CA1202146A

CA1202146A - Fused 5,6,5-membered heterocyclic electroactive polymers

Info

Publication number: CA1202146A
Application number: CA000441331A
Authority: CA
Inventors: Victor P. Kurkov
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1982-11-17
Filing date: 1983-11-16
Publication date: 1986-03-18
Also published as: GB2130595A; FR2536077A1; KR840006501A; KR910003207B1; JPS59102951A; NL8303958A; IT1194459B; GB8330598D0; FR2536077B1; GB2130595B; IL70045A; IL70045A0; DE3341627A1; US4522745A; IT8323726A1; IT8323726A0

Abstract

ABSTRACT OF THE DISCLOSURE
A tractable and reversible electroactive polymer which comprises a charged polymer backbone of recurring units of a fused 5,6,5-membered aromatic heterocyclic ring system wherein the 5-membered rings contain at least one nitrogen and a second heteroatom selected from the group consisting of O, S, Se, Te and substituted N, and a suffi-cient concentration of a charge-compensating ionic dopants associated therewith.

Description

FUSED 5,6,5-MEMBER
HETEROCYCLIC ELECTROACTIVE POLYMERS
BACKGROUND OF THE INVENTION
. . .
This invention rela-tes -to electroactive organic polymeric materials. More specifically, this invention relates to novel dopant modified heterocyclic electroactive organic polymers.
Recen-tly, research has been conducted into organic polymeric materials in order -to modify their room temperature electrical conductivi-ty by reac-ting them with electron donor or acceptor molecules. The electron donor or acceptor molecules, generally known in the art as n- and p-type dopants respectively, can transformthe organic polymeric materials so tha-t these modified organic polymeric materials exhibit semiconducting and metallic room -temperature electrical conductivity. Polyacety-lene is an example of an organic polymeric material whose room temperature electrical conductivity can be modified over several orders of magnitude above its insulator state, by the incorpora-tion of dopant molecules, A. J. Heeger et al, United States Patent 4,222,903. Other examples of organic polymeric materials whose room -temperature electrical conductivity can be enhanced by several orders of magnitude over their insulator s-tate by means of incorporation of dopan-t molecules are poly-p-phenylene, polypyrrole, poly-1,6 heptadiyne~ and polyphenylene vinylene.
However, all of the above recited examples are of organic polymeric ma-terials which are comple-tely insoluble or infusable and hence are completely in-tractable.
O-ther examples of organic polymers whose room tempera-ture electrical conduc-tivity can be modified with the ,~, I.a aid of dopants are polyphenylene sulfide and poly-m-phenylene.
However, -the above recited materials though being tractable in their original virgin state, undergo irreversible chemistry when reacted with dopants whi.ch modify their room temperature electrical conductivity.

3~
~. ~

This irreversible chemistry imparts upon these dopant modified organic polymeric ma-terials a s-tate oE intractability. Upon re-moval of -the dopiny agents, these materials do not revert to the chemical structure which they originally exhibited prior to be-ing modified by the dopants. The inorganic rnaterial polysulfur nitride is also considered a polymeric conductor. As with the previously recited polymeric materials, polysulfur nitride is also completely intractable.
For use in a wide variety of electronic device applica-tions, it is highly desirable to have available organic poly-meric elec-trically conducting materials having a preselec-ted room temperature conductivity which can be varied over a broad range. This range should preferably extend from the insulator state of the unmodified organic polymeric material through the semiconducting regime and extending into the highly conducting metallic state. It is also desirable tha-t these organic poly-meric electrically conducting materials should be -tractable and hence processable so that useful articles of any desired shape and size can be fabricated. Tractable organic polymers are those which can be readily shaped, formed, molded, pressed, cast, etc., into desired articles from the liquid state, i.e. either from the melt, fluid glassy state, or from solution after the completion of the polymerization reaction of the organic poly-meric material.
SUMMARY OF THE INVENTION
I have inven-ted an electroactive polymeric material comprising a dopant modified organic polymer whose room tempera-ture elec-trical conductivity is controlled in a highly selective and reversible manner. Electroactive polymer is defined as a polymer having a conductivity which has been modified with elec-i :'`'.2"

~q~
~2a-tron acceptor or donor dopants -to be grea-ter than the conduc--tivity o:E the virgin state of the polymer. The electroac-tive organic polymeric material is fabricated from a virgin polymer, by modifying the polymer with electron donor dopants or electron acceptor dopants. The virgin polymer is completely .3_ tractable and processable and exhibits excellent mechanical and thermal properties as well as being highly stable to oxidative degradation. The electroactive organic polymeric material is comprised of recurring units of a fused 5,6,5-membered nitrogen-containing unsaturated heterocyclic ring system and charge compensating ionic dopants. The recurring ~mits are diradicals.
A diradical is defined as a molecule that has -two unsatisfied positions available for linking into a polymer chain. The recurring diradicals are directly linked to one another, or may be connected to one another via connecting units. A connecting unit is defined as any atom or group of atoms which can link the diradicals together into a polymer chain. The connecting unit must be conjugated or maintain the pi orbital overlap with the heterocyclic recurring units.
Thus in its broadest aspect this invention provides a tractable electroactive polymer comprising a charged polymer backbone and charge compensating ionic dopant(s) associated therewith, wherein said polymer backbone is capable of under-going reversible oxidation or reversible reduction, or both, to form said charged polymer backbone, said polymer backbone com-prising diradical repeat units selected from the following group:
(a) fused 5,6,5 membered aromatic heterocyclic ring systems wherein the 5-membered rings contain at least one nitrogen and a second heteroatom selected from O, S, Se, Te, and substituted N;
(b) fused 5,6,5 membered aromatic heterocyclic ring systems wherein the 5-membered rings contain at least one nitrogen and a second heteroatom selected from O, S, Se, Te, and substituted N, interspersed with connecting units; and (c) mixtures of (a) and (b).

~q ~3 ~f D~ A /r' -3a-An n-type electroactive organic polymer is obtained by reacting the vlrgin polymer with reducing or electron donor dopants. Electron donor dopants induce n-type conductivity in the polymer by donating electrons to the polymer and reducing the polymer to a polyanion and the dopant is oxidized to a charge neutralizing cation. Similarly, a p-type electroactive organic polymer is ob-tained by reacting the virgin polymer with oxidizing electron acceptor dopants. Electron acceptor dopants induce p-type conductivity in -the polymer by oxidizing the polymer to a polycation and the dopant is reduced to a charge neutralizing anion.
~ lternatively, the polymers can be oxidized or reduced to their electroactive, i.e. conductive, form using electrochemical techniques. In this me-thod, also known as electrochemical doping, the polymer is immersed in a suitable electrolyte solution and used as one electrode of an electro-chemical cell. Upon passing an electric current through the cell, the polymer is reduced or oxidized (depending upon the direction of current flow) and charge compensa-ting cationic or anionic dopants from , .~

the supporting electrolyte are incorporated into the poly-05 mer. For both types of doping, the resulting electroac-tive polymer consists of a charged polymer backbone incor-porating charge compensating ionic dopants. The charges of the polymer and the charge compensating dopants balance so that the electroactive polymer is electrically neutral.
The oxidation or reduction proceeds by an electron transfer.
The desired value of the room temperature elec-trical conductivity of the dopant modified electroactive organic polymer is preselected by controlling the level of incorporation of the dopants into the virgin polymer.
Alternatively, the desired value of the room temperature electrical conductivity of the dopant modified electro-active organic polymer is preselected by controlling the length of the reaction time between the virgin polymer and dopants.
The highly selective and reversible modification of the electrical conductivity of the dopant containing organic polymeric material together with the tractability and processability of the virgin polymer is highly desir-able in that the fabrication of useful ar~icles anddevices such as primary and secondary batteries, and photovoltaic devices. Furthermore, the materials described in this invention can be utilized as active components in such devices and articles as electrochromic displays and photolithographic processes.
DETAILED DESCRIPTION OF THE INVENTION
_ Electroactive organic polymers are fabricated from the modification of tractable and processable virgin polymers consisting of recurring diradical units of fused 5,6,5 membered nitrogen-containing aromatic, heterocyclic ring system by suitable dopants. The polymers are com-posed of repeating diradical units derived from fused 5,6,5-membered nitrogen-containing ring systems wherein the heteroatoms are in the five-membered rings. The five-membered rings contain at least one nitrogen atom and asecond heteroatom selected from the group consisting of O, Z~

S, Se, Te or substituted N. For n-type polymers, acidic proton substituents on the nitrogen atoms cannot be present.
Optionally, the diradicals are separated in the polymer chain by connecting units which can maintain pi orbital overlap with the 5,6,5-membered heterocyclic ring systems. Suitable connecting units are O, S, aryl, sub-stituted aryl, alkenyl, thioalkenyl, thioaryl, diaryl sulfides and the like. Phenylene and biphenylene are preferred connecting units. Of course the connecting units can be the same or different between adjacent recurring units in the polymer chain.
More specifically, the electroactive polymers are fabricated with recurring units comprising positional diradicals derived from fused 5,6,5-membered heterocyclic rings and mixtures thereof. The ring systems are numbered as follows:

Z' Z
I.

(x~

II.

wherein either X or Z and either X' or Z' is N; and the ~0 remaining position is selected from O, S, Se, Te, or N-Rl.
Rl is lower alkyl Cl-C6, aryl, cyclo alkyl, and alko~y.

Preferred fused ring systems contain 0 and N or N-Rl and N or S
and N in the 1 or 3 and 5 or 7 positions in structure I. 0 and N or N-Rl and N or S and N in the 1 or 3 and 6 or ~ positions in structure II are pre~erred. Preferably Rl is phenyl, methyl or methoxy. The Rl excludes H for n-type polymers.
The above structures illustrate nitrogen in the X and X' position. If nitrogen were in the Z or Z' position, then the double bond would be between the 1 and 2, and 6 and 7 positions for structure I and 2 and 3, and 6 and 7 positions for structure II. Of course, alternating the nitrogens between, for example, X and Z' positions would put the doub]e bonds between 2 and 3, and 6 and 7 for structure I and 1 and 2, and 6 and 7 for structure II.
Suitable examples of nitrogen-containing fused 5,6,5-membered heterocyclic recurring units of structures I and II
are diradicals of: 1,7 dialkyl-benzo [1,2-d:4,5- d']dimidazole;
1,7-dimethyl-benzo [1,2-d:4,5-d']diimidazole; benzo[l,2-d:5,4-d']bisthiazole, benzo [1,2-d:4,5-d']bisthiazole, benzo[l,2-d:4,5-d'] bisselenazole; benzo~l,2-d:4,5-d'~bistellurazole;
selenazolo[5,4-f]benzothiazole; 1,8-dialkylbenzo[1,2-d:3,4-d']diimidazole; 1,8-dimethylbenzo[1,2-d:3,4-d'~diimidazole;
benzo [1,2-d:5,4-d']bisoxazole; benzo[l,2-d:4,5-d'~ bisoxazole;
benzo[l,2-d:3,4-d'~-bisoxazole; benzo[l,2-d:3,4-d'] bisthia-zole; their substituted derivatives, and mixtures thereof.
The diradicals can be linked through carbon atoms at the 2,6; 2,4; 2,8; 6,4 and 6,8; in struct~re I, and at the 2,4;

2,5; 2,7; 5,7; and 7,8 positions in structure II. Connections at the 2,6 position in the polymer is preferred for structure I. Connections at the 2,7 position is preferred for structure II. For example, a preferred struct~re I recurring unit is a 2,6 diradical illustrated as follows:

X' X
S - 6 ~ ~ ~ 2 \ 7, ~ l /

A preferred structure II recurring unit is a 2,5 diradica]
illustrated as follows:

8 1 ~z 3 Z' 5 2~
The polymer can be a homopolymer of the diradi-cals and the substituted derivatives thereof or a copoly-mer of the diradical units. A homopolymer is defined as a polymer comprising the same recurring diradical unit.
copolymer is defined as a polymer comprising different diradicals. In addition, the polymer is a copolymer if the same or different recurring diradical units are inter-spersed with connecting units.
Fused 5,6,5-heterocyclic polymers which are precursors to my novel electroactive polymers of the present invention are known in the art and are generally synthesized by condensation polymerizatlon of suitable monomers. Other methods, known in the art, such as nucleophilic displacement of a dihalo- compound with a disodium salt of a dimercapto compound can also be used.
The polymer is rendered electroactive by assoc-iating with the virgin polymer a sufficient concentration of an electron donor dopant or an electron acceptor ~Z6~

dopant. A sufficient concentration is defined as an amount capable of rendering the polymer more conductive than the virgin state. Preferably, it is that concentra-tion which, when associated with the polymer, effects a significant increase in the conductivity, i.e. on the order of about 10% or greater.
A suitable positively charged compensating dopant can be a cation such as the alkali metal ions, alkali earth metal ions, Group III metal ions, and organic cations such as R4i -~+, RXi-+N ~ , and ~ ~N-RX3i where RXi is a straight- or branched-chain alkyl of Cl-C6 groups. Mixtures of these charge-compensating dopants can be employed. These ionic dopants produce n-type conductivity when associated with a reduced or negatively charged polymer.
A suitable negatively charged compensating dopant, i.e. anionic dopants, can be an anion such as the halogen ions, other ions such as AsF4 , and preferably ions such as AsF6 , C104 , PF6 , S03CF3 , BF4 , N03 , POF4 , CN , SiF5 , SbC16 , SbF6 , HS04 , organic anions ions such as CH3C02 , (acetate), C6H5C02 (benzoate), CH3C6 H4S03 (tosylate), and the like.
Mixtures of the charge-compensating dopants can be employed, These ionic dopants produce a p-type conduc-tivity when associated with an oxidized or positively charged polymer polycation.
The electroactive polymers of the invention have the following formula:

(~Sd) ~R-~ X ~)a ( R ~ ~ n [M~S]d ~0 ~r~
~6 g where a is either O or l; b is either O or l; c is either O or l; n is an integer between l and l,OOO; d is an S integer between l and 2,000; S is an integer l, 2, or 3;
R is either an unsubstituted or substituted fused nitro-gen-containing 5,6,5-membered heterocyclic diradical ring system; R' is identical to R or different 5,6,5-membered heterocyclic ring system; X" is a connecting unit compris-ing of a single atom or a group of atoms; Y" is a con-necting unit which is identical to X" or a dif~erent atom or group of atoms from ~"; and M is an atom or a group of atoms acting as a charge-compensating anionic or cationic dopant whose electrical charge is opposite to the charge exhibited by the recurring units of the polymer backbone:
~ R t X ~ ~Y )~

2~ The repeat units form the polyanion or poly-cation of the electroactive polymer.
The diradical R group is, for example, a substi-tuted or unsubstituted fused 5,6,5-membered nitrogen-con-taining heterocyclic ring previously defined.
More specifically, R and R' are unsubstituted or substituted diradicals previously recited or mixtures of diradicals which are linked to one another either directly or via the connecting units X" and Y" by forming bridges.
Preferably the linkages are formed at the 2,6 position for str~cture I and the 2,5 position for structure II.
The connecting units X" and Y" can be selected from the group comprising: -0-; -S-; -N-; -CH=CH-;

-C=C-; -CH=CH-CH=CH-; -CH=CH-S-CH=CH-; ~ ;
~o~;~S~;~;~;
--S~ S~S--;

~Z~23 ~6 ol ~ CH=CH- ~ ; ~ C-C ~ ; ~ ;

N- ~ ;

~ ; ~ CH=CH-; -CH=CH ~ CH=CH-;
1~

~ CRV=cR~i ~ ; and -CRVii=cRv~ Ar - N - Ar wherein Rl is defined previously, and RV, RVi and RVii are H or methyl, methoxy, halogen and mixtures thereof R2 is lower alkyl Cl-C4 or p-substituted phenyl and Ar is phenylene or biphenylene. Biphenylene, vinylene, phenylene, and --~ N~

connecting groups are preferred connecting units.
The molecular weight determines the physical properties of the electroactive polymer. Preferably, n is from 5 to 500 or greater. Molecular weights of the poly-mer should be between 500 and 100,000. A preferred molecular weight is 10,000 or above.
The enhancement in conductivity of the electro-active polymer above the conductivity of polymer in the virgin state is determined by d. The value for d is not greater than 2 n. The conductivity is increased and adjusted by increasing d. Conductivities in the semi-conductor region can generally be achieved wlth d valuesof about 5 percent the n value.
Preferred electroactive polymers have d adjusted so that the conductivities are greater than about lxlO 10 ~0 ohm 1 cm 1, and most preferably greater than lxlo 4 ohm 1 For example, the virgin polymer, poly 2 ,6-(p-phenylene)-benzo[1,2-d:4,5-d']-bisthiaZole, has a conductivity of about 10-15 ohm 1 cm 1. The treatment of the polymer with an 0.5 M solution of sodium anthracenide (an electron donor) in tetrahydrofuran results in measured conductivity of about 3x10-2 ohm~l cm~1. Similarly, the virgin polymer poly 2,6-(p-phenylene)-benzo [1,2-d:5,4-d']bisoxazole has a conductivity of about 10 15 ohm~l cm 1, The treatment of the polymer with an 0.5 M
solution of sodium anthracenide in tetrahydrofuran results in a measured conductivity of about 6x10-3 ohm 1 cm 1 A suitable example of an electroactive -R-X"-R'-Y"- polymer is poly-2,2'-(m-phenylene)-6,6'-(p-phenylene)bibenzo[l,2-d:5,4d'] bisoxazole plus a cationic 2U dopant, The polymer has the formula N N N N (-Sd) ~o o~(o/~ [M+S~

The R and R are the same for the above polymer. ~owever, R and Rl and X" and Y" can be different. For example, the alternating or random copolymer of poly 2,6-(p-phenylene)-benzo[l,2-d:5,4-d'] bisoxazole-2,6-(m-phenylene)-benzo[l,2-d:5,4-d']bisthiazole.
When a is 1, and b and c are zero, R' and Y"
drop out and the polymer has the following formula:

(~Sd) R - X"~ S~ d Preferred polymers of the R-X'' structure are:
Poly2,6-(p-phenylene)-benzo[1,2-d:5,4-d']bisoxazole:

~2~

~-Sd) Q5 ~ [M ]d Poly2,6-(m-phenylene)-benzo[1,2-d:5,4-d']bisoxazole:
(-Sd) ~ ~ ~ n [M+S]d Poly2,6-(p-phenylene)-benzo[1,2~d:4,5-d']bisoxazole:
(-Sd) _~N ~ >~ [ M+ S ~

Poly2,7-(p-phenylene)-benzo[1,2-d:3,4-d']bisoxazole:
2~
~ (-Sd) 0~
N N n ~ O ~ ~ [M+S]d Poly2,7-(p-phenylene)-benzo[1,2-d:5 t 6-d']bisoxazole:

~ (-Sd) 0 ~ ~
~O~N n The same structures are preferred for N and S,i.e. benzobisthiazoles, and N and N-Rl, i.e. dialkyl-dimidazoles polymers.
More specifically, the following preferred recurring repeat units occur when a eq~als 1; b and c ol equal O; Z and Z' are N-R1 wherein Rl is methyl; and X and X' are nitrogen; and X" is p-phenyl.
Poly 2,6-(p-phenylene)-1,7-dimethyl-benzo[1,2-d:4,5-d']diimidazole (-Sd) ~ N ~ N ~ [M+S]d l l n Suitable preferred sulfur-containing recurring units are obtained when a equals l; b and c are O; Z and Z' are sulfur; and X and X' are nitrogen; and X" is p-phenylene. More specifically, the recurring units are as follows:
2~ Poly 2,6-(p-phenylene)-benzo[1,2-d:5,4-d;]bis-thiazole:

(-Sd) 2 5 ~N~ 5~ [M ]d Another preferred sulfur-containing recurring units are disclosed hereinafter. The recurring units occur when a equals l; b and c equal O; Z' is S; Z is N;
X' iS N; X iS S; and X" is p-phenylene.
Poly 2,6-(p-phenylene)-benzo[1,2-d:4,5-d']bis-thiazole:

(-Sd) [M~S]d When a and c are 1 and b is zero, Y" drops out and the polymer has the formula:

(lSd) ~R~ X" -R .3 [M- ]d A suitable copolymer occurs when R is the 2,6 diradical of benzo[l,2-d:5,4-d']bisoxazole, X" is p-phenylene~ and R' is the 2,6 diradical of benzo[l,2-d:4,5-d']bisthiazole and the polymer has the formula:

__~No~N~ N S>~ (-Sd ) When a, b, and c are zero, Rl, X", Y" drop out 2~ and the polymer is a homopolymer and has the formula:

(+Sd) ~R 3 n [~S~d Poly 2,6-benzo[1,2-d:5,4-d']bisoxazole ~ N ~ N ~ (-Sd) Polymer Fabrication The starting material for preparing the electro-active polymers of this invention are polymers and copoly-mers comprising recurring units of fused nitrogen-contain-ing aromatic heterocyclic ring system. Preferably therecurring units are fused 5,6,5-membered heterocycles wherein a nitrogen and another heteroatom are in the 5-membered rings. These polymers and copolymers are well known materials having been synthesized in a variety of ways.

~2!(~

~leterocyclic polymers containing fused 5,6,5 ring systems are most commonly synthesized by polycondensation polymerization of dicarboxylic acids or their derivatives with suitable tetra-functional aromatic monomers. The fused hetero-cyclic xings are formed in the course of the polymerization reaction. For example, poly-2,6-(m-phenylene)-3,5-dimethyl--diimidazo--benzene can be synthesized according to the procedure o~ K. Mitsuhashi and C. S. Marvel, L. Polym. Sci., (A), 3, 1661 (1965). The procedure involves mel-t polycondensation polymerization o~ 1,3-dimethylamino-4,6-diamino-benzene with diphenyl isophthalate.
Polymers containing 2,6-benzo-bisoxazole units in the main chain can be synthesized by the procedure of J. F. Wolfe and F. B. Arnold, Macromolecules, 14, 909 (1981). According to their procedure, poly2,6-(p-phenylene)-benzo[1,2-d:5,4-d']bis-oxazole is prepared by a poly(phosphoric) acid catalyzed polycondensation polymerization of 4,6-diamino-1,3-benzenediol dihydrochloride with terephthalic acid under a staged tempera-ture regime.
A similar procedure is used for the preparation of polymers with 2,6-benzobisthiazole units described by J. F. Wolfe, B. H. Loo, and F. E. Arnold, Macromolecules, 14, 915 (1981).
Thus, poly2,6-(p-phenylene)-benzo ~1,2-d:4,5-d']-bisthiazole is prepared by a polyphosphoric acid catalyzed poly-condensation reaction of 2,5-diamino-14-benzenedithiol dihydrochloride with terephthalic acid. These polymers are tractable and can be processed from acid solutions, and possess good thermal and mechanical properties.

z~
-15a-Tractable Polymer Fabrica-tion Subsequent to polymerization, articles such as fibers, ribbons, or free-standing films are cast from solution. The solution is formed by dissolving the desired polymer in an acidic solvent such as sulfuric ~, ~ A

acid, formic acid, methane sulfonic or polyphosphoric acid. The solution temperature is from about 25C to about 200C and preferably from 25-100C. The polymers are coagulated into the previously mentioned articles or films in a basic coagulation bath. For free-standing films, the polymers are fabricated from solutions contain-ing about 2 to 25% polymer dissolved in the solvent. Atconcentrations which exceed 10%, the cast films take on an anisotropic morphology. The anisotropic property enhances the conductivity in the anisotropic direction. An amine, for example triethylamine, dissolved in a protonic solvent such as H2O and preferably ethyl alcohol comprises the coagulation bath. The bath is maintained at a lower tem-perature than the dissolution temperature of the polymer in the solvent. Usually room temperature is selected as the operating temperature of the coagulation bath. The fabricated articles are dried. Elevated temperatures, usually 60C, and reduced pressure accelerated the drying process. Drying is continued until no further weight loss is observed.
Alternatively, films are cast into water, com-prising the coagulation bath, followed by neutralization in aqueous bicarbonate. Neutralized films are washed in water and dried at elevated temperatures, 60-100C, under reduced pressure.
Pol~_er Conductivity Modification After fabrication of the desired articles from the polyfused heterocyclic polymers by means of the proce-dure described above, the articles are rendered electro-active by, for example, chemical or electrochemical procedures. The articles can be rendered electroactive in an atmosphere which is inert with respect to the polymer and dopant, by contacting them with suitable dopants. An inert atmosphere is defined as an atmosphere which does not react with the polymer, the dopant, or the electro-active polymer. For example, the atmosphere can be argon, helium, and nitrogen and the like. The inert liquid medium should be able to wet and swell the polymer but not ~2~2~

react with it. The doping can also be carried out in an 05 inert liquid medium such as tetrahydrofuran, acetonitrile and the like. l'he dopants can be oxidants or electron accepting molecules, or reductants or electron donating moleculesO Both types of dopants may be in the form of gases or vapors, pure liquids or liquid solutions.
Preferably, oxygen and water moisture are excluded during and after the doping process because the conductive poly-mers tend to degrade, i.e. lose conductivity, when exposed thereto.
For example, the polymer can be contacted with lS alkali naphthalides or alkali anthracenides such as sodium naphthalide, potassium naphthalide, or sodium anthracenide in a tetrahydrofuran solution. The dopant concentration can be from about 0.001 to about l molar anà preferably from about 0.01 to about 0.5 molar in T~F or other suit-2~ able solvent. Alternative doping methods are taught inU.S. Patent 4,204,216. An e~ample of an electron accep~or dopant is AsF5.
The electron donor or acceptor dopants reduce or oxidize the polymer and are incorporated as charge compen-sating ionic dopants. The incorporation of the dopantsinto the polymer can be observed by a color change in the polymer as well as an enhanced conductivity. For example, a virgin polymer film having a brown color darkened in color upon doping and the measured conductivity increases by many orders of magnitude.
Alternatively, the polymers can be oxidized or reduced to their conductive forms using electrochemical techniques. In this method, herein referred to as elec-trochemical doping, the polymer is immersed in a suitable electrolyte solution and used as one electrode of an elec-trochemical cell. Upon passing an electric current through such a cell the polymer becomes reduced (or oxidized, depending upon the direction of current flow) and charge-compensating cations (or anions) from the sup-porting electrolyte become incorporated into the polymer.This doping also proceeds with the characteristic color ~32~

change described above, Thus, the polymer can be electrochemi-cally doped with whatever appropriately charged ion is present in the electrolyte solution. Electrolyte solutions are com-prised of a salt dissolved in a solvent. Suitable solvents are acetonitrile, tetrahydrofuran, 2-methyl-tetrahydrofuran, propylene carbonate, dimethylformamide, dimethylsulfoxide and the like. Alternative electrolytes are specified in Canadian Application Serial No. 418,618, filed December 24, 1982, entitled "Bat-teries Fabricated With Electroactive Polymers".
Suitable cations are Li , Na , K , (CH3)4N , (C2H5)4N and (C4Hg)4N . Suitable anions are Cl , Br , C104 , BF4 , and PF6 . The ex-tent of doping can be easily controlled by adjust-ing the amount of charge electrochemically injected into the polymer, either by controlling the magnitude of the current used (galvanostatic charging) or by controlling the potential of the polymer electrode with respect to a reference electrode (potentiostatic charging).
The above-described electrochemical doping process is completely reversible. The polymer can be "undoped" and returned to its original, neutral, non-conducting state simply - by applying a current opposite in sign to that used for the doping process. Upon complete undoping the color of -the polymer reverts back to its original color. Thus, for example, a reduced i.e. n-type conductivity conducting poly 2,6-(p-phenylene)-benzo[1,2-d:4,5-d']bisthiazole, polymer can be reoxidized completely to its neutral, non-conducting form, and the charge-compensating cations incorporated during the electro-chemical reduction process are expelled from the article during electrochemical re-oxidat:ion.

~3$3L~t;i -18a-Having described the methods of fabrication and thQ basic polyfused heterocyclic systems, the following examples are intended to be illus-trative of the invention and not meant to limit the scope thereof. Modification which would be obvious to one of ordinary skill in the art are contemplated to be within the scope of the invention.

~ 02~

EXAMPLES
. . .
Example 1 Preparation of Poly2,6-(p,phenylene)-benzo __ _ [1,2-d:5,4-d']bisoxazole __ _ Monomer Synthesis Preparation of 4,6 Diamino 1,3-dihydroxybenzene Both the monomer and the polymer were prepared according to the procedure of J. F. Wolfe and F. E.
Arnold, Macromolecules 14, 909 (1981).
To 50g (0 45 moles) of resorcanol in 8~ ml of pyridine was added dropwise 78.5g (1 mole) of acetyl chloride~ The reaction was stirred at room temperature overnight.
The reaction mixture was poured into 400 ml of water and extracted with ether. After drying over Na2SO4 the product was distilled. B.P.114/lmmHg. 70.3g (80%) of diacetyl resorcinol was recovered.
70.3g (0.36 moles) of diacetyl resorcinol was added dropwise to 250 ml of fuming (90%) nitric acid cooled in ice to maintain the temperature at 10C. The addition took 3 hrs. The reaction mixture was poured into 2.5 1 of ice water, forming a white precipitate. The precipitate was filtered off, washed and boiled with 300 ml of 30% hydrochloric acid for one half hour.
1,3-dihydroxy-4,6-dintrobenzene was recrystallized from ethylacetate.
7.81g (.039 moles) of 1,3-dihydroxy-4,6-dinitro~
benzene in 125 ml of 30% hydrochloric acid and 50 ml of tetrahydrofuran was hydrogenated over 1.2g of 5% palladium on carbon at 50 psig of hydrogen. After 47 hours, the reaction was diluted with 225 ml of water and acidified with 200 ml of concentrated hydrochloric acid. The pre-cipitated product was recrystallized four times from water-hydrochloric acid system under N2.

dL~VA~

Analysis: Calculated* Found %C 33.82 33O98 ~H 4.73 4.75 %N 13.15 13.16 *for C6H8O2H2 2HCl Polymer Synthesls 1.562g (7.3459 moles) of 4,6-diamino 1,3-di-hydroxybenzene and 1,2258g (7.3785 mmoles) of terephthalic acid (sublimed) in 128g of polyphosphoric acid (Aldrich) was stirred mechanically under nitrogen blanket heated as follows:
room temp.2 hrs. 130C 3 hrs.
55C16 hrs. 150C 3 hrs.
70C 3 hrs. 170C 3 hrs.
95C 3 hrs. 185C 3 hrs.

200C 16 hrs.

The polymerization solution became progressively more viscous. The polymer was precipitated in methanol, stirred in concentratred ammonium hydroxide, filtered and washed wtih water and methanol. It was then continuously extracted with methanol for 16 hrs. and dried in vacuo at 70C.
Analysis: Calculated* Found %C 71.80 67.21 ~H 2.58 2.68 ~N 11.96 11.13 *for (Cl4H6N2O2)n intrinsic velocity, etaint = 1.7dl/g in methane sulfonic acid at 30C. The polymer had the formula:

~ N - ~ N ~ n 2~

~1 Example 2 Preparation of Poly2,6-(p-phenylene)-~5 1,7-dimethyl-benzo[1,2-d:4,5d'ldiimida ole Monomer Synthesis Preparation of 1,3-dimethylamino-4,6-diaminobenzene The title monomer was synthesized according to the procedure of K. Mitsuhashi and C. S. Marvel, L. Polym.
Sci., (A), 3, 1661 (1965).
A 1 1 3-neck flask provided with an addition funnel, reflux condenser, magnetic stirrer and a thermo-meter was charged wtih 120 ml (257 moles) of nitric acid and 240 ml of sulfuric acid.
38.64g (0.265 moles) of n-dichlorobenzene was added dropwise over a period of 6 hrs. while cooling the reaction mixture in an ice bath. After the addition was complete, ~he solution was heated at 70C for 70 min. The solution was cooled and poured into 1 1 of ice water where the product precipitated as a yellow solid. The product was filtered off and recrystallized from çthanol to give 42.8g (69~ yield) of 1,3-dichloro-4,6-dinitrobenzene.
M.P. 106-108C.
40g (0,169 moles) of 1,3-dichloro-4,6-dinitrQ-benzene in 85 ml of nitrobenæene was heated at 160C in a 500 ml 3-neck flask provided with a mechanical stirrer, reElux condenser, and a gas inlet tube just above the liquid. A slow stream of methylamine was passed over the liquid over a period of 6 hrs. The solution was cooled and 84 ml of methanol added. The product was filtered off, washed and recrystallized from dimethylformamide-methanol. 30.8~ (81~) of 1,3-dimethylamino-4,6-dinitro-benzene was recovered. M.P. 329-330C.
Analysis: Calculated* Found %C42.48 42.87 %H4.46 4.49 ~N24.77 25.08 *for C8HloN4O~
8g of 1,3-dimethylamino-4,6-dinitrobenzene was hydrogenated over PtO2 catalyst at 30 psig of hydrogen in ~2~

acetic acid solvent. After 91 hrs. the product was isolated as the hydrochloride salt. It was recrystallized twice from H2O-HCl.
Analysis: Calculated* ound ~C30.79 29.83 %H5.81 6.00 %N17.~5 17.39 *for C8H18N4C4 Polymer Synthesis 1.592g (5.1043 mmoles) of 1,3-dimethyl-amino-4,6-diaminobenzene and 0.%459g of terephthalic acid (sublimed) in 128g of polyphosphoric acid (Aldrich) was stirred mechanically under nitrogen blanket and heated as follows:
room temp.2 hrs. 130C3 hrs.
55C16 hrs. 150C3 hrs.
70C3 hrs. 170C3 hrs.
95C3 hrs. 185C3 hrs.
200C16 hrs.
The polymer was coagulated in water, filtered and washed.
It was then neutralized in 5% aqueous sodium bicarbonate solution, filtered, and continuously extracted with methanol.
Analysis: Calculated* Found ~C73.~3 61.81 ~14.65 4.77 %N21.52 16.11 *for C16H12N4 The polymer had the formula:

= N_ _ '01 Example 3 Preparation of Poly 2,6-(p-phenylene)-05 benzo~l,2-d:4,5-d']bisthiazole _ Monomer Synthesis The requisite monomer and the above polymer were synthesized according to the procedure of J. F. Wolfe, B. H~ Loo, and F. E. Arnold, Macromolecules 14, 915 ( lg8 1 ) .
51.0g (Oq472 moles) of p-phenylenediamine was added to a solution of 92 ml of concentrated hydrochloric acid with 3.3g of activated carbon in 420 ml of degassed water. The mixture was warmed to 50C and fiLtered.
145.8g (1.92 moles) of ammonium thiocynate was added to the filtrate and the solution heated at 100C for 15.5 hrs. under a reflux condenser. The light yellow product was filtered off, washed with water and dried in vacuo.
93.5g (87.5~ yield) of p-phenylenedithiourea was obtained. M.P. 256-260.
Analysis: Calculated* Found %C42.46 42.84 %H4.45 4039 %N24 76 23.95 *for C8HloN4S2 147g (0.92 moles) of bromine in 60 ml of chloro-form was added slowly (to keep the temperature <50C) to a suspension of 90.5g (0.4 moles) of p-phenylenedithiourea in 420 ml of dry chloroform under N2. The orange slurry was stirred at room temperature for 18 hrs followed by reflux for 24 hrs. After cooling, the product was fil-tered off and washed with chloroform. The product was stirred in an aqueous sodium bisulfite solution (60g/450 ml of water) for 6 hrs. It was then filtered, washed with water, and recrystallized from glacial acetic acid.
74.5g (84~) of 2,6-diamino-benzo[1,2-d:4,5-d']
bisthiazole was recovered.

Analysis: Calculated* Found %C43.23 37.81 %H2.72 2.93 ~N25.20 16.86 *for C8H6N4S2 72g (0.32 moles) of diaminobenzobisthiazole was added to a solution of 294.3g of potassium hydroxide in 310 ml of deaerated water under nitrogen. The reaction mixture was stirred mechanically and refluxed for five hrs. It was then cooled in ice, and the light yellow solid collected by filtration in a glove box. The product was suspended in 1 1 of 6N hydrochloric acid and then filtered. Recrystallization from hydrochloric acid gave 18.9g (23%) of 2,5-diamino-1,4-benzenedithiol dihydro-chloride.
~nalysis: Calculated* Found ~C29.39 29.37 %H4.11 4.17 ~N11.42 11.16 *for C6HloN2S2C12 Polymer Synthesis 4.9643g (20.246 mmoles) of 2~5-diamino-1~4-ben-zenedithiol in 38.5g of polyphosphoric acid was stirred mechanically under nitrogen at 60C for 18 hrs. The tem-perature was raised to 110C and 3.3593g (20.22 mmoles) of terephthalic acid (sublimed) was added followed by 52g of 30 polyphosphoric acid. The yellow solution was then heated as follows:
165C5 hrs.
165C12 hrs.
180C12 hrs.
195C12 hrs.
The polymer was coagulated in water forming a fiber spindle. Coagulated polymer was filtered off, washed with water, and ground in a Waring blender. It was then neutralized in a 5% aqueous sodium bicarbonate solu-tion, filtered, washed, and dried.
* Trademark 5.4g (100%) of poly2,6-(p-phenylene)benzo [1,2-d:4,5-d']bisthiazole was obtained.
Analysis: Calculated* Found ~C63.13 59.86 ~H2.27 2.40 %N10~52 10.16 lU *for (C14H6N2S2)n Eta int = 2.5 dl/g(in methane sulfonic acid at 30C. The polymer had the formula:

Example_4 Preparation of Poly 2,6~(m-phenylene) benzo[l,2-d:4,5-d']bisthiazole

3.0353g (12.379 mmoles) of 2,5-diamino-1,4-ben-2U zenedithiol dihydrochloride and 2.05029 (12.3409 mmoles) of isophthalic acid were polymerized in 70g of polyphos-phoric acid using the same procedure as described in Example 3.
3.16g (96~) of poly2,6-(m-phenylene)-benzo [1,2-d:4.5~d;]bisthiazole was isolated.
Analysis: Calculated* Found ~C63.13 62.09 ~H2.27 2.27 ~N10.52 10.35 *for (Cl~H6N2S2)n The polymer had the formula:

~ S~ N~

Example 5 Preparation of Films and Wires A 2.5% (wt) solution of poly2,6-(p-phenylene)-benzo[l,2-d:5,4-d']bisoxazole (Example 1) in methanes~l-fonic acid was prepared by dissolving 0.5g of polymer in ~r~
~3 19.5g of methanesulfonic acid at room temperature. Thereafter, free standing films were cast from this solution and coagulated in H2O or a 10% solution of triethylamine in ethanol. Similarly, platinum wires, for electrochemical studies, were coated with the polymer solution and coagulated in the above baths. Follow-ing coagulation in water, the films were neutralized in a 5%
solution of NaHCO3. Following neutralization, films were thoroughly washed and dried in vacuo at 70C.
Examples 6-8 Platinum-coated wires and free-standing films were cast for Examples 2, 3, and 4 in accordance with the procedures outlined in Example 5.
Example 9 Chemical Doping of Poly2,6-(p-phenylene) benzo[l,2-d:4,5-d']bisthiazole A transparent brown film of the polymer of Example 3 was placed in a jar, in a dry box with a dry argon atmosphere.
After 30 minutes, an O.lN solution of sodium anthracenide in tetrahydrofuran was poured into the jar. The film reacted immediately, changing to a darker color. The doped film con-ductivity was measured by a standard four point probe conduc-tivity instrument. The four point probe procedure is described in Canadian Application Serial No. 403,132, fi]ed ~ay 17, 1982 entitled "Electroactive Polymers". The measured conductivity oE the polymer was 3xlO ohm 1 cm 1. Upon exposure to air, the dark color disappears instantly and the polymer resumes its original color. The infrared spectra of the original undoped film and the air-exposed doped film were the same. The infra-red of the dark,doped film was opaque with no transmittance between 4,000 and 200 cm 1, indicating metallic behavior. This experiment shows that the doped polymer films are surprisingly ~3~
-26a-good electrical conductors.
Example 10 Electrochemical Doping of the Polymer of Example 1 A 5-inch pla-tinum wire was coated with a thln film of the polymer of Example 1, by dipping the wire into a 2.5~ solution of the polymer in methanesulfonic acid.
05 The film-coated wire was coagulated in water, neutralized in 5% sodium bicarbonate solution, washed in H2O, and dried in a vacuum oven at 60C.
The polymer-coated wire was connected to an E. G.
and G. Princeton Applied Research Apparatus comprising a Universal programmer and a Potentiostat/Galvanostat, with recorder. The polymer-coated end of the wire was then immersed into a 0 l M solution of tetraethylammonium tetrafluoroborate in acetonitrile. A linear potential sweep, varying from 0 to -2.7 volts vs. SCE was applied to the polymer-coated wire. A cathodic current began to flow when the potential reached -1.6 volts, and a cathodic current peak was observed at -2.l volts. This indicates the uptake of electrons by the polymeric repeat units. At this point, the polymer is negatively charged and contains tetraethylammonium cations as the charge compensating dopant species. In effect, the polymer was made electro-active by the application of a potential of about --2.l volts in the presence of an electrolyte solution capable of providing charge-compensating dopant ions. Upon rever.sing the direction of the potential sweep, an anodic current peak was observed at nearly the same voltage.
This indicates reversible removal of the electrons previously injected into the polymer. This procedure returns the polymer to its original uncharged, undoped state.
Example ll Electrochemical Doping of Example 2 A 5-inch platinum wire was coated with a thin film of the polymer of Example 2, by dipping the wire into a 2.~ solution of the polymer in methanesulfonic acid.
The film-coated wire was coagulated in water, neutralized in 5~ sodium bicarbonate solution, washed in H2O, and dried in a vacuum oven at 60C~
The polymer-coated wire was connected to an E.G.
and G. Princeton Applied Research Apparatus comprising a Universal proyrammer and a Potentiostat/Galvanostat, with ~ ~as~A ~ ' ~ ~ ~ ~ ~ 4 recorder. The polymer-coated end of the wire was then 05 immersed into a 0.1 M solution of tetraethylammonium tetrafluoroborate in acetonitrile. A linear potential sweep; varying from 0 to -2.7 volts vs. SCE was applied to the polymer-coated wire~ A cathodic current began to flow when the potential reached -2.1 volts, and a cathodic ~ current peak was observed at -2.3 volts. This indicates the uptake of electrons by the polymeric repeat units. At this point, the polymer is negatively charged and contains tetraethylammonium cations as the charge-compensating dopant species In effect, the polymer was made electro~
active by the application of a potential of about -2.3 volts in the presence of an electrolyte solution capable of providing charge-compensating dopant ions. Upo reversing the direction of the potential sweep, an anodic current peak was observed at nearly the same voltage.
This indicates reversible removal of the electrons previously injected into the polymer. This procedure returns the polymer to its original uncharged, undoped state.
Example 12 Electrochemical Doping of the Polymer of Example 3 A 5-inch platinum wire was coated with a thin film of the polymer of Example 3, by dipping the wire into a 2.5% solution of the polymer in methanesulfonic acid.
The film-coated wire was coagulated in water, neutralized in 5% sodium bicarbonate solution, washed in ~2~ and dried in a vacuum oven at 60C.
The polymer-coated wire was connected to an E. G. and G. Princeton Applied Research Apparatus compris-ing a Universal programmer and a Potentiostat/Galvanostat, with recorder, The polymer-coated end of the wire was then immersed into a 0.1 M solution of tetraethylammonium tetrafluoroborate in acetonitrile. A linear potential sweep, varying from 0 to -2.7 volts vs. SCE was applied to the polymer-coated wire. A cathodic current began to flow when the potential reached ~ volts, and two cathodic current peaks were observed at 01.~ and --20 0 volts. This

4~;

indicates the sequential uptake of two electrons by the polymeric repeat units. At this point, the polymer is negatively charged and contains tetraethylammonium cations as the charge-compensating dopant species. In effect, the polymer was made electroactive by the application of a potential of about -2.0 volts in the presence of an elec-trolyte solution capable of providing charge-compensating dopant ionsO Upon reversing the direction of the poten-tial sweep, two anodic current peaks were observed at nearly the same voltages. This indicates reversible removal of the two electrons previously injected into the polymer. This procedure returns the polymer to its original uncharged, undoped state.
Example 13 Electrochemical Doping and Conductivity Measurement of Free-standing Films of Example 3 A l/2" diameter disc of a l mil thick film of the polymer of Example 3 was immersed in an electrolyte solution of O.l M tetraethylammonium tetrafluoroborate and tightly held up against flat gold-coated electrode with a fine nylon mesh screen. This electrode was connected to the same apparatus described in Example lO. As the poten-tial of the gold-coated electrode in contact with the - polymer was brought negative of -l.5 volts, the initially pale yellow transparent polymer film became dark and opaque. After holding the potential of the electrode at -2 2 volts vs. SCE for approximately 8 minutes, the film was removed from the electrochemical cell, rinsed with acetonitrile to remove any excess electrolyte solution and allowed to dry in an argon atmosphere. Four point probe conductivity measurement of the resulting electrochemic-ally doped film reveals a conductivity of 2.3xlO 4 ohm l cm l. In effect, the polymer film was doped to a conductive state by the application of a potential of 02.2 volts in the presence of an electrolyte solution.

Example l4 Electrochemical Doping And Conductivity S M surement of the Polymer of Example 4 A one-half inch diameter disc of a l mil thic~
film of the polymer of Example 4 was immersed in an elec-trolyte solution !of O.lM tetraethylammonium tetrafluoro-borate in acetonitrile and tightly held up against a flat gold electrode with a fine nylon screen. This electrode was connected to the same apparatus described in Example lO The potential of the platinum electrode in contact with the polymer was brought to -2.5 volts V5. SCE and held for 8 minutes. The film was then removed from the electrochemical cell, rinsed with acetonitrile to remove any excess electrolyte solution and allowed to dry in an argon atmosphere. Four-point probe conductivity measure-ment of the resulting electrochemically doped film revealed a conductivity of 2.3xlO 4 ohm l cm l. In effect, the polymer film was doped to a conductive state by the application of a potential of -2.5 volts in the presence of an electrolyte solution. This corresponds to reduction of the polymer to an n-type conducting state.
Example 15 Chemical Doping of the Polymer of Example l -The procedure of Example 9 was repeated with the polymer of Example l. The conductivity was 6xlO 3 ohm l cm~l xample l6 Chemical Doping o the Polymer of Example 4 The procedure of Example 9 was repeated with the polymer of Example 4. The conductivity was l. 3xlo 6 ohm l m~l Example 17 Electrochemical Doping of the Polymer of Example 4 A 5-inch platinum wire was coated with a thin film of the polymer of Example 4~ by dipping the wire into a 2.5% solution of the polymer in methanesulfonic acid.
The film-coated wire was coagulated in water, neutralized ~3~

in 5~ sodium bicarbonate solution, washed in H2O, and dried in a vacuum oven at 60C.
The polymer-coated wire was connected to an E.G
and G. Princeton Applied Research Apparatus comprising a Universal programmer and a Potentiostat/Galvanostat, with recorder. The polymer-coated end of the wire was then immersed into a O.l M solution of tetraethylammonium tetrafluoroborate in acetonitrile. ~ linear potential sweep, varying from 0 to -2.7 volts vs. SCE was applied to the polymer-coated wire. A cathodic current began to flow when the potential reached -2.0 volts, and a cathodic current peak was observed at -2.25 volts~ This indicates the uptake of electrons by the polymeric repeat units. At this point, the polymer is negatively charged and contains tetraethylammonium cations as the charge-compensating dopant species. In effect, the polymer was made electro-active by the application of a potential of about -~.7 volts in the presence of an electrolyte solution capable of providing charge-compensating dopant ions. Upon reversing the direction of the potential sweep, an anodic current peak was observed at nearly the same voltage.
This indicates reversible removal of the electrons previously injected into the polymer. This procedure returns the polymer to its original uncharged, undoped state,

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A tractable electroactive polymer comprising a charged polymer backbone and charge compensating ionic dopant(s) asso-ciated therewith, wherein said polymer backbone is capable of undergoing reversible oxidation or reversible reduction, or both, to form said charged polymer backbone, said polymer backbone comprising diradical repeat units selected from the following group:
(a) fused 5,6,5 membered aromatic heterocyclic ring systems wherein the 5-membered rings contain at least one nitrogen and a second heteroatom selected from O, S, Se, Te, and substituted N;
(b) fused 5,6,5 membered aromatic heterocyclic ring systems wherein the 5-membered rings contain at least one nitrogen and a second heteroatom selected from O, S, Se, Te, and substituted N, interspersed with connecting units; and (c) mixtures of (a) and (b).

2. The electroactive polymer according to Claim 1 wherein the recurring 5,6,5-membered heterocyclic ring systems are joined through the outer 5-membered rings.

3. The electroactive polymer according to Claim 1 wherein the recurring units are selected frorn the group consisting of 1,7-dialkyl-benzo[1,2-d:4,5-d']diimidazole; 1,7-dimethyl-benzo[1,2-d:4,5-d'] diimidazole; benzo[1,2-d:5,4-d']bisthiazole;
benzo [1,2-d:4,5-d']bisthiazole; benzo[1,2-d:4,5-d'] bisselena-zole; selenazolo[5,4-f]benzothiazole; 1,8-dialkyl-benzo[1,2-d:
3,4-d']diimidazole; 1,8-dimethyl-benzo[1,2-d:3,4-d']diimidazole;

benzo[1,2-d:5,4-d']bisoxazole; benzo[1,2-d:4,5-d']bisoxazole;
benzo[1,2-d:3,4-d']-bisoxazole; benzo[1,2-d:3,4-d']bisthiazole;
benzo[1,2-d:4,3-d']bisthiazole; their substituted derivatives, and mixtures thereof.

4. The electroactive polymer according to Claim 2 wherein the charge-compensating ionic dopant is a cation selec-ted from the group consisting of the alkali metal ions, alkali earth metal ions, Group III metal ions, wherein Rxi is a straight- or branched-chain alkyl of C1-C6 groups, or mixtures of said cations.

5. The electroactive polymer according to Claim 3 wherein the recurring units are N-dialkyl benzodiimidazoles.

6. The electroactive polymer according to Claim 3 wherein the recurring units are benzobisoxazoles.

7. The electroactive polymer according to Claim 3 wherein the recurring units are benzobisthiazoles.

8. The electroactive polymer according to Claim 2 wherein the fused 5,6,5-membered recurring units are intersper-sed with connecting units selected from the group consisting of phenylene, biphenylene, -CH=CH-, and mixtures thereof.

9. The electroactive polymer according to Claim 7 wherein the recurring units are N-dialkyl benzodiimidazoles.

10. The electroactive polymer according to Claim 7 wherein the recurring units are benzobisoxazoles.

-33a-

11. The electroactive polymer according to Claim 7 wherein the recurring units are benzobisthiazoles.

12. The electroactive polymer according to Claim 1 wherein the charge-compensating ionic dopant is an anion selected from the group consisting of AsF4-, AsF6-, Clo4-, PF6-, SO3CF3-, BF4-, NO3-, POF4-, CN-, SiF5-, SbCl6-, SbF6-, HSO4-, acetate, benzoate, tosylate, or mixtures thereof.

13. A tractable electroactive polymer which comprises a charged polymer backbone and charge compensating ionic dopants associated therewith, wherein said polymer backbone is capable of undergoing reversible oxidation, or reversible reduction, or both, to form said charged polymer backbone, and wherein said charged tractable electroactive polymer is of the formula:

wherein a is 0 or 1; b is 0 or 1; c is 0 or 1; n is an integer from 1 to 1,000; d is an integer from 1 to 2,000; s is an integer 1, 2, or 3; R is a fused nitrogen-containing 5,6,5-membered unsaturated diradical-heterocyclic ring system; R' is the same as R or a different fused nitrogen-containing 5,6,5-membered unsaturated diradical heterocyclic ring system; X" is a connecting unit; Y" is the same connecting unit as X" or a different connecting unit; and M is a charge-compensating ionic dopant of oppo-site electrical charge to the charge of the polymer back-bone.

14. The electroactive polymer according to Claim 13 wherein R and R' are 2,6 diradicals of the formula:

wherein X and X' positions or Z and Z' positions are N, and the other position is selected from the group consist-ing of O, S, Se, Te, or N-R1 wherein R1 is lower alkyl C1-C6, aryl, cyclo alkyl and alkoxy.

15. The electroactive polymer according to Claim 13 wherein R and R' are 2,7 diradicals of the formula:

wherein X and X' positions or Z and Z' positions are N, and the other position is selected from the group consist-ing of O, S, Se, Te, or N-R1 wherein R1 is lower alkyl C1-C6, aryl, cyclo alkyl and alkoxy.

16. The electroactive polymer according to Claim 14 wherein R and R' are 2,6 diradicals of the formula:

wherein X, X' and Z are selected from the group consisting of O, S, Se, Te, and N-R1, wherein R1 is lower alkyl C1-C6, aryl, cycloaryl and alkoxy.

17. The electroactive polymer according to Claim 15 wherein R and R' are 2,7 diradicals of the formula:

wherein X, X' and Z are selected from the group consisting of O, S, Se, Te, and N-R1 wherein R1 is lower alkyl C1-C6, aryl, cycloalkyl, and alkoxy.

18. The electroactive polymer according to Claim 13 wherein a is 1, b and c are zero, and the polymer has the formula:

19. The electroactive polymer according to Claim 18, wherein X" is selected from the group consisting of: -O-; -S-; -CH=CH-;
-C?C-; -CH=CH-CH=CH-; -CH=CH-S-CH=CH-; ;
wherein R1 lower alkyl C1-C6, aryl, cyclo alkyl, and alkoxy, and Rv, Rvi and Rvii are H, methyl, methoxy, halo-gen and mixtures thereof; Ar is phenylene or biphenylene, and R2 is lower alkyl C1-C4.

20. The electroactive polymer according to Claim 19 wherein the charge-compensating ionic dopant M is a cation selected from the group consisting of the alkali metal ions, alkali earth metal ions, Group III metal ions, and and wherein Rxi is a straight- or branched-chain alkyl of C1-C6 groups, or mixtures of said cations.

21. The electroactive polymer according to Claim 18 wherein the polymer has the formula:

22. The electroactive polymer according to Claim 18 wherein the polymer has the formula:

23. The electroactive polymer according to Claim 18 wherein the polymer has the formula:

24. The electroactive polymer according to Claim 18 wherein the polymer has the formula:

25. The electroactive polymer according to Claim 13 wherein a, b and c are zero, and the polymer has the formula:

26. The electroactive polymer according to Claim 25 where the polymer is poly 2,6 benzo[1,2-d:5,4-d']bisoxazole plus an anionic charge compensating dopant.

27. The electroactive polymer according to Claims 5, 6 or 7 wherein the charge compensating ionic dopant is a cation selected from the group consisting of alkali metal ions, alkali earth metal ions, Group III metal ions, wherein Rxi is a straight or branched chain alkyl of C1-C6 groups, or mixtures of said cations.

28. The electroactive polymer according to Claims 21 or 22 wherein the charge compensating ionic dopant is a cation selected from the group consisting of alkali metal ions, alkali earth metal ions, Group III metal ions, wherein Rxi is a straight or branched chain alkyl of C1-C6 groups, or mixtures of said cations.

29. The electroactive polymer according to Claims 23 or 24 wherein the charge-compensating ionic dopant is a cation selected from the group consisting of alkali metal ions, alkali earth metal ions, Group III metal ions, wherein Rxi is a straight or branched chain alkyl of C1-C6 groups, or mixtures of said cations.

30. The tractable electroactive polymer according to Claims 1 or 13 wherein the molecular weight is between 500 and 100,000.

31. The tractable electroactive polymer according to Claims 1 or 13 wherein the molecular weight is equal to, or greater than, 10,000.

32. The tractable electroactive polymer according to Claim 13 wherein n is from 5 to at least 500.