other hand, when X is SO ₃ , the above electrochemical reaction is pH independent over a much wider pH range of about 1-14 (II
In the formula, pKa is about 1 when X = SO ₃ and M ₂ = H). That is, sulfonic acid derivatives are charged at virtually any pH, and carboxylic acid derivatives are charged only at low hydrogen ion concentrations. Thus, adjusting the conductivity of the carboxylic acid derivative by changing the pH of the polymer solution is easier than adjusting the conductivity of the corresponding sulfonic acid derivative. That is, the selection of a particular Bronsted acid component depends on the particular application. The conductivity of these self-doping polymers is at least about 1 S / cm (see Example 14), and typically the chain length is about several hundred monomer units. Typically chain lengths range from about 100 to about 500 monomer units with higher molecular weights being preferred.

In the practice of the present invention, Bronsted acid groups are introduced into the polymer to render the polymer self-doped. The Bronsted acid group may be introduced into the polymer and then polymerized or copolymerized. It is also possible to prepare a polymer or copolymer of an unsubstituted monomer of formula I or II and then introduce Bronsted acid groups into the polymer backbone.

It is within the skill of the art to covalently bond the Bronsted acid groups to the polymer or polymers. See, for example, Journal of American Chemical Society, 70, 1556 (1948). As an example, N-bromosuccinimide (NBS) can be used to link an alkyl group on the monomer or polymer backbone to an alkyl halide, as shown in Scheme III:

Embedded image The halide is then treated with sodium cyanide / sodium hydroxide or sodium sulfite and then hydrolyzed to the carboxylic acid or sulfonic acid, respectively. This reaction is shown in Scheme IV:

[Chemical 15] Another example showing the addition of Bronsted acid groups with ether linking groups is shown in Scheme V:

Embedded image

The synthesis of various monomers useful in the practice of the present invention is shown in Examples 1-12 below. The polymer of the present invention is, for example, Synth. Metals, Vol.
81 (1984) by the electrochemical method or by Wudl et al., J. Org. Chem. 49.
Vol. 3, 382 (1984), Udol et al., Mol. Cryst.
Liq. Cryst. 118, 199 (1985), M. Kobayashi et al., Synth.Metals. 9, 77 (198)
4 years) and can be synthesized by a chemical coupling method.

When synthesized by the electrochemical method (ie on the anode), the polymeric zwitterion is made directly. Use of the chemical coupling method produces a neutral polymer.
The preferred synthetic method is the electrochemical method, exemplified below by the preparation of substituted polyheterocyclic species. Monomer III:

[Chemical 17] (Wherein Ht, Y ₁ , R ₁ , X and M ₁ are as described above) together with an electrolyte such as tetrabutylammonium perchlorate or tetrabutylammonium tetrafluoroborate in a suitable solvent. , For example acetonitrile (sulfonic acid derivative, ie X =
Gives especially during suitable are) in the case of SO _3. Prepare a working electrode of platinum or nickel, indium tin oxide (ITO) coated glass or other suitable material,
A counter electrode (cathode) of platinum or aluminum, preferably platinum, is prepared. A current of about 0.5 to 5 mA / cm ² is applied to the electrodes, and the electrolytic polymerization reaction is carried out for several minutes to several hours depending on the desired degree of polymerization (or the thickness of the polymer film on the substrate). The temperature of the polymerization reaction can be in the range of about -30 ° C to about 25 ° C, but is preferably about 5 ° C to about 25 ° C.

The reduction of the zwitterionic polymer thus prepared to the neutral, undoped form can be accomplished by electrochemical reduction or by any mild reducing agent such as methanol in acetone or iodination. It can be carried out by treating with sodium. This process should proceed for at least several hours to ensure completion of the reaction. Alkyl esters having 1 or 2 carbon atoms and a sulfonic acid monomer (X = SO _3), for example, by polymerizing a methyl ester (see Example 14 and 15), whereas, carboxylic acid derivative (X =
CO ₂ ) may be prepared in the acid form. After polymerizing the sulfonic acid derivative, the methyl group is removed by treatment with sodium iodide or the like.

The polyaniline represented by the formulas II and IIa can be electrochemically synthesized as described above or can be prepared by reacting phenylenediamine with an appropriately substituted cyclohexanedione. Scheme VI below illustrates this latter synthesis:

Embedded image (R ₂ and M ₂ are as defined above) Copolymerization of different types of monomers of formula I or II can be carried out according to the same procedure described above. In a preferred embodiment, at least one of the majority of the monomer as described above -R ₁ -X-M ₁ group or -R ₂
Substituted with -X-M ₂ group.

Composites of polymers of Formulas I and II can be made with water-soluble polymers such as polyvinyl alcohol (see Example 17) or polysaccharides. Depending on the structure, the self-doping polymer of the present invention may be considerably brittle, and therefore by further using a polymer material to form a composite material, a polymer having increased flexibility and reduced brittleness can be obtained. The film can be cast from an aqueous solution of the polymer provided by Formula I or II which also contains a predetermined amount of one or more additional water soluble polymers. Since the procedural key criterion in this step is to dissolve these two or more polymers in water, the only practical limitation for the additional polymer is that it be water soluble.

The self-doped polymers of the present invention offer unique advantages over conventional conductive polymers used as electrodes in electrochemical cells, which require exogenous dopants. Because the counterion is covalently attached to the polymer, cell capacity is not limited by electrolyte concentration or solubility. This means that in optimized cells the total amount of electrolyte and solvent can be reduced considerably and the energy density of the cells thus obtained can be increased. The readily available kinetics of ion transport provided by the novel self-doping mechanism leads to rapid charge and discharge as well as faster electrochromic switching. Electrodes made with the polymers of the present invention can be made from these polymers or from conventional substrates coated with these polymers. Conventional substrates can include, for example, indium tin oxide coated glass, platinum, nickel, palladium or any other suitable anode material. When used as an electrode, internal self-doping of the polymer results in the transition represented by Scheme I.

The self-doping type conductive polymer of the present invention is
Also, long-term performance offers unique advantages over conventional conductive polymers for use in various device applications where the dopant ions are not constantly mobile. Examples of such applications are Schottky diodes,
Including processing of field effect transistors. In self-doped polymers, the dopant ions are covalently attached to the polymer chain, thus eliminating the ion diffusion problem (eg, near the junction or interface). Furthermore, since the conductive polymer of the present invention is water-soluble, it is possible to conveniently use water as a medium, and it is not necessary to use an organic solvent, thus eliminating the disadvantages associated with the use of an organic solvent, such as toxicity and pollution. can do.

Although the invention has been described with reference to specific preferred embodiments, the above description and the following examples are not intended to limit the scope of the invention as claimed. Other aspects, advantages and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.

[0029]

EXAMPLES Example 1 2,5-Diethoxycarbonyl-1,4-cyclohexa
Preparation of Polymer of Ndione and p-Phenylenediamine 8.51 g in 380 ml of freshly distilled butanol
(33.21 mmol) 2,5-diethoxycarbonyl-1,4-cyclohexanedione was suspended and to this was added 3.59 g p-phenylenediamine dissolved in 20 ml butanol, then 40 ml glacial acetic acid was added. The resulting mixture was heated to reflux for 36 hours, then exposed to oxygen for 12 hours at reflux, hot filtered, the solids washed with ether and extracted in a Soxhlet extractor with the following solvents. Chloroform (6 days),
Chlorbenzene (5 days), and ether (4 days).
This treatment yielded 8.42 g of dark solids. Elemental analysis and IR were as follows.

Calculated: C 65.84, H 6.1
4, N 8.53 C ₁₃ H ₁₈ N ₂ O ₄ Found: C 65.55, H 6.21, N
8.71. IR (KBr, νcm ⁻¹ ): 3350w, 3240w, 2
980m, 2900w, 1650s, 1600s, 15
10s, 1440m, 1400w, 1220s, 109
0w, 1065s, 820w, 770m, 600w, 4
95w.

Example 2 Polyaniline dicarboxylic acid The polymer (diester form) obtained in Example 1 was suspended in DMF and treated with a 50% (weight) aqueous sodium hydroxide solution. The reaction mixture was heated to 100 ° C under rigorous anoxic conditions.
Heated for 8 hours. The mixture was cooled, poured into an ice / HCl mixture and filtered. Infrared absorption of this product (I
R) spectrum showed the following intrinsic absorption peak. 31
00-2900 br, 1600s, 1500s, 121
0s.

Reference Example 1 Combination of 2- (3-thienyl) -ethyl methanesulfonate
The formation of freshly distilled dry pyridine 10 ml 2-(3- thienyl) ethanol (Aldrich Chemical Co.) 5.0 g
(3.9 × 10 ^-2 mol) was dissolved in the solution, and the temperature was 5 to 1
At 0 ° C, 3.62 ml of methanesulfonyl chloride (1.2
Equivalent amount) in 20 ml of pyridine was added. The addition was done gradually over about 15-20 minutes. The reaction mixture was stirred at room temperature overnight and then poured into a separatory funnel containing water and ether to quench. The layers were separated and the aqueous phase was extracted three times with ether. Combine the organic extracts and combine
% Hydrochloric acid once, then water, Na ₂ SO ₄
Dried in. The solvent was evaporated to give 5.3 g of a light brown oil (yield 65%). Also, tlc (CHCl ₃ ) showed a single spot. Chromatographic purification on silica gel gave a light yellow oil.

NMR (CDCl ₃ , δ for TMS):
2.9s, 3H; 3.1t, 2H; 4.4t, 2H;
7.0-7.4 m, 3H. IR (neat, ν cm ^-1 ): 3100w, 2930w,
2920w, 1415w, 1355s, 1335s, 1
245w, 1173s, 1080w, 1055w, 97
0s, 955s, 903m, 850m, 825w, 79
5s, 775s, 740w. Mass spectrum (MS) 206.0.

Reference Example 2 Synthesis of 2- (3-thienyl) -ethyl iodide The above methanesulfonate (5.3 g, 2.6 × 10 ^-2)
Mol) was added to a 30 ml acetone solution of 7.7 g (2 equivalents) of NaI, and the mixture was reacted at room temperature for 24 hours. Precipitated C
H ₃ SO ₃ Na was filtered off. The filtrate was poured into water, extracted with chloroform, and the organic phase was dried with MgSO ₄ . Evaporation of the solvent gave a light brown oil which was chromatographically purified to give 5.05 g of a light yellow oil (yield 82.5
%) Was obtained. The NMR and IR spectra were as follows.

NMR (CDCl ₃ , δ for TMS):
3.2m, 4H; 7.0-7.4m, 3H. IR (KBr, ν cm ⁻¹ ): 3100 m, 2960 s,
2920s, 2850w, 1760w, 1565w, 1
535w, 1450m, 1428s, 1415s, 13
90w, 1328w, 1305w, 1255s, 122
2m, 1170s, 1152m, 1100w, 1080
m, 1020w, 940m, 900w, 857s, 84
0s, 810w, 770s, 695s, 633m. MS 238.

Reference Example 3 Sodium 2- (3-thienyl) ethanesulfonate
5.05 g (0.5 equivalents) of the above iodide was added to 10 ml of an aqueous solution of 5.347 g (4.2 × 10 ^-2 mol) of formed Na ₂ SO ₃ and the reaction mixture was heated to 70 ° C. for 45 hours. . The resulting mixture was evaporated to dryness and washed with chloroform to remove unreacted iodide (0.45g),
Further, it was washed with acetone to remove sodium iodide.
The remaining solid was a mixture of the desired sodium salt contaminated with excess sodium sulfite, which was used in the next step without further purification. The NMR and IR spectra were as follows.

NMR (δ for D ₂ O, TMS propane sulfonate): 3.1s, 4H; 7.0-7.4.
m, 3H; IR (KBr, νcm ⁻¹ , Na ₂ SO ₃ peak subtracted):
1272m, 1242s, 1210s, 1177s, 1
120m, 1056s, 760m, 678w.

Reference Example 4 Synthesis of 2- (3-thienyl) ethanesulfonyl chloride To a stirred suspension of 2 g of the salt mixture prepared in Reference Example 3,
2 ml of distilled thionyl chloride was added dropwise. The mixture was stirred for 30 minutes. A white solid obtained by quenching with ice water was filtered off and recrystallized from chloroform-hexane to obtain 800 mg of white crystals. The melting point was 57-58 ° C. NMR and I
The R spectrum was as follows:

NMR (CDCl ₃ , δ for TMS):
3.4m, 2H; 3.9m, 2H; 7.0-7.4m,
3H. IR (KBr, ν cm ⁻¹ ): 3100w, 2980w,
2960w, 2930w, 1455w, 1412w, 1
358s, 1278w, 1260w, 1225w, 11
65s, 1075w, 935w, 865m, 830m,
790s, 770w, 750m, 678s, 625m. The elemental analysis was as follows. Calculated: C34.20, H3.35, Cl 16.8
_{3, S30.43 C 6 H 7 Cl} O 2 S 2 Found: C34.38, H3.32, Cl 16.6
9, S30.24

Reference Example 5 Methyl 2- (3-thienyl) -ethanesulfonate (others)
Name: thiophen-3- (2-ethanesulfonic acid methyl ester)
The above-mentioned acid chloride (produced according to Reference Example 4 above)
To a stirred solution of 105 mg (5 x 10 ^-4 mol) in 1.5 ml of freshly distilled (from molecular sieves) methanol was added at room temperature 1.74 ml (2 equivalents) of N, N-diisopropylethylamine. Was added. 1 reaction mixture
Stir for 2 hours, then transfer to a separatory funnel containing dilute aqueous hydrochloric acid and extract 3 times with chloroform. The organic phases were combined, dried over Na ₂ SO ₄ and evaporated to give a light brown oil. This was purified by chromatography on silica gel with chloroform as the eluent. The resulting colorless solid (90% yield) had a melting point of 27-28.5 ° C. IR, UV and NMR spectra were as follows.

IR (neat film, νcm ^-1 ): 310
0w, 2960w, 2930w, 1450m, 1415
w, 1355s, 1250w, 1165s, 985s,
840w, 820w, 780m, 630w, 615w. UV-visible [λ max, MeOH, nm (ε)]: 234
(6 × 10 ³ ). NMR (CDCl ₃ , δ for TMS): 7.42 ~
7.22q, 1H; 7.18-6.80m, 2H;
85s, 3H; 3.6-2.9m, 4H. The elemental analysis was as follows. Calculated: C 40.76, H 4.89, S 3
1.08 C ₇ H ₁₀ O ₃ S _{2 found} : C 40.90, H 4.84, S 3.
0.92

Reference Example 6 2-Carboxyethyl-4- (3-thienyl) butanoic acid
Synthesis of ethyl 11.2 g (69.9) in 60 ml of freshly distilled DMF.
2.85 g (69.94 mmol) of a 60% NaH oil dispersion was added to a stirred solution of 4 mmol) of diethyl malonate. After stirring for 30 minutes, 20 ml
15.86 g (66.61 mmol) of 2 in DMF of
A solution of-(3-thienyl) ethyl iodide (produced by the method described above) dissolved therein was added dropwise over 10 minutes. The reaction mixture was stirred at room temperature for 1 hour and then heated to 140 ° C. for 4 hours. After cooling, the reaction was poured into ice cold dilute hydrochloric acid and then extracted 6 times with ether. The organic phases were combined, washed with water, dried over Na ₂ SO ₄ and evaporated to give a brown oil. Chromatographic separation on silica gel (hexane 50% in chloroform) gave a colorless oil in 98% yield. The results of elemental analysis were as follows. In addition, NMR and IR spectra are also shown.

Calculated: C 57.76, H 6.7
1, S 11.86 C ₁₃ H ₁₈ O ₄ S measured value: C 57.65, H 6.76, S 1
1.77. NMR (CDCl ₃ , δ for TMS): 7.40-
7.20t, 1H; 7.10-6.86d, 2H;
18q, 4H; 3.33t, 1H; 2.97 to 1.97.
m, 4H; 1.23t, 6H. IR (neat film, νcm ^-1 ): 2980w, 173
0s, 1450w, 1370w, 775w.

Reference Example 7 Synthesis of 2-carboxy-4- (3-thienyl) butanoic acid 1.4 g (24.96 mmol) of potassium hydroxide was added to 7.0.
The diester prepared in Reference Example 6 (765 mg, 2.83 mmol) was added to a solution dissolved in 50 ml of 50% aqueous ethanol solution. The resulting reaction was stirred at room temperature for 2 hours and then refluxed overnight. The resulting mixture is ice-10%
Poured into HCl and then extracted three times with ether. The organic phases were combined and dried over Na ₂ SO ₄ to yield 90
A white solid was obtained in%. This was recrystallized from chloroform-hexane to give colorless needle crystals. It had the following properties:

Melting point: 118-119 ° C. NMR (DMSO / d6, δ for TMS): 12.
60, 2H; 7.53 to 6.80m, 3H; 3.20
t, 1H; 2.60t, 2H; 1.99q, 2H. IR (KBr, ν cm ⁻¹ ): 2900w, 1710s,
1410w, 1260w, 925w, 780s. The elemental analysis values were as follows. Calculated: C 56.45, H 5.92, S 1
8.83 C ₉ H ₁₀ O ₄ S Found: C 56.39, H 5.92, S 1
8.67.

Reference Example 8 Synthesis of 4- (3 -thienyl) butyl methanesulfonate 4- (3-thienyl) butanoic acid (CA69: 18565)
x, 72: 112265k) was prepared by standard thermal decarboxylation of the carboxylic acid prepared in Reference Example 7.
This compound was also reduced using standard methods to give 4-
(3-thienyl) butanol (CA70: 68035)
r, 72: 112265k). 1.05 g (6.
To a solution of 7 × 10 ⁻³ mol) 4- (3-thienyl) butanol in 25 ml freshly distilled dry pyridine was added 0.85 g (1.1 eq) methanesulfonyl chloride at 25 ° C. . This addition was done gradually over several minutes. The reaction mixture was stirred at room temperature for 6 hours, then poured into a separatory funnel containing water-HCl and ether and quenched. The organic phase is separated and the aqueous phase is once 10%
It was extracted with hydrochloric acid, extracted with water and dried over Na ₂ SO ₄ .
Evaporation of the solvent gave 1.51 g of a light brown oil (yield 95
%) Was obtained. tlc (CHCl ₃ ) showed a single spot. The results of the analysis were as follows.

Calculated: C 46.13, H 6.0
2, S 27.36 C ₉ H ₁₄ O ₃ S ₂ measured value: C 45.92, H 5.94, S 2
7.15. NMR (CDCl ₃ , δ for TMS): 2.0-1.
5 brs, 4H; 2.67 brt, 2H; 2.97s, 3
H; 4.22t, 2H; 7.07 to 6.80d, 2H:
7.37-7.13, 1H.

Reference Example 9 Synthesis of 4- (3-thienyl) butyl iodide The above-mentioned methanesulfonate prepared in Reference Example 8 (1.5
1 g, 6.4 × 10 ⁻³ mol) was added to a solution of 1.93 g (2 equivalents) of NaI in 14 ml of acetone, and the mixture was reacted overnight at room temperature. The reaction mixture was heated to reflux for 5 hours. The precipitated CH ₃ SO ₃ Na was filtered off. The filtrate is poured into water and extracted with chloroform, the organic phase is MgSO 4.
Dried at ₄ . Evaporation of the solvent gave a light brown oil which was purified by chromatography (silica gel, 6 in chloroform).
0% hexane) and 1.34 g of colorless oil (yield 78%)
I got The measured values were as follows.

NMR (CDCl ₃ , δ for TMS):
1.53 to 2.20 m, 4H; 2.64t, 2H;
17t, 2H; 6.83 to 7.10d, 2H; 7.13
~ 7.37t, 1H. IR (KBr, νcm ⁻¹ ): 2960s, 2905s, 2
840s, 1760w, 1565w, 1535w, 14
50s, 1428s, 1415s, 1190s, 750
s, 695m, 633m. MS 266.0. The elemental analysis was as follows. Calculated: C 36.10, H 4.17, I 47.6.
8, S 12.05 C ₈ H ₁₁ IS found: C 37.68, H 4.35, I 45.2
4, S 12.00.

Reference Example 10 Combined with sodium 4- (3-thienyl) butane sulfonate
2 m of Na ₂ SO ₃ adult 1.271g (1 × 10 ^-2 mol)
In an aqueous solution, the above-mentioned iodide 1.
34 g (0.5 eq) was added. The reaction mixture was heated to reflux for 18 hours. The resulting mixture was evaporated to dryness, then washed with chloroform to remove unreacted iodide and with acetone to remove sodium iodide.
The remaining solids were a mixture of the desired sodium salt contaminated with excess sodium sulfite and used in subsequent steps without further purification. The measured values were as follows.

NMR (D ₂ O, δ for TMS propane sulfonate): 1.53 to 1.97 m, 4H;
47-3.13m, 4H; 6.97-7.20d, 2
H; 7.30 to 7.50q, 1H. IR (KBr, ν cm ^-1 , Na ₂ SO ₃ peak subtraction): 2
905w, 1280m, 1210s, 1180s, 12
42m, 1210s, 1180s, 1130s, 106
0s, 970s, 770s, 690w, 630s, 60
5s.

Reference Example 11 4- (3-thienyl) butanesulfonyl chloride 1.00 g of the above salt mixture (from Reference Example 10) was added to 10 ml.
1.43 to the stirring liquid suspended in freshly distilled DMS of
g of distilled thionyl chloride was added dropwise. The mixture was stirred for 3 hours. The ice-quenched solution was extracted twice with ether, then the organic phase was dried over Na ₂ SO ₄ to give a pale yellow oil.
6 mg was isolated and the oil was crystallized slowly (mp 26-27 ° C) after chromatography (using silica gel and chloroform). NMR etc. were as follows.

NMR (CDCl ₃ , δ for TMS):
1.45 to 2.38 m, 4H; 2.72t, 2H;
65t, 2H; 6.78 to 7.12d, 2H; 7.18.
~ 7.42, 1H. IR (neat film, νcm ^-1 ): 3120w, 292
0s, 2870m, 1465m, 1370s, 1278
w, 1260w, 1160s, 1075w, 935w,
850w, 830m, 776s, 680m, 625w,
585s, 535s, 510s. The elemental analysis was as follows. Calculated: C 40.25, H 4.64, Cl 14.
85, S 26.86 C ₈ H ₁₁ Cl O ₂ S _{2 found} : C 40.23, H 4.69, Cl 14.
94, S 26.68.

Reference Example 12 Methyl 4- (3-thienyl) butanesulfonate (Also known as:
Thiophen-3- (methyl 4-butanesulfonate))
362 mg of the above acid chloride prepared in Synthesis Reference Example 11 (1.
5 x 10 ^-3 mol) into a stirred solution of 6 ml of freshly distilled (by molecular sieves) methanol.
92 mg (2 eq) N, N-diisopropylethylamine was added at room temperature. The reaction mixture was stirred for 2 hours, then transferred to a separatory funnel containing dilute aqueous HCl and extracted 3 times with chloroform. The organic phases are combined and combined with Na ₂ SO
After drying at ₄ , the solvent was evaporated to give a light brown oil.
The oil was chromatographed on silica gel using 40% hexane in chloroform as the eluent.
The colorless oil obtained (yield 84%) had the following properties:

Elemental analysis value: Calculated value: C 46.13, H 6.02, S 2
_{7.36 C 9 H 14 S 2 O} 3 Found: C 45.97, H 5.98, S 2
7.28. IR (neat film, νcm ^-1 ): 3100w, 297
0m, 2860w, 1460m, 1410w, 1350
s, 1250w, 1160s, 982s, 830m, 8
00m, 770s, 710w, 690w, 630w, 6
13w, 570m. UV-vis [λ max, MeOH, nm (ε)]: 220
(6.6 × 10 ³ ). NMR (CDCl ₃ , δ for TMS): 7.33-
7.13 (t, 1H), 7.03 to 6.77 (d, 2
H), 3.83 (s, 3H), 3.09 (t, 2H),
2.67 (t, 2H), 2.2-1.5 (m, 4H).

Reference Example 13 Polymerization of thiophen-3-acetic acid

[Chemical 19] According to the electrochemical polymerization method described in "Synth. Metals" (described above) by S. Hotta et al., Using acetonitrile as a solvent and LiCl ₄ O ₄ as an electrolyte, at room temperature, thiophene-3- Acetic acid was polymerized. A bluish black film formed. This has the formula Ia (Y ₁ = H, R ₁ =
-CH ₂ -, indicating the formation of Ht = S, X = zwitterionic polymers CO _2). When this polymer film was electrochemically cycled, it was observed that the color changed from bluish black to tan. This indicates that the polymer was reduced from the zwitterionic form to the neutral form of formula I. The infrared spectrum is consistent with the proposed structure.

Reference Example 14 Poly (thiophen-3- (2-ethanesulfonic acid) nato
Lithium salt) thiophene-3- (2-ethanesulfonic acid methyl) (formula V) was prepared by the method previously described.

Embedded image The polymerization of this monomer was carried out by the same method as in Reference Example 13 except that the polymerization temperature was kept at -27 ° C. The resulting polymer ("P3-ETS Methyl", VI) was treated with sodium iodide in acetone to remove the methyl group from the sulfonic acid functional group and the corresponding sodium salt of the polymer, poly (thiophene-3- ( 2-ethanesulfonic acid) sodium salt) ("P3-ETSNa") (Formula VII) was obtained in sufficient yield (about 98%).

[Chemical 21]

[Chemical formula 22] The above polymer methyl ester and polymer sodium salt were characterized by infrared and visible UV absorption spectroscopy and elemental analysis (see FIGS. 1 and 2). It has been found that the sodium salt is soluble in water in all proportions and has been found to be cast from an aqueous solution into a film.

An electrochemical cell was constructed in glass and electrochemical doping and charge storage was demonstrated by an in situ photoelectrochemical spectrometer. The cell consisted of a film of the above polymer on an ITO coated glass (serving as the anode), a platinum counter electrode (cathode), a silver / silver chloride reference electrode, and a tetrabutylammonium perchlorate electrolyte. FIG. 5 shows a series of visible and near infrared spectra of P3-ETSNa taken with cells charged sequentially to a high open circuit voltage. The results obtained are typical of conducting polymers in that the π-π ^* transition is exhausted, with a consequent transition to the two characteristic near infrared bands of oscillator strength. The results in Figure 5 demonstrate both reversible charge storage and electrochromism.

Electrical conductivity was measured by the standard 4-probe technique using a polymer film cast from water on a glass substrate with all contacts pre-deposited. Upon exposure to bromine vapor, the electrical conductivity of P3-ETSNa increased to about 1 S / cm.

Reference Example 15 Poly (thiophene-3- (4-butanesulfonic acid) nato
( Saltium) thiophene-3- (4-butane sulfonate methyl) (formula VIII) was prepared by the method previously described.

[Chemical formula 23] The polymerization was carried out under the same conditions and methods as described in Reference Examples 13 and 14. The resulting polymer (“P3-BTS methyl”, formula IX) was treated with sodium iodide in acetone to give poly (thiophene-3- (4-)
Butanesulfonic acid) sodium salt) ("P3-BTSN
a ", formula X) was obtained.

[Chemical formula 24]

[Chemical 25] The polymerized methyl ester (Formula IX) and the corresponding sodium salt (Formula X) were characterized by spectrophotometry (IR, UV visible) and elemental analysis. The sodium salt was soluble in water in all proportions and allowed film formation by casting from aqueous solutions.

An electrochemical cell was constructed according to Reference Example 14 to demonstrate electrochemical doping and charge accumulation via in situ photoelectrochemical spectroscopy measurements. 6 to 7 are P
1 shows a series of visible and near infrared spectra taken for cells charged to increasing open circuit voltages of 3-BTSNa and P3-BTS methyl. Similar to Reference Example 14, π−π
^* It was found to be typical of conductive polymers in that the transition was exhausted and the oscillator strength was shifted to two characteristic infrared bands accordingly. Similar to Reference Example 14, FIG.
Results ~ 7 demonstrate both reversible charge storage and electrochromism.

Reference Example 16 Poly (thiophen-3- (2-ethanesulfonic acid))
Production and Analysis Thiophene-3- (2-ethanesulfonic acid) sodium salt polymer (formula I) (Ht = S, Y _{1
= H, R 1 = -CH 2} CH 2 -, X = SO 3, M 1 = N
a) was prepared, dissolved in water, and subjected to ion exchange chromatographic separation of a cation exchange resin in an acidic form to prepare an aqueous solution of poly (thiophen-3- (2-ethanesulfonic acid)). Atomic absorption spectrometry of the dark reddish brown effluent showed that the hydrogen had been completely replaced by sodium. FIG. 8 shows the results of cyclic voltammetry performed on a polymer film (“P3-ETSH” / ITO glass working electrode, platinum counter electrode, silver / silver chloride reference electrode in acetonitrile, fluoroboric acid-trifluoroacetic acid electrolyte). . In the figure, P3-ETSH is silver / in a strongly acidic medium.
It is an electrochemically tough polymer when cycled between +0.1 V and +1.2 V vs. silver chloride. The figure shows two closely spaced oxidation waves, the first one corresponding to the change from orange to green. The polymer was cycled and a corresponding color change was observed at 100 mV / sec with no noticeable change in stability.

An electrochemical cell was constructed in glass and electrochemical doping and charge accumulation was demonstrated by in situ photoelectrochemical spectroscopy measurements. The cell consisted of a polymer film on ITO glass (anode), a platinum counter electrode (cathode), a silver / silver chloride reference electrode in acetonitrile, fluoroboric acid-trifluoroacetic acid electrolyte. FIG. 9 shows the visible and near-infrared spectrum of P3-ETSH measured for cells sequentially charged with an open circuit voltage.
In this case, the polymer was observed to spontaneously dope in the strongly acidic electrolyte. The results in Figure 9 demonstrate both reversible charge storage and electrochromism. Controlling the self-doping level in a short time was achieved by applying a voltage below the balanced circuit voltage.

Reference Example 17 Preparation of Polymer Complex Poly (thiophen-3- (2-ethanesulfonic acid))
(Formula I) (Ht = S, Y 1 = H, R 1 = -CH 2 CH 2
-, produced by _{X = SO 3, M 1 =} H, "P3-EtSH") Reference Example 16, was used in the preparation of the complex as follows. The above compound was mixed with an aqueous polyvinyl alcohol solution, a neutral polymer was cast, and dried to obtain a film. The free-standing dark orange film (charge neutral, unlike blue-black zwitterionic polymers) has excellent mechanical properties (flexible, smooth, flexible), and chemical doping and I was able to dedope. The manufacturing method of this conductive polymer composite is P3-E.
It has broad applicability to the use of any water soluble polymer in connection with TSH or P3-BTSH.

[Brief description of drawings]

FIG. 1 is an infrared spectrum of poly (thiophen-3- (methyl 2-ethanesulfonate)).

FIG. 2 is an infrared spectrum of poly (thiophen-3- (2-ethanesulfonic acid) sodium salt).

FIG. 3 is an infrared spectrum of poly (thiophen-3- (methyl 4-butanesulfonate)).

FIG. 4 is an infrared spectrum of poly (thiophen-3- (4-butanesulfonic acid) sodium salt).

FIG. 5 shows a series of visible and near infrared spectra of poly (thiophen-3- (2-ethanesulfonic acid) sodium salt).

FIG. 6 shows a series of visible near infrared spectra of poly (thiophen-3- (4-butanesulfonic acid) sodium salt).

FIG. 7 shows a series of visible near infrared spectra of poly (thiophen-3- (methyl 4-butanesulfonate)).

FIG. 8 shows the results of cyclic voltammetry performed on a film of poly (thiophen-3- (2-ethanesulfonic acid)).

FIG. 9 shows a series of visible near infrared spectra of poly (thiophen-3- (2-ethanesulfonic acid)).

Claims (3)

[Claims] 1. A water-soluble, self-doping conductive polymer composed of a plurality of monomer units, 0.01 to 100 mol% of which is composed of units having the following structure (II): (In the formula, Y ₂ , Y ₃ and Y ₄ are independently hydrogen and -R _2-.
Selected from the group consisting of X-M ₂ , R ₂ is absent or is a linear or branched alkylene, ether, ester or amide component having 1 to 10 carbon atoms, and X is Or And M ₂ is selected from the group consisting of H, Li, Na and K). 2. The following structure (II): (In the formula, Y ₂ , Y ₃ and Y ₄ are independently hydrogen and -R _2-.
X ₂ is selected from the group consisting of X-M ₂ and R ₂ is absent or is a linear or branched alkylene, ether, ester or amide component having 1 to 10 carbon atoms, and X is Or And M ₂ is selected from the group consisting of H, Li, Na and K) in preparing a water-soluble self-doping conductive polymer having the following structure (IV): (In the formula, R ₂ and X are as defined in the above formula (II), and Y ₂ , Y ₃ and Y ₄ are independently hydrogen and —R ₂ —
X-M ₃ , wherein M ₃ is M ₂ or an alkyl group having 1 to ₂ carbon atoms) is prepared; and an electrolytic solution containing a monomer having a working electrode and a counter electrode is prepared in the electrolytic solution. Immersion; voltage is applied to the working electrode and the counter electrode, thereby polymerizing the monomer at the working electrode; when M ₃ is an alkyl group having 1 to 2 carbon atoms, M ₃ is replaced with M ₂ A method for producing a water-soluble self-doping type conductive polymer having a structure (II), which comprises the step of substituting 3. A method for producing a self-doped polyaniline, which comprises the steps of preparing a polyaniline diester and hydrolyzing the diester to convert it into a corresponding dicarboxylic acid.