CA1202141A - Electroactive polymers - Google Patents

Electroactive polymers

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Publication number
CA1202141A
CA1202141A CA000403132A CA403132A CA1202141A CA 1202141 A CA1202141 A CA 1202141A CA 000403132 A CA000403132 A CA 000403132A CA 403132 A CA403132 A CA 403132A CA 1202141 A CA1202141 A CA 1202141A
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Prior art keywords
electroactive polymer
polymer according
diradicals
carbon atoms
polymer
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CA000403132A
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French (fr)
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Yoram S. Papir
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Chevron USA Inc
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Chevron Research and Technology Co
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Priority claimed from US06/370,231 external-priority patent/US4519937A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/20—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/16—Radicals substituted by halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/28—Radicals substituted by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0688—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polyquinolines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/114—Poly-phenylenevinylene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers

Abstract

ABSTRACT OF THE DISCLOSURE
Tractable doped electroactive polymers, compris-ing recurring units of a fused nitrogen-containing unsatu-rated heterocyclic ring system, are fabricated from the virgin polymer by contacting the polymer with donor or acceptor conductivity modifier atoms or groups of atoms.

Description

ELECTROAC~IV~ POLYMERS
BACKGR0UND OE' THE INVENTION
This invention relates to electroactive organic poly-meric materials. More specifically, this invention relates to incorporating electroactiva~ing agents known in the art as dopants.
~ ecently, research has been conducted into organic polymeric materials in order to modify their room temperature electrical conductivity by reacting them with electron donor or acceptor molecules. The electron donor or acceptor molecules, generally known in the art as n- and p-type dopants respective-ly, can transform the organic polymeric materials so that these modified organic polymeric materials exhibit semiconducting and metallic room temperature electrical conductivity. Polyacety-lene is an example of an organic polymeric ma~erial whose room temperature electrical conductivity can be modiied over several orders of magnitude above i-ts insulator state, by the incorporation of ~opant molecules, A. J. Heeger et al, U.~.
patent 4,222,903. Other examples of organic polymeric mater-ials whose room temperature electrical conductivi-ty can be enhanced by several orders oE magnitude over their insulator state by means of incorporation of dopant molecules are poly-p-phenylene, polypyrrole, poly-1,6 heptadiyne, and polyphenylene vinylene. However, all of the above recited examples are of organic polymeric materials which are completely insoluble or infusable and hence are completely intractable.
Other examples of organic polymers whose room temp-erature electrical conductivity can be modified with the aid of dopants are polyphenylene sulEide and poly-m-phenylene. How-ever, -the above recited ma-terials -though being trac-table in their original virgin state, undergo irreversible chemistry when reacted with dopants which modi:Ey their room temperature electrical conductivity. This irreversible chemistry imparts upon these dopan-t - la -,r modified organic polymeric materials a state of intract~
ability. Upon removal of the doping agents, these mate-05 rials do not revert to the chemical structure which they oriyinally exhibited prior to being modified by the dopants. The inorganic material polysulfur nitride is also considered a polymeric conduc-tor. As with the pre-viously recited polymeric materials, polysulfur nitride is also completely intractable.
For use in a wide variety of electronic device applications, it is highly desirable to have available organic polymeric electrically conducting materials having a preselected 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 that these organic polyme~ic electric-ally conducting materials should be tractable and hence processable so that use~ul 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 polymeric material.
SUMMARY OF THE lNv~NlION
I have invented an electroactive polymeric mate-rial comprising a dopant modified organic polymer whose room temperature electrical 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 electron acceptor or donor dopants to be greater than the conductivity of the virgin state of the polymer. The electroactive organic polymeric material is fabricated from a virgin polymer, which in itself is completely tractable and processable and which exhibits excellent mechanical and thermal properties as well as being highly stable to oxidative degradation, by 3~

modi~ying the polymer with a concluctivity modifier, i.e. elec-tron donor dopants or electron acceptor dopants. l'he electro-active org~nic polymeric material is comprised of recurring units of a fused nitrogen-containing unsa-turated heterocyclic ring system and a conductivity modifier. More specifically, the electroactive polymer i5 a charged, either posi-tive or negative, polymer backbone incorporating charge-compensating ionic dopants, i.e. ions oE opposite charge to the charge o-f the polymer backbone~ The recurring units are diradicals. ~he diradicals are directly linked to one another, or may be con-nected to one another via connecting units. A connec~ing unit i5 defined as any a-tom or group of atoms which can link the hereinabove diradicals together into a polymer chain.
Thus in its broadest aspect this invention provides a tractable electroactive polymer comprising a linear charged polymer backbone and charge compensating ionic dopant~s) asso-ciated therewith wherein said linear polymer backbone is capable of undergoing reversible oxidation or reversible reduc-tion, or both, to form said linear charged polymer backbone, said linear polymer backbone comprising diradical repeat units selected from the following group: (a) fused nitrogen-con-taining unsaturated heterocyclic ring systems, (b) fused nitro-gen-containing unsaturated heterocyclic ring systems inter-spersed with connecting units' and tc) mixtures of (a) and (b)-Preferably, in these polymers in the fused ni-trogen-containing ring systems not more than two nitrogen atoms are joined sequentially.
Further, it is preferred that in these polymers in the nitrogen-containing ring system the atoms at the ring .~,. ~, , ~

- 3a ~

fusion points are other than nitrogen.
An n-~ype electroactive organic polymer is obtained by reacting the virgin polymer with reducing or electron donor dopants. Electron donor dopants induce n-type conductivity in the polymer by donating an electron to the polymer and reducing same to a polyanion and the dopant is oxidized to a cation.
Similarly, a p-type electroactive oryanic polymer is obtained 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 an anion. The desired value of the room temperature electrical 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 roo~ temperature elec-trical conductivity of the dopant modified electroactive organic polymer is preselected by controlling the length of the reaction time between the virgin polymer and dopants. Further-more, the highly selective and reversible modification oE the room temperature electrical conductivity of the virgin polymer can proceed by either chemical or electrochemical means. The highly selective and reversible modification of the electrical conductivity oE the dopant containing organic polymeric material togethcr with the tractability and processability of t~le virgin polymer is highly desirable in that the fabrication of useful articles and devices such as primary and secondary batteries, photovoltaic devices, Schottky type devices can be accomplished. Furthermore, the materials described in this invention can be utilized as active components in such devices and articles as electrochromic displays and photolithographic processes.
DET~ILED Dr:SCl~PTION O~ Tll~ INVE~TIO~
Electroactive organic polymers are fabricated from the modification of tractable and processable virgin polymers consisting of recurring units of fused nitrogen-containing ~msaturated, heterocyclic ring system by suit-able conductivity modifiers. The polymers are composed of repeating diradical units derived from fused six-member nitrogen-containing ring systems wherein each ring contains no more than three nitrogens bonded sequentially. A
diraclical is defined as a molecule that has two unsatisfied positions available for linking into the polymer chain. Optionally, the diradicals are separated in the po]ymer chain by connecting units.
The fused rings contain from one through six nitrogen atoms. The nitrogen atoms are distributed between the fused rings with three or fewer nitrogens bonded sequentially in a ring. Suitable examples of single nitrogen fused ring systems are any of the diradicals of quinoline and isoquinoline.
Suitable examples of two-nitrogen fused ring systems are any of the diradicals of cinnoline; quinazoline; quinoxaline; 2-phenyl-quinoxaline; phthalazine;
1,5-naphthyridine; 1,6-naphthyridine; 1,7-naphthyridine; 1,8-naphthyridine;
- 2,6-naphthyridine; copyrine; and the like. Suitable examples of three-nitrogen fused ring systems are any of the diradicals of 1,2,4-benzotriazine; pyrido-[3,2-d] pyrimidine; pyrido[4,3-d] pyrimidine; pyrido[3,4-d] pyrimidine;
pyrido[2,3-d] pyrimidine; pyrido[2,3-b] pyrazin~; pyrido[3,4-b] pyridazine;
pyrido[2,3-d] pyr:idazine; pyrido[3,4-d] pyridazine; and the like. Suitable examples of four-nitrogerl fused ring systems are any of the diradicals of pyridazino[4,5-d] pyridaz:ine; pyr:imido~5,~-d] pyrimi-line, pteri-dine;pyri~i.do[~,5~d] pyridazine, pyrimido[4,5-d] pyrimidine;
pyrazino[2,3~b~pyrazine; pyrazino[2,3-d] pyridazine; pyrida-æinoC4,5-d3 pyridazine:pyri.mido[~,5-c] pyridazine: p~razino[2,3-c] pyridazine; pyridoC3,2-d]-as-triazine; pyrido[2,3-e]-as-tri-azine' and the like. Suita~le exampl.es of five-nitrogen fused ring systems are any of the diradicals of pyrimido [~,5-e3-as-triazine; pyrimido~5,~-d3-as-triazinei and the like. Suitable examples of six-nitrogen fused ring systems are any of the di-radical.s of as-triazino[6,5-d]-as-triazine and the like. A11 the previously mentioned fused nitrogen ring systems are known and disclosed in The Ring Index, second edition, and Supplements I, II and III; Patterson et al, American Chemical Society. The molecules are synthesized into polymers by methods known in the art such as treatment with Zncl2 or ~eCl3 and an alkyliodide, or by dichlorination followed by reaction with appropriately disub-stituted molecules such as: disodium sulfide, disodium salt of ethylene glycol, and the like. The diradicals can be modified with substi-tuents which modify the polymer properti.es such as electron donating or withdrawing groups by methods known in the art.
Suitable compounds in which one or more of the nitro-gens are saturated with hydrogen or by bonding in the fused ring or in the ionic form, include any diradical of quinolinium;
pyridazino[l,2-a] pyridazine; 2H-pyrido[1,2-a] pyrazine;
pyrido[1,2-a] pyrimdine-5-ium; pyrimido[1,2-a] pyrimidine-5-ium;
and 2H-pyrazino[1,2-a~-pyrazine. The compounds are known and disclosed in The Ring Index and Supplements I, II and III. The polymers are fabricated by methods known in the art.
For example, an electroactive polymer can be fabri-cated with recurring units of positional diradicals of quino-line, substituted quinoline, isoquinoline, substituted isoquin--~ oline and mixtures thereof. The diradicals can be linked at the 2,4; 2,5; 2,6; 2,7; 2,8; 3,5; 3,6; 3,7; 3,8; 4,6; 4,7;
4,8; 5,7; 5,8; and 6,8 positionsJ but connections at the 2,6 and 3,6 positions in the polymer are preferred. The quinoline ring system is numbered as follows:

~3~

The isoquinoline ring system is numbered as follows:
Nl ~ i~J

For example, the 296 diradical of quinoline has the formula:
,~

A preferred diradical of quinoline or isoquinoline is substituted in the 4 position. Preferably, the diradical is substituted with a phenyl group.
The diradicals can be separated by one or more connecting units.
Preferred connecting units are bi-phenyl, -CH=CH-, and -C - C-. The connecting units can be the same or different between adjacent diradicals in the polymer chain.
The polymer can be a homopolymer of the diradicals of quinoline, isoquinoline and the substituted deriva-tives thereof or a copolymer of the diradicals. A homopolymer is defined as a polymer fabricated comprising the same recurring diraclical. A copolymer is defined as a polymer comprising different cliradicals. In addition, the polymer is a copolymer if the same or diEferent recurring di-radicals are interspersed with connecting units.
The polymer is rendered elec-troactive by incorpor-ating into the viryin polymer a conductivity modifier. More specifically, the polymer is rendered electroactive b~ adding electrons to (reducing) or removing electrons Erom (oxidizing) the virgin polymer backbone. This can be accomplished by in-'0 corporating into the virgin polymer a conductivity modifier which is either an electron donor. dopant or an electron acceptor dopant. An electron donor dopant donates an electron to the polymer, the polymer becoming reduced to a polyanion and the dopant becoming oxidized to a cation. An electron acceptor dopant rernoves an elec-tron from the polymer, the polymer be-coming oxidized to a polycation and the dopan-t becoming reduced to an anion. ~lternatively, the polymer can be rendered elec-troactive by electrochemical oxidation or reduction. In this case an electron is removed ~rom or added to the polymer from an electrode, and charge compensatiny anions or cations, respectively, are incorporated into the polymer from t'ne supporting electrolyte solution.
In both cases the resulting electroactive polyme~
consists of a charged polymer backbone incorporating charge-compensa-ting ionic dopants. ~ suitable positively charged compensating dopant can be a cation such as the alkali metal ions, alkali earth me-tal ions, group III metal ions and organic cations such as R4i_N+ RXi-+ ~ , and ~ ~N_p~3i ~here RXi is a straight or branched chain alkyl of Cl-C6 groups. Mixtures oE these charge compensa-ting dopants can be employed. These ionic dopants produce n-type conduc-tivity when associated with a reduced or negatively charged polymer poly-anion.

f~

A suitable negatively charged compensating dopant, l.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 , ~F4 , N03-, POF4-, CN-, SiF5-, SbC16-, Sb~6-, HSO~ , organic anions ions such as CE-I3C02-, (acetate), C6~sC02-, (benzoate), CH3C6H4S03-, (tosylate) and the like.
Mixtures of the charge compensating dopants can be employed.
These ionic dopants produce a p-type conductivity when asso-ciated with an oxidized or positively charged polymer poly-cation.
The dopant modified electroactive polymer has a charge opposite to the conductivity modifier, i.e. ionic dopant. I'he charges on the dopant modified electroactive poly-mer and the ionic dopant balance so that the dopant modified electroactive polymer is an electrically neutral system. The association of -the virgin polymer with electron donor dopants produces an electroactive polymer which exhibits n-type conduc-tivity. More specifically, reduction of the virgin polymer and the incorporation of cationic charge compensating dopants pro-duces a polymer which exhibits n-type conductivi-ty. The asso-ciation of the virgin polymer with electron acceptor dopants produces an electroactive polymer with p-type conductivity.
More specifically, oxidation of the polymer and incorporation of anionic charge compensating dopants produces a polymer with p-type conductivity.
The electroactive polymers of th0 invention have the following Eormula:
(+Sd) (+S) R t-X ) a ( R ) c ( Y ) b } (Md) rl ,. .

where a is either 0 or ], b is either 0 or 1; c is either 0 or 1, n is an integer between 2 anc1 20,000; d is an integer between 1 and 40,000; s is an integer 1, 2, or 3: R i5 a fused nitrogen-containing unsaturated diradical-heterocyclic ring system; R' is the same as R or a differen-t ~used unsaturated heterocyclic ring system; X is a connec-ting unit comprising of a single atom, or a group o atoms; Y is a connecting unit wl~ich is identical to or different from ~; and M is a ch~rge-compensating ionic dopant of opposite electrical charge to the charge oE the polymer backbone wherein the polymer backbone is capable of undergoing reversible oxidation or a reversible reduction, or both, to form said charged polymer backbone.
Preferahly in these polymers in the fused nitrogen-containing ring systems the atoms at the ring fusion points are other than nitrogen.
The repeat units form the polyanion or polycation of the electroactive polymer.
The diradical R group is a substituted or unsubstitu-ted fused six-member nitrogen-containing rings. The diradicals contain from one to six nitrogens distributed between the ~used six~member rings wherein each ring contains no more -than 3 nitrogens bonded sequentially. Suitable R groups are the di-radicals of molecules recited previously which contain from one to six nitrogens. Preferred two ni-trogen fused ring systems would be composed of substituted or unsubstituted diradicals of quinoxaline.
More specifically, R and R' are unsubstituted or substituted quinolinic and isoquinolinic diradical or mixtures of diradicals which are linked -to one another either directly or via the connecting units X and Y by forming bridges.

" ~

- ~a -Preferahly the bridges are Eormed at the 2,6 and 3,6 posi-tions~
The connecting units X and Y can be selected from the group COmprl slng:
-0-; -S-; -CH=CH- -C--C-~i ~~ S,~

CH-C~ ~ ; ~ C-C _ ~ ;_ ~ ;

~ _ cRv=c ~ , and -cRVii= cRvli :,' wherein RV, Rvi and R~ii are H or methyl and mixtures oS thereof. Blphenyl, vinyl and acetylene connecting groups are preerred connecting units.
The size of n determines the physical properties o the electroactive pol~mer. Preferably, n is rom lO to lO,000 when c is zero. Most preferably, n is from 50 to 5,000 when c is zero. Tractable films are formed with electroactive polymer whose n exceeds 50. A preferred molecular weight is lO,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 conductivity is increased and adjusted by increasing d. For example, the virgin homopolymer of 2,Ç-~4-phenylquinoline) has a con-ductivity of about lO~l5 ohms~l cm~l. Incorporating about 20 weight percent of a charge compensating ionic dopant such as Na~ in the electroactive polymer increases the conductivity to about 102 ohms l cm l. Preferred electro-active polymers are doped polymers that have conductiv-ities greater than about lxlO-l0 ohm l cm l r most preferably greater than lx10-4 ohm~l cm~l. Conductivities in the range of semiconductors can be achieved when d is from about lO to about lO00. Greater concentrations of the charge compensating ionic dopant M increase the conductivity to the metallic conductivity regime. The charge compensating cationic or anionic dopant M is selected from the previously recited dopants and the likeO
M remains the same for all the following preferred poly-mers.
The R and R' groups are the same or different.
When a is l, b and c are zero, R' and Y drop out and the polymer has the following formula:

(+ Sd) ~R-~X) ~ (Md)(+S) when a, b, and c are zerot R', X, Y drop out and the poly-mer has the formula-~5 ~
(~Sd) ~ER~n ( ~ ( ~ S ) A preferred R or R' is selected from the group consisting of the diradicals of quinoline, substituted quinoline, isoquinoline and substituted isoquinoline. A
preferred diradical is a 2,6 substituted quinoline of the formula:

Riii Riv "~

wherein Rii, Riii and RiV are substituent groups selected from H; hydroxy; carboxy; amino; alkyl 1 to 4 carbon atoms; alkoxy 1 to 4 carbon atoms; an alkylthio of 1 to 4 carbon atoms; a cycloaliphatic group of 5 or 6 carbon atoms; an alkenyl group of 2 to 4 carbon atoms; an aryl group of 6 to 10 carbon atoms; an aryl group of 6 to 10 carbon atoms substituted by 1 to 3 alkyl groups of 1 to 4 carbon ~toms, alkenyl groups of 2 to 4 carbon atoms, alkynyl groups o~ 2 to 4 carbon atoms, alkoxy groups of 1
3 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms r dialkyl amino groups of 1 to 4 carbon atoms t an alkylthiol of 1 to 4 carbon atoms; or a 5~ or 6-member nitrogen containing unsaturated heterocyclic group. The nitrogen atom~ in the above polymers can be quaternized by -~ 35 reaction with quaternizing agents, e.g. dimethyl sulfateu The term "alkyl" refers to both straight- and branched-chain alkyl groups~ Suitable examples are methyl, ethyl, propyl, isopropyl, butyl t i-butyl, s-butyl, and t-butyl.

JLf~i~.3~

~1 The term "alkoxy" refers to the group R ~
wherein Rl is alkyl. Suitable examples are methoxy, ethoxy, propoxy, isopropoxy, butoxy, i-butoxy, s-butoxy, and t-butoxy.
The term "alkylthio" refers to such examples as methylthio, ethylthio, propylthio, isopropylthio, butyl-thio, i butylthio, t-butylthio, and s-butylthio.
Suitable examples of cycloaliphatic are cyclo-pentyl, cyclohexyl, 3-methylcyclopentyl~ and the like.
~ he term "alkenyl" refers ~o unsaturated alkyl groups having a double bond [e.gO~ CH3CH=C~(CH2)2] and includes both straight- and branched-chain alkenyl groups such as ethenyl~ but-3-enyl, prope~yl, and the like.
The term "aryl" refers ~o an aromatic hydrocar-bon radical such as phenyl, naphthyl, and the like. Suit-able examples of an aryl substituted with an alkyl are 2-tolyl, mesityl, 3-isopropylphenyl and the like. Suitable examples of an aryl substituted with an alkenyl are 3-styryl, 4~ propenylphenyl, and the like, Suitable aryl groups substituted with an alkoxy are l-methoxy-2 naph~
thyl, 3-n-butoxyphenyl, and the like. Suitable aryl groups ~ubstituted with a cyano group are 4 cyanophenyl,
4-cyano-1-naphthyl, and the like. Suitable examples of an aryl with a halogen are 4-fluorophenyl, 3-chloro-4-bromo-l-naphthyl, and the like. Suitable examples of an aryl substituted with a dialkyl amino are 3-dimethylamino-phenyl, 6-diethylamino-2-naphthyl, and the like. Suitable examples of an aryl substituted by an alkylthio are 4 butylthiophenyl, 3-methylthio-2-naphthyl, and the likeO
Suitable examples of 5- or 6-member nitrogen containing heterocyclic groups are 3-pyrrolyl, 4-pridyl, and the like.
Preferred polymers of 2,6 substituted quinoline occur when Rii and RiV are H. A preferred polymer is obtained when Rll and RlV are H and Rlll is phenyl, i.e.
poly 2,6-(4-phenylquinoline).

~.3'~

~Sd) 0S -' ~ /

~ / (Md) 1~ Another preferred group of polymers are obtained when Riii is phenyl and Rii and RiV are selected from the group of ~ubstituents previously recited.
Still another preferred polymer is fabricated from 2,6-(4-phenylquinoline~ diradicals wherein a CH3+
lS moiety is directly linked to the nitrogen of the quinoline diradical, i.e. quaternized.

~ (~Sd) ~
~J/ (~d) / CH3 ~ll Another preferred polymer is fabricated of 2,6-(4-(4'pyridyl)quinoline) and/or its quaternized analog~ When R and Rl are the same and are the 2,6 quinolinic diradical unit, the recurring repeat unit of the dopant modified electroactive polymer is:

(iSd) ~ ~1~ T x ~ d) Rlll RlV ~, wherein Rll, Rlll, and Rl~ are substituents selected from the groups recited above and X and Y are the connecting units pre~iously rec.ited. M is a previously recited con-ductivity modifierO
A preferred poly~er has the formula 3 ~ (ISd) ~ ~ _ O ~ ~ (Md ) wherein Rii and RiV are H, Riii is phenyl a, b and C are 1, X is O diradical and Y is a Phenyl diradical.
_ Another preferred polymer has the formula ~ Sd) ~ (Md~j wherein Rii and RiV are H, Riii is phenyl, a and c are l, b is zero, and X is a biphenyl diradicalD
Another preferred polymer has the ormula:

( I Sd ) COOH COOH

( ) ( i S ) ~ N ( ~

wherein Rii and Ri~ are H, Riii.is -COOH, a is 0, b and c are l, and Y is a biphenyl diradical.
Another preferred polymer has the formula:

s ,. ,~., . ~, (+Sd) ~ r~ n(Md)(_S) wherein R , R and R v are H, a is 0, b and c are 1 and Y is biphenyl diradical.
Another preEerred polymer has the formula:
CH3 CH3 (+Sd) (+S) ,~'~`11,~ (~1 ~ (Md) wherein R and R are H, R is -CH3, a is 0, b and c are 1 and Y is _~z_~

and Z is a connecting unit selected from the connec~ing units for X and Y.
Another preferred polymer has the formula 0l (+Sd) (+S) ~' ~ ~ ~ _ n wherein Rii and R are H, R is -0~, a and c are 1, b is zero, and xiS ~
Another preferred polymer is obtained when R and R' are substituted quinoline diradicals wherein R i and R

are H, a is 1, b is 1, c is 1, X is -CRVil=CRvii- and Y is -CRVii=C~-. The polymer has the formula:

Riii - ~Sd) Riii Rvii ~ ( d) ~ R~ii n Still another preferred polymer is when Riii is phenyl and RVii is H, When R or R' are substituted isoquinoline dira-dical, a preferred diradical has the formulaO

~'0 X~ }~vi~i wherein RViii~ RiX, and Rx are selected from the same substituent groups as Rii t Riii, and RiV. Similar poly-mers to the previously recited preferred quinoline poly-mers are also preferred for isoquinolineO
A preferred electroactive poly(phenyl quin-oxaline) polymer has the formula:
_ -~N N~ Sd) (~S~

_ ~ N ~ N ~ O ~ ( d)n where R and R' are phenyl quinoxaline, a is C, b and c are 1 and Y is - ~ o ~ _ .
~0 Polymer Fabricatlon The .starting ma~erial for preparing the electroactive polymers of this invention are polymers and copolymers com-prisiny recurring units of fused nitrogen containing unsatur-ated heterocyclic ring system. Preferably the recurring units are quinolin~ or isoquinoline or subs-tituted quinoline or isoqulnoline. These polymers and copolymers are well Xnown ma~erials having been synthesized in a variety of ways. For example, quinoline, isoquinoline, or substituted derivatives thereof can be converted into polymers by treatmen~ wi-th zinc chloride or by -treatmen-t with FeC13 and an alkyliodide, Rabinovich et al, Dokl. Akad. Nauk SSSR 1971, 199(4), 835-7 and Smirnov et al, Vysokomol Soedin Ser B 1971, 13(6), 395-6, respectively. The method is also suitable to polymerize the o-ther diradicals previously recited.
Other polymers are made by a synthetic route involving the reaction of ~he dichloro or dibromo derivatives of fused nitrogen containing unsaturated heterocyclic units with magnesium in ether followed by contacting with a nickel salt. The dihalo derivatives having halogens in essentially all possible combinations are known. This route provides a method of prepaxing polyquinolines or polyisoquinolines having bridges through any two of ~he seven possible points o~ attach ment.
The dihalo compounds are also useiul in forming copolymers with other interconnecting groups. For example reactions with sodium sul~ide gives a sulfur atom between each nitrogen heterocycle. Reaction with dihydroxy or disodium salts of dihydroxy compounds give ether-type copolymers.

~ .~

~ nother me~hoc1 of makincJ the polymeric starting material is by a syn-thesis involving the Einal reaction of an appropria~e diketone wi~h an appropriate aminodiacyl-~enzene in the presence of a base or an acid catalys-t as discussed in Korshak et al, Vysokomol, Soedin., Ser B9(3), 171~2(1967);
Shopov, I, Vysokomol.Soedin., Ser B 1969, 11(4) 248; Garapon, J
et al, Macromolecules 1977, 10(3) 627-32; Stille, J.K et al, Polym. Prepr., Am Chem. Soc., Div. Polym. Chem 1976, 17(1), 41-45; Stille, J.K. Pure Appl. Chem. 1978, 50(4), 273-280;
Baker, G. L. et al Macromolecules 1979, 12(3), 369 73; and Beever, W. H. et al Macromolecules 1979, 12 (6), 1033-8.
Still another method of prepariny polyquinolines useful as starting materials for the compounds of this inven-tion is by the condensation polymeri~ation of appropriate di-(aminophenyl) compounds with appxopriate di(alpha,gamma-diketo)compounds, see V. Korshak et al, Vysokomol Soedin, Ser B9(3), 171, (1967). The resulting polymers have structures of formula - -C~I3 CH3 ~Z1~

where zl is 0 or OEI2CH2.
The di(aminophenyl) compounds may contain a variety of substituents but mus-t have an unsubstituted position or-tho to the amino group. Typical compounds include 4,4'-diaminobi-phenyl, 3,3'-diaminobiphenyl, 2,4'-diaminobiphenyl, 2,2'3,3'-tetramethyl-4,4'-diaminobiphenyl, di(4-aminophenyl) methane, di(4-aminophenyl) ether, 1,2-di(4-aminophenyl) ethane, 1,2-di-(4-aminophenyl) ethylene, and the like.

., ~.

" ~

The di(alpha,gam~na-diketo) compounds compris~ those compounds wherein the diketones are joined at the alpha-position through various connecting groups. These compounds have the s-tructure:
O O O O
.. .. ,~ "
CH3 - c-c~I2 - ~-z--C~C~12--~-CE13 1 wher~in Z is a connectiny group. Typical connec-ting groups include the X and Y connecting groups having 2 or more atoms, French Pat. 1,468,677 and J. Polym. Sci. Part C, #16 Part 8, 4653 (196~).
The preferred method for making the polyquinoline polymeric starting material is in accordance with the proce-dures outlined by W. H. Beever, et al., Journal of Polymer Science: Polymer Symposium 65, pp. 41-53 1978; S. 0. Norris, et al., Macromolecules, Vol. 9, No. 3, May-June, 1976, pp.
496-505, J. Pharm. Sci. 57 784 (1968), and J. ~eterocycle Chem.
_ 107 (1974).
Tractable Polymer Fabrication Subsequen-t to polymerization, articles such as fibers, ribbons, or free-standing films are cast from solution.
The solution is Eormed by dissolving the desired polymer in a solvent which consists of sulfuric acid, formic acid, or a mixture of P20s and m-cresol. The solution temperature is from about 25C to about 200C and preferably at about 140CI most preferably 100C. The polymers are coagulated into solid shapes such as fibers, ribbons, or free-standing films in a basic coagulation bath. For ~ree-s-tanding films, the polymers are fabricated from solutions containing about 2 to 25~ polymer dissolved in the solvent. At concentrations which exceed 10~, the cast films take on an anisotropic morphology. The aniso-r~

tropic property enhances the cc>ncluctivity in the anisotropicdirection. ~n amlne, for example triethylamine, dissolved in a protonic solven-t such as ~120 and preferably ethyl alcohol comprises -the coagulation bath. The bath ls maintained at a lower temperature ~han the dissolu~ion temperature of -the poly-mer in the solvent. ~sually room -temperature i8 selected as -the operating temperature of the coagulation bath. The fabri cated articles are dried. Elevated temperatures, usually 60C, and reduced pressure accelerated the drying process. Drying is 0 continued until no further weight loss is observed.
Polymer Conductivity Modification AEter fabrication of the desired articles from the polyfused heterocyclic quinolinic polymers by means of the procedure 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 conductivity modifiers, i~e.
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 doping can also be carried out in an i.nert liquid medium such as tetrahydroEuran, acetonitrile and the like. The dopants can be oxidizing or electron accepting molecules, or reducing molecu]es, or reducing or electron donating molecules. 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 polymers tend to degrade, i.e. lose conduc-tivity, when exposed thereto.

.~y . ~

For example, the polymer can be contacted with alkali naphthalides or alkali anthracenic1es such as sodium naphtha-lide, potassium naphthalide, or sodium anthracenide in a tetra-hydrofuran solution. The conductivity modifier concentration can be from about 0.001 to about 1 molar and preferably from about 0.01 to about 0.5 molar in the THF or o-ther suitable solven~. ~lternative doping methods are taught in U.S. patent 4,~04,216.
I~ is unclear at -the present time exactly ho~ the electron donor or acceptor dopants are incorporated into the polymer. However, the incorporation of the dopants into the polymer can be observed by a color change in the polymer as well as an enhanced conductivity. For example, a virgin poly-mer film having a yellow or orange - 20a -co:lor, changes to a blue or black color with a metallic luster ~lpon doping ~nd the rneasured conductivity increases by ~any orders of magnitude.
Alternatively, the polyquinoline pol~mers can be oxidized or reduced to their conductive forms using electro-chemical techniques. In this method, herein reEerred to as electrochemical doping, the poly~er is immersed in a suitable electrolyte solution and used as one electrode of an electro-chemical cell. Upon passing an electric current through such a cel] the polymer becomes reduced (or oxidized, depending upon the direction of current flow) and charge compensating cations (or anions) Erom the supporting electrolyte become incorporated into the polymer, This doping also proceeds with the character-istic color change described above. Thusl the polymer can be electrochemically doped wlth whatever appropriately charged ion is present in the electrolyte solution. Electrolyte solutions are comprised of a salt dissolved in a solvent. Suitable sol-vents are acetonitrile, tetrahydrofuran, 2-methyl-tetrahydro-Euran, propylene carbonate, dimethyl-~ormamide, dimethyl-sulfoxide and the like. Suitable cations are Li+, Na~~, K+, (CH3)4N~, (C2Hs)4N+ and (C4Hg)~N+. Suitable anions are Cl-, Br-, C104-, BF4-, and PF6-. The extent of doping can be easily controlled by adjusting 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 respec-t to a refer-ence electrode (potentiostatic charging).
The above--described electrochemical doping process is completely reversible. The polymer can be "undoped" and re-turned 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, Eor example, a re~uced~ conducting polyquinoline polymer can be reoxidized completely to its neutral, non-conducting form, and the charge-71 ~D,i ~

compensating cations incorporated during the electrochemical reduction process are expellecl from the article during electro-chemical re-oxidation.
Having described the methods o~ Eabrication and the basic polyfused heterocyclic systems, the following examples are intended -to be illustrative 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.
EXAMPLES
Example la Preparation oE 2-methyl-2-(4-nitrophenyl)-1,3-dioxolane P-Nitroacetophenone (1.65g, 10 m mol), ethylene glycol (5 ml, 89 m mol), triethyl or-thoforma-te (2.96 g, 20 m mol), and p-toluenesulfonic acid (0.086 g, 0.5 m mol) were combined in methylene chloride (4 ml). The solution was heated with an oil bat'n (50-70C, 6 hrs), cooled to room -temperature, and poured into excess 10% sodium hydroxide solution. The phases were separated and the aqueous phase was extracted twice with methylene chloride. The combined organic phase was washed three times with water and dried with anhydrous sodiu~ sul-phate. Evaporation of the solvent left a light yellow product (1.78 g) with mp. 69-71C, (lit. 73-75C, see J. Pharm. Sci. _, 784 (1968)).
Example lb Preparation of
5-(2-Methyl-1,3-dioxolan-2yl)-3-phenyl-2,1-benzisoxazole Phenylacetonitrile (0.84 g, 7.2 m mol) and 2-methyl-2-(4-nitrophenyl)-1,3-dioxolane (mp. 69-71C) (].50 g, 7.2 m mol) were added to a room temperature solution of sodium hydroxide (1.44 g, 36 m mol) in methanol (8 ml). A slight exotherm was noted and stirring was continued Eor 16 hrs. The mixture was filtered and the collected solid washed several times with water and once with cold methanol to yield a yellow powder (1.60 g) with mp. 137C (lit~ mp. 137-138C, see J. Heterocyclic Chem. 11, 107 (1974)).

Example lc Preparation of 05 2-Amino-5-(2-methyl-1,3-dioxolan-2-yl) benzophenone 5-(2-Methyl-1,3-dioxolan-2yl)~3-phenyl-2,1-ben-zisoxazole (1.50 9, 5.3 m mol), triethyl amine (0.3 ml) and 5~ palladium on carbon (0.15 g) were combined ln dry tetrahydrofuran (13 ml). The apparatus wa flushed with nitrogen and then hydrogen. A static hydrogen atmosphere was maintained (1 atm.) and the progress of the reaction followed by gas chromatography. The starting material and product have re~ention times of 11.15 and 11.33 min.
respectively. When conversion was complete, the mixture was filtered through a pad o Celite to yield a clear yellow solution. Evaporation of the solution yielded a yellow solid ~1.35 g) of mp. 108-111C.
Example ld Preparation of 5-Acetyl-2-aminobenzophenone 2-Amino-5-(2-methyl-1,3-dioxolan-2-yl) benzo-phenone (1.0 g, 3.54 m mol) was dissolved in 30 ml absolute ethanol. To this was added lM perchloric acid (14 ml). The resulting mixture was stirred at room tem-perature for 18 hrs. The mixture was made basic with 3N
sodium hydroxide solution and then extracted with several portions of methylene chloride. The combined methylene chloride extracts were washed with water, dried with anhy-drous sodium sulfate, and evaporated to yield a yellow 30 product (0.79 g) of mp. 158-161C. A portion of the product was recrystallized from a mixture of methylene chloride and hexane to yield material of mp. 158-162C.
Example le Preparation of Poly 2,6-(4-phenylquinoline) A solution was prepared from phosphorous pent-oxide (1.07 g, 7.5 m mol) and reshly distilled m-cresol (2.5 ml) by heating at 140C for 2.5 hrs. under nitrogen.
The solution was cooled to room temperature and 5-acetyl-2-aminobenzophenone (0.30 g, 1.28 m mol) and m-cresol (1.3 ml) were added. The solution was heated to, and .
* Trade Mark ~' malntained at 120C for 48 ~Irs. T~l~ h~t so~ution was poured ~,7ith stirring into a mixture of 95% ethano] (60 ml) and triethylanline (6 ~ll) to yield a fibrous yel]ow solid whicll was ~clshecl t~ice ~itll ~thanol in a Waring blender.
It was then extracted with ethanol (19 hrs) in a Soxlet apparatus and dried to give an orange product (0.26 g, 1.28 m mol).
Examp:le 2 Preparation of Films of Poly 2,6-(4-phenylquinoline) Films A solution was prepared from phosphorous pentoxide (0.8 g, 5.6 m mol) and distilled m-cresol (2.5 ml) by heating at 110-120C under Argon.
The solution was cooled to room temperature and poly 2,6-(4-phenylquinoline) (0.051 g, 0.25 m mol) added. The mixture was heated to 140C to yield a viscous deep red solution. Free-standing films were prepared by spreading a few drops of this solution on a heated glass plate and quenching in a bath of triethylamine (10%) and ethanol (90%). The clear yellow films were pressed between la~ers of filter paper and dried in a vacuum oven.
Example 3 Doping of Poly 2,6-(4-phenylquinoline) The transparent, yellow film prepared in Example 2 was placed in a jar, in a dry box with a dry argon atmosphere. After 30 minutes, a dimethoxyethane solution of sodium naphthalide was poured into the jar.
The film reacted immediately, changing to a dark color; green blue in transmitted light and purple-green ~:ith metallic sheen in reflected light.
Upon exposure to air, the dark color disappears instantly, and the polymer resumes its original appearance.
Example 4 Conductivity ~leasurement of Poly 2,6-(4-phenylquinoline) The procedure of example 3 was followed except the Eilm was first wet with tetrahydrofuran (THF) and then treated with O.l~f sodium naphthalide, dissolved in THF. Upon addition of the sodium naphthalide, the polymeric film * Trade Mark .~

turned deep blue with a metallic luster. The surface of the film was rinsed with THF. l'he conductivity of the doped film (2.54 x 10-3 cm thick) was measured using a 4-point probe apparatus of the Signature Co. The 4 points of the apparatus form a single line. A DC voltage (VE) is applied across the outermost two points, and the voltage (Vl) of the current is measured across the inner two points. From these values a conduc~ivity is calculated as follows:

VE = 0.1 volts VI = 0.06 volts (measured) R = 1074 (VE/VI) = 1790 ohms/square rho = Rxt = 1730 x 2.54 x 10-3 = 4.55 ohm centimeters sigma = l/rho = 0.22 ohm~l centimeter~

where:
VE = impressed voltage t = film thickness VI = measured voltage R = resistance of the surface-rho = resistivity of the article sigma ~ conductivity 1074 = instrument and unit conversion factor The washed, but undoped polymer, was not conduc-tive, but actually was an insulator having a conductivity of 10 15 ohms 1 centimeter 1 as measured on the same appa-ratus, (See J. Polym. Sci. Poly. Symp., 65, 41 (1978).
This same value (10-15) was measured on the doped film after turning yellow upon exposure to air.
The infrared spectra of the original undoped film and the air-exposed doped film were the same. The-infrared o the dark, sodium naphthalide doped film was opaque with no absorption between 4000 and 600 cm 1, indi-cating metallic behavior. This experiment show$ that the doped polyquinoline films are surprisingly good electrical conductors.

~:, f~ ~- JL

~1 -~6 Example 5 Conductivity Measurement of Poly 2,6-(4-phenylquinoline) Films were also doped as in Example 4 but with potassium naphthalide and after these films had been kept for 6 days in a vacuum dry box at a pressure less than 10-6 mm Hg, the following conductivity value was obtained:

VE = 36 mv ~I = 55 mv t = 2.54 x 10-3 cm rho = 1.78 ohm cm. sigma = 0O56 ohm~l cm~

Values of this magnitude show the doped polymer to be electroactive in that it is a conductor of electricity.
Example 6a 1~ Preparation of bis-4-Nitrophenylether l-Fluoro-4-nitrobenzene (20.0 g, 0.142 mol), 4-nitrophenol (19.7 g, 0.142 mol), and potassium fluoride (28.3 g, 0:486 mol) were combined in 75 ml dimethylsulf-oxide and heated to reflux for 0.5 hrs, The mixture was cooled and left at room temperature overnightO
The precipitate was collected and washed with water, It was dissolved in warm toluene, separated from a water layer and dried with magnesium sulfate~ Concentra~

tion and cooling yielded 28u8 g of product (mp 144-146C~

in two crops.
Example 6b Preparation of 5,5'-Oxybis-(3 phenyl-2,1-benzisoxazole) Phenylacetonitrile (17.72 g, 0.151 mol) and bis-4-nitrophenylether (19.52 g, 0.075 mol) were added to a room temperature solution of sodium hydroxide (30.01 g, 0.75 mol) in methanol (150 ml) and heated at reflux for 9 hrs. The reaction mixture was cooled to room temperature and diluted with 50 ml of 50% methanol in water and then cooled in an ice bath. The precipitate was collected and 3 washed with cold methanol. This solid was dissolved in warm toluene, dried with magnesium sulfate, concentrated, and cooled to yield 7.55 g. Recrystallization from warm toluene gave S.l9 g of product mp 208-209Co A second, unidentified material, mp 158 165C, was also isolated.
~0 p~

Example 6c Preparation of 05 4,4~-Diamino-3,3'-dibenzoyldiphenylether 5,5'-Oxybis-(3-phenyl-2,1-benzisoxazole) (4,92 9r 12.~ m mol) and triethylamine (1.35 ml) were combined in tetrahydrofuran (50 ml) under a nitrogen atmo-sphere. Palladium on carbon (5%, 0.41 g) was added and then hydrogen was slowly passed through the system for 15 hours. The mixture was filtered through Celite and eva-porated to a yellow oil which was crystallized from a mixture of toluene and hexane ( io to 1) to yield 4.33 g ~87~) of the desired product. This was further purified by recrystallization from methanol to yield 2.43 g with mp 154-155C.
Example 6d Preparation of a Quinoline Copolymer rom 4,4'-Diamino-3,3'-dibenzoyldiphenyl ether and p-Diacetylbenzene A solution was prepared from phosphorous pent-oxide (5.6 g, 39.4 m mol) and freshly distilled m-cresol (20 ml) by heating to 140C. A portion of this solution (7.6 ml) was used to dissolve 4,4'-diamino-3,3'-dibenzoyl-diphenyl ether~(0.5005 g, 1.225 m mol) and p-diacetylben~
zene (0.1987 g, 1.225 m mol). The solution was maintained at 110-120C for 48 hrs. The mixture was cooled and poured into a mixture of triethylamine (10 ml) and 95%
ethanol (100 ml) to yield a white fibrous product. The product was dissolved in chloroform (15 ml) and precipita-ted with ethanol. This was repeated to finally yield 0.10 g of whitet fibrous polymer. A film was prepared by dis-solving 25.7 mg in 0.52 g of the above phosphorous pent-oxide-m-cresol solution at 60C, placing a few drops on a warm glass plate, and spreading ~ith a warm blade. After quenching in a g0% ethanol - 10% triethyl amine bath, a free-standing film was obtainedO This polymer has the structure:

~3 ~1 _ Example 7 Doping and Conductivity Measurement of the Polymer of Example 6 Films of the polymer of Example 6d were kept in a dry box for 2 weeks at less than 10 ppm water and oxy-lS gen. Thereater the films were doped with sodium naph-thalide as described in Example 3. Upon doping, the films turned a deep metallic blue in color. Conductivity measurements gave:
VE, = 4~5 mV rho = 40.9~ ohm cm.
VI = 0.3 mV sigma = 0.024 ohm 1 cm~
R ~ 16110 ohms per square Example 8a Preparation of 5~Bromo-3-phenyl-2,1-benzisoxazole Phenylacetonitrile (8.1 g, 69 m mol) was added to a room temperature solution of potassium hydroxide (85~) (74 g, 1.1 mol) in methanol (150 ml). To this was added 4-bromo l-nitrobenzene (12~7 g, 63 m mol~ suspended in methanol ~130 ml). An exotherm was noted and the reac-tion was maintained at 50C for 5 hrs. After cooling to room temperature, water (400 ml) was added. ~he precipi-tate was collected and washed with waterO The crude prod-uct (13.15 gj was crystallized from hot methanol (200 ml) to yield yellow needles (9~52 g, mp 113-116C).
Example 8b Preparation of 2-Amino-S-bromobenzophenone S~Bromo-3-phenyl-2,1-benzisoxaæole (7.5 g, 28.6 m mol), water (14.6 ml), and zinc dust (9.3 g, 143 m mol) were combined. Acetic acid (8.6 ml, 143 m mol) was added and the mixture was stirred and heated at 80C for 90 minutes. ~Eter coolin~ to room temperature, both the liquid and solid ~ortion of the reaction were extracted with methylene chloride. The combined me-thylene chLoride solutions was washed once with sodium hydroxide solution (10~) and several times with water~ Drying (sodium sulfate) and evaporation yielded the desired product (7.42 ~) of mp. 92-102C.
EX~MPLE 8c Preparation o-f 4,4'-Diamino-3,3'-dibenzoylbiphenyl 4-Bromo-2-aminobenzophenone (0~55 g, 2.0 m mol) was dissolved in dry and deoxygenated dimethylformamide (10 ml) in an inert atmosphere box. To this was adcled in portions bis(l,5-cyclooctadiene)nickel (0) (0.55 g, 2.0 m mol). The reaction was moved from the inert atmosp'here box to a vacuum-argon manifold using standard Schlenk-wave techniques. The reaction was heated at 50-55~C for 4 hrs. and left at room temperature overnight. ~he mixture was poured into 200 ml of water which was made sli~htly basic with sodium hydroxide. The water was extracted several times with e-thyl acetate which after drying with sodium sulfate and evaporation gave a dark brown liquid (0.48 g). Recrystallization from hexane yielded 100 mg of yellow hrown solid mp 180-185C.
Example 8d Preparation of a Polymer from 4,4'-Diamino-3,3' dibenzoylbiphenyl and 4,4'-diacetylbiphenyl 4,4'-Diamino-3,3'-dibenzoylbiphenyl (80.0 mg, 0.204 m mol) and ~,4'-diacetylbiphenyl (48.6 mg, 0.204 m mol) were combined in a solution prepared from phosphorous pen-toxide (0.348 g, 2.45 m mol) and freshly distilled m-cresol (1.2 ml) and heated at 120-130C for 46 hrs. T'he ho-t reaction mixture was poured with stirring into a mixture of triethylamine (6 ml) and 95% ethanol (60 ml). I'he fibrous red precipitate was stirred in the basic bath until i-ts color changed to yellow.
It was washed with water and dried at 80C to yield 120 mg of yellow powder .~

I~ ~'~' I'J

- ~o mp > 320C. E'ilms of this material were prepared by dissolving 50 mg at 120C, in m-cresol (0.75 m:L) containing phosphorous pentoxide (0.2 g). A few drops o:E this solution were spread on a glass plate and quenched in a bath of triethylamine (10%) and ethanol (90%) to yield a free-standing yellow film. This co-polymer has the structure: ~ _ ThereaEter, the polymer was rendered conductive in accordance with the procedure outlined in Example 3. The con-ductivity was measured in accordance with the procedures out-lined in Example 4. The conductivity of the doped polymer was 0.024 ohm~l cm~l.
Example 9 Preparation of Poly 2,6-(4-(4'chlorophenyl)quinoline) This polymer was prepared by essentially the same process as described in Example l, except that 4-chlorophenyl acetonitrile was used in place of phenylacetonitrile. Analysis of the polymer gave the following results. Calculated for (ClsHgNCl):C, 75.80%; H, 3.39%, N, 5.89%, Cl, 14.92%. E`ound:
C, 76.81%; H, 3.64~; N, 5.86%, the remainder being Cl. The polymer has the structure:

r ~J
n .~

~ :31 ~

Thereafter, the polymer was rendered concluctive in accordance with the procedure outlined in Example 3. The conduc-tivity was measured in accordance with the procedures outlined in Example 4. The conductivity of the doped polymer was 0.02 ohm-l cm-l.
Example 10 Electrochemically Doping Quinoline Polymers A 5-inch platinum wire was coated with a thin film of the polymer of Example 1, by dipping the wire into a 5~ solu-tion of the polymer in a m-cresol/P20s mixture. The film-coated wire was neutrali~ed by dipping into a 10% triethylamine - 90~ ethanol solution and dried in a vacuum oven at 60C.
The polymer coa-ted wire was connected to an ~.G. and G. Princeton Applied Research Apparatus comprising a Universal programmer and a Potentiostat/Galvanostat, with recorder. The polymer coa-ted end of the wire was then immersed into a 0.1 M solution o-f lithium tetrafluoroborate in acetonitrile. A potential, varying from 0 to -3.0 volts vs. SCE was applied to the platinum wire. The output current was essentially nil until the potential reached abou-t -1.5 volts at that point the cathodic current increased rapidly and peaked at -2.25 volts. Upon reversal of t'ne potential sweep, an anodic current was observed which peeked at -1.5 volts.
When the initial -1.5 volt potential was applied, the polymer adhering to the wire turned from a pale yellow to a dark metallic color, which color disappeared upon raising the voltage to more than -1.5 volts.
This behavior indicates an initial resistance to passage of curren-t followed by a rapid uptake of electrons resulting in a charged electroactive polymer con-taining li-thium iOIlS as the charge compensating dopant. In effect the polymer was made electroactive by the application of a potential of about -2 volts in the presence of an electrolyte solution capable of providing a charge compensa-ting dopant.

Example 11 Electrochemically Doping Quinoline Polymers The same experiment as Example 10 was carried out except that the lithium tetrafluoroborate was replaced by tetrabutyl ammonium bromide.
Essentially the same results were obtained as in Exarnple 10. In this case the polymer coated wire was alternately charged and discharged without any loss in activity. The metallic color came and went as the polymer was charged and discharged.
This experiment indicates that the charged electroactive polymer can be used as an electron source. One useful application is as the anode of a battery. It also shows that the electroactive polymer is able to incorporate into its structure organic charge compensating ionic dopants.
Example 12 Electrochemically Doping oE a Poly(phenyl-quinoxaline) A 5-inch platinum wire was coated with a thin film of a polymer of the structure ~ N ~ ~

by dipping the wire into a 5% solution of the polymer in an m-cresol/P2/05 mixture. The virgin polymer was purchased through the Aldrich Chemical Co.
and is a product of Scientific Polymer Product, Inc., 6265 Dean Parkway, Ontario, ~ew York Catalogue ~330 lot 101. The polymer is 100% solids in m-cresol. The film-coated wire was neutralized by dipping into a 10% triethyl-amine - 90% ethanol solution and dried in a vacuum oven at 60C.
The polymer coated wire was connnected 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 immersecl into a 0.L M solution of lithium tetrafluoroborate in acetonitrile. A potential, varylng Erom 0 to -3.0 volts vs. SCE was applie~ to the platinum wire. The output current was essentially nil until the potential reached about -1.5 volts. At that point the cathodic current increased rapidly and peaked at -2.0 volts. Upon reversal of the potential sweep, an anodic current was observed which peaked at -1.25 volts. When the initial -1.5 vol-t po-tential was applied, the polymer adhering to the wire turned from a pale yellow to a dark metallic co.or, which color disappeared upon raising the voltage to more than -1.5 volts.
This behavior indicates an initial resistance to passage of current followed by a rapid uptake of electrons resulting in a charged polymer con-taining lith~lum ions as the charge compensating dopant. In effect the polymer was made electroactive by the application of a po-tential of about -2 volts in the presance of an electrolyte capable of providing charge compen 5 ating ionic dopants.
Example 13a Preparation of 4-Acetyl-2-(4'-methoxy)benzoyl Aniline Mono~er 38.2 g of NaOH was dissolved in metanol (200 ml) in a l-liter 3-neck flask provided with a mechanical stirrer, reflux condenser, N2 inlet and a heating mantle. 28014 g (0.19 mol) of p-methoxyphenyl-acetonitrile was added followed by 40 g (0.191 moles) of p-nitro-aceto-phenone ethylene glycol ketol.
The reaction was stirred mechanically under reflux for 22 hours.
The produc-t was Eiltered off, washed with water and recrystallized from methanol.
The product had the formula:

~ N
~0 LI ~

~llZ()~

Analysis calculated for C181ll704N
Calc Fnd.
% C 69.~4 68.16%
H 5.50 5.41 N 4.50 4.26 Example 13b llydrogenation of the product of Example 13a 17.12 g (0.055 mol) of the product of Example 13a was dissolved in 150 ml of tetrahydrofuran and 4 ml of triethylamine in a 500 ml 3-neck flask provided with a gas inlet tube, reflux condenser, thermometer and a magnetic stirrer. 1.2 g of 5% Pd/carbon catalyst was added.
The flask was flushed with nitrogen and then coImected to a slow stream of hydrogen.
The reaction was stirred magnetically at room temperature for 9 hours.
Thin layer chromatography indicated complete reaction.
The reaction was flushed with nitrogen, and the catalyst filtered off through celite.
The filtrate was evaporated to an oily residue, 19.3 g.
The product had the formula:
~NH2 \~

OCH~
Example 13c Hydrolysis of the product of Example 13b 19.1 g of the product of Example 13b was dissolved in 60 ml of tetrahydrofuran and 30 ml of water ~z~

in a 250 ml round bottom flask. The pH of the solution was adjusted to approximately 3 with conc. HCl and the reaction allowed to stand at room temperature for approxi-mately 18 hours.
Thin layer chromatoyraphy showed complete hydro-lysis.
The reaction mixture was poured into 300 ml of saturated Na2CO3 solution and extracted three times with an equal volume of methylene chloride.
The combined methylene chloride solution was washed with water, dried and evaporated to give 14.5 g of yellow residue.
The product was recrystallized from methylene-chloride hexane m.p. 119-123C.
The product had the formula:

,~" NH 2 0 ~3 Analysis calculated for C16H15O3N
Calc. Fnd.
% C71.36 71.33%
% H 5.61 5.69 % N 5.20 5,78 Example 13d Preparation of Poly [2,6-(4-p-methoxyphenyl)quinoline]
The catalyst solution was prepared by dissolving 9.44 g (66.5 mmoles) of P2OS (weighed in a dry box) in 24 ml of m-cresol (Aldrich gold label) in a 50 ml 3~neck round bottom flask fitted with a mechanical stirrer, reflux condenser and an N2 inlet.

,'d ' ,h ~ ~'P~q~

The catalyst solution was mechanically stirred and heated in an oil bath at 105C, under an N2 blanket, until the solution became homogeneous (approximately 2-1/2 hours). 3 g (11~16 mmoles) of the monomer of Example 13c was added followed by 10 ml of m-cresol. The temperature of the oil bath was increased to 120 and the polymerization reac~ion run of this temperature for 48 hours~ The color of the solution changed from gold to deep red and the solution became more viscous.
The polymerization solution was poured slowly into 500 ml of a 10% solution of triethylamine in ethanol and stirred at room temperature overnight. On neutraliza-tion the polymer formed a spindle.
The polymer was collected by filtration, washed with ethanol and extracted with ethanol in a Soxhlet extractor overnight.
Following the extraction, it was filtered and dried in vacuo at 70C to give 2.3 g (88.5%) of dry polymer.
The polymer had the formula:

~r~_ Analysis:
Calc.*Fnd.
% C 82.38 78.52 H 4.75 4.40 N 6.01 5.52 [nj = .83 dl/g (measured in H2SO4).
Thereafter, the polymer was rendered conductive in accordance with the procedures for Example 3 using 0.5 molar solution of sodi~m anthracenide-in T~F instead of ~!; based on C16Hll NO as the repeating unit.

4~

sodium naphthalide. The conductivity was measured in accordance with Example 4~ The polymer had a conductivity 05 of 205 ohm~I cm 1~
Example 14 Preparation of --Poly[2,6-(1-Methyl-4-phenyl)quinolinium]metasulfate Poly 2,6-(4-phenylquinoline) coated platinum wires were placed in a 50 ml round bottom flask and covered with 10 ml of Dimethyl sulfate (Aldrich~. The flask was fitted with a reflux condenser and a drying tube inside a hood. The reaction was allowed to stand at room temperature overnight and then heated at reflux for
6 hours.
After cooling, dimethyl sulfate solution was de~anted off and the wires quenched with approximately 30 ml of a 10% solution of triethylamine in ethanol~ Follow-ing neutralization the w~res were thoroughly washed with ethanol and dried in vacuo at 80C~
The polymer had the formula:

25~ 3 C~3S3l 30CH3 n The polymer was rendered conductive in accord-ance with Example 3. However, the dopan~ was 0.5 molar sodium anthracenide in THF. The conductivity of the polymer was 0075 ohm 1 cm 1 as measured in acco~dance with Example 4.

nl Example 15 05 _ Electrochemical Doping of Poly[2,6~ methyl-4-phenyl)quinolinium]
A 5~inch platinum wire was coated with a thin film of poly 2,6-(4-phenylquinoline) as in Example 10.
The polymer was then quaternized as in Example 14.
The resulting polymer coated wire was connected to the apparatus described in Example 10 and immersed into a 0.1 M solution of tetraethylammonium tetrafluoroborate in acetonitrile. A linear potential sweep varying from -O.5 to -1.3 volts vs. SCE was applied to the platinum lS wire. The output current was essentially nil until the potential reached about -OJ8 volts~ at which point the cathodic current increased rapidly, peaking at -1.1 volts.
Upon reversal of the potential sweep, an anodic current was observed, peaking at -0.8 volts.
2~ This behavior indicates an initial resistance to current flow followed by a rapid uptake of electrons to ~orm a reduced polymer. In effect the polymer was made electroactive by the application of a potential of about -l.l volts vs. SCE in the presence of an electrolyte solution.
Example 16 Electrochemical Doping of Copolymer From 4~41-Diamino-3,3'-dibenzoyldiphenylether and p-diacetylbenzene A 5-inch platinum wire was coated with a thin film of the polymer of Example 6d by dipping the wire into a 5% solution of the poly~er in a m-cresol/P205 mixture.
The film-coated wire was neutralized by dipping into a lO~
triethylamine - 9o% ethanol solution and dried in a vacuum oven at 60C.
The polymer coated wire was connected to the apparatus described in Example 10 and immersed into a 0.1 M solution of tetraethylammonium tetrafluoroborate in acetonitrile A linear potential sweep, varying from 0 to -2.5 volts vs, SCE was applied to the platinum wire The output current was essentially nil until the potential ~39 -reached a~out -1.7 volts. At that point the cathodic current increased rapidly to a maxim-lm at -2.2 volts and exhibited a doub]e wave with a peak separation of 200 mV. Upon reversal of the potentlal sweep an anodic current, also ex'nibiting a double wave, was observed at -1.8 volts. When the initial -1.1 volt potential was applied, the polymer adhering to the wire changed Erom a nearly colorless transparent appearance to a dark, metallic color. This color disappeared upon raising the voltage to greater than 1.5 volts.
This behavior indicates an initial resistance to current flow followed by a rapid uptake of electrons resulting in a charged polymer containing tetraethylammonium ion as the charge compensa-ting ionic dopant. In effect the polymer was made electroactive by the application of a potential o-f about -2.2 volts V5. SCE in the presence of an electrolyte solution capahle of providing charge compensating ionic dopants.
Example 17 Electrochemical Doping oE Copolymer from 4,~'-Diamino-3,3'-dibenzoylbiphenyl and 4,A' diacetyl~iphenyl A 5-inch platinum wire was rotated with a thin film of the polymer of Example ~d by dipping the wire into a 5%
solution of the polymer in m-cresol/P2Os mixture. The ~ilm-coated wire was neutralized by dippin~ into a 10~ triethyl-amine-90~ e-thanol solution and dried in a vacuum oven at 60~C.
The polymer coated wire was connected to the appar-atus described in Example 10 and immersed into a 0.1 M solution of tetraethylammonium tetraEluoroborate in acetonitrile. A
linear potential sweep, varying from 0 to -2.5 volts vs. SCE
was applied to the platinum wire. The output current was essentiall~ nil until the poten-tial reached a valve of -1.7 volts. At that point the cathodic current increased rapidly, peaking at -2.0 volts. Upon reversal of the po-tential sweep, an anodic current was observed, peaking at -1.6 volts when the initial .~

-1.7 volt potential was applied, the polymer adhering to the wire turned from pale yellow to a dark, metallic - color. This color disappeared upon raising the voltage to greater than -1.4 volts.
This behavior indicates an initial resistance to current flow followed by a rapid uptake of electrons resulting in a charged polymer containing tetraethylammo-nium ion as the charge compensating ionic dopant. In effect the polymer was made electroactive by the applica-tion of a potential of about -2.0 volts vs. SCE in the presence of an electrolyte solution capable of providing charge compensating ionic dopants.
Example 18 Electrochemical Doping of Poly 2,6-(4-(4'-chlorophenyl)quinoline) A 5-inch platinum wire was coated with a thin 2~ film of the polymer of Example 9 by dipping the wire into a 5% solution of the polymer in a m cresol/P205 mixture.
Thé film-coated wire was ne1~tralized by dipping into a 10%
triethylamine-90% ethanol solution and dried in a vacuum oven at 60C.
The polymer-coated wire was connected to the apparatus described in Example lO and immersed into a 0~1 M solution of tetrabutylammonium bromide in aceto-nitrile. A linear potential sweep, varying from 0 to -203 volts vs. SCE was applied to the platinum wire. The out-put current was essentially nil until the potential reached about -1.5 volts. At that point the cathodic current increased rapidly, peaking at -l.~ voltsO Upon reversal of the potential sweep an anodic current was observed, peaking at 1,3 volts. When the initial -1.5 volt potential was applied, the polymer adhering to the wire turned to a dark metallic color. Thls color disappeared upon raising the voltage to greater than -1.2 volts.
This behavior indicates an initial resistance to current flow followed by a rapid uptake of electrons ~3 ~1 resulting in a charged polymer containing tetraethylammo-0 nium ion as the charge compensating ionic dopant. In effect the polymer was made electroactive by the applica-tion of a potential of about -1.8 volts vs. SCE in the presence of an electrolyte solution capable of providing charge compensating ionic dopants.
Example 19 Electrochemical Doping of Poly 2,6-(4-(4'-methoxyphenyl)quinoline) A 5~inch platinum wire was coated with a thin film of the polymer of Example 13d by dipping the wire into a 5% solution of the polymer in a m-cresol/P205 mix-ture. The film-coated wire was neutralized by dipping into a 10% triethylamine-9o% ethanol solution and dried in a vacuum oven at 60C.
The polymer coated wire was connected to the appara~us described in Example 10 and immersed into a 0.1 M solution of tet~abutylammonium bromide in aceto-nitrile. A linear potential sweep, varying from 0 to -2.3 volts vs. SCE was applied to the platinum wire. The out-put current was essentially nil until the potential reached about -1~5 volts. At that point the cathodic current increased rapidly, peaking at -2.1 volts. Upon reversal o the potential sweep an anodic current was observed, peaking at -1.5 volts. When the ini~ial -1.5-volt potential was applied, the polymer adhering to the wire turned to a dark metallic color. This color disappeared upon raising the voltage to greater than -1~3 volts~
l'his behavior indicates an initial resistance to current flow followed by a rapid uptake of electrons resulting.in a charged pol~mer containing tetraethylammo-nium ion as the charge compensating ionic dopant. In effect the polymer was made electroactive by the applica-tion of a potential of about -2.1 volts vs. SCE in the presence of an electrolyte solution capable of providing charge compensating ionic dopants.

. .

Example 20 Doplng and Conductivity Measurement of Poly 2,6-(4-phenylquinoline) The polymer poly 2,6-(4-phenylquinoline) was doped and rendered electroactive and the conductivity thereof was determined in accordance with Examples 3 and 4. However, the conductivity modifier was 0.5 molar sodium anthracenide in TIIF. The conductivity of the electroactive polymer was 20 ohm 1 cm 1.
Example 21 Doping and Conductivity Measurement of Poly 2,6-(4-(4'-chloro-phenyl)quinoline) The polymer of Example 9 was doped and rendered electroactive and the conductivity thereof was determined in accordance with Examples 3 and 4.
However, the conductivity modifier was 0.5 molar sodium anthracenide in THF.
The conductivity of the electroactive polymer was 1.25 ohm cm Example 22 Doping and Conductivity Measurement of Poly 2,6-(4-phenylquinoline) The polymer poly 2,6-(4-phenylquinoline) was doped and rendered electroactive and the conductivity thereof was determined in accordance with Examples 3 and 4. However, the conductivity modifier was 0.1 molar sodium anthracenide in THF. The conductivity of the electroactive polymer was 15 h -1 -1 Example 23 Doping and Conductivity Measurement of Poly 2,6-(4-phenylquinoline) The polymer poly 2,6-(4-phenylquinoline) was doped and rendered electroactive and the conductivity thereof was determined in accordance with Examples 3 and 4. However, the conductivity modifier was 0.01 molar sodium anthracenide in THF. The conductivity of the electroactive polymer was 15 ohm 1 cm 1.

Example 24 Doping ancl Conductivity Measurement of Poly 2 9 6-(4-phenylquinoline) Tl~e polymer poly 2,6-(4-phenylquinoline) was doped and rendered electroactive and the conductivity thereof was determined in accordance with Examples 3 and 4. However, the concluctivity modifier was 0.005 molar sodium anthracenide in THE. The conductivity of the electroactive polymer was 2.75 ohm cm -42a-71~

Claims (65)

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 linear charged polymer backbone and charge compensating ionic dopant(s) associated therewith wherein said linear polymer backbone is capable of undergoing reversible oxidation or reversible reduction, or both, to form said linear charged polymer backbone, said linear polymer backbone comprising diradical repeat units selected from the following group:
(a) fused nitrogen-containing unsaturated heterocyclic ring systems;
(b) fused nitrogen-containing unsaturated heterocyclic ring systems interspersed with connecting units; and (c) mixtures of (a) and (b).
2. The electroactive polymer according to claim 1 wherein the recurring units of the charged polymer backbone are diradicals of fused six-member nitrogen-containing molecules.
3. The electroactive polymer according to claim 2 wherein the diradicals have from one to six nitrogen atoms distributed within and among the fused six-member rings wherein each ring contains three or less nitrogens bonded sequentially.
4. The electroactive polymer according to claim 3 wherein the fused rings contain one nitrogen and are positional diradicals of quinoline, isoquinoline, and quinolinium.
5. The electroactive polymer according to claim 3 wherein the fused rings contain two nitrogens and are positional diradicals of cinnoline; quinazoline; quinoxaline; 2-phenyl-quinoxaline, phthalazine; 1,5-naphthyridine; 1,6-naphthyridine;

1,7-naphthyridine; 1,8-naphthyridine; 2,6-naphthyridine;
copyrine.
6. The electroactive polymer according to claim 3 wherein the fused rings contain three nitrogens and are positional diradicals of 1,2,4-benzotriazine; pyrido[3,2-d]pyr-imidine; pyrido[4,3-d]pyrimidine; pyrido[3,4-d]pyrimidine;
pyrido[2,3-d] pyrimidine; pyrido[2,3-b]pyrazine; pyrido [3,4-b]pyridazine; pyrido[2,3-d]pyridazine; and pyrido[3,4-d]
pyridazine.
7. The electroactive polymer according to claim 3 where-in the fused rings contain four nitrogens and are positional diradicals of pyridazino [4,5-d]pyridazine; pyrimido[5,4-d]-pyrimidine; pteridine; pyrimido[4,5-d] pyridazine; pyrimido-[4,5-d]pyrimidine; pyrazino[2,3-b]pyrazine; pyrazino [2,3-d]
pyridazine; pyridazino [4,5-d] pyridazine; pyrimido [4,5-c]
pyridazine; pyrazino [2,3-c] pyridazine; pyrido [3,2-d]-as-triazine; and pyrido [2,3-e]-as-triazine.
8. The electroactive polymer according to claim 3 where-in the fused rings contain five nitrogens and are positional diradicals of pyrimido [4,5-e]-as-triazine and pyrimido[5,4-d]-as-triazine.
9. The electroactive polymer according to claim 3 where-in the fused rings contain six nitrogen atoms and are position-al diradicals of as-triazino [6,5-d]-as-triazine.
10. The electroactive polymer according to claim 3 where-in the recurring units are diradicals of quinolinium.
11. The electroactive polymer according to claim 2 where-in the recurring units are positional diradicals of quinoline, isoquinoline, substituted derivatives thereof, or mixtures thereof.
12. The electroactive polymer according to claim 11 wherein said quinoline and substituted quinoline recurring units are diradicals connected a-t the 2,6 and 3,6 positions;
and mixtures of said diradicals.
13. The electroactive polymer according to Claim 11 wherein said isoquinoline and substituted isoquinoline recurring units are diradicals connected at the 2,6 and .
3,6 positions and mixtures of said diradicals.
14. The electroactive polymer according to Claim 11 wherein the recurring units are selected from the group consisting of quinoline diradicals or quinoline diradicals having a substituent in the 4-position.
15. The electroactive polymer according to Claim 14 wherein the quinoline and substituted quinoline recurring units are diradicals connected at the 2,6 and 3,6 posi-tions and mixtures of said diradicals.
16. The electroactive polymer according to Claim 2 wherein the recurring units are selected from the group consisting of isoquinoline diradicals or isoquinoline diradicals having a substituent in the 4-position.
17. The electroactive polymer according to Claim 16 wherein the diradical units are connected at the 2,6 and 3,6 positions and mixtures thereof.
18. The electroactive polymer according to Claim 2 wherein the recurring units are quinoline diradicals and substituted quinoline diradicals and wherein the diradi-cals are interspersed by a connecting unit and the diradi-cals are connected at the 2,6 and 3,6 positions and mix-tures thereof.
19. The electroactive polymer according to Claim 2 wherein the recurring units are isoquinoline diradicals and substituted diradicals and wherein the diradicals are connected at the 2,6 and 3,6 positions and mixtures thereof.
20. The electroactive polymer according to Claim 2 where-in the recurring units are diradicals selected from the group consisting of quinoline, substituted quinoline, isoquinoline, substituted isoquinoline, and mixtures thereof, wherein said diradicals are connected at the 2,6 and 3,6 positions and mixtures thereof.
21. The electroactive polymer according to Claim 20 wherein the recurring units are quinoline and isoquinoline diradicals.
22. The electroactive polymer according to Claim 20 wherein the recurring units are substituted quinoline and iso-quinoline diradicals.
23. The electroactive polymer according to Claim 20 wherein the recurring units are quinoline and substituted iso-quinoline diradicals.
24. The electroactive polymer according to Claim 20 wherein the recurring units are substituted quinoline and substituted isoquinoline diradicals.
25. The electroactive polymer according to Claim 3 where-in the recurring unit has the formula:

26. The electroactive polymer according to Claims 1, 18 or 20 wherein charge compensating ionic dopant is a cation selected 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.
27. A tractable electroactive polymer which comprises a charged polymer backbone and charge compensating ionic dopants associated therewith of the formula:

wherein a is 0 or 1; b is 0 or 1; c is 0 or 1; n is an integer from 2 to 20,000; d is an integer from 1 to 40,000; S is an integer 1, 2, or 3; R is a fused nitrogen-containing unsaturated diradical-heterocyclic ring system; R' is the same as R or a different fused unsaturated 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 opposite electrical charge to the charge of the polymer backbone wherein the polymer backbone is capable of undergoing reversible oxidation or a reversible reduction, or both, to form said charged polymer backbone.
28. The electroactive polymer according to claim 27 wherein R and R' are diradicals of fused six-member nitrogen-containing units.
29. The electroactive polymer according to claim 28 wherein R and R' contain from one to six nitrogen atoms distributed within and among the fused six-member rings wherein each ring contains three or fewer nitrogens bonded sequentially.
30. The electroactive polymer according to claim 29 wherein the R and R' are substituted.
31. The electroactive polymer according to claim 30 wherein R and R' are quinoxaline or substituted quinoxaline.
32. The electroactive polymer according to claim 30 wherein R and R' is quinoline, isoquinoline diradical and sub-stituted derivatives thereof, X and Y connect R and R' at the 2,6 and 3,6 positions.
33. The electroactive polymer according to claim 32 wherein R and R' are 2,6-quinoline with the formula Rii, Riii and Riv are a substituent group selected from H;
hydroxy, carboxy; amino; alkyl 1 to 4 carbon atoms; alkoxy 1 to 4 carbon atoms, an alkylthio of 1 to 4 carbon atoms; a cyclo-aliphatic group of 5 to 6 carbon atoms; an alkenyl group of 2 to 4 carbon atoms; an aryl group of 6 to 10 carbon atoms; an aryl group of 6 to 10 carbon atoms substituted by 1 to 3 alkyl groups of 1 to 4 carbon atoms, alkenyl groups of 1 to 4 carbon atoms, alkynyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms, dialkyl amino groups of 1 to 4 carbon atoms, an alkylthiol of 1 to 4 carbon atoms; a 5- or 6-member nitrogen containing unsaturated heterocyclic group.
34. The electroactive polymer according to claim 33 wherein Rii and Riv are H.
35. The electroactive polymer according to claim 34 wherein Rii and Riv are H, a is 1, b is 0, c is 0, X is -CRVii-CRvii and the recurring unit has the following formula wherein Rvii is selected from hydrogen or methyl and wherein M is a cation.
36. The electroactive polymer according to claim 27 wherein not more than two nitrogen atoms, in the nitrogen-containing unsaturated heterocyclic ring system, are joined sequentially.
37. The electroactive polymer according to claim 34 wherein Riii is H, a is 0, b and C are 1, Y is a biphenyl diradical and the recurring unit has the formula:

and wherein M is a cation.
38. The electroactive polymer according to claim 34 wherein Riii is -CH3, a is 0, b and c are 1, Y is and Z is a connecting unit chosen from -O-; -S-; -CH=CH-;
and -CRvi=CRvii-; in which Rv, Rvi and Rvii are each hydrogen and methyl; and the recurring unit has the formula:

and wherein M is a cation.
39. The electroactive polymer according to claim 27 wherein in the fused nitrogen containiny ring system the atoms at the ring fusion points are other than nitrogen.
40. The electroactive polymer-according to claim 34 wherein Riii is phenyl and the recurring unit has the formula:

and wherein M is a cation.
41. The electroactive polymer according to claim 40 wherein the Riii is phenyl substituted in the 4 position with a halogen and the recurring unit has the formula:

42. The electroactive polymer according to claim 40 wherein the Riii is phenyl substituted in the 4 position with an OCH3 group and the recurring unit has the formula:

43. The electroactive polymer according to claim 40 wherein X is -O-, a is 1, b is 1, c is 1, Y is a para phenyl diradical, and the recurring unit has the formula:

44. The electroactive polymer according to claim 40 wherein a is 1, X is biphenyl diradical, b is zero, c is 1 and the recurring unit has the formula:

45. The electroactive polymer according to claim 40 wherein the nitrogen in R and R' is substituted with a CH3+ ion and a and b are zero and the recurring unit has the formula:
46. The electroactive polymer according to claim 40 wherein a is zero and b and c = 1, R = R' and is phenyl-quinoxaline, and Y is and the recurring unit has the formula:

47. The electroactive polymer according to claim 27, 33 or 40 wherein the connecting units X and Y are selected from the group consisting of -O-; -S-; -CH=CH-; -C?C-;

and -CRvii=CRvii;

wherein RV, Rvi, and Rvii are H or methyl; and mixtures of said connecting units.
48. The electroactive polymer according to claim 27, 33 or 40 wherein c is zero and n is from 10 to 20,000.
49. The electroactive polymer according to claim 48 wherein n is from 50 to 5,000.
50. The electroactive polymer according to claim 27 wherein R and R' are isoquinoline with the formula:

Rviii, Rix and Rx are a substituent group selected from; H;
hydroxy; carboxy; amino; alkyl 1 to 4 carbon atoms; alkoxy 1 to 4 carbon atoms; alkylthio of 1 to 4 carbon atoms, a cyclo-aliphatic group of 5 or 6 carbon atoms; an alkenyl group of 2 to 4 carbon atoms; an aryl group of 6 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms substituted by 1 to 3 alkyl groups of 1 to 4 carbon atoms, alkenyl groups of 1 to 4 carbon atoms, alkynyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, 1 to 3 cyano, 1 to 3 halogen atoms, dialkyl amino groups of 1 to 4 carbon atoms, an alkylthio of 1 to 4 carbon atoms; and a 5- or 6-member nitrogen containing heterocyclic group.
51. The electroactive polymer according to claim 50 wherein the connecting units X and Y are selected from the group consisting of -O-, -S-, -CH=CH-, -C-C-, , and -CRvii=CRvii wherein Rv, Rvi and Rvii are H or methyl, and mixtures of said connecting units.
52. The electroactive polymer according to claim 30, 32 or 51, wherein a is 1, b and c are zero and the recurring unit has the formula:

?R-(X)a?
53. The electroactive polymer according to claim 30, 31 or 32 wherein a, b and c are zero and the recurring unit has the formula:
?R?.
54. The electroactive polymer according to claim 27, 31 or 32 wherein c is zero and n is from 10 to 20,000.
55. The electroactive polymer according to claim 27, 31 or 32 wherein c is zero and wherein n is from 50 to 5,000.
56. The electroactive polymer according to claim 27, 30 or 31 wherein the charge compensating ionic dopant 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.
57. A polymer which comprises recurring units of the formula:

wherein R is alkoxy C1-C4 or a halogen.
58. The electroactive polymer according to claim 1 where-in not more than two nitrogen atoms in the nitrogen-containing unsaturated heterocyclic ring system, are joined sequentially.
59. The electroactive polymer according to claim 1 where-in in the fused nitrogen containing ring system the atoms at the ring fusion points are other than nitrogen.
60. The electroactive polymer according to claim 33, 36 or 39 wherein the charge compensating ionic dopant 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.
61. The electroactive polymer according to claim 1 wherein the fused nitrogen-containing unsaturated heterocyclic ring systems are interspersed with connecting units.
62. The electroactive polymer according to claims 1, 27 or 33 wherein the molecular weight is equal to, or greater than, 10,000.
63. The electroactive polymer according to claim 27, 33 or 40 wherein c is zero, and n if from 10 to 10,000.
64. The electroactive polymer according to claim 27, 33 or 40 wherein c is zero, and n is from 50 to 5,000.
65. The elecroactive polymer according to claim 31 or 32 wherein c is zero, and n is from 10 to 10,000.
CA000403132A 1981-05-18 1982-05-17 Electroactive polymers Expired CA1202141A (en)

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US26491581A 1981-05-18 1981-05-18
US264,915 1981-05-18
US30441081A 1981-09-21 1981-09-21
US304,410 1981-09-21
US370,231 1982-04-22
US06/370,231 US4519937A (en) 1981-09-21 1982-04-22 Electroactive polymers

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CA1202072A (en) * 1981-12-28 1986-03-18 Yoram S. Papir Batteries fabricated with electroactive polymers
DE3249532T1 (en) * 1982-11-17 1985-01-10 Chevron Research Co., San Francisco, Calif. Electroactive polymer
CA1242483A (en) * 1983-10-26 1988-09-27 Toshikazu Shishikura Secondary battery
US4613211A (en) * 1983-11-21 1986-09-23 Chevron Research Company Electrochromic devices
US5053478A (en) * 1987-03-04 1991-10-01 Moore James A Production and processing of thermally stable polyenaminonitriles
US4966954A (en) * 1987-03-04 1990-10-30 Rensselaer Polytechnic Institute Production and processing of thermally stable polyenaminonitriles and polyaminoquinolines therefrom
DE4024120A1 (en) * 1990-07-30 1992-02-06 Basf Ag AMIONBENZOPHENON SULPHONIC ACIDS
TW349948B (en) * 1995-10-31 1999-01-11 Janssen Pharmaceutica Nv Farnesyl transferase inhibiting 2-quinolone derivatives

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US4222903A (en) * 1978-05-04 1980-09-16 University Patents, Inc. P-Type electrically conducting doped polyacetylene film and method of preparing same
US4230604A (en) * 1978-10-30 1980-10-28 Conoco, Inc. Polymeric electrical conductance dependent upon electrical potential

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IL65709A0 (en) 1982-08-31
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GB2103227A (en) 1983-02-16
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GB2143245B (en) 1985-10-16
NL8202016A (en) 1982-12-16
KR830010134A (en) 1983-12-26
IT8221304A0 (en) 1982-05-17
DE3218762A1 (en) 1983-02-24

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