JPH07292081A - Soluble, processible, doped conductive polymer, and conductive polymer blend containing same - Google Patents

Abstract

PURPOSE: To obtain soluble, processable, doped electrically conductive polymers excellent in mechanical properties, adhesion strength, etc., by doping a specific electrically conductive polymer with a protonic acid having a long carbon chain or a large substituent.

CONSTITUTION: (A) An electrically conductive polymer having a structure of formula I (wherein X is S, NH or O; R is a group of formula II, a group of formula III, a group of formula IV, a group of formula V, a group of formula VI, a group of formula VII or the like; (y) is 3-22; (n) is 1-22; and R' is H, -CH₃ or -OCH₃) [e.g. poly(3-dodecylthiophene)] and (B) a protonic acid having a long carbon chain or a comparatively large substituent (e.g. dodecylbenzenesulfonic acid) are prepared. Then, component (A) and component (B) are separately dissolved in an organic solvent (e.g. chloroform) and by thoroughly mixing the two resulting solutions, component (A) is doped with component (B). The resulting soluble, processable, doped electrically conductive polymer is formed into an electrically conductive film which is suitable as an antistatic packaging material for electronic parts, etc.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to soluble, processable, doped conductive polymers and their conductive polymer blends, in particular both doped with protic acids having long carbon chains or relatively large substituents. The present invention relates to a conductive polymer and a conductive polymer blend thereof.

[0002]

BACKGROUND OF THE INVENTION Conjugated conductive polymers have been widely studied because of their growing interest in applications in antistatic coatings, conductive coatings, electromagnetic shielding, electrode coatings, and the like. Many attempts have been made to dope acids in conjugated conducting polymers. Doping agents often used in conventional conjugated heterocyclic conductive polymers are FeCl ₃ , SbF ₅ , AsF.
₅ , Lewis acids such as NOPF ₆ or SnCl ₄ . An oxidation reaction proceeds during such a doping process. The conducting polymer loses electrons and produces delocalized polarons and / or bipolarons on its conjugated chains. This increases the conductivity of the conductive polymer.

In contrast to the usual conjugated heterocyclic conducting polymers, a commonly used doping agent for polyaniline is the protic acid. No oxidation reaction occurs, but the imine group is converted to an imine salt. The positive charge of the N atom of the imine salt can delocalize the benzene ring, thus increasing the conductivity of the polyaniline doped with protonic acid. A commonly used protic acid is Macromolecules, page 22.649 (1
989) and Synth.Met. 24.255 (1988).
As disclosed in the _{year) H 2 SO 4, HCl,} HF
Or it is HBF ₄ .

Doping renders the conducting polymer backbone more rigid so that the polymer chains aggregate and the polymer precipitates out of solution. This limits the use of doped conductive polymers. There are two ways to remedy the aforementioned drawbacks. One method is by chemical means. It has been disclosed to synthesize a neutral conductive polymer film by this chemical method and to immerse it in a solution containing an oxidizing agent for doping. Synth.Met.41-4
According to page 3.825 (1991), the dopants used are FeCl ₃ , Fe (ClO ₄ ) ₃ and Synth.M.
et.22.103 (1987) shows NOPF ₆ , and Mol.Cryst.Liq.Cryst.125, p.309 (1).
985) indicates a hydrochloric acid solution.

Another method is by the electrochemical method. Synth. Met. 9.381 (1984) discloses that a conductive polymer film is synthesized by an electrochemical method. This conductive polymer film was synthesized to produce a supporting electrolyte (Bu) ₄ NClO ₄
It is disclosed that the anions of the above are also doped into the film at the same time. However, it is difficult to obtain brittle, insoluble and large area films, regardless of whether the doping is done by chemical or electrochemical methods. Therefore, the application of this film is restricted.

It has been disclosed to include a non-conducting conventional polymer in the conductive polymer to form the conductive polymer composite film. This can be achieved by electrochemical or chemical methods. J. Polym. Sci. Polymer Chemistry Edition 23.1687 (1985) describes that polypyrrole / polychlorination by immersing an anode coated with a vinyl chloride film in a solution containing a suitable solvent, a pyrrole monomer and an electrolyte. It is disclosed that a conductive composite film of vinyl can be prepared.
The vinyl chloride (PVC) film swells in the solution and allows pyrrole to penetrate into the PVC film to form a composite film. Also, Macromolecules 24.1242 (1991) discloses that polyaniline / polyvinyl alcohol composite films were prepared in our laboratory.

Conductive polymer composite films can also be prepared by chemical methods. J. Chem. Soc., Ch
em.Commun.148 (1986) contains 3 of ferric chloride.
A polypyrrole / polypropylene composite film is prepared by placing a polypropylene film at the interface between a 0% solution and a 10% solution of pyrrole, and the two solutions diffuse into polypropylene to form a large amount of polypyrrole and the composite film Is disclosed to make.

Also, Polymer J. 189 (1), page 95 (1986), prepares a polypyrrole / polyvinyl alcohol composite film by exposing a polyvinyl alcohol film containing ferric chloride to a pyrrole monomer vapor. It discloses that you can do it.

Also, Synth.Met. C467 (198
9 years) for poly (3-octylthiophene) to be blended with polyethylene, polystyrene and ethylene-vinyl acetate copolymer in a molten state, and to process the polymer blend to produce a film for doping the film. It has been disclosed that doped composite films can be prepared by dipping in a FeCl ₃ / CH ₃ NO ₂ solution or by exposure to iodine vapor.

All of the aforementioned polymer composite films have the common drawback that the monomers cannot be evenly dispersed in the matrix film. So far, soluble and processable doped polymeric heterocyclic compounds have not been disclosed. Also, no protic acid having long carbon chains or relatively large substituents doped therein was disclosed.

[0011]

Accordingly, one object of the present invention is to provide a soluble and processable conductive polymer doped with a protic acid having long carbon chains or relatively large substituents. .

Another object of the present invention is a soluble, processable, doped conductive polymer blend capable of improving the mechanical properties of the conductive polymer and increasing the bond strength between the conductive polymer and the substrate. Is to provide.

[0013]

In order to solve the above-mentioned problems, a soluble and processable material containing (a) a conductive polymer and (b) a protonic acid having a long carbon chain or a relatively large substituent group. To provide a doped conductive polymer.

Further, (a) a conductive polymer, and (b)
It is to provide a soluble and processable doped conductive polymer comprising a protonic acid having a long carbon chain or a relatively large substituent, and (c) a non-conductive polymer.

Further, poly (3-alkylthiophene)
(P3AT) and a protic acid having a long carbon chain or a relatively large substituent are separately dissolved in an organic solvent. When the two solutions are mixed well, a doped conductive polymer solution is produced. The conductive polymer obtained is still soluble and can be dissolved in common organic solvents such as chloroform, toluene, xylene, benzene or tetrahydrofuran. Also, the conductive polymer solution can be cast to produce a flexible, free-standing film. The conductive polymer may be 3,4-disubstituted polythiophene, polypyrrole and polyfuran. 3-
The substituent is

[0016]

[Chemical 1]

In these formulas, y is 3 to 2
2 is an integer selected from 2, n is an integer selected from 1 to 22, and Y is

[0018]

[Chemical 2]

Or

[0020]

[Chemical 3]

[0021]

The 4-substituent also includes H, --CH ₃ and OCH ₃ . The conductive polymer has N- whose substituents are an alkyl group, an alkaryl group, an alkoxy group, an aralkyl group, an allyl group, a hydroxyl group, a nitro group, chlorine and bromine.
It may be a substituted polypyrrole.

Doping with a protic acid in a conjugated conducting polymer is beyond the skill of those skilled in the art. The protic acid used according to the invention is relatively compatible with the conducting polymer and the solvent. Furthermore, the conductive polymer does not precipitate because it is doped with a protonic acid. Since the protic acid also acts as a plasticizer, the doped conductive polymer does not shrink and is not brittle.

The protonic acid used is dodecylbenzenesulfonic acid, α-camphorsulfonic acid and any organic sulfonic acid (R ″-) soluble in toluene, chloroform, xylene, benzene or tetrahydrofuran (THF).
SO ₃ H) and R ″ is

[0025]

[Chemical 4]

Where m is an integer selected from 4 to 22.

In addition, the doped conductive polymer solution can be blended with the non-conductive polymer in solution. In this way, the mechanical properties of the conductive film can be improved. Also, the adhesiveness between the conductive film and the substrate can be increased. The resulting film is air and humidity resistant and can be used in antistatic packaging materials and electromagnetic interference shielding for electronic components.

As these non-conductive polymers soluble in a solvent selected from toluene, chloroform, xylene, benzene and THF, polystyrene, polymethacrylic acid ester, polyvinyl ester, polyacrylic acid ester, polyvinyl chloride, poly There are alkanes, polycarbonates, polyesters and polysiloxanes.

The non-conductive polymer used in the embodiment of the present invention is polyvinyl acetate, polystyrene, poly (n-propyl methacrylate), poly (methyl methacrylate), poly (isobutylene), poly (n-butyl methacrylate), ethylene-vinyl acetate copolymer. And polyethylmethacrylate. The non-conductive polymer used may be a copolymer composed of at least two monomers selected from styrene, methacrylic acid ester, acrylic acid ester, vinyl chloride and vinyl ester.

[0030]

EXAMPLES Examples of the present invention will be described in detail below.
This example does not limit the scope of the invention. This is because many variations and modifications will be apparent to those skilled in the art. All conductivity in this example was measured by the 4-probe method.

Example 1 Poly (3-dodecylthiophene) (P3DDT) was added to 0.3%.
25 g and 0.016 g of dodecylbenzenesulfonic acid (DBSA) were separately dissolved in an appropriate amount of chloroform. The DBSA solution was gradually added to the P3DDT solution and stirred well to obtain a brown doped conductive polymer solution. The resulting uniform solution was cast to produce a dark, flexible, free-standing film with a metallic sheen. The conductivity of this film is 3.8 × 10 ^-4 S / c as shown in Table 1.
It was m.

Example 2 0.1% of poly (3-octylthiophene) (P3OT) was added.
94 g and 0.20 g of DBSA were separately dissolved in an appropriate amount of toluene. The DBSA solution was gradually added to the P3OT solution and stirred well to obtain a greenish brown doped conductive polymer solution. The resulting homogeneous doped solution was concentrated and cast to produce a dark, flexible, free-standing film with a metallic sheen. The conductivity of this film was 4.6 × 10 ^-1 S / cm as shown in Table 1. UV-Vis spectra of undoped and doped P3OT toluene solutions are shown in Figures 1 (a) and 1 (b), respectively. Doped P3OT solution is 8
It was found to have a pronounced polaron / bipolaron absorption at wavelengths above 18 nm and 1200 nm, indicating the doping of P3OT by DBSA.

Example 3 0.194 g of P3OT and 0.033 g of DBSA were separately dissolved in an appropriate amount of chloroform. The DBSA solution was slowly added to P3OT and stirred well to obtain a brown doped conductive polymer solution. The resulting uniform solution was cast to produce a dark, flexible, free-standing film with a metallic sheen. The conductivity of this film was 7.3 × 10 ⁻³ S / cm as shown in Table 1. This film is stable under ambient conditions and has a glass transition temperature (T
g) is -46 ° C.

Example 4 0.194 g of P3OT and 0.016 g of DBSA were separately dissolved in an appropriate amount of chloroform. The DBSA solution was gradually added to the P3OT solution and stirred well to obtain a brown doped conductive polymer solution. The resulting uniform solution was cast to produce a dark, flexible, free-standing film with a metallic sheen. The conductivity of this film is 6.0 × 10 ⁻⁴ S / cm as shown in Table 1,
The glass transition temperature (Tg) was -14 ° C. The IR spectra of the solution-cast undoped and doped P3OT films are shown in Figures 2 (a) and 2 (b), respectively.
Shown in. Wave number 1309, 1182, 1 when doped
It was found to give rise to five new peaks at 083, 1040, and 1012 cm ^-1, which are due to the formation of polaron and bipolaron in P3.
T (transition) mode stretching vibration of OT ring and O of DBSA
= S = O due to asymmetric and symmetric vibrations. These modes are associated with translational motion of intrinsic charge defects (polarons or bipolarons) resulting from electron-phonon interactions.

Example 5 0.194 g of P3OT and 0.007 g of DBSA were separately dissolved in an appropriate amount of toluene. DBSA solution P
The solution was gradually added to the 3OT solution and stirred well to obtain a brown doped conductive polymer solution. The resulting homogeneous solution was cast to produce a dark, flexible, free-standing film with a metallic sheen. As shown in Table 1, the conductivity of this film was 9.2 × 10 ⁻⁵ S / cm, and the glass transition temperature (Tg) was −13 ° C.

Example 6 0.13 of poly (3-butylthiophene) (P3BT) was added.
8 g and 0.026 g of DBSA were separately dissolved in an appropriate amount of toluene. The DBSA solution was gradually added to the P3BT solution and stirred well to obtain a brown doped conductive polymer solution. The resulting homogeneous solution was cast to produce a dark, flexible, free-standing film with a metallic sheen. The conductivity of this film is 7.3 x 10 as shown in Table 1.
It was ^-3 S / cm.

Example 7 0.138 g of P3BT and α-camphorsulfonic acid (α
-CSA) and 0.019 g were separately dissolved in an appropriate amount of chloroform. The α-CSA solution was gradually added to the P3BT solution and stirred well to obtain a brown doped conductive polymer solution. The resulting homogeneous solution was cast to produce a dark, flexible, free-standing film with a metallic sheen.
The conductivity of this film is 4.6 × 1 as shown in Table 1.
It was 0 ⁻⁴ S / cm.

[0038]

[Table 1]

Example 8 The following reagents were separately dissolved in an appropriate amount of toluene to form a solution. (1) 0.25g of P3DDT, (2) DBS
0.013 g of A, (3) polyvinyl acetate (MW50
0.02 g of solution (3) and solution (3) were dissolved at 50 ° C. and cooled to room temperature. Solution (2) is gradually added to Solution (1)
And mixed well to form a mixed solution. Then, the solution (3) was gradually added to the mixed solution and stirred sufficiently,
A brown solution of the doped conductive polymer blend was obtained. The resulting homogeneous solution was cast to produce a dark, free-standing film with a metallic sheen. The conductivity of this film is 5.5 × 10 ⁻⁵ S / cm as shown in Table 2.

Example 9 The same procedure as in Example 8 was used. As a reagent (1) P3
0.25 g of DDT, 0.019 g of (2) α-CSA
And (3) polystyrene (MW 125,000-35)
0.00 g) was separately dissolved in an appropriate amount of chloroform. The resulting homogeneous solution was cast to produce a dark colored, free-standing film with a metallic sheen. The conductivity of this film is 1.8 × 10 ⁻⁴ S / cm as shown in Table 2.
Is.

Example 10 The same procedure as in Example 8 was used. As a reagent (1) P3
DDT 0.25g, (2) α-CSA 0.007g
And (3) 0.02 of poly (n-propyl methacrylate)
Dissolve 5 g separately in an appropriate amount of chloroform, and add the reagent (3)
Was melted at 50 ° C., cooled to room temperature, and the resulting homogeneous solution was cast to produce a dark-colored, free-standing film with metallic luster. The conductivity of this film is 6.6 × 10 ⁻⁶ S / cm as shown in Table 2.

Example 11 The same procedure as in Example 8 was used. As a reagent (1) P3
0.194 g of OT, 0.20 g of (2) DBSA and 9.7 g of (3) polystyrene were separately dissolved in an appropriate amount of toluene. The resulting solution was greenish brown. The solution was cast to produce a dark purple, translucent, free-standing film. The conductivity of this film is 5.5 × 10 ⁻⁴ S / cm as shown in Table 2. Curve (c) of FIG. 1 shows the U of the doped conductive polymer blend solution.
The V-Vis spectrum is shown. This doped conducting polymer blend solution was found to have polaron / bipolaron absorption at a wavelength of 819 nm.

Example 12 The same procedure as in Example 8 was used. As a reagent (1) P3
OT 0.194 g, (2) DBSA 0.20 g and (3) polymethylmethacrylate (MW 350.00
9.7 g of 0) was separately dissolved in an appropriate amount of toluene, and the reagent (3) was dissolved at 50 ° C. The resulting homogeneous solution was cast to produce a dark colored, free-standing film with a metallic sheen. The conductivity of this film is 4.4 × as shown in Table 2.
It is 10 ⁻⁴ S / cm.

Example 13 The same procedure as in Example 8 was used. As a reagent (1) P3
OT 0.194g, (2) DBSA 0.20g and
(3) Polyisobutylene (MW 2.100.000)
0.194 g was separately dissolved in an appropriate amount of chloroform,
Reagent (3) melted at 50 ° C. The resulting homogeneous solution
Cast to produce a dark, self-supporting film with metallic luster
I made it. The conductivity of this film is 1.
2 x 10 ^-FiveS / cm.

Example 14 The same procedure as in Example 8 was used. As a reagent (1) P3
0.194 g of OT, 0.026 g of (2) DBSA and 0.03 g of (3) polymethylmethacrylate were separately dissolved in an appropriate amount of toluene, and the reagent (3) was dissolved at 50 ° C. The resulting homogeneous solution was cast to produce a dark colored, free-standing film with a metallic sheen. The conductivity of this film is 4.4 × 10 ⁻³ S / cm as shown in Table 2.

Example 15 The same procedure as in Example 8 was used. As a reagent (1) P3
0.194 g of OT, 0.026 g of (2) DBSA and 0.03 g of (3) n-butyl polymethacrylate were separately dissolved in an appropriate amount of toluene, and the reagent (3) was dissolved at 50 ° C. The resulting homogeneous solution was cast to produce a dark colored, free-standing film with a metallic sheen. The conductivity of this film is 8.4 × 10 ⁻⁴ S / cm as shown in Table 2.

Example 16 The same procedure as in Example 8 was used. As a reagent (1) P3
0.194 g of OT, 0.026 g of (2) DBSA and 0.03 g of (3) polystyrene were separately dissolved in an appropriate amount of toluene. The resulting homogeneous solution was cast to produce a dark colored, free-standing film with a metallic sheen. The conductivity of this film is 8.7 × 10 ⁻³ S as shown in Table 2.
/ Cm, the glass transition temperature (Tg) is -12 ° C.

Example 17 The same procedure as in Example 8 was used. As a reagent (1) P3
0.194 g of OT, 0.016 g of (2) DBSA and 0.03 g of (3) polystyrene were separately dissolved in an appropriate amount of toluene. The resulting uniform solution was cast to produce a dark, flexible, free-standing film with a metallic sheen. The conductivity of this film is 1 × 10 as shown in Table 2.
^{At -4} S / cm, the glass transition temperature (Tg) is -10 ° C. Curve (c) in FIG. 2 shows the IR spectrum of a film of doped conductive polymer blend. It is observed that this film has new stretching vibrational peaks due to vibrational modes induced by doping and DBSA's O = S = O asymmetric and symmetrical vibrations. These peaks are 1304 cm ^-1 , 1181c
It is located at m ^-1 , 1080 cm ^-1 and 1037 cm ^-1 .

Example 18 The same procedure as in Example 8 was used. As a reagent (1) P3
0.194 g of OT, 0.007 g of (2) DBSA and 0.03 g of (3) polystyrene were separately dissolved in an appropriate amount of toluene. The resulting homogeneous solution was cast to produce a dark colored, free-standing film with a metallic sheen. The conductivity of this film is 7.7 × 10 ^-5 S as shown in Table 2.
/ Cm, the glass transition temperature (Tg) is -6.4 ° C.

Example 19 The same procedure as in Example 8 was used. As a reagent (1) P3
0.194 g of OT, 0.01 g of (2) DBSA and 0.03 g of (3) ethylene-vinyl acetate copolymer having a vinyl acetate content of 45% were separately dissolved in an appropriate amount of toluene, and the reagent (3) was Melted at 50 ° C. The resulting homogeneous solution was applied to glass to form a film. The conductivity of this film is 1.2 × 10 ⁻⁶ S / as shown in Table 2.
cm.

Example 20 The same procedure as in Example 8 was used. As a reagent (1) P3
OT 0.138 g, (2) DBSA 0.033 g and (3) polyethyl methacrylate (MW 250.00
0.028 g of 0) was separately dissolved in an appropriate amount of chloroform. Reagent (3) melted at 50 ° C. The resulting homogeneous solution was cast to produce a dark colored, free-standing film with a metallic sheen. The conductivity of this film is 2.2 × 10 ⁻³ S / cm as shown in Table 2.

[0052]

[Table 2]

Example 21 A solution of the doped conductive polymer blend prepared in Example 16 was applied to an epoxy resin substrate and air dried. The adhesion of the applied film to the substrate was very good. The film-coated substrate coated with the conductive polymer blend solution was rubbed with a cloth to immediately place the substrate on a piece of paper to test for electrostatic charge generation. No suction of the piece of paper against the coated substrate was observed, indicating that no static electricity was generated. However, it was confirmed that when the substrate coated with the solution of the conductive polymer blend was not covered with the film, the substrate was sucked when it was rubbed with a cloth. Comparing the above two substrates, it can be seen that the substrate coated with the conductive polymer blend has good antistatic properties. Thus, films of conductive polymer blends can be used in electronic packaging or as antistatic coatings for plastics and fibers.

The advantages and usefulness of the present invention are illustrated by the following figures and tables. FIG. 1 shows a UV-Vis spectrum of a conductive polymer solution according to the present invention. In this figure, curve (a) is the undoped P3OT / toluene solution,
Curve (b) corresponds to the doped P3OT / toluene solution of Example 2 and curve (c) corresponds to the doped P3OT / polystyrene / toluene solution of Example 11. Both the curve (b) and the curve (c) are about 8
It can be seen that it shows a peak at 18 nm and absorption of light over 1500 nm. These absorptions are P3OT
Shows that polaron / bipolaron was generated in the main chain of. However, curve (a) shows no absorption at wavelengths above 500 nm. From the result of the spectroscopic measurement, P
The 3OT can be doped with dodecylbenzene sulfonic acid with redox reaction and polaron / bipolaron formation in the backbone. Also, Polaron /
Doped P3OT after blending with polystyrene which exhibits bipolaron absorption shows that the doping state of P3OT is maintained after blending.

FIG. 2 shows the IR spectrum of a conductive polymer film according to the invention, curve (a) showing undoped P
3OT, curve (b) shows the doped P3OT of Example 4
The film, and curve (c), shows the film of the doped P3OT / polystyrene blend of Example 17. Compared to curve (a), curves (b) and (c)
Is the C = C ring produced and the polaron after doping /
C- in the P3OT ring resulting from the formation of bipolaron
Due to C stretching vibration, a new peak is shown in the range of 1400 cm ^{-1 to} 1000 cm ^-1 .

Table 1 shows the conductivity of the films of Examples 1 to 7 in which three types of poly (3-alkylthiophyene) (P3AT) were doped with plutonic acid at various levels. The molar ratio of the protonic acid to the repeating unit of P3AT varies from 0.02 to 0.6.

Table 2 shows Examples 8-20 in which doped P3AT was blended with some non-conductive polymers.
Shows the conductivity of the film. The molar ratio of protonic acid to P3AT repeating unit varies from 0.1 to 50.

From the results of Table 1 and Table 2, it can be concluded as follows. That is, from Examples 1 to 7, when doping with a protic acid at a low molar ratio of about 0.02, a minimum value of 10 for antistatic use is obtained.
It is possible to obtain a conductivity as high as 10 ⁻⁴ S / cm, which is two orders of magnitude higher than ⁻⁶ S / cm.

Example 4 and Example 17 and Example 5
Compared to Example 18 at a weight ratio of 0.15, doped P3 after blending with a non-conductive polymer.
It can be seen that AT still holds the conductivity in the same order of magnitude.

In addition, from Examples 11, 12 and 13 the inclusion of about 2% by weight of doped P3AT in the polymer blend is relatively high, about 10 ^-5 S /.
It can be seen that a conductivity of cm can be achieved.

[0061]

The protonic acid used in the present invention acts as a plasticizer and a dope. The addition of such a protic acid can prevent the doped polymer from shrinking and becoming brittle, and can improve the compatibility between the conductive polymer and the non-conductive polymer, so that the mechanical properties of the conductive film can be improved. And the adhesive strength between the conductive film and the substrate is increased.

[Brief description of drawings]

FIG. 1 shows the case where the solvent is toluene in the UV-Vis spectrum of the conductive polymer of the present invention.

FIG. 2 shows an IR spectrum of the conductive polymer film of the present invention.

Claims (29)

[Claims] 1. A conductive polymer having the following chemical structure: In this formula, X is selected from the group consisting of S, NH and O, and R is Selected from the group consisting of, y is an integer selected from 3 to 22, n is an integer selected from 1 to 22, and Y is R ′ is H, —CH ₃ and —O.
Soluble and processable doped conductive material comprising a conductive polymer selected from the group consisting of CH ₃ and (b) a protic acid having a long carbon chain or relatively large substituents. Polymers. 2. The doped conductive polymer according to claim 1, wherein X is S and R is — (CH ₂ ) _y CH _2.
3. A soluble, processable, doped conductive polymer, wherein 3 is an integer selected from 3, 7 and 11 and R'is H. 3. A soluble, processable, doped conductive polymer according to claim 2, characterized in that y is 3. 4. A soluble, processable, doped conductive polymer according to claim 2, characterized in that y is 7. 5. A soluble, processable, doped conductive polymer according to claim 2, characterized in that y is 11. 6. A soluble, processable, doped conductive polymer according to claim 1 wherein the conductive polymer is polypyrrole. 7. The doped conductive polymer according to claim 6, wherein the conductive polymer is selected from N-substituted polypyrrole and 3,4-disubstituted polypyrrole. Conductive polymer. 8. The doped conductive polymer of claim 1, wherein the conductive polymer is polyfuran. 9. A doped conductive polymer according to claim 8, wherein the conductive polymer is 3,4-disubstituted polyfuran. 10. The doped conductive polymer of claim 1, wherein the protonic acid has the chemical structure R ″ —SO ₃ H, where R ″ is A soluble and processable doped conductive polymer, characterized in that m is an integer selected from the group consisting of 4 to 22, selected from the group consisting of: 11. The doped conductive polymer of claim 10, wherein R ″ is And a soluble and processable doped conductive polymer, wherein m is 11. 12. The doped conductive polymer according to claim 10, wherein R ″ is A soluble and processable doped conductive polymer characterized in that: 13. A conductive polymer having the following chemical structure: In this formula, X is selected from the group consisting of S, NH and O and R is Y is an integer selected from 3 to 22, n is an integer selected from 1 to 22, and Y is A conductive polymer selected from the group consisting of H, —CH ₃ and —OCH ₃ , and (b) a long carbon chain or a relatively large substituent. A soluble, processable, doped conductive polymer blend comprising a protic acid and (c) a non-conductive polymer. 14. The doped conductive polymer blend of claim 13, wherein X is S and R is-(C
H ₃ ) _y CH _{3 wherein} y is an integer selected from 3, 7, 11 and R ′ is H. Soluble and processable doped conductive polymer blend. 15. The doped conductive polymer blend of claim 14 wherein y is 3. 16. The doped conductive polymer blend of claim 14, wherein y is 7. 17. A doped conductive polymer blend according to claim 14, characterized in that y is 11. 18. A doped, conductive polymer blend according to claim 13, wherein the conductive polymer is polypyrrole. 19. A doped conductive polymer blend according to claim 18, wherein the conductive polymer is selected from the group consisting of N-substituted polypyrrole and 3,4-disubstituted polypyrrole. Possible doped conductive polymer blends. 20. The doped conductive polymer blend of claim 13 wherein the conductive polymer is polyfuran. 21. The doped conductive polymer blend according to claim 20, wherein the conductive polymer is 3,4-
A soluble and processable doped conductive polymer blend characterized by being a disubstituted polyfuran. 22. The doped conductive polymer blend according to claim 13, wherein the protonic acid is R ″ —SO ₃
In this formula, R ″ is A soluble, processable, doped, conductive polymer blend selected from the group consisting of: m is an integer selected from 4 to 22. 23. The doped conductive polymer blend of claim 22, wherein R "is A soluble, processable, doped conductive polymer blend having the following chemical structure, wherein m is 11. 24. The doped conductive polymer blend of claim 22, wherein R ″ is A soluble and processable doped conductive polymer blend characterized by having a chemical structure of: 25. The doped conductive polymer blend of claim 13 wherein the non-conductive polymer is soluble in organic solvents. 26. The doped conductive polymer blend of claim 25, wherein the non-conductive polymer is soluble in an organic solvent selected from the group consisting of toluene, chloroform, xylene, benzene and tetrahydrofuran. A soluble, processable, doped conductive polymer blend featuring. 27. The doped conductive polymer blend of claim 13, wherein the non-conductive polymer is polystyrene, polymethacrylic acid ester, polyacrylic acid ester, polyvinyl ester, polyvinyl chloride, polyalkane, polycarbonate, polyester. And a soluble and processable doped conductive polymer blend selected from the group consisting of: and a polysiloxane. 28. The doped conductive polymer blend according to claim 13, wherein the non-conductive polymer is at least two selected from the group consisting of styrene, methacrylic acid ester, acrylic acid ester, vinyl chloride and vinyl ester. A soluble and processable doped conductive polymer blend characterized in that it is a copolymer of monomers. 29. The doped conductive polymer blend of claim 13, wherein the non-conductive polymer is polyvinyl acetate, polystyrene, poly (n-propyl methacrylate), poly (methyl methacrylate), poly (isobutylene), poly (n-methacrylate). -A soluble, processable, doped, conductive polymer blend characterized in that it is selected from the group consisting of butyl, ethylene vinyl acetate copolymer and polyethylmethacrylate.