WO1990013601A1

WO1990013601A1 - Conductive polymer-polyamide blends and method of producing same

Info

Publication number: WO1990013601A1
Application number: PCT/US1990/001844
Authority: WO
Inventors: Randy Edwin Cameron
Original assignee: Lockheed Corporation
Priority date: 1989-05-12
Filing date: 1990-04-10
Publication date: 1990-11-15

Abstract

Solution blending of (a) a conductive polymer containing carbon-nitrogen linkages, such as polyaniline, having an organic group or an inorganic group, e.g., derived from an anhydride or an aromatic multisulfonic acid, covalently linked to nitrogen atoms of the polymer and (b) a polyamide, e.g., nylon, in a suitable solvent. On removal of solvent, a continuous phase blend of the conductive polymer and the polyamide is formed, having good electrical conductivity and strength. The solution blend can be formed into tough conductive films or fibers having good flexibility.

Description

I CONDUCTIVE POLYMER-POLYAMIDE BLENDS AND METHOD OF PRODUCING SAME

BACKGROUND OF THE INVENTION This application is a continuation-in-part of U.S. Application Serial No. 158,478, filed February 22, 1988, of Stuart I. Yaniger and Randy E. Cameron, and assigned to the same Assignee as the present application. This invention relates to the production of electrically conductive polymer materials and is particularly concerned with the solution blending of conductive polyaniline and conductive polyaniline derivatives, with polyamideε, to produce cured materials having electrical conductivity, such as fibers and films. The free-base form of polyaniline is believed to comprise subunits having the formula:

where n is between 0 and 1. The oxidation state of polyaniline referred to as "e eraldine" is believed to have a value of n of about 0.5. This free-base form of polyaniline is an electrical insulator. Reaction of emeraldine free-base with protonic acids of the form HX, where X is, for example, Cl, causes the polymer to undergo an insulator to conductor transition, as disclosed in A. G. MacDiar id, et al., Mol. Cryst. Liq. Cryεt. 121, 173 (1985) . Conductive polyaniline of this type has been employed in batteries as disclosed, for example, in French Patent No. 1,519,729. However, a number of difficulties have been encountered with the prior art materials noted above. Thus, the conductive polyaniline acid salts are, with a few exceptions, insoluble in most solvent media. None of the polyanilines can be melted. The emeraldine free-base and the conductive forms thereof noted above tend to form powders on removal of the

SUBSTITUTE SHEET solvent. With some effort, films can be cast; however, they are quite fragile and brittle, easily crumbling to form a powder. The conductive acid salts lose their conductivity when exposed to liquid water. This loss is due to deprotonation. The conductivity loss is reversible; treatment of the deprotonated material with protic acids restores the conductivity. Further, conductive regions in an insulating matrix tend toward diffusion. For example, if one makes a conductive trace of polyaniline acid salt on a substrate of emeraldine free-base, the trace remains spatially stable for only a short time, eventually spreading out until the substrate has a constant conductivity throughout. Some of these problems were addressed in U.S. Applications Serial No. 920,474 filed October 20, 1986, of S.I. Yaniger, and Serial No. 013,305 filed February 11, 1987, of S. I. Yaniger, et al, both assigned to the same assignee as the present application. In these applications, it is disclosed that Lewis acids, for example, alkylating agents, can be used to make the insulating emeraldine free-base into a conductive polymer salt. Use of proper Lewis acids resulted in conductive polyanilines with the Lewis acid as a side chain. These derivatizred polyanilines are more water stable and processable than the prior art emeraldine acid salts. Additionally, no diffusion between "doped" conducting and "undoped" insulating regions was observed. Thus, in the above U.S. Application, Serial No. 920,474, a base-type non-conductive polymer, such as polyaniline, can be reacted with, for example, methyl iodide, to form an electrically conductive polymer in which the methyl group is covalently linked to the nitrogen atoms of the polymer. In the above U.S. Application, Serial No. 013,305, emeraldine free-base can be reacted with reagents of the form RS0₂C1, e.g., tosyl chloride, to form an electrically conductive polymer in which the -S0₂R groups are covalently linked to the nitrogen atoms of the polymer.

SUBSTITUTESHEET U.S. Application Serial No. 158,477 filed February 22, 1988, of S. I. Yaniger and R. E. Cameron and assigned to the same assignee as the present application, discloses reaction of a base-type non-conductive polymer, such as polyaniline, with an anhydride, such as tosylic anhydride or benzophenone tetracarboxylic dianhydride, and forming an electrically conductive polymer in which the -S0₂R and -COR groups are covalently linked to the nitrogen atoms of the conductive polymer. In U.S. Application Serial No. 226,484, filed August 1, 1988, by R. E. Cameron, and assigned to the same assignee as the present application, there is disclosed conductive multisulfonic acid derivatives of polyaniline which are highly thermally stable. In general, however, the conductive polymers of the above applications tend to be brittle, and there is a lack of flexibility and elongation ability in such conductive materials, resulting in inferior mechanical properties. It would be desirable to blend the relatively brittle conducting polymer with a flexible polymer to form a blend having both the desired electrical properties and good flexibility. To achieve high electrical conductivity, the proportion of conductive polymer to non-conductive polymer in the blend must be relatively high (e.g., greater than 50%) in order for charge to be transferred effectively between polymer chains. Unfortunately, at high polyaniline loadings, the blend materials tend to phase separate, that is, the polyaniline aggregates into clumps within the non-conductive polymer matrix. These clumps are separated by the matrix material, and the blend thus is an insulator. Further, the mechanical properties of the material suffer upon phase separation. It would be desirable to form blends where the polyaniline is dispersed evenly on a molecular level at all loadings, to thus form a conductive polymer blend.

SUBSTITUTESHEET In the above U.S. Application Serial No. 158,478, of which the present application is a continuation-in-part, there is disclosed a conductive polymer blend formed by first reacting a base-type non-conductive polymer containing carbon- nitrogen linkages, such as polyaniline, with a carbonyl anhydride, such as 3,3', 4,4 '-benzophenone tetracarboxylic dianhydride, to form a conductive polymer containing polyimide-like groups covalently linked to nitrogen atoms of the base-type polymer, mixing such conductive polymer with non-conductive polyimide in a suitable solvent, removing the solvent, and forming a conductive continuous phase blend of the polyimide and the conductive polymer. The conductive polymer-polyimide blends of the above application are useful for making conductive films or fibers. Examples of other conductive polymer mixtures are set forth in the following patents. Patent No. 4,025,463 to Trevoy discloses amine salts of linear polyaniline compounds as semiconductors alone or in combination with a co-dissolvable binder material. Among a large variety of binders listed in the patent are polyamides. These compounds are stated to be useful in the formation of semiconductor compositions including self-supporting films and fibers. Patent No. 4,747,966 to Maeno, et al, discloses an electrically conductive thermoplastic resin composition comprising (1) at least one thermoplastic resin, such as polyamide resin, (2) at least one metallic powder, such as nickel, copper, iron or aluminum, and (3) a diphosphonic acid derivative. An object of the present invention is the provision of improved electrically conductive polymer materials of the class of conductive polyaniline blended with a polyamide. Another object is to provide conductive polymer materials having improved elongation and flexibility, mechanical properties, including toughness, and thermal stability, in the

SUBSTITUTESHEET form of a continuous phase blend of a conductive polymer, e.g., conductive polyaniline, and a polyamide. A still further object is to render polyamides conductive by doping with a conductive polymer, particularly an improved relatively highly conductive form of polyaniline, to produce an easily processable, conductive polymer blend. A still further object is to provide novel procedure for blending polyaniline in the solution phase with a polyamide, whereby on removal of the solvent, the resulting polymer blend can be processed to yield conductive fibers, films or bulk materials.

SUBSTITUTESHEET SUMMARY OF THE INVENTION The above objects are achieved and a conductive polymer blend is produced according to the invention by solution blending in a suitable solvent a mixture of (a) an electrically conductive polymer containing carbon-nitrogen linkages and having an organic or inorganic group covalently linked to nitrogen atoms of the polymer, particularly a conductive polyaniline or a polyaniline derivative, and (b) a polyamide, removing the solvent and forming a continuous phase blend of the conductive polymer and the polyamide. The invention is carried out by first reacting a base- type non-conductive polymer containing carbon-nitrogen linkages, particularly from the family of the polyanilines, with a cation donor compound capable of covalently binding to the nitrogens of the polymer, such as a carbonyl or sulfonyl anhydride, to thereby form an electrically conductive polymer, e.g., a derivatized polyaniline having an organic or inorganic group covalently linked to nitrogen atoms of the base-type polymer, e.g., as described in the above U.S. Application Serial No. 158,477 of S. I. Yaniger, et al. The conductive polymer so formed is mixed with a polyamide, such as nylon, e.g. , in certain ranges of proportions as described hereinafter, in a suitable solvent, such as N-methyl pyrrolidone (NMP) , to form a completely miscible blend of the two components in the solution phase. The blend is solution processable and upon removal of the solvent, the mixture forms a continuous phase blend, the blended materials resulting in an electrically conductive resin which is strong and can be formed into very flexible, stretchable conductive materials, such as fibers and films. Another advantage of these blends is improved morphology of cast films. For example, emeraldine free-base has a large optical non-linearity in the near infrered (about 1 micron wavelength) . It cannot at present be used in non-linear optical devices because, cast films of the polymer are

SUBSTITUTESHEET fibrillar in nature and tend to scatter light rather than transmit it. Suitable polymer blends, according to the invention, form a continuous phase, with no fibrillar structure. It is again necessary to achieve a high loading of the polyaniline into the optically inactive polyamide so that the large optical activity of the emeraldine is not diluted. This cannot be achieved by prior art technology, as mentioned above. Another advantage of this invention is that the polyamide matrix serves as a physical barrier against environmental degradation or hydrolysis, since such polyamides are extremely hydrophobic. If desired, in the above procedure, the electrically conductive polymer, e.g., conductive polyaniline, can be formed in situ, during solution blending with the polyamide component, by incorporating in the solvent solution the non- conductive polymer, e.g., polyaniline, and the cation donor compound for reaction with such non-conductive polymer, to form the resulting conductive polymer, in solution with the polyamide component. Thus, the present invention discloses a technique for increasing the electrical conductivity of a polyamide, without materially adversely affecting, or without decreasing, the mechanical properties thereof.

SUBSTITUTESHEET DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS Conductive Polymer Component In preferred practice, a base-type non-conductive polymer containing carbon-nitrogen linkages is first reacted with a cation donor compound to form a polymer salt in which a covalent bond is formed between the nitrogens of the polymer and such donor cation. A preferred form of non-conductive polymer can be represented as follows:

H H HH o- N - A - N = A = N - A - N

-) .. where A is a carbon-containing group, such as aryl, particularly the benzene ring, as in polyaniline, and including naphthyl and biphenyl, and substituted benzene, naphthyl or biphenyl groups, such as the alkyl substituted derivatives, e.g., 2-methyl biphenyl, butyl naphthalene, 2- methyl aniline, and aryl substituted derivatives, e.g., beta phenyl naphthalene and beta tolyl naphthalene; and y is an integer ranging from about 1 to about 1,000, e.g., about 10 to about 100. Thus, the above non-conductive polyaniline family of polymers can be further characterized as consisting of polyaniline, its naphthyl and biphenyl derivatives, and alkyl and aryl .substituted polyaniline and its alkyl and aryl substituted naphthyl and biphenyl derivatives. The preferred non-conductive polymer containing carbon- nitrogen linkages is the basic polymeric starting material, polyaniline emeraldine free-base (PFB) .

SUBSTITUTESHEET Other polymeric starting materials can include other non- conductive base-type polymers containing carbon atoms linked to nitrogen, such as cyanogen polymer containing the recurring unit:

The starting materials of the invention can also include non-conductive mixtures and blends of the above polymers, and copolymers of the above polymers and other polymers, such as a blend of polyaniline and polymethylmethacrylate, and polymer alloys, such as polybenzimidazole-polyimide alloys, containing carbon-nitrogen groups. Thus, the term "non-conductive polymer" as employed herein is intended to denote any of the above homopolymer or copolymer materials. The invention will be described hereinafter, however mostly in terms of the use of the preferred non-conductive free-base polyaniline as polymeric starting material. This is a high polymer having a molecular weight of the order of 50,000 to 80,000. Lower molecular weight forms of polyaniline can also be employed, such as an oligomer of polyaniline containing 8 sub-units and having a molecular weight of about 800 to 900. The preferred conductive polymers according to the invention are those prepared by reacting the non-conductive polymer containing carbon-nitrogen linkages, such as polyaniline, with a cation donor compound capable of covalently binding to the nitrogens of such polymer to form an electrically conductive polymer. Thus, the resulting conductive polymer containing carbon-nitrogen linkages has an organic or inorganic group covalently linked to nitrogen atoms of the polymer, and an anion associated with such nitrogen atoms to form a polymer salt.

SUB_STITUTESHEET Such conductive polymers and their method of formation are described in the above-noted applications. Thus, for example, the free-base polyaniline can be treated and reacted with an R⁺ donor compound, such as RX, R₃OX, R₂S0₄, R'S0₂C1 or R_jSiQ, where R, R'S0₂ or R_jSi is group which readily forms a covalent bond with nitrogen, and wherein R, R¹ and R" each can be alkyl containing from 1 to 20 carbon atoms, e.g., methyl, ethyl and the like, and aryl, e.g., p-toluene sulfonyl (tosyl) , benzyl, tolyl, xylyl, and other aromatic moieties, and X is an anion such as halogen, e.g., Cl^~, I~ or Br^""; PF₆ ^" SbCl₆~, and substituted and unsubstituted benzene sulfonate, and the like, and Q is a halogen, such as Cl. The above reaction forms a conductive polymer salt having a group as defined above covalently linked to the nitrogen atoms. Thus, the reactant which forms a covalent chemical bond with the nitrogen of the polyaniline free-base or equivalent polymer noted above, can be, for example, one of the above R⁺ donor compounds, such as an alkyl halide, wherein the alkyl group can contain from 1 to 20 carbon atoms, such as methyl iodide, or dimethylsulfate. The reaction for converting the base-type non-conductive polymer to a conductive polymer can be represented as follows, where, for example, RX is the R⁺ donor compound: H H I ( - A - N - A - N = A = N - A - N - )_y ^RX

H X~ X^" H

IIA ( A - N - A - N⁺ = A = N⁺ - A - N

> y ^o:

R R

R X~ X~ R

IIB ( A - N - A - N⁺ = = A = N⁺ - A - N - ) or

R R

R + + R

IIC ( A - N⁺ - ^■ A - N = A = N - A - N⁺ ^" ) y

R R R R X~ X~ X~ X~

SUBSTITUTE SHEET where A and y are as defined above. According to another preferred embodiment, as disclosed in the above U.S. Application Serial No. 158,477, base-type non-conductive polymers containing carbon-nitrogen linkages, particularly from the family of polyaniline, can be converted to conductive polymers by reacting the non-conductive polymer with an anhydride, such as R-S0₂-0-S0₂R' , R-CO-O-CO-R¹ , or R- CO-0-S0₂R', or mixtures thereof, where R and R' are alkyl or aryl, e.g., tosylic anhydride, benzophenone tetracarboxylic dianhydride, or o-sulfobenzoic anhydride, according to the general reaction shown above, and forming an electrically conductive polymer in which the S0₂R and COR groups are covalently linked to the nitrogen atoms of the conductive polymer and the anion of the conductive polymer is the S0₃R' or 0₂CR' group. According to still another preferred embodiment as disclosed in above U.S. Application Serial No. 226,484, base- type non-conductive polymers containing carbon-nitrogen linkages, particularly from the family of polyaniline, are converted to conductive polymers of high thermal stability, by reacting the non-conductive polymer with a multiprotic acid in the form of an aromatic multisulfonic acid, e.g., having the formula R(S0₃H)_n, where R is aryl, such as benzene or naphthalene, or their substituted derivatives, and n is an integer of at least 2, preferably 2 to 4, such as m-benzene disulfonic acid, or mixtures thereof, to form a polymer salt in which the -S0₃H groups are covalently linked to the nitrogens of the polymer through the hydrogen bond. The molar proportions of cation donor compound to non- conductive, e.g., nitrogen-containing polymer free-base, can be varied but is sufficient to increase the electrical conductivity of the polymer. Thus, for example, in the case of the above donor compounds RX, R₃0X, R₂S0₄, R'S0₂C1 and R^SiQ and the anhydrides, the molar proportions of donor compound to nitrogen-containing polymer can range from about 0.01 to

SUBSTITUTE SHEET about 2 cation groups, e.g., S0₂R⁺ or C0R⁺ groups in the case of the anhydride, per nitrogen, and in the case of polyaniline, such molar proportions can range from about 0.01 to about 8, per polymer repeat unit. Where an aromatic multisulfonic acid is employed as cation donor compound, a range of proportions of about 1/16 to about 2 moles of multisulfonic acid per nitrogen of each polymer unit is employed and, in the case of polyaniline, from about 1/8 to about 2 moles of multisulfonic acid, for every 2 aniline units in the polyaniline chain. The reaction can be carried out as a heterogeneous reaction wherein the polymer starting material is not dissolved but is reacted directly with the cation donor compound, e.g., anhydride, or the polymer starting material, such as polyaniline non-conductive free-base, can be dissolved in a suitable solvent which does not react irreversibly with such donor compound, e.g., N-methyl pyrrolidone, dimethylsulfoxide (DMSO) , dimethylformamide (DMF) , formic acid, dimethylacetamide (DMAC) , acetonitrile, tetrahydrofuran (THF) , and pyridine. The reaction is generally carried out at about ambient or room temperature, e.g. 20 - 25" C, or at higher or lower temperatures. The rate of reaction can range widely, depending on the particular cation donor compound reactant employed. Thus, the reaction rate can range from almost instantaneous to several hours or longer. The conductivity of the resulting conductive polymers, e.g., conductive polyaniline, can be varied by reducing or increasing the number of covalently linked side chains on the nitrogen atoms, as by controlling the degree of completeness of the reaction and/or by varying the types of cation donor compound employed in producing such side chains on the polymer.

SUBSTITUTE SHEET The disclosures of the above applications are incorporated herein by reference with respect to the conductive polymer component of the present invention and its method of preparation. The Polyamide Component The polyamide component which is blended with the above conductive polymer can be any suitable polyamide which can be mutually dissolved with the conductive polyaniline component in a suitable solvent to form a blend. Examples of suitable polyamides are nylon, such as Nylon 8 having the recurring unit:

Nylon 6/6 having the recurring unit:

IV 4c0NH-(CH₂)₆-NH-C0(CH₂)₄J-

Nylon 6 having the recurring unit:

Nylon 6/12 having the recurring unit:

VI 4CONH-(CH₂)₁₀ -NH-CO(CH₂) -

and Nomex having the recurring unit:

VII

The above examples of suitable polyamides are marketed by DuPont. The polyamides which can be employed according to the invention have a molecular weight ranging from about 10,000 to about 500,000 gm/mol.

SUBSTITUTE SHEET The conductive polymer can be blended in a wide range of proportions with non-conductive polyamide component, generally ranging from about 1 to about 99% conductive polymer to 1 to about 99% non-conductive polyamide component, by weight of the mixture. Particularly to obtain higher conductivity, it is preferred to employ about 50 to about 99% conductive polymer and about 1 to about 50% non-conductive polyamide component, by weight. Such blending can be carried out by mixing the conductive polymer with non-conductive polyamide component in a suitable solvent, such as N-methyl pyrrolidone or formic acid. Other solvents which can be employed are noted above. If desired, the reaction of the non-conductive base-type polymer, such as polyaniline, with the appropriate cation donor compound, e.g., anhydride or multisulfonic acid, can be carried out in a suitable solvent, such as N-methyl pyrrolidone, and the polyamide component can then-be added to the resulting reaction mixture containing the resulting conductive base-type polymer. Instead of blending the derivatized conductive polymer, e.g., polyaniline, with polyamide component, the non- conductive polyaniline can be mixed with cation donor compound, e.g., an anhydride or multisulfonic acid, in solvent solution with polyamide component, and the reaction to form the conductive polymer, e.g., conductive polyaniline, takes place in situ during blending thereof with the polyamide component.. When employed to form a coating, the resulting blend in which the conductive polymer and polyamide components are completely soluble is applied to any suitable substrate, either conductive or non-conductive, such as glass, quartz, metal or plastic, and the solvent is evaporated. When the solvent is evaporated, a tough, flexible film in the form of a continuous phase blend of the conductive polymer and the polyamide component is obtained, which has high electrical conductivity. The proportions of base-type polymer and

SUB_STITUTESHEET polyamide component in the continuous phase blend forming the conductive film is the same as that noted above in preparing the solutions of the blends. Thus, with approximately 50% loading of conductive polyaniline by weight, the films of the blend of polyaniline and polyamide can have a conductivity, e.g. of 10^"2 S/cm. This conductivity can be altered by changing the weight fraction of polyaniline in the blend. Both the conductive polymer, particularly conductive polyaniline, and the polyamide, are quite thermostable, and the resulting blend of the two polymers is a continuous single phase having high thermostability. The blended polymer also has the good mechanical properties of the polyamide component while having the good electrical conductivity properties of the conductive base-type polymer, such as conductive polyaniline. The continuous single-phase blends of the conductive polymer and non-conductive polyamide component produced according to the invention do not separate out upon forming a film from the blend. Instead of forming a blend of the two components and the blend used to form a film or coating, the conductive polymer and polyamide component blend can be processed to form fibers. This can be achieved, e.g., by pultruding the blend while some solvent is still present in the material. The following are examples of practice of the invention: Example 1: 5 grams of PA (polyaniline) free-base and 5 grams of Nylon 8 are dissolved in 100 ml of formic acid. To this solution is added 2.5 grams o-sulfobenzoic anhydride. This solution contains about 60% of conductive PA and about 40% of Nylon 8 (polyamide) . The solution is cast on a glass sub- strate to form a film. The resulting film is heated at 40⁶C. under air flow for 2 hours. The cured film is electrically

SUBSTITUTE SHEET conductive, with a conductivity of 0.01 S/cm, is flexible and strong. Example 2: The solution of Example 1 is subjected to a pultrusion process to pull fibers from the solution, which are conductive, stretchable and strong. Example 3: The procedure of Example 1 is repeated except employing 0.5 gram m-benzene disulfonic acid or 0.5 gram tosylic anhydride in place of the o-sulfobenzoic anhydride. Similar results to Example 1, are obtained, except conductivity is 0.5 S/cm. Example 4: . The procedure of Example 1 is followed except using 150 ml N-methyl pyrrolidone (NMP) in place of formic acid. Results similar to Example 1 are obtained. Example 5: The procedure of Example 4 is followed, except p- toluenesulfonic anhydride is used in place of o-sulfobenzoic anhydride, and in the same amount. Results obtained are similar to Example 4, except conductivity is 0.06 S/cm. Example 6: The procedure of Example 4 is followed, except methyl p- toluenesulfonic acid is used in place of o-sulfobenzoic anhydride, and in the same amount. Results similar to Example 4 are obtained, except conductivity is 0.03 S/cm. Example 7: The procedure of Example 1 is followed except using Nylon 6/6 in place of Nylon 8 and in the same amount. Results similar to Example 1 are obtained.

_SUBSTITUTESHEET Example 8 : The procedure of Example 1 is followed except employing Nylon 6 or Nylon 6/12 in place of Nylon 8 and in the same amount. Results similar to Example 1 are obtained. Example 9: The procedure of Example 1 is followed except employing Nomex in place of Nylon 8 and in the same amount. Results similar to Example 1 are obtained. The electrically conductive polymer blends of the invention have utility in the production of conductive composites, electronic components, electrical conductors, electrodes, batteries, switches, electrical shielding material, resistors, capacitors, and the like. From the foregoing, it is seen that the invention provides a novel class of conductive polymer materials which can be readily cast into tough, flexible conductive films, or formed into fibers or bulk materials^", by solution blending conductive, preferably nitrogen-containing, polymers, such as conductive polyaniline, as described above, with a polyamide component. The resulting resin blend increases the electrical conductivity of the polyamide component without decreasing its mechanical integrity. The result is a conductive resin of superior strength, toughness, flexibility and processibility. While particular embodiments of the invention have been described for purposes of illustration, it will be understood that various changes and modifications within the spirit of the invention can be made, and the invention is not to be taken as limited except by the scope of the appended claims.

SUBSTITUTE SHEET

Claims

WHAT IS CLAIMED IS; 1. A process for producing a conductive polymer blend which comprises: solution blending in a suitable solvent a mixture of (a) a conductive polymer containing carbon-nitrogen linkages and having an organic group covalently linked to nitrogen atoms of the polymer, and (b) a polyamide, removing said solvent, and forming a conductive continuous phase blend of said conductive polymer and said polyamide.

2. The process of claim 1, said conductive polymer being selected from the group consisting of conductive polyaniline, its naphthyl and biphenyl derivatives, and alkyl and aryl substituted polyaniline and its alkyl and aryl substituted naphthyl and biphenyl derivatives.

3. The process of claim 2, wherein said conductive polymer has an organic group derived from an anhydride or an aromatic multisulfonic acid covalently linked to the nitrogen atoms of said polymer.

4. The process of claim 2, wherein said conductive polymer is polyaniline and said conductive polyaniline has an organic group derived from an anhydride or an aromatic multisulfonic acid covalently linked to the nitrogen atoms of said polyaniline.

5. The process of claim 1, employing about 1 to about 99% of said conductive polymer and about 1 to about 99% of said polyamide, by weight of the mixture.

6. The process of claim 1, wherein said polyamide has a molecular weight ranging from about 10,000 to about 500,000 g /mol.

7. The process of claim 1, wherein said polyamide is nylon.

SUBSTITUTESHEET

8. The process of claim 2, wherein said conductive polymer is polyaniline, employing about 1 to about 99% of said conductive polymer and about 1 to about 99% of said polyamide, by weight of the mixture, and wherein said polyamide is selected from the group consisting of polyamides having the recurring units:

4cONH-(CH₂)₆-NH-CO(CH₂) - ,

CONH-(CH₂)₅f ,

-JCONH-(CH₂)₁₀-NH-CO(CH₂)₄J- , and

4COHN-r ι-NH-CO- θ f •

9. A process for producing a conductive polymer blend which comprises: reacting a base-type non-conductive polymer containing carbon-nitrogen linkages selected from the group consisting of polyaniline, its naphthyl and biphenyl derivatives and alkyl and aryl substituted polyaniline and its alkyl and aryl substituted naphthyl and biphenyl derivatives, with a compound capable of converting said non-conductive polymer to a conductive polymer, and forming said conductive polymer having an organic or inorganic group convalently linked to nitrogen atoms of said polymer, solution blending a polyamide with said conductive polymer in a suitable solvent, removing said solvent, and forming a conductive continuous phase blend of said conductive polymer and said polyamide.

SUBSTITUTE SHEET

10. The process of claim 9, wherein said reaction to form said conductive polymer is carried out in situ during solution blending with said polyamide.

11. The process of claim 9, wherein said polyamide is nylon.

12. The process of claim 9, wherein said compound is a carbonyl anhydride or a sulfonyl anhydride, and forming anhydride groups covalently linked to nitrogen atoms of said polymer.

13. The process of claim 9, wherein said compound is an aromatic multisulfonic acid.

14. The process of claim 9, wherein said compound is selected from the group consisting of RX, R₃OX, R₂S0₄, R'S0₂C1 and R₃SiQ, where R, R'S0₂ or R₃Si is a group which forms a covalent bond with nitrogen and wherein R, R¹ and R" is alkyl containing from 1 to 20 carbon atoms or aryl, • and Q is a halogen.

15. The process of claim 9, employing about 1 to about 99% of said conductive polymer and about 1 to about 99% of said polyamide, by weight of the mixture.

16. The process of claim 15, wherein said polymer is polyaniline.

17. The process of claim 16, wherein said compound is a carbonyl anhydride or a sulfonyl anhydride, and forming anhydride groups covalently linked to nitrogen atoms of said polymer.

18. The process of claim 16, wherein said compound is an aromatic multisulfonic acid, and forming -S0₃H groups covalently linked to nitrogen atoms of said polymer through the hydrogen bond.

_SUBSTITUTESHEET

19. A blend of (a) a conductive polymer containing carbon-nitrogen linkages and having an organic or inorganic group covalently linked to nitrogen atoms of the polymer, and (b) a polyamide, in a suitable solvent, said blend being capable of forming films, fibers and bulk materials upon evaporation of the solvent.

20. The blend of claim 19, wherein said conductive polymer is derived from a polymer having the formula:

( - A - N - A - N = A = N - A - N - )_y

where A is aryl and y is an integer of from about 1 to about 1,000.

21. The blend of claim 19, said conductive polymer selected from the group consisting of conductive polyaniline, its naphthyl and biphenyl derivatives, and alkyl and aryl substituted polyaniline and its alkyl and aryl substituted naphthyl and biphenyl derivatives.

22. The blend of claim 21, employing about 1 to about 99% of said conductive polymer and about 1 to about 99% of said polyamide, by weight of the blend.

23. The blend of claim 22, wherein said conductive polymer is conductive polyaniline, and said conductive polyaniline has an organic group derived from an anhydride or an organic multisulfonic acid covalently linked to the nitrogen atoms of said polyaniline.

24. The blend of claim 21, wherein said polyamide is nylon.

SUBSTITUTE SHEET

25. The blend of claim 23, wherein said polyamide is selected from the group consisting of polyamides having the recurring units:

+C0NH-(CH₂)₆-NH-C0(CH₂)₄- ,

4C0NH-(CH₂)₁₀-NH-CO(CH₂)^~j- and

26. An electrically conductive solid polymer material, comprising a continuous phase blend of (a) a conductive polymer containing carbon-nitrogen linkages selected from the group consisting of conductive polyaniline, its naphthyl and biphenyl derivatives, and alkyl and aryl substituted polyaniline and its alkyl and aryl substituted naphthyl and biphenyl derivatives, and having an organic or inorganic group covalently linked to nitrogen atoms of the polymer, and (b) a polyamide, said polymer material containing about 1 to about 99% of said conductive polymer and about 1 to about 99% of said polyamide, by weight.

27. The electrically conductive polymer material of claim 26, said polymer material containing about 50% to about 99% of said conductive polymer and about 1% to about 50% of said polyamide, by weight.

28. The electrically conductive polymer material of claim 26, wherein said conductive polymer has an organic group derived from an anhydride or an aromatic multisulfonic acid covalently linked to the nitrogen atoms of said polymer.

SUBSTITUTE SHEET

29. The electrically conductive polymer material of claim 26, wherein said polymer is polyaniline, and said conductive polyaniline has an organic group derived from a multisulfonic acid covalently linked to the nitrogen atoms of said polyaniline.

30. The electrically conductive polymer material of claim 26, wherein said polymer is polyaniline, and said conductive polyaniline has an organic group selected from the class consisting of R, R'S0₂ and R₃Si covalently linked to the nitrogen atoms of said polyaniline, where R, R' and R" is alkyl or aryl.

31. The electrically conductive polymer material of claim 26, wherein said polyamide is nylon.

32. The electrically conductive polymer material of claim 28, wherein said polyamide is nylon.

33. The electrically conductive polymer material of claim 28, wherein said polymer is polyaniline and wherein said polyamide is selected from the group consisting of polyamides having the recurring units:

4CONH-(CH₂)₆-NH-CO(CH₂)₄j ,

+CONH-(CH₂)₅ ,

4CONH-(CH₂)₁₀-NH-CO(CH₂)₄| , and

SUBSTITUTESHEET