DE69421164T2 - Soluble and processable doped electrically conductive polymer and polymer mixture thereof - Google Patents

Description

The invention relates to a soluble and processable doped electrically conductive polymer and a polymer mixture thereof, more preferably it relates to a doped polymer and a doped polymer mixture thereof, both of which are doped with a protonic acid having a long carbon chain or a larger substituent group.

Conjugated conductive polymers have been widely studied due to the growing interest in their use in antistatic coatings, conductive paints, electromagnetic shields, electrode coatings and the like. Attempts have been made to dope the conjugated conductive polymers with acids. The dopant which has been frequently used in a general conjugated heterocyclic conductive polymer is a Lewis acid such as FeCl3, SbF5, AsF5, NOPF6 or SnCl4. An oxidation reaction is applied during such a doping process. The polymer loses electrons and a delocalized polaron and/or bipolaron is formed on the conjugated chain thereof. This causes the polymer to have an increased electrical conductivity.

In contrast to the general conjugated heterocyclic conductive polymer, the dopant often used in a polyaniline is a protonic acid. No oxidation reaction occurs, but the imine group turns into an imine salt. Since the positive charge on the N atom of the imine salt can delocalize to the benzene ring, the acid-doped polyaniline has an increased conductivity. The protonic acid often used is H2SO4, HCl, HF or HBF4, as described in Macromolecules, 22, 649(1989) and Synth. Met., 24, 255(1988).

The dopant makes the main chain of the polymer more rigid, which leads to aggregation of the polymer chains, and thus the polymer precipitates out of the solution. This limits the applications of the doped conductive polymers. There are two ways to improve the disadvantages mentioned above. One way is a chemical method. It is described that a neutral conductive polymer film is synthesized by a chemical method, then it is immersed in a solution containing an oxidizing agent for doping. The dopants used include FeCl₃, Fe(ClO₄)₃ [Synth. Met., 41-43, 825(1991)], NOPF6 [Synth. Met., 22, 103(1987)] and hydrochloric acid solution [Mol. Cryst. Liq. Cryst., 125, 309(1985)].

Another way is an electrochemical method. It is described that a conductive polymer film is synthesized by an electrochemical method. The conductive polymer film is synthesized, and the anion of the supporting electrolyte (Bu)₄NClO₄ is also doped into the film at the same time [Synth. Met., 9, 381(1984)]. However, regardless of whether the doping is achieved by the chemical or electrochemical method, the resulting film is brittle and insoluble; and a large area film is difficult to obtain. Thus, the application is limited.

The incorporation of a conductive polymer with a non-conductive conventional polymer to form a conductive polymer composite film has been described. This can be accomplished by an electrochemical or chemical process. Paoli et al. describe that a conductive polypyrrole/poly(vinyl chloride) (PVC) composite film can be prepared by immersing an anode coated with a PVC film in a solution containing an appropriate solvent, pyrrole monomer, and an electrolyte. The PVC film will swell in the solution, allowing the pyrrole to infiltrate into the PVC film, forming the composite film [J. Polym. Sci., Polym. Chem. Ed., 23, 1687(1985)]. A polyaniline/poly(vinyl alcohol) composite film has also been prepared in our laboratory [Macromolecules, 24, 1242(1991)].

A conductive polymer composite film can also be prepared by a chemical process. Brocchi et al. describe that a polypyrrole/polypropylene composite film is prepared by placing a polypropylene film at the interface of a 30% ferric chloride solution and a 10% pyrrole solution. The two solutions diffuse into the polypropylene, allowing polypyrrole to form in the bulk, thus yielding a composite film [J. Chem. Soc., Chem. Commun., 148(1986)]. Ojio et al. describe that a polypyrrole/poly(vinyl alcohol) composite film can be prepared by exposing a poly(vinyl alcohol) film containing ferric chlorite to pyrrole monomer vapor [Polymer J., 189(1), 95(1986)]. Laakso et al. describes that a doped composite film can be prepared by mixing a poly-3-octylthiophene with polyethylene, polystyrene and ethylene/vinyl acetate copolymer in the molten state, then processing the polymer mixture to form a film and immersing the film in a FeCl3/CH3NO2 solution or exposing the film to iodine vapor for doping [Synth. Met., 28, C467(1989)].

All of the above-mentioned polymer composite films have a common disadvantage in that the monomers cannot be distributed uniformly in the matrix film. So far, a doped polyheterocyclic compound, which is soluble and processable, not described. Also, no protonic acid with a long carbon chain or a large substituent group doped into it has been described so far.

An object of the present invention is therefore to provide a soluble processable conductive polymer doped with a protonic acid having a long carbon chain or a larger substituent group.

Another object of the present invention is to provide a soluble and processable doped polymer blend which can improve the mechanical properties of the polymer and increase the bonding strength between the polymer and the substrate.

In accordance with the many aims and purposes of the present invention, there is provided a soluble and processable doped conductive polymer including: (a) a conductive polymer; and (b) a protonic acid having a long carbon chain or larger substituent group.

The present invention further provides a soluble and processable doped conductive polymer blend including: (a) a conductive polymer; (b) a protonic acid having a long carbon chain and a larger substituent group; and (c) a non-conductive polymer.

The above-mentioned conductive polymer (a) has the following chemical structure:

wherein X is selected from the group consisting of S, NH and O;

where -R is selected from the group consisting of

-(CH₂)yCH₃,

-O-(CH2 )nCH3 , -(CH2 )n-O-(CH2 )nCH3 , -(CH2 -CH2 -O)n-CH3 , -(CH2 )nCOOH, -(CH2 )nCOOY, -O-CH2 -CH2 -O-(CH2 )nCH3 ;

where y is an integer chosen from 3 to 22;

where n is an integer chosen from 1 to 22;

where -Y is selected from the group consisting of

-(CH₂)nCH₃,

where n is as defined above;

wherein -R' is selected from the group consisting of -H, -CH₃ and -OCH₃

where p is an integer chosen from 60 to 8000.

The present invention can be more fully understood by reading the following detailed description and examples, with reference to the accompanying drawings, in which:

Figure 1 shows UV-Vis spectra of the conductive polymer solutions of the present invention wherein the solvent is toluene;

Fig. 2 shows IR spectra of the conductive films of the present invention.

A poly(3-alkylthiophene) (P3AT) and a protonic acid with a long carbon chain or a large substituent group are separately dissolved in an organic solvent. The two solutions are thoroughly mixed to produce a doped conductive polymer solution. The resulting polymer is still soluble and can be dissolved in a general organic solvent such as chloroform, toluene, xylene, benzene or tetrahydrofuran. Also, the polymer solution can be cast to form a soft free-standing film.

The conductive polymers can be 3,4-disubstituted polythiophenes, polypyrroles and polyfurans.

The 3-substituted groups include the following:

-(CH2)yCH3,

-(CH2 )nCH3 , -(CH2 )n-O-(CH2 )nCH3 , -(CH2 -CH2 -O)n-CH3 , -(CH2 )nCOOH, -(CH2 )nCOOY , -O-CH2 -CH2 -O-(CH2 )nCH3 ;

where y is an integer chosen from 3 to 22;

n is an integer chosen from 1 to 22;

Y -(CH₂)nCH₃ or

is.

The 4-substituent groups include: -H, -CH3, and -OCH3. The conductive polymers can be N-substituted polypyrroles, wherein the substituted groups are alkyl, alkaryl, alkoxy, aralkyl, aryl, hydroxy, nitro, chlorine, and bromine.

Doping of a protonic acid in the conjugated conductive polymer cannot be expected by those skilled in the art. According to the present invention, the protonic acid used is relatively compatible with the conductive polymer and the solvent. Moreover, the conductive polymer will not precipitate due to the doping of the acid. The protonic acid can also act as a plasticizer, which is why the doped conductive polymer cannot shrink and is not brittle.

The protonic acids used include dodecylbenzenesulfonic acid, d-camphorsulfonic acid and any organic sulfonic acids (R"-SO₃H) which are soluble in toluene, chloroform, xylene, benzene or tetrahydrofuran (THF).

where R"

CH₃(CH₂)m-,

CF₃(CH₂)m-

is;

where m is an integer chosen from 4 to 22.

Furthermore, the doped conductive polymer solution can also be mixed with a non-conductive polymer in a dissolved state. In this way, the mechanical properties of the conductive film can be improved and the adhesion between the conductive film and the substrate can also be increased. The resulting film is resistant to air and moisture and can be used in the antistatic packaging materials for electronic components and electromagnetic interference shields. These non-conductive polymers, which are soluble in a solvent selected from toluene, chloroform, xylene, benzene and THF, include polystyrenes, poly(methacrylic acid esters), poly(vinyl esters), poly(acrylic acid esters), poly(vinyl chloride), poly(alkanes), poly(carbonates), poly(esters) and poly(siloxanes). The polymers used in the embodiments of this invention are poly(vinyl acetate), poly(styrene), poly(n-propyl methacrylate), poly(methyl methacrylate), poly(isobutylene), poly(n-butyl methacrylate), ethylene/vinyl acetate copolymer and poly(ethyl methacrylate). Also, the non-conductive polymer used can be a copolymer with more than one monomer selected from styrenes, methacrylic acid esters, acrylic acid esters, vinyl chloride and vinyl esters.

The following specific examples are intended to more fully demonstrate this invention, without being a limitation as to the scope thereof, since numerous modifications and variations will be apparent to those skilled in the art. All conductivities in the examples were measured using the four probe method.

EXAMPLE 1

0.25 g of poly(3-dodecylthiophene) (P3DDT) and 0.016 g of dodecylbenzenesulfonic acid (DBSA) were separately dissolved in an appropriate amount of chloroform. The DBSA solution was slowly added to the P3DDT solution and stirred thoroughly to obtain a doped conductive polymer solution with brown color. The resulting homogeneous solution was cast to form a soft free-standing film with dark color and metallic luster. The conductivity of the film was 3.8 x 10-4 S/cm, as shown in Table 1.

EXAMPLE 2

0.194 g of poly(3-octylthiophene) (P3OT) and 0.20 g of DBSA were separately dissolved in an appropriate amount of toluene. The DBSA solution was slowly added to the P3OT solution and stirred thoroughly to obtain a doped conductive polymer solution with greenish-brown color. The resulting homogeneous doped solution was concentrated and then cast to form a soft free-standing film with dark color and metallic luster. The conductivity of the film was 4.6 x 10-1 S/cm, as shown in Table 1. The UV-Vis spectra of these undoped and doped P3OT solutions in toluene are shown in Fig. 1(a) and (b), respectively. It was found that the doped P3OT solution exhibited significant polaron/bipolaron absorptions at 818 nm and above 1200 nm, indicating doping of P3OT with 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 the P3OT solution and thoroughly stirred to obtain a doped conductive polymer solution with brown color. The resulting homogeneous solution was cast to obtain a soft free-standing film with dark color and metallic luster. The conductivity of the film was 7.3 x 10-3 S/cm as shown in Table 1. This film was stable under ambient conditions and had a glass transition temperature (Tg) of -46ºC.

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 slowly added to the P3OT solution and thoroughly stirred to obtain a doped conductive polymer solution with brown color. The resulting homogeneous solution was cast to obtain a soft free-standing film with dark color and metallic luster. The film had a conductivity of 6.0 x 10-4 S/cm as shown in Table 1 and a glass transition temperature (Tg) of -14°C. The IR spectra of the undoped and doped P3OT film cast from the solution are as shown in Fig. 2(a) and (b), respectively. It was found that the doping induced five additional peaks at wavenumbers 1309, 1182, 1083, 1040 and 1012 cm 1, which can be assigned to stretching vibrations of the T (transition) mode on the ring of P3OT, resulting from the generation of polaron and bipolaron, and to asymmetric and symmetric vibrations of O = S = O of DBSA. These T modes are related to the translational motion of intrinsic charge defects (polarons or bipolarons) arising 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. The DBSA solution was slowly added to the P3OT solution and stirred thoroughly to obtain a doped conductive polymer solution with brown color. The resulting homogeneous solution was cast to form a soft free-standing film with dark color and metallic luster. The conductivity of the film was 9.2 x 10-5 S/cm, as shown in Table 1, and the Tg thereof was -13°C.

EXAMPLE 6

0.138 g of poly(3-butylthiophene) (P3BT) and 0.026 g of DBSA were separately dissolved in an appropriate amount of toluene. The DBSA solution was slowly added to the P3BT solution and thoroughly stirred to obtain a doped conductive polymer solution with brown color. The resulting homogeneous solution was cast to form a soft free-standing film with dark color and metallic luster. The conductivity of the film was 7.3 x 10-3 S/cm, as shown in Table 1.

EXAMPLE 7

0.138 g of P3BT and 0.019 g of d-camphorsulfonic acid (d-CSA) were separately dissolved in an appropriate amount of chloroform. The d-CSA solution was slowly added to the P3BT solution and stirred thoroughly to obtain a doped conductive polymer solution with brown color. The resulting homogeneous solution was cast to form a soft free-standing film with dark color and metallic luster. The conductivity of the film was 4.6 x 10-4 S/cm, as shown in Table 1.

EXAMPLE 8

The following reagents were separately dissolved in an appropriate amount of toluene to prepare solutions: (1) 0.25 g of P3DDT, (2) 0.013 g of DBSA, and (3) 0.02 g of poly(vinyl acetate) (Mw = 500,000), with solution (3) slowly dissolved at 50°C and then allowed to cool to room temperature. Solution (2) was slowly added to solution (1) and thoroughly stirred to obtain a mixed solution. Then solution (3) was slowly added to the mixed solution and thoroughly stirred to obtain a brown colored solution of a doped conductive polymer blend. The resulting homogeneous solution was cast to obtain a free-standing film with dark color and metallic luster with a conductivity of 5.5 x 10-5 S/cm as shown in Table 2.

EXAMPLE 9

The same procedure as described in Example 8 was used. The reagents: (1) 0.25 g of P3DDT, (2) 0.019 g of d-CSA and (3) 0.03 g of polystyrene (Mw = 125,000 to 350,000) were separately dissolved in an appropriate amount of chloroform. The resulting homogeneous solution was cast to form a free-standing film with dark color and metallic luster. The conductivity of the film was 1.8 x 10-4 S/cm, as shown in Table 2.

EXAMPLE 10

The same procedures as described in Example 8 were used. The reagents: (1) 0.25 g of P3DDT, (2) 0.007 g of d-CSA and (3) 0.025 g of poly(n-propyl methacrylate) were separately dissolved in an appropriate amount of chloroform, with the reagent (3) being dissolved at 50°C and then left to cool at room temperature. The resulting homogeneous solution was cast to form a free-standing film with dark color and metallic luster. The conductivity of the film was 6.6 x 10-6 S/cm, as shown in Table 2.

EXAMPLE 11

The same procedures as described in Example 8 were used. The reagents: (1) 0.194 g P3OT, (2) 0.20 g DBSA and (3) 9.7 g poly(styrene) were separately dissolved in an appropriate amount of toluene. The resulting solution had a greenish-brown color. It was then cast to form a translucent free-standing film with a dark purple color and a conductivity of 5.5 x 10-4 S/cm as shown in Table 2. Referring to Figure 1, curve (c) shows the UV-Vis spectrum of the doped conductive polymer blend solution. This doped conductive polymer blend solution was found to have a polaron/bipolaron absorption at a wavelength of 819 nm.

EXAMPLE 12

The same procedures as described in Example 8 were used. The reagents: (1) 0.194 g P3OT, (2) 0.20 g DBSA and (3) 9.7 g poly(methyl methacrylate) (Mw = 350,000) were separately dissolved in an appropriate amount of toluene, with the reagent (3) dissolved at 50°C. The resulting homogeneous solution was cast to form a free-standing film of dark color and metallic luster with a conductivity of 4.4 x 10-4 S/cm as shown in Table 2.

EXAMPLE 13

The same procedures as described in Example 8 were used. The reagents: (1) 0.194 g P3OT, (2) 0.20 g DBSA and (3) 0.194 g poly(isobutylene) (Mw = 2,100,000) were separately dissolved in an appropriate amount of chloroform, with the reagent (3) being dissolved at 50°C. The resulting homogeneous solution was cast to form a free-standing film having a dark color with metallic luster and a conductivity of 1.2 x 10-5 S/cm as shown in Table 2.

EXAMPLE 14

The same procedures as described in Example 8 were used. The reagents: (1) 0.194 g P3OT, (2) 0.026 g DBSA and (3) 0.03 g poly(methyl methacrylate) were separately dissolved in an appropriate amount of toluene, with the reagent (3) being dissolved at 50°C. The resulting homogeneous solution was cast to form a free-standing film of dark color and metallic luster with a conductivity of 4.4 x 10-3 S/cm, as shown in Table 2.

EXAMPLE 15

The same procedures as described in Example 8 were used. The reagents: (1) 0.194 g of P3OT, (2) 0.026 g of DBSA and (3) 0.03 g of poly(n-butyl methacrylate) were separately dissolved in an appropriate amount of toluene, with the reagent (3) being dissolved at 50°C. The resulting homogeneous solution was cast to form a free-standing film of dark color and metallic luster with a conductivity of 8.4 x 10-4 S/cm, as shown in Table 2.

EXAMPLE 16

The same procedures as described in Example 8 were used. The reagents: (1) 0.194 g P3OT, (2) 0.026 g DBSA and (3) 0.03 g polystyrene were separately dissolved in an appropriate amount of toluene. The resulting homogeneous solution was cast to form a free-standing film of dark color and metallic luster with a conductivity of 8.7 x 10-3 S/cm as shown in Table 2 and having a Tg of -12°C.

EXAMPLE 17

The same procedures as described in Example 8 were used. The reagents: (1) 0.194 g of P3OT, (2) 0.016 g of DBSA and (3) 0.03 g of polystyrene were separately dissolved in an appropriate amount of toluene. The resulting homogeneous solution was cast to form a soft free-standing film of dark color and metallic luster with a conductivity of 1 x 10-4 S/cm as shown in Table 2 and a Tg of -10°C. Referring to Fig. 2, curve (c) shows the IR spectrum of the doped conductive polymer blend film. It can be found that this film exhibits new stretching vibration peaks attributed to doping-induced vibration modes and asymmetric and symmetric vibrations of O = S = O from DBSA. These peaks were located at 1304, 1181, 1080 and 1037 cm-1.

EXAMPLE 18

The same procedures as described in Example 8 were used. The reagents: (1) 0.194 g P3OT, (2) 0.007 g DBSA and (3) 0.03 g polystyrene were separately dissolved in an appropriate amount of toluene. The resulting homogeneous solution was cast to form a free-standing film of dark color and metallic luster with a conductivity of 7.7 x 10-5 S/cm as shown in Table 2 and having a Tg of -6.4°C.

EXAMPLE 19

The same procedures as described in Example 8 were used. The reagents: (1) 0.194 g of P3OT, (2) 0.01 g of DBSA and (3) 0.03 g of ethylene-vinyl acetate copolymer containing 45% vinyl acetate were separately dissolved in an appropriate amount of toluene, with the reagent (3) being dissolved at 50°C. The resulting homogeneous solution was coated on glass to form a film with a conductivity of 1.2 x 10-6 S/cm as shown in Table 2.

EXAMPLE 20

The same procedures as described in Example 8 were used. The reagents: (1) 0.138 g P3OT, (2) 0.033 g DBSA and (3) 0.028 g poly(ethyl methacrylate) (Mw = 250,000) were separately dissolved in an appropriate amount of toluene, with the reagent (3) dissolved at 50°C. The resulting homogeneous solution was cast to form a free-standing film of dark color and metallic luster with a conductivity of 2.2 x 10-3 S/cm as shown in Table 2.

APPLIED EXAMPLE 1

The doped conductive polymer blend solution prepared in Example 16 was coated onto the epoxy resin substrate and allowed to dry. Adhesion of the coated film to the substrate was observed to be fairly good. The coated substrate was rubbed with a cloth and immediately tested for static electric charge generation by placing the substrate on shredded paper. No attraction of the shredded paper to the coated substrate was observed, indicating that no static electric charge was generated. However, the uncoated substrate was observed to which attracted the shredded paper after being rubbed with a cloth. Comparing the two substrates, it can be seen that the substrate coated with the conductive polymer blend had good antistatic electrical properties. Thus, the conductive polymer blend film can be used in packaging for electronic components or as an antistatic coating for plastics and fibers.

The advantages and utility of this invention can be further illustrated by the following drawings and tables.

Figure 1 shows UV-Vis spectra of the conductive polymer solutions of the present invention, where curve (a) represents the undoped P3OT/toluene solution; curve (b) represents the doped P3OT/toluene solution of Example 2; and curve (c) represents the doped P3OT/polystyrene/toluene solution of Example 11. It can be noted that both curves (b) and (c) show the peak at about 818 nm, and show extended absorptions up to 1500 nm. The absorptions result from the formation of polaron/bipolaron on the main chain of P3OT. However, curve (a) shows no absorption above 500 nm. It can be concluded from the spectroscopic observations that P3OT can be doped by dodecylbenzenesulfonic acid accompanied by a redox reaction and formation of polaron/bipolaron in the main chains. The doped P3OT after mixing with polystyrene, which also shows polaron/bipolaron absorptions, shows that the doping state of P3OT is still maintained after mixing.

Fig. 2 shows IR spectra of the conductive polymer films of the present invention, wherein curve (a) represents the undoped P3OT film; curve (b) represents the doped P3OT film of Example 4; and curve (c) represents the doped P3OT-polystyrene blend film of Example 17. It can be noted that, in comparison with curve (a), curves (b) and (c) show new peaks in the range of 1,400 to 1,000 cm-1 due to the generated C=C ring and C-C stretching vibrations on the ring of P3OT resulting from the formation of polaron/bipolaron after doping.

Table 1 shows the conductivities of the films from Example 1 to Example 7 in which three types of poly(3-alkylthiophene)s (P3AT's) are doped with protonic acids in different doping amounts. The molar ratio of protonic acid to the repeating unit of P3AT varies from 0.02 to 0.6.

Table 2 shows the conductivities of the films from Example 8 to Example 20, in which the doped P3AT's are mixed with several non-conductive polymers. The molar ratio of protonic acid to the repeating unit of P3AT varies from 0.1 to 50.

According to the results listed in Tables 1 and 2, the following can be concluded.

With respect to Examples 1 to 7, doping with protonic acid with a molar ratio of as little as 0.02 can achieve a conductivity of as high as 10⁻⁴ S/cm, which is two orders of magnitude higher than the lowest value of 10⁻⁶ S/cm for antistatic application.

By comparing Example 4 with Example 17 and comparing Example 5 with Example 18, it is known that at the weight ratio of 0.15, the doped P3AT, after mixing with a non-conductive polymer, still retains the conductivity at the same order of magnitude.

Furthermore, with respect to Examples 11, 12 and 13, it was found that the penetration of only about 2 wt.% of the doped P3AT into the polymer blend can lead to relatively high conductivity of about 10-5 S/cm.

The protonic acid used in this invention acts as a plasticizer as well as a dopant. The addition of such a protonic acid can prevent the doped polymer from shrinking and becoming brittle, and it can improve the compatibility between the conductive polymer and the non-conductive polymer, thereby improving the mechanical properties of the conductive film and increasing the bonding strength between the conductive film and the substrate. Table 1: The relationship between the content of protonic acid and the conductivity of the doped poly(3-alkylthiophene)s

P3DDT: Poly(3-dodecylthiophene)

P3OT: Poly(3-octylthiophene)

P3BT: Poly(3-butylthiophene)

A1: Dodecylbenzenesulfonic acid

A2: d-Camphorsulfonic acid Table 2: The conductivities of the conductive composite films

P3DDT: Poly(3-dodecylthiophene)

P3OT: Poly(3-octylthiophene)

P3BT: Poly(3-butylthiophene)

A1: Dodecylbenzenesulfonic acid

A2: d-Camphorsulfonic acid

PVAc: Poly(vinyl acetate)

PS: Polystyrene

PPMA: Poly(n-propyl methacrylate)

PMMA: Poly(methyl methacrylate)

PIB: Poly(isobutylene)

PBMA: Poly(n-butyl methacrylate)

EVA: Ethylene-vinyl acetate copolymer

PEMA: Poly(ethyl methacrylate)

Claims (29)

1. A doped conductive polymer which is soluble in a general organic solvent and is processable, comprising (a) a conductive polymer having the following chemical structure: wherein X is selected from the group consisting of S, NH and O; where -R is selected from the group consisting of -(CH₂)yCH₃, -O-(CH2 )nCH3 , -(CH2 )n-O-(CH2 )nCH3 , -(CH2 -CH2 -O)n-CH3 , -(CH2 )nCOOH, -(CH2 )nCOOY, -O-CH2 -CH2 -O-(CH2 )nCH3 ; where y is an integer chosen from 3 to 22; where n is an integer chosen from 1 to 22; where -Y is selected from the group consisting of -(CH₂)nCH₃, where n is as defined above; wherein -R' is selected from the group consisting of -H, -CH₃ and -OCH₃; where p is an integer selected from 60 to 8000; and (b) a protonic acid or proton donor with a long carbon chain or a larger substituent group as dopant. 2. Doped conductive polymer according to claim 1, wherein X is S ; wherein -R is -(CH₂)yCH₃; where y is an integer chosen from 3, 7, 11; where -R' has the meaning -H. 3. Doped conductive polymer according to claim 2, wherein y is 3. 4. Doped conductive polymer according to claim 2, wherein y is 7. 5. Doped conductive polymer according to claim 2, wherein y is 11 . 6. The doped conductive polymer of claim 1, wherein the conductive polymer is polypyrrole. 7. The doped conductive polymer of claim 6, wherein the conductive polymer is selected from the group consisting of N-substituted polypyrroles and 3,4-disubstituted polypyrroles. 8. The doped conductive polymer of claim 1, wherein the conductive polymer is polyfuran. 9. The doped conductive polymer of claim 8, wherein the conductive polymer is 3,4-disubstituted polyfuran. 10. Doped conductive polymer according to claim 1, wherein the protonic acid or the proton donor has the following chemical structure: R"-So3H wherein R" is selected from the group consisting of CH₃(CH₂)m-, CF₃(CH₂)m-, where m is an integer chosen from 4 to 22. 11. Doped conductive polymer according to claim 10, wherein R"- has the meaning has; where m is 11. 12. Doped conductive polymer according to claim 10, wherein R" is. 13. A mixture of doped conductive polymer which is soluble and processable in a general organic solvent, comprising: (a) a conductive polymer having the following chemical structure: wherein X is selected from the group consisting of S, NH and O; where -R is selected from the group consisting of -(CH₂)yCH₃, -O-(CH2 )nCH3 , -(CH2 )n-O-(CH2 )nCH3 , -(CH2 -CH2 -O)n-CH3 , -(CH2 )nCOOH -(CH2 ) nCOOY, -O-CH2 CH2 -O-(CH2 )nCH3 ; where y is an integer chosen from 3 to 22; where n is an integer chosen from 1 to 22; where -Y is selected from the group consisting of where n is as defined above; wherein -R' is selected from the group consisting of -H, -CH₃ and -OCH₃; where p is an integer chosen from 60 to 8000; (b) a protonic acid or a proton donor with a long carbon chain or a larger substituent group as a dopant, and (c) a non-conductive polymer. 14. A mixture of doped conductive polymer according to claim 13, where X has the meaning S; wherein -R is -(CH₂)yCH₃; where y is an integer chosen from 3, 7, 11; where -R' has the meaning -H. 15. A doped conductive polymer blend according to claim 14, wherein y is 3. 16. A doped conductive polymer blend according to claim 14, wherein y is 7. 17. A doped conductive polymer blend according to claim 14, wherein y is 11 . 18. The doped conductive polymer blend of claim 13, wherein the conductive polymer is polypyrrole. 19. The doped conductive polymer blend of claim 18, wherein the conductive polymer is selected from the group consisting of N-substituted polypyrroles and 3,4-disubstituted polypyrroles. 20. A doped conductive polymer blend according to claim 13, wherein the conductive polymer is polyfuran. 21. The doped conductive polymer blend of claim 20, wherein the conductive polymer is 3,4-disubstituted polyfuran. 22. A mixture of doped conductive polymer according to claim 13, wherein the protonic acid or proton donor has the following chemical structure: R"-SO₃H wherein R" is selected from the group consisting of CH₃(CH₂)m-, CF₃(CH₂)m- where m is an integer chosen from 4 to 22. 23. A mixture of doped conductive polymer according to claim 22, wherein R"- has the meaning has; where m is 11. 24. A mixture of doped conductive polymer according to claim 22, wherein R" is. 25. A doped conductive polymer blend according to claim 13, wherein the non-conductive polymer is soluble in an organic solvent. 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. 27. A doped conductive polymer blend according to claim 13, wherein the non-conductive polymer is selected from the group consisting of polystyrenes, polymethacrylic acid esters, polyacrylic acid esters, polyvinyl esters, polyvinyl chloride, polyalkanes, polycarbonates, polyesters and polysiloxanes. 28. The doped conductive polymer blend of claim 13, wherein the non-conductive polymer is a copolymer of more than one monomer, wherein the monomers are selected from the group consisting of styrenes, methacrylic acid esters, acrylic acid esters, vinyl chloride, and vinyl esters. 29. The doped conductive polymer blend of claim 13, wherein the non-conductive polymer is selected from the group consisting of polyvinyl acetate, polystyrene, poly-n-propyl methacrylate, polymethyl methacrylate, poly-iso-butylene, poly-n-butyl methacrylate, ethylene-vinyl acetate copolymer, and polyethyl methacrylate.