NL8202016A - ELECTRO-ACTIVE POLYMERS. - Google Patents

Description

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1 Electroactive polymers.

The present invention relates to electroactive organic polymeric materials. More particularly, the present invention relates to the incorporation of electro-activators known in the art as dope agents.

Recently, research has been conducted on organic polymeric materials to modify their electrical conductivity at room temperature by reacting the materials with electron donor or acceptor molecules. The electron donor or acceptor molecules, generally known in the art as n- or dope agents. p-type, the organic polymeric materials can convert such that these modified organic polymeric materials exhibit semiconductive and metallic electrical conductivity at room temperature. Polyethyne is an example of an organic polymer material, the electrical conductivity of which at room temperature can modify several orders of magnitude above its insulator state by the incorporation of dope molecules, see U.S. Patent 4,222,905. Other examples of organic polymeric materials, of which the electrical conductivity at room temperature can be increased several orders of magnitude above their insulator state by incorporation of dope molecules include poly-p-phenylene, poly-pyrrole, poly-1,6-heptadynyne, and polyphenylene vinylene. However, all the aforementioned examples are organic polymeric materials which are completely insoluble or fusible and therefore are completely unmanageable.

Other examples of organic polymers whose electrical conductivity can be modified at room temperature using dope agents are polyphenylene sulfide and poly-m-phenylene. However, the aforementioned materials, although manageable in their original invoked state, become an irreversible chemistry when reacted with dope agents, which modify their electrical conductivity at room temperature. This irreversible chemistry gives these dope agent-modified organic polymeric materials a state of intractability. Ma 55 removal of the dope agents do not return these materials to the chemical structure they originally showed before 8202016 '%' .......

. - 2 -

V

. that they were modified with the dope agents? The inorganic poly-sulfur nitride material is also considered a polymeric conductor. Like the polymer materials cited above, poly sulfur nitride is also completely unwieldy.

For use in a wide variety of electronic device applications, it is highly desirable to have organic polymeric electrically conductive materials available with a preselected conductivity at room temperature that can be varied over a wide range. This range should preferably extend from the insulator state of the unmodified organic polymer material, through the semiconductive region, and extend to the highly conductive metallic state. It is also desirable that these organic polymeric, electrically conductive materials should be manageable and consequently processable so that useful articles of any desired shape and size can be manufactured. Manageable organic polymers, are those polymers that can be easily molded, compressed, cast, etc. into desired products of the liquid state, ie, either from the melt, the flowable glassy state, or from solution after the completion of the polymerization reaction of the organic polymeric material.

An electroactive polymer material was found containing an organic polymer modified with a dope, the electrical conductivity of which is controlled in a highly selective and reversible manner at room temperature. Electro-polymer is defined as a polymer with a conductivity, which has been modified with electron acceptor or donor dopants to a value greater than the conductivity of the pristine polymer state. The electro-active organic polymer material is made from an untreated polymer, which itself is fully manageable and processable, and which exhibits excellent mechanical and thermal properties, such as high stability to oxidation degradation, by more modifying the polymer with a conductivity modifying agent, ie electron donor dope agents or electron acceptor dope agents. The electroactive organic polymer material is composed of repeating units of a fused, nitrogen-containing, unsaturated heterocyclic ring system and a conductivity modifier. More specifically, the 8202016 V * - 3 - electroactive polymer is a charged, positive or negative, polymer chain in which charge compensating ionic dope agents are. i.e., opposite charge ions to the charge of the polymer chain. The repeating units are 5 diradicals. The diradicals are directly linked together or may be linked together via linking units. A linking unit is defined as any atom or group of atoms capable of binding the aforementioned diradicals together in a polymer chain.

An n-type electroactive organic polymer is obtained by reacting the untreated polymer with reducing or electron donor dope agents. Electron donor dope agents generate n-type conductivity in the polymer by delivering an electron to the polymer and reducing it to a polyanion and the dope agent is oxidized to a cation.

Similarly, an p-type electroactive organic polymer is obtained by reacting the untreated polymer with oxidizing electron acceptor dope agents. Electron acceptor dope agents generate p-type conductivity in the polymer by oxidizing the polymer to a polycation and the dope agent is reduced to an anion. The desired room temperature electrical conductivity of the dope agent-modified electroactive organic polymer is preselected by controlling the level of incorporation of the dope agents into the untreated polymer. Also, the desired room temperature electrical conductivity of the dope agent-modified electroactive organic polymer is preselected by controlling the length of the reaction time between the untreated polymer and the dope agents. Torch 50 can proceed the highly selective and reversible modification of the room temperature electrical conductivity of the untreated polymer by either chemical or electrochemical methods.

The highly selective and reversible modification of the electrical conductivity of the dope-containing organic polymeric material along with the manageability and processability of the untreated polymer is highly desirable in that the manufacture of useful articles and devices such as primary and secondary batteries, photovoltaic devices, devices of the Schottky type can be realized. Torch, the materials disclosed in the present invention can be used 8202016 * * - 4 - V v as active components in devices and articles such as electrochromic displays and photolithographic processes.

Electroactive organic polymers are manufactured by the modification of manageable and processable untreated polymers, which consist of repeating units of an annelated, nitrogen-containing, unsaturated, heterocyclic ring system by suitable conductivity modifiers.

The polymers are composed of repeating, diradical units derived from fused nitrogen-containing six-ring systems, in which each ring contains no more than three successively bonded nitrogen atoms. A diradical is defined as a molecule, which has two unsaturated positions, which are available for cross-linking in the polymer chain. Optionally, the diradicals in the polymer chain are separated by linking units.

The fused rings contain one to six nitrogen atoms. The nitrogen atoms are distributed between the fused rings with three or fewer nitrogen atoms sequentially bonded in a ring.

Suitable examples of fused ring systems with a single nitrogen atom are the diradicals of quinoline and isoquinoline. Suitable examples of fused ring systems with two nitrogen atoms are any of the diradicals of cinnoline, quinazoline, quinoxaline, 2-phenylquinoxaline, phthalazine, 1,5-naphthyridine, 25 1, naphthyridine, 1,7-naphthyridine, 1,8-naphthyridine , 2,6-naphthyridine, copyrine and the like. Suitable examples of fused ring systems with three nitrogen atoms are any of the diradicals of 1,2,5-benzotriazine, 1,2,4-benzotriazine, pyrido [3,2-d] pyrimidine, pyrido [4,3-cl ] pyrimidine, pyrido [3,4-d] pyrimidine, pyrido-30 [2,3-d] pyridine, pyrido [2,3- "b] pyridazine, pyrido [3,4-b] pyLicazine, pyrido [ 2,3-d] pyridazine, pyrido [3,4-d] pyridazine, etc. Suitable examples of fused ring systems with four nitrogen atoms are any of the diradicals of pyridazine [4> 5-c] pyridazine, pyrimido [5j4- < l] pyrimidine, pteridine, pyrimido [4> 5-d] -35 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] py 2? Lazine, pyrazino [2,3-c] pyridazine, pyrido [3,2-d] -v-triazine, pyrido [2,3 -e] -as-triazine and the like Suitable examples of fused ring systems with five nitrogen atoms are any of the diradicals of pyrimido [4> 5-e] -as-8202016 * 5 - triazine, pyrimido [5, 4-d] -v-triazine and of such. Suitable examples of fused ring systems with six nitrogen atoms are any of the diradicals of as-triazino [6,5-d] -v-triazine, s-tetrazino [1,2-a] -s-tetrazine and the like. All of the aforementioned fused nitrogen ring systems are known and described in "The Ring Index, Second Printing and Supplements I, II and III, Patterson et al. American Chemical Society. The molecules are processed into polymers by known methods such as ZnClg treatment or PeCl 2 and an alkylyodide or by dichloro ring followed by reaction with suitably disubstituted molecules such as disodium sulfide, the disodium salt of ethylene glycol, etc. The diradicals may be modified with substituents which modify the polymer properties such as electron donating or withdrawing groups according to self-known methods.

Suitable compounds in which one or more of the nitrogen atoms are saturated with hydrogen or by bonding in the fused ring or in the ionic form include each diradical of quinolizinium, 9aH-oliiholine, pyridazino [1,2-a] pyridazine, 20 2H- pyrido [1,2-a] pyrazine, pyrido [1,2-a] pyrimidin-5-ium, pyrimido [1,2-a] pyrimidin-5-inm and 2H-pyrazino [1,2-a] pyrazine.

The compounds are known and described in the Ring Index and supplements I, II and 1EI. The polymers are prepared by methods known per se.

For example, an electroactive polymer can be made with repeating units of positional diradicals of quinoline, substituted quinoline, isoquinoline, substituted isoquinoline, and mixtures thereof. The diradicals can be bound at the 2.4? 2.5? 2.6; 2.7; 2.8; 3.5? 3.6? 3.7? 3.8; 30 4.6; 4.7; 4.8; 5.7; 5.8 and 6.8 positions, but compounds at the 2.6 and 3.6 positions in the polymer are preferred. The quinoline ring system is numbered as in formula 1. The isoquinoline ring system is numbered as in formula 2. For example, the 2,6-diradical of quinoline has the formula 3 · A preferred 35-diradical of quinoline or isoquinoline is 4 substituted position. Preferably, the diradical is substituted with a phenyl group.

The diradicals may be separated by one or more linking units. Preferred linking units are 40 biphenyl, -CH = CH- and -C 1 -C-. The linking units may be the same or different between 8202016-6 adjacent diradicals in the polymer chain.

i

The polymer can be a homopolymer of the diradicals of quinoline, isoquinoline and its substituted derivatives or a copolymer of the diradicals. A homopolymer is defined as a manufactured polymer, which contains the same repeating diradical. A copolymer is defined as a polymer containing various diradicals. Furthermore, the polymer is a copolymer when the same or different repeating diradicals have dispersed linking units.

The polymer is made electroactive by including a conductivity modified agent in the untreated polymer. More specifically, the polymer is made electroactive by adding electrons to (reduction) or removing electrons * from (oxidation) of the untreated polymer chain.

This can be accomplished by including in the untreated polymer a conductivity modifying agent, which is either an electron donor dopant or an electron acceptor dopant. An electron donor dopant delivers an electron to the polymer, the polymer is reduced to a polyanion, and the dope agent is oxidized to a cation. An electron acceptor dopant removes an electron from the polymer, the polymer is oxidized to a polycation, and the dopant is reduced 25 "to an anion. Also, the polymer can be made electroactive by electrochemical oxidation or reduction. In this case an electron is removed from or added to the polymer from an electrode and charge compensating anions or cions are incorporated into the polymer from the electrolyte support solution.

In both cases, the electroactive polymer obtained consists of a charged polymer chain with charge-compensating ionic dope agents. A suitable positively charged compensating dope may be a cation such as the alkali metal ions, alkaline earth metal ions, Group III metal ions of the periodic table and inorganic cations of formulas 4> 5 and 6, wherein H is a straight or branched chain alkyl 1 to 6 carbon atoms. Mixtures of this charge of dope compensating agents can be used. These ionic dope agents give n-type conductivity when combined with a reduced or negative 8202016-7 charged polymer polyanion.

A suitable negatively charged compensating dope agent, ie anionic dope agents, may be an anion such as the halo ion, other ions such as Asi1 ^ - and preferably ions such as 5 ase6 ", cio4", pp6 ~, so ^ ce ^, bp4 ", ïïo3", pop4 ", CH", SiP5 ',

ShGlg, ShPg, HSO4 ~, organic anions such as CH2CO2 (acetate), CgH2COg (benzoate), CH2C8H2 SO4 (tosylate) and the like. Mixtures of the charge compensating dope agents can be used. These ionic dope agents give p-type 10 conductivity when combined with an oxidized or positively charged polymer polycation.

The dope agent-modified electroactive polymer has a charge opposite to the conductivity modifier, i.e., ionic dope agent. The charges on the dope agent-modified electroactive polymer and the ionic dope agent are balanced such that the dope agent-modified electroactive polymer is an electrically neutral system. The association of the untreated polymer with electron donor dopants gives an electroactive polymer, which exhibits n-type conductivity. More particularly, reduction of the untreated polymer and the incorporation of cationic charge compensating dope agents gives a polymer exhibiting n-type conductivity. The association of the untreated polymer with electron acceptor dopants gives an electroactive polymer with p-type conductivity. More specifically, oxidation of the polymer and incorporation of anionic charge-compensating dope agents gives a polymer with p-type conductivity.

The electroactive polymers of the invention have the formula 7, wherein a is 0 or 1, b is 0 or 1, c is 0 or 1, n is an integer between 1 and 20,000, d is an integer between 1 and 40,000, s is 1, 2 or 3, R is an unsubstituted or substituted, nitrogen-containing heterocyclic diradical ring system, R 'is identical to or different from R, X is a linking unit 35 consisting of a single atom or a group of atoms, Y is a linking unit identical to or different from X and M is an atom or group of atoms, which acts as a charge-compensating ion dopant, the electric charge of which is opposite to the charge, which shown by the recurring units of formula 8.

8202016 - 8 -

The repeating units form the polyanion or polycation of the electroactive polymer.

The diradical group R ia a substituted or unsubstituted, fused nitrogen-containing six-ring system. The 5 diradicals contain one to six nitrogen atoms distributed between the fused six-rings, each ring containing no more than three nitrogen atoms in sequence. Suitable groups R are the diradicals of molecules as mentioned above, which contain one to six nitrogen atoms. Preferred two nitrogen atoms containing fused ring systems are substituted or unsubstituted diradicals of quinoxaline.

More particularly, R and R * are an unsubstituted, or substituted quinoline and isoquinoline, diradical or mixtures of diradicals, which are linked together directly or through the linking units X and Y by bridging. Preferably, the bridges are formed at the 2,6 and 5 »6 positions.

The linking units X and Y can be selected from the group consisting of: -0-, -Si, -CH = CH-, -C = C- and the units

/ Y YI YII

of formulas 9 to 17 wherein R, R and R are I or methyl and 20 mixtures thereof. Biphenyl, vinyl and acetylene compound groups are preferred compound units.

The magnitude of n determines the physical properties of the electroactive polymer. Preferably n is 10 to 10,000 when c is 0. Most preferably n is from 50 to 5000 when c is 0.

Manageable films are formed with an electroactive polymer, n of which is greater than 50. A preferred molecular weight is 10,000 or higher.

The increase in the conductivity of the electroactive polymer over the conductivity of the polymer in the untreated state is determined by d. Conductivity is increased and adjusted by magnifying d. For example, the untreated polymer of 2,6- (4-phenylquinoline) has a conductivity of Ί 5 ^ - * ongeveer 1 about 10 µm cm. Incorporation of about 20 wt% of a charge compensating ionic dope agent, such as Na + into the electroactive polymer, increases conductivity to about 2 -1 -1 10 ohm cm. Preferred electroactive polymers are doped polymers having conductivities greater than -4 -1 -1 1x10 ohm cm. Conductivities in the semiconductor range can be achieved when d is from about 10 to about 1000.

40 Greater concentrations of the charge-compensating, ionic dopant- ... 8202016 a-9-agent M increases the conductivity to the metallic conductivity range. The charge compensating, cationic or anionic dope agent M is selected from the aforementioned dope agents and the like. M shows the same for all subsequent preferred polymers.

Groups S and 1 'are the same or different. When a is 1, b and c are 0, R 'and Y drop out and the polymer has the formula 18. When a, b and c are 0, R', X and Y drop out and the polymer has the formula 19 A preferred group 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 II III Quinoline of formula 20, wherein R, R and R substituents are selected from hydrogen, hydroxy, carboxy, amino, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, 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 20 carbon atoms substituted with 1 to 3 alkyl groups of 1 to 4 carbon atoms, alkenyl groups of 2 to 4 carbon atoms, alkynyl groups with 2 to 4 carbon atoms alkoxy groups of 1 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms, dialkylamino groups of 1 to 4 carbon atoms, an alkylthiol of 1 to 4 carbon atoms or a nitrogen-containing unsaturated 5- or 6-ring heterocycle. The nitrogen atoms in the foregoing polymers may have been quaternized by a reaction with quaternizing agents, for example dimethyl sulfate.

The term "alkyl" refers to either straight or branched chain alkyl groups. Suitable examples are methyl, ethyl, porpyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.

The term "alkoxy" refers to the R O-goup of which R is alkyl. Suitable examples are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec.butoxy and tert.butoxy.

The term "alkylthio" refers to examples such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobuiylthio, tert-butylthio and sec-butylthio.

Suitable examples of cycloaliphatic groups are cyclopentyl, cyclohexyl, 3-methylcyclopentyl and the like.

The term "alkenyl" refers to unsaturated double bond 8202016-10 -alkyl groups [eg, CHlCHCHCHCHCH] g] and includes both straight and branched chain alkenyl groups such as ethenyl, buten-3-yl, propenyl and the like.

The term "aryl" refers to an aromatic hydrocarbon group such as phenyl, naphthyl and the like. Suitable examples of alkyl-substituted aryl groups are 2-tolyl, mesityl, 3-isopropylphenyl and the like. Suitable examples of alkenyl-substituted aryl groups are 3-stytyl, 4-iso-propenylphenyl and the like. Suitable alkoxy-substituted aryl groups are 1-methoxy-2-naphthyl, 3-n-butoxyphenyl and the like. Suitable aryl groups substituted with a cyano group are 4-cyanophenyl, 4-cyano-1-naphthyl and the like. Suitable examples of halogen-substituted aryl are 4-fluorophenyl, 3-chloro-4-bromo-1-naphthyl and the like. Suitable examples of aryl groups substituted with a dialkylamino group are 3-himethylamino-. phenyl, 6-diethylamino-2-naphthyl and the like. Suitable examples of alkylthio-substituted aryl groups are 4-butylthiophenyl, 3-methylthio-2-naphthyl and the like. Suitable examples of nitrogen-containing 5- or 6-membered heterocyclic rings are 3-pyrolyl, 4-pyridyl and the like.

Preferred polymers of 2,6-substituted quinoline come II IY

for when R and R are hydrogen. A preferred polymer

II IY III

is obtained when R and R are hydrogen and R is phenyl, i.e. poly-2,6- (4-phenylquinoline). (See compound 25 21).

Another preferred group of polymers is obtained,

III II IY

when R is phenyl and R and R are selected from the above group of substituents.

Rye another preferred polymer is prepared from 2,6- (4-30 phenylquinoline) diradicals, wherein a CH + + portion is directly bonded to the nitrogen of the quinoline diradical, i.e., quaternized. (See compound of formula 22).

Another preferred polymer is prepared from 2,6- (4- (4'-pyridyl) quinoline) and / or its quattrified analog. When R and R 'are equal and the 2,6-quinoline diradical unit, the repeating unit of the dope agent-modified electroactive polymer is the compound of formula 23 wherein R 2, R 2 * and R 1 substituents are selected from the aforementioned groups and X and T are the linking units mentioned above. M is a previously mentioned conductivity 8202016 - 11 -. - modifying agent.

A preferred polymer is of formula 24, wherein E 1 '

IY III

and E are hydrogen, E is phenyl, a, b and c are 1, X is the 0-diradical and Y is a phenyldiradical.

Another preferred polymer has the formula 25 wherein

II 17 III

E and E are hydrogen, E is phenyl, a and c are 1, b is 0 and X is a biphenyl diradical.

Another preferred polymer has the formula 26, wherein II 17 III

E and E are hydrogen, E is -COOH, a is 0, b and c are 1, 10 and Y is a biphenyl diradical.

Another preferred polymer has the formula 27 wherein II III 17 E, E and E are hydrogen, a is 0, b and c are 1 and X is a biphenyl diradical.

Another preferred polymer has the formula 28, wherein II 17 III

E and E are hydrogen, E is methyl, a is 0, b and c are 1 and Y is the group of formula 29 and Z is a linking unit selected from the linking units for X and Y.

Another preferred polymer has the formula 30, wherein

II 17 III

E and E are hydrogen, E is hydroxy, a and c are 1, b is 0 and X is the group of formula 31.

Another preferred polymer is obtained when E and II 17

Ef are substituted quinoline diradicals, wherein E and E

711 711 are hydrogen, a is 1, b is 1, c is 1, X is -CE = CE and Y is 711 -CE = CH ~. The polymer has the formula 32.

Yet another preferred polymer is when E4 is phenyl and E4 is hydrogen.

When E or E1 is a substituted isoquinoline diradical 7IIII, a preferred diradical has the formula 33 wherein E,

IX X II

E and E are selected from the same substituent groups as E, III 17 30 E and E. Polymers similar to the aforementioned preferred quinoline polymers are also preferred for isoquinoline.

A preferred electroactive poly (phenylquinoxaline) polymer is of the formula 34 wherein E and Ef are phenyl-35 quinoxaline, a is 0, b and c are 1 and Y is the group of formula 35.

Polymer preparation.

The starting material for the preparation of the electroactive polymers of the present invention are polymers and copolymers which contain repeating units of a fused nitrogen unsaturated heterocyclic ring system containing nitrogen.

Preferably the repeating units are quinoline or isoquinoline or substituted quinoline or isoquinoline. These polymers and copolymers are known products which are prepared in various ways. For example, quinoline, isoquinoline or substituted derivatives thereof can be converted to polymers by treatment with zinc chloride or by treatment with FeCl, and an alkyl iodide Rabinovich et al., Dokl. Akad. Nauk SSSR 1971? 199 (4), 895-7 and Smirnov et al., Yysokomol Soedin Ser B 1971, 10 13 (8), 395-6 * The method is also suitable for polymerizing the other diradicals mentioned above.

Other polymers are prepared by a synthetic route which involves the reaction of the 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 with halogen atoms in substantially all possible combinations are known.

This route provides a process for the preparation of bridged polyquinoline or polyisoquinolines by any two of the seven possible touch points.

The dihalogen compounds are also suitable for forming copolymers with other interconnecting groups. For example, reactions with sodium sulfide give a sulfur atom between each nitrogen-containing heterocyclic ring. Reaction with dihydroxy compounds or disodium salts of dihydroxy compounds give ether type copolymers.

Another process for the preparation of the polymeric starting material is according to a synthesis, which involves the final reaction of a suitable diketone with a suitable aminodiacylbenzene in the presence of a basic or an acidic catalyst as discussed in Eorshok et al., Yysokomol, Soedin., Ser B9 (5), 171-2 (1967); Shopov, I, Yysokomol, 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 35 1976, 17 (1), 41-45; silent, J.K. Pure Appl. Chem. 1978, 50 (4), 273-280; Baker, G.L. et al., Macromolecules 1979, 12 (3), 369-73 and Beever, W. Ξ. et al., Macromolecules 1979, 12 (6), 1033-8 *

Yet another process for the preparation of polycholine, which are useful as starting materials for the compounds of the present invention, is by the condensation poly (8202016 - 13 - *) polymerization of suitable di (aminophenyl) compounds with suitable di (alpha, gamma-diketo) compounds, see Y. Eorshak et al.,

Yysokomol Soedin, Ser B9 (3), 171 (1967) The resulting polymers * 1 have structures of formula 36, wherein Z is O or CHgCl 3.

The di (aminophenyl) compounds may contain various substituents, but should have an unsubstituted position ortho to the amino group. Common compounds include 4> 4 '- iaminophenyl, 3' 3 'diaminophenyl.

2,4- <iaminobiphenyl, 2,2,3 »3'-tetramethyl-4,4, -cliaminobiphenyl, 10 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, gamma-diketo) compounds include those compounds in which the diketones at the alpha position are joined by different linking groups. These compounds have the structure of formula 37 »in which Z is a linking group.

Conventional linking groups include the X and Y linking groups having 2 or more atoms, see French Patent 1,468,677 and J. Polym. Sci. Part C, No. 16, Part 8, 4653 (19 ^ 8).

The preferred method for preparing the polyquinoline -20 polymeric starting material is according to the methods set forth by W. Ξ. Beever et al., Journal of Polymer Science: Polymer Symposium 65, (1978) 41-53, S. 0. Norris et al., Macromolecules, 2, no. 3, 496-505 (1976), J. Pharm. Sci. 21 (1968) 784 and J. Heterocycle Chem. (1974) 107 · Preparation of Lantable Polymers.

After the polymerization, production products such as fibers, strips or free-standing films are poured from solution. The solution is formed by dissolving the desired polymer in a solvent consisting of sulfuric acid, formic acid or a mixture of PgOp. and m-cresol. The solution temperature is from about 25 ° C to about 200 ° C and preferably at about 140 ° C and most preferably 100 ° C. The polymers are coagulated into solid forms such as fibers, strips or free-standing films in a basic coagulation bath. For free-standing films, the polymers are prepared from solution containing about 2 to 25% polymer dissolved in the solvent. At concentrations greater than 10%, the cast films assume an anisotropic morphology. The anisotropic property increases conductivity in the anisotropic direction. An amine, for example triethylamine, dissolved in a protonic solvent such as HgO and preferably ethanol is present in the 8202016-14 coagulation bath. The bath is maintained at a temperature lower than the solution temperature of the polymer in the solvent. Usually room temperature is chosen as the operating temperature of the coagulation bath. The manufactured articles are dried. Increased temperatures, usually 60 ° C and reduced pressure accelerated the drying process. Drying is continued until no further weight loss is observed.

Modification of the conductivity of the polymer.

After production of the desired articles from the polyannelated heterocyclic quinoline polymers by the above-described method, the articles are made electroactive by, for example, chemical or electrochemical methods. The articles can be made electroactive in an atmosphere which is inert with respect to the polymer and the doping agent by contacting them with suitable conductivity modifying agents, ie doping agents. . An inert atmosphere is defined as an atmosphere that does not react with the polymer, the dopant or the electroactive polymer. For example, the atmosphere can be argon, 2Q helium, nitrogen and the like. Dipping can also be performed in an inert liquid medium such as tetrahydrofuran, acetonitrile and the like. The dope agents can be oxidizing or electron accepting molecules or reducing and electron donating molecules. Both types of dope agents can be in the form of gases or vapors, pure liquids or liquid solutions. Preferably oxygen and moisture are excluded during and after the doping process, because the conductive polymers tend to degrade, ie lose conductivity, at exposure to it.

For example, the polymer may be in contact with alkali metal naphthalides or alkali metal anthracenides, such as sodium naphthalide, potassium naphthalide or sodium anthracenide in a tetrahydrofuran solution. The concentration of the conductivity modifying agent may be from about 0.001 to about 1 molar, and preferably from about 0.01 to about 0.5 mdair, in the THE or other suitable solvent. Other doping methods are taught in U.S. Patent 4,204,21β.

It is currently unclear how exactly the electron donor or acceptor dopants are incorporated into the polymer.

40 However, the incorporation of the dope agents into the polymer can be observed 8202016 - 15 - * by a color flagging in the polymer as well as increased conductivity * For example, an untreated polymer film of a yellow or orange color changes to a blue or black color with a metal luster after doping and the measured conductivity increases by many orders of magnitude.

Also, the polyquinoline polymers can be oxidized or reduced to their conductive forms using electrochemical techniques. In this method, referred to herein as electrochemical doping, the polymer is immersed in a suitable electrolyte solution and used as one electrode of an elect0 electrochemical cell. After passing an electric current through such a cell, the polymer is reduced (or oxidized depending on the direction of the current) and charge compensating cations (or anions) are incorporated into the polymer from the supporting electrolyte. This doping also proceeds with the characteristic color change as described above. Therefore, the polymer can be electrochemically doped with whatever suitably charged ion is present in the electrolyte solution. Electrolyte solutions contain a salt dissolved in a solvent. Suitable solvents are acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, propylene carbonate, dimethylformamide, dimethyl sulfoxide and the like. Suitable cations are li +, Na +, K +, (OR ^) jB +, (C ^^ N * and (Ο ^ Η ^ Ν *). Suitable anions are Cl, Br ”, C10 ^" ", BF ^ ~ and PFg ~. The degree of doping can be easily controlled by controlling the amount of charge injected electrically into the polymer, either by controlling the magnitude of the current used (galvanostatic charge) or by controlling the potential of the polymer electrode with respect to to a reference electrode (potentio-static charge).

50 The electrochemical doping process described above is fully reversible. The polymer can be "de-doped" and returned to its original, neutral, non-conductive state simply by applying a current which is significantly opposite to that used for the doping process. After complete de-doping, the polymer's color returns from black to its original color. Thus, for example, a reduced, conductive polyquinoline polymer can be completely reoxidized to its neutral, nonconductive form and the charge compensating cations, which are reduced during the electrochemical reduction. process are expelled from the products during the electrochemical reoxidation.

Examples.

Example Ia.

5 Preparation of 2-methyl-2- (4-nitrophenyl) -1,3-dioxolane.

p-Nitroacetophenone (1.65g, 10mmol), ethylene glycol (5ml, 89mmol), triethyl orthoformate (1.96g> 20mmol) and p-toluene sulfonic acid (0.086g, 0.5mmol) were added in 4ml dichloromethane brought together. The solution was heated with an oil bath (50-70 ° C) for 6 hours, cooled to room temperature and poured into an excess of 10% sodium hydroxide solution. The phases were separated and the aqueous phase was extracted twice with dichloromethane. The combined organic phases were washed three times with water and dried with anhydrous sodium sulfate. Evaporation of the solvent left a pale yellow product (1.78 g) with a melting point of 69-71 ° C (according to the literature 75 ° 75 ° C, see J. Pharm. Sci. 5Z, (19 ^ 8). ) 784)

Example 1b-1. Preparation of 5- (2-Methyl-1,3-dioxolan-2yl) -3-phenyl-2,1-benzisoxazole.

20 Enylacetonitrile (0.84 g, 7> 2 mmol) and 2-methyl-2- (4-nitrophenyl) -1,3-dioxolan (mp 69-71 ° C) (1.50 g, 7> 2 mmol ) were added to a solution of sodium hydroxide (1.44 Sr mmol) in 18 ml of room temperature methanol. A weak exotherm was observed and the stirring treatment was continued for 16 hours.

The mixture was filtered and the collected solid was washed several times with water and once with cold methanol to give a yellow powder (1.60 g) with a melting point. 137 ° C (mp. according to literature 137-138 ° C, see J. Heterocyclic Chem. Jn, (1974) 107) -30 Example 10.

Preparation of 2-Amino-5- (2-methyl-1,3-dioxolan-2-yl) benzophenone.

5- (2-Methyl-1,3-dioxolan-2yl) -3-phenyl-2,1-benzisoxazole (1.50 g, 5> 3 mmol), triethylamine (0.3 ml) and 5% palladium on charcoal 33 (0.15 s) were pooled in 13 ml of dry tetrahydrofuran. The equipment was flushed with nitrogen and then with hydrogen. A static hydrogen atmosphere was maintained (98.7 kPa) and the progress of the reaction was monitored by gas chromatography.

The starting material and product had retention times of resp.

11.15 and 11.33 min. When the conversion was complete, the 8202016-17 mixture was filtered through a pad of celite to obtain a transparent yellow solution. Evaporation of the solution gave a yellow solid (1.35 g) with a melting point. of -108-111 ° C.

Example Id.

5 Preparation of 5-Acety 1-2-aminob etc or enon.

2-Amino-5- (2-methyl-1,3-dioxolan-2-yl) benzophenone (1.0 g, 3.54 mmol) was dissolved in 30 ml of absolute ethanol. To this were added 14 ml of 1 molar perchloric acid. The resulting mixture was stirred at room temperature for 18 hours. The mixture was made alkaline with 3N sodium hydroxide solution and then extracted with a few portions of dichloromethphane. The combined dichloromethane extracts were washed with water, dried with anhydrous sodium sulfate and evaporated to yield a yellow product (0> 79 g) with a mp. 158-161 ° C was obtained. Part of the product was recrystallized from a mixture of dichloromethane and hexane to obtain a product with a melting point. 158-162 ° C.

Example Ie.

Preparation of poly 2,6- (4-phenylquinoline).

A solution was prepared from phosphospentoxide (1.07 g, 7.5 mmol) and freshly distilled m-cresol (2.5 ml) by heating at 140 ° C under nitrogen for 2.5 hours. The solution was cooled to room temperature and 0.30 g (1.26 mmol) 5-acetyl-2-aminobenzophenone and 1.3 ml m-cresol were added. The solution was heated to 120 ° C and held for 48 hours. The solution was poured into a mixture of 60 ml of 95% ethanol and 6 ml of triethylamine with stirring to give a fibrous yellow solid, which was washed twice with ethanol in a Waring blender. Then, it was extracted with ethanol in a Soxl et apparatus for 19 hours and dried to yield an orange product (0.26 g, 1.28 mmol).

Example II.

Preparation of films of poly-2,6- (4-phenylquinoline).

A solution was prepared from phosphorus pentoxide (0.8 g, 5.6 mmol) and distilled m-cresol (2.5 ml) by heating to 110-120 ° C under argon. The solution was cooled to room temperature and 0.051 g (0.25 mmol) of poly-2,6- (4-phenylquinoline) was added. The mixture was heated to 140 ° C to obtain 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 10% triethylamine and 90% ethanol. The clear gel films were pressed between layers of filter paper and dried in a vacuum oven.

Example III.

Doping of poly-2,6- (4-phenylquinoline).

The transparent gel film prepared in Example II was placed in a beaker in a dry canister with a dry argon atmosphere. After 30 min, a dimethoxyethane solution of sodium naphthalide 10 was poured into the beaker. The film reacted immediately, changing to a dark color; teal in transmitted light and purplish green with a metallic luster in reflected light. After exposure to air, the dark color disappears immediately and the polymer returns to its original appearance.

Example IV.

Conductivity measurement of poly-2,6- (4-phenylquinoline).

The method of Example III was followed except that the film was first wetted with tetrahydrofuran (TEE1) and then treated with 0.1 µm sodium naphthalide dissolved in THF. After addition of the sodium naphthalide, the polymer film turned dark blue with a metallic sheen. The surface of the film was rinsed with THE. The conductivity of the doped film (2.54 x 10 inch cm thick) was measured using a 4-point test device from Signature Co. The 4 points of the device form a single 25 line. A DC voltage (VE) is applied across the outer two points and the voltage (V1) of the current is measured across the inner two points. A conductivity is calculated from these values as follows: VE = 0.1 volts VI = 0.06 volts (measured) 30 R = 1074 (VE / VI) = 192.5 ohm / m2 rho = Ext = 1790 x 2.54 x 10 ^ = 4.55 ohm centimeters Λ Λ sigmH; = 1 / rho = 0.22 ohm "centimeter" where: VE = applied voltage 35 t = film thickness VI = measured voltage R = resistance of the surface rho = resistivity of the product sigma = conductivity 40 1074 = instrument and unit conversion factor.

8202016 - 19 - * The washed, but not doped, polymer was not conductive, but was actually an insulator with a conductivity -15 -1 -1 of 10 ohm centimeters as measured in the same equipment

(see J. Folym. Sci. Poly. Symp., £ 6, (1978) 41) This same value, -15X

5 (10) was measured on the doped film after yellowing after exposure to air.

The infrared spectra of the original undoped film and air-exposed doped film were the same.

The infrared of the dark sodium naphthalide-doped film -1 was opaque with no absorbance between 4,000 and 600 cm, indicating a metal behavior. This experiment shows that the doped polyquinoline films are surprisingly good electrical conductors.

Example V.

Conductivity measurement of poly-2,6- (4-phenylquinoline).

Films were also dipped as in Example IV, but with potassium naphthalide and after these films were placed in a dry vacuum canister at a pressure below 1.3 x 10 for 6 days. kPa the following gp Conductivity value was obtained: 20 VE = 36 mv VI = 55 mv t = 2.54 x 10 -1 cm -1 -1 rho - 1.78 ohm cm. sigma = 0.56 ohm cm.

Currents of this magnitude show that the doped polymer is electroactive in that it is a conductor of electricity.

^ Example Custard.

Preparation of bis-4-nitrophenyl ether.

1-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 of dimethyl sulfoxide and left for 30 min. reflux-50 J cooling heated. The mixture was cooled and kept at room temperature overnight.

The precipitate was collected and washed with water. The precipitate was dissolved in warm toluene, separated from the water layer and dried with magnesium sulfate. Concentration and cooling gave 28.8 g of product (mp 144-146 ° C) in two yields.

Example VIb.

Preparation of 5> 5'-Oxybis- (3-phenyl-2,1-benzisoxazole). Phenylacetonitrile (17.72 g, 0.151 mol) and bis-4-nitrophenyl ether (19.52 g, 0.075 mol) were added to a solution of sodium 40 hydroxide (30.01 g, 0.75 mol) in 150 ml methanol of room temperature was added and refluxed for 9 hours. The reaction mixture was cooled to room temperature and diluted with 50 ml of 50% aqueous methanol and then cooled in an ice shad.

The precipitate was collected and washed with cold methanol. This solid was dissolved in warm toluene, dried with magnesium sulfate, concentrated and cooled to yield 7.55S. Recrystallization from warm toluene gave 5 19 g of product with a melting point. 108-109 ° C. A second, unidentified material with a melt. 158-165 ° C was also isolated.

Example VIc.

Preparation of Diamino-J 5-dibenzoyldiphenyl ether.

5.5, -Oxybis- (5-phenyl-2,1-benzisoxazole) (4.92 g, 12.0 mmol) and triethylamine (1.35 ml) were combined in 50 ml of tetrahydrofuran under a nitrogen atmosphere. Palladium on charcoal (5%, 0.41 g) was added and then hydrogen was slowly passed through the system over 15 hours. The mixture was filtered through celite and evaporated to a yellow oil which was crystallized from a mixture of toluene and hexane in a ratio of 10: 1 to yield 4.53 g (87%) of the desired product. Bit product was further purified by recrystallization from methanol, 2.43 S, m.p. 154-155 ° C were obtained.

Example VId.

Preparation of a quinoline copolymer from 4,4'-diamino-3, 3'-dibenzoyl diphenyl ether and p-diacetylbenzene.

A solution was prepared from phosphorus pentoxide (5.6 g, 59.4 mmol) and freshly distilled m-cresol (20 ml) by heating at 140 ° C. A portion of this solution (7.6 ml) was used to dissolve 4,4-diamino-3,3'-dibenzoyldiphenyl ether (0.5005 g, 1.225 mmol) and p-diacetylbenzene (0.1987 g, 1.225 mmol) to unload. The solution was kept at 110-120 ° C for 48 hours. The mixture was cooled and poured into a mixture of 10 ml triethylamine and 100 ml 95% ethanol to yield a white fibrous product. The product was dissolved in 15 ml of chloroform and precipitated with ethanol. This was repeated to a final yield of 55.10 g of white fibrous polymer. A polymer was prepared by dissolving 25.7 mg in 0.52 g of the aforementioned phosphorus pentoxide-m-cresol solution at 60 ° C, placing a few drops on a warm glass plate and spreading with a warm sheet. After quenching in a bath of 90% ethanol and 10% triethylamine, a 40 free-standing film was obtained. This polymer has the structure with 8202016 «- 21 - formula 38

Example 711.

Doping and conductivity measurement of the polymer of Example VI.

Films of the polymer of Example VId were kept in a dry canister for less than 10 ppm water and oxygen. The films were then doped with sodium naphthalide as described in Example III. After doping, the films turned a deep metallic blue. Conductivity measurements gave: 10 VE = 4.5 mV rho = 40.92 ohm cm.

-1 -1 VI = 0.3 mV sigma = 0.024 ohm cm R = 1732 ohm / m ^.

Example Villa.

Preparation of 5-Bromo-3-phenyl-2,1-benzisoxazole.

Phenylacetonitrile (8.1 g, 69 mmol) was added to a solution of potassium hydroxide (85%) (74 g, 1.1 mol) in 150 ml of methanol at room temperature. To this were added 12.7 g (63 mmol) of 4-bromo-1-nitrobenzene suspended in 130 ml of methanol. An exoterm was observed and the reaction was kept at 50 ° C for 5 hours. After cooling to room temperature, 400 ml of water were added. The precipitate was collected and washed with water. The crude product (15> 15 g) was crystallized from 200 ml of warm methanol to yield yellow needles (9.52 g, mp.

113 ° -116 ° C).

Example TlIIb.

Preparation of 2-amino-5-bromobenzophenone.

5-Bromo-3-phenyl-2,1-benzisoxazole (7.5 g, 28.6 mmol), water (14.8 ml) and zinc dust (9.3 g, 145 mmol) were brought together, 8.6 ml (143 mmol) acetic acid was added and the mixture was mixed 30 and heated at 80 ° C for 90 min. After cooling to room temperature, both the liquid and solid parts of the reaction were extracted with dichloromethane. The combined dichloromethane solutions were washed once with 10% sodium hydroxide solution and several times with water. Drying (sodium sulfate) and evaporation gave the desired product (7.42 gm) with a melting point. from 92-102 ° C.

Example VIIIc. .

Preparation of 4> 4 & amino-3,3'-dibenzoyl biphenyl.

4-Bromo-2-aminobenzophenone (0.55g, 2.0mmol) was dissolved in dry 40 and oxygen-liberated dimethylformamide (10ml) in a canister with 8202016-22 inert atmosphere. To this was added 0.55 S (2.0 mmol) bis (1,5-cyclooctadiene) nickel (o). The reaction was transferred from the inert atmosphere canister to a vacuum argon manifold using standard Schlenk-5 wave techniques. The reaction was heated to 50-55 ° C for 4 hours and kept at room temperature overnight. The mixture was poured into 200 ml of water, which was made weakly alkaline with sodium hydroxide. The water was extracted several times with ethyl acetate, and after drying with sodium sulfate and evaporation gave a dark brown liquid (0.48 S). Recrystallization from hexane gave 100 mg of a yellow-brown solid with a melting point. 180-185 ° C.

Example VlIId.

Preparation of a polymer from 4> 4'-Clianri: no-3> 3'-dibenzoyl-biphenyl and 4'-4'-Cliacetylbiphenyl.

4> 4, -Hiamino-3,3 "Cl.ibenzoylbiphenyl (80.0 mg, 0.204 mmol) and 4,4'-diacetylbiphenyl (48.6 mg, 0.204 mmol) were combined in a solution prepared from phosphorus pentoxide (0.348 g, 2.45 mmol) and freshly distilled m-cresol (1.2 ml) and heated at 120-130 ° C for 46 hours. The warm reaction mixture was poured into a mixture of 6 ml triethylamine and 60 ml 95% ethanol with stirring. The fibrous red precipitate was stirred in the alkaline bath until its color changed to yellow. The precipitate was washed with water and dried at 80 ° C, taking 120 mg of a yellow powder with a melting point. > 320 ° C were obtained. Films of this material were prepared by dissolving 50 mg at 120 ° C in 0.75 ml m-cresol containing 0.2 g phosphorus pentoxide. A few drops of this solution were spread on a glass plate and quenched in a bath of 10% triethylamine and 90% ethanol to obtain a free standing yellow film. Hit copolymer has structure 30 with formula 39 *

After that, the polymer was made conductive by the method set forth in Example III. Conductivity was measured according to the methods outlined in Example IV. The -1 -1 conductivity of the doped polymer was 0.024 ohms cm. Example IX.

Preparation of poly-2, é- (4- (4'-chlorophenyl) quinoline).

The polymer was prepared essentially according to the same procedure as described in Example I, except that 4-chlorophenyl acetonitrile was used instead of phenylacetonitrile. Analysis 40 of the polymer gave the following results. Calculated for 8202016-23- (C 1 HgHCl); C 75.80%, Ξ 3.59%, N 5.89%, Cl 14.92%. Found: O C 76.81%, H 3.64%, H 5.86%, the balance was chlorine. The polymer has the structure of formula 40. Then, the polymer was made conductive by the method set forth in Example III. Conductivity was measured according to the methods outlined in Example 11. The conductivity of the doped polymer was 0.02 ohm "*" cm -1.

Yoorbeeld X.

Electrochemical doping of quinoline polymers.

A 12.5 cm platinum wire was coated with a thin film of the polymer of Example I, through the wire in a 5% solution of the polymer in a mixture of m-cresol and PgOj. dipping. The film-coated wire was neutralized by dipping in a 10% triethylamine-90% ethanol solution and dried in a vacuum oven at 10 ° C.

The polymer coated wire was connected to an E.G. and G. Princeton Applied Research apparatus consisting of a Universal programmer and a potentiostat / galvano state with recorder. The polymer coated end of the wire was then dipped in a 0.1 molar solution of lithium tetrafluoroborate in acetonotrile. A potential ranging from 0 to 3.0 volts relative to SCE was applied to the platinum wire. The output current was essentially 0 until the potential reached about -1.5 volts and at that point the cathode current increased rapidly and peaked at -2.25 volts. After reversal of the potential arrow, an anode current was observed, which peaked at -1.5 volts. When the initial potential of -1.5 volts was applied, the polymer bonded to the wire changed from a weak yellow color to a dark metal color, which color disappeared after increasing the voltage to more than -1.5 volts.

This behavior indicates an initial resistance to the passage of current followed by a rapid electron uptake resulting in a charged electroactive polymer containing the lithium ions as the charge compensating dopant.

In fact, the polymer was made electroactive by applying a potential of about -2 volts in the presence of an electrolyte solution capable of providing a charge-compensating dope agent.

8202016 - 24 -

Example XI.

Electrochemical doping of quinoline polymers.

The same experiment as in Example X was performed except that the lithium tetrafluoroborate was replaced by tetra-5-butylammonium bromide. Essentially the same results as in Example X were obtained. In this case, the polymer coated wire was alternately charged and discharged without any loss of activity. The metal 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. A suitable application is as the anode of a battery. The experiment also shows that the electroactive polymer is capable of incorporating organic charge compensating ionic dopant agents into its structure.

Example XII.

Electrochemical doping of a poly (phenyl-quinoxaline).

A 12.5 cm platinum wire was coated with a thin film of a polymer of the formula 34 structure by dipping the wire in a 5% solution of the polymer in a mixture of m-cresol and PgO 2. The untreated polymer was purchased through Aldrich Chemical Co. and is a product of Scientific Polymer Product, Inc., 6265 Dean Parkway, Ontario, New York Catalog 330 lot 101. The polymer is 100% solids in m-cresol. The film-coated wire was neutralized by immersion in a 10% triethylamine-90% ethanol solution and dried in a vacuum oven at 60 ° C.

The polymer coated wire was connected to an E.G. and G. Princeton Applied Eesearch device consisting of a Uni-30 versal programmer and a potentiostat / galvanostat with a recorder. The polymer coated end of the wire was then dipped in a 0.1 molar solution of a lithium tetrafluoroborate in acetonitrile. A potential ranging from 0 to -3.0 volts relative to SCE was applied to the platinum wire. The output current was essentially zero until the potential reached about -1.5 volts. At this point, the cathode current increased rapidly and peaked at -2.0 volts. After reversal of the potential arrow, an anode current with a peak at -1.25 volts was observed. When the original potential of 40-1.5 volts was applied, the polymer bonding on the 8202016 - 25 wire changed from a light yellow to a dark metal color, which color disappeared after increasing the voltage to more than -1.5 volts.

This behavior indicates an initial resistance to the passage of current followed by a rapid uptake of 5 electrons resulting in a charged polymer, containing lithium ions "as the charge compensating dopant. In fact, the polymer was made electroactive by applying a potential of about -2 volts "in the presence of an electrolyte capable of providing charge-compensating ionic dopants.

Example XlIIa.

Preparation of 4-Acetyl-2- (4-methoxy) Benzoylaniline Monomer.

38.2 g of NaOH were dissolved in 200 ml of methanol in a 1 liter 3-neck flask equipped with a mechanical stirrer, reflux condenser, nitrogen inlet and heating mantle. 28.14 g (0.19 mol) of p-methoxyphenylacetonitrile were added, followed by 40 S (0.191 mol) of p-nitro-aetophenonethylene glycol ketol. The reaction was stirred mechanically under reflux for 22 hours.

The product was filtered off, washed with water and recrystallized from methanol. The product has the formula 41

Analysis calculated for

Ber. Gev.

% c 69.44 68.16% 25 Ξ 5.50 5.41 N 4.50 4.26.

Example XlIIb.

Hydrogenation of the product of Example XlIIa.

17.12 g (0.055 mol) of the product of Example XlIIa 30 were dissolved in 150 ml of tetrahydrofuran and 4 ml of triethylamine in a 500 ml 3-neck flask equipped with a gas inlet tube, reflux condenser, thermometer and magnetic stirrer. 1.2 g of 5% Pd / carbon catalyst were added.

The flask was purged with nitrogen and then connected to a slow flow of hydrogen.

The reaction was stirred magnetically at room temperature for 9 hours.

Thin layer chromatography indicated complete reaction. The reaction was purged with nitrogen and the catalyst was filtered through 40 celite. The filtrate was evaporated to an oil-like residue, 19.3 g. The product has the formula 42.

Example XIIIc.

Hydrolysis of the product of Example XlIIb.

19.1 g of the product of Example XlIIb were dissolved in 60 ml of tetrahydrofuran and 30 ml of water in a 250 ml round bottom flask. The pH of the solution was adjusted to about 5 with concentrated hydrochloric acid and the reaction was kept at room temperature for about 18 hours. Thin layer chromatography indicated complete hydrolysis. The reaction mixture was poured into 300 ml of a saturated sodium carbonate solution and extracted three times with an equal volume of dichloromethane. The combined dichloromethane solutions were washed with water, dried and evaporated, yielding 14.5 g of a yellow residue.

The product was recrystallized from dichloromethane-hexane and had a melting point. 119-123 ° C. The product has the formula 43 *

Analysis calculated for C16E15 ° 31T

Ber. Gev.

% 0 71.36 71.33%% H 5.61 5.69 20% N 5.20 5.78.

Example XlIId.

Preparation of poly [2,6- (4-p-methoxyphenyl) quinoline].

The catalyst solution was prepared by dissolving 9.44 (86.5 mmol) of PgO2 (weighed in a dry can) in 24 ml of m-cresol (Aldrich gold 25 label) in a 50 ml 3-neck round bottom flask, which is equipped with a mechanical stirrer, reflux condenser and nitrogen inlet.

The catalyst solution was stirred mechanically and heated in an oil bath under a nitrogen cover until the solution became homogeneous (approximately 2.5 hours). 5 g (11.16 mmol) of the monomer of Example XIIIc were added followed by 10 ml of m-cresol. The oil bath temperature was raised to 120 ° C and the polymerization reaction was conducted at 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 slowly poured into 500 ml of a 10% solution of triethylamine in ethanol and stirred overnight at room temperature. After neutralization, the polymer formed a pivot.

The polymer was collected by filtration, washed with ethanol, and extracted with ethanol in a Soxhlet apparatus overnight. After the extraction, it was filtered and dried under reduced pressure at 70 ° C to yield 2.3 g (88.5%) of dry polymer. The polymer has the formula 44.5. Analysis:

Ber.35 Gev.

% C 82.38 78.52 H 4.75 4.40 N 6.01 5.52 [n] = 0.83 dl / g (measured in ^ SO ^).

The polymer was then made conductive according to the methods of Example III using a 0.5 molar solution of sodium anthracenide in THE instead of sodium naphthalide. Conductivity was measured according to Example IY.

-1 -1 15 The polymer had a conductivity of 2.5 ohm cm.

Yoorbeeld XIY.

Preparation of poly [2,6- (1-methyl-4-phenyl) quinolinium] meta sulfate.

Poly-2,6- (4-phenylquinoline) coated platinum wires were placed in a 50 ml round bottom flask and covered with 10 ml dimethyl sulfate (Aldrich). The flask was fitted with a reflux condenser and a drying tube in a fume hood. The reaction was left at room temperature overnight and then refluxed for 6 hours.

After cooling, the dimethyl sulfate solution was decanted and the threads were quenched with about 30 ml of a 10% solution of triethylamine in ethanol. After neutralization, the threads were washed thoroughly with ethanol and dried under reduced pressure at 80 ° C. The polymer has the formula 45 · The polymer 30 was made conductive according to example III. However, the dope agent was 0.5 molar sodium anthracenin in THE. The conductivity -1 -1 -1 of the polymer was 0.75 ohm cm as measured according to Example IY.

Yoorbeeld XY.

Erootrochemical doping of poly [2,6- (1-methyl-1,4-phenyl) quinolinium].

A 12.5 cm platinum wire was coated with a thin film of poly-2,6- (4-phenylquinoline) as in Example X. The polymer was then quaternized as in Example XIY.

The obtained polymer coated wire was connected to the apparatus described in Example 820206-28 and immersed in a 0.1 molar solution of tetraethylammonium tetrafluoroborate in acetonitrile. A linear potential ranging from -0.5 to -1.5 volts relative to SOE was applied to the platinum wire.

The output current was substantially zero until the potential reached about -0.8 volts, at which point the cathode current increased rapidly with a peak at -1.1 volts. After potential reversal, an anode current with a peak at -0.8 volts was observed.

This behavior indicates an initial resistance to current followed by a rapid uptake of electrons to form a reduced polymer. In fact, the polymer was made electroactive by applying a potential of about -1.1 volts to SCE when an electrolyte solution was present.

Example XVI.

Electrochemical doping of a copolymer from 4> 41-di-amino-3,5'-dibenzoyldiphenyl ether and p-diacetylbenzene.

A 12.5 cm platinum wire was coated with a thin film of the polymer of Example VId by dipping the wire in a 5% solution of the polymer in a mixture of m-cresol and PgO2. The film-coated wire was neutralized by dipping in a 10% triethylamine-90% ethanol solution and dried in a vacuum oven at 60 ° C.

The polymer coated wire was connected to the apparatus described in Example X and immersed in a 0.1 molar solution of tetraethylammonium tetrafluoroborate in acetonitrile. A linear potential arrow ranging from 0 to -2.5 volts relative to SCE was applied to the platnia wire. The output current was substantially zero until the potential reached approximately -1.7 volts. At this point, the cathode current increased rapidly to a maximum bin -2.2 volts and showed a double wave with a peak separation of 200 mV. After reversing the potential, an anode current, which also showed a double wave, was observed at -1.8 volts. When the original potential of 35 -1> 7 volts was applied, the polyadhesive poly changed more from a nearly colorless transparent appearance to a dark metallic color. This color disappeared after increasing the voltage to more than -1.5 volts.

This behavior indicates an initial resistance to current 40 followed by a rapid uptake of electrons, resulting in a charged polymer, containing tetraethylammonium ion as the charge-compensating ionic dopant. In fact, the polymer was made electroactive by applying a potential of about -2.2 volts to SCE 5 in the presence of an electrolyte solution capable of providing charge-compensating ionic dopants.

Example XVII.

Electrochemical doping of a copolymer of ± 4> 4'-di-amino-3,3'-dibenzoyldiphenyl and 4> 4'-diacetyldiphenyl.

A 12.5 cm platinum wire was wrapped with a thin film of the polymer of Example VlIId by dipping the wire in a 5% solution of the polymer in a mixture of m-cresol and PgOj. The coated wire was neutralized by immersion in a 10% triethylamine-90% ethanol solution and dried in a vacuum oven at 60 ° C.

The polymer coated wire was attached to the apparatus described in Example X and immersed in a 0.1 molar solution of the tetraethyl ammonium trifluoroborate in acetonitrile. A linear potential ranging from 0 to -2.5 volts relative to SCE was applied to the platinum wire. The output current was essentially zero until the potential reached -1.7 volts. At this point, the cathode current increased rapidly with a peak at -2.0 volts. After potential reversal, an anode current with a peak at -1.6 volts was observed. When the initial potential of -1.7 volts was applied, the wire-bonding polymer changed from light yellow to a dark metal color. This color disappeared after increasing the voltage to more than -1.4 volts.

The behavior indicates an initial resistance to current followed by a rapid uptake of electrons, resulting in a charged polymer containing tetraethylammonium ion as the charge-compensating ionic dopant. In fact, the polymer was made more electroactive by applying a potential of about -2.0 volts to SCE in the presence of an electrolyte solution capable of providing charge compensating ionic dopants.

Example XVIII.

Electrochemical doping of poly-2,6- (4- (4'-chlorophenyl) -quinoline).

A 12.5 cm platinum wire was coated with a thin film of 8202016-30 the polymer of Example IX by dissolving the wire in a 5% solution of the polymer in a mixture of m-cresol and P0. 2 5 dipping. The film-coated wire was neutralized by dipping in a 10% triethylamine-90% ethanol solution and dried in a vacuum oven at 60 ° C.

The polymer coated wire was attached to the apparatus described in Example X and immersed in a 0.1 molar solution of tetrabutyl ammonium bromide in acetonitrile. A linear potential ranging from 0 to -2.3 volts relative to 10 SCE was applied to the platinum wire. The output current was essentially zero until the potential reached about -1.5 volts. At this point, the cathode current increased rapidly with a peak at -1.8 volts. After potential reversal, an anode current with a peak at -1.3 volts was observed. When the original potential of 15-1.5 volts was applied, the wire-bonding polymer changed to a dark metallic color. This color disappeared after increasing the voltage to more than -1.2 volts.

This behavior indicates an initial resistance to current followed by a rapid uptake of electrons, resulting in a charged polymer containing tetraethylammonium ion as the charge compensating ionic dopant. In fact, the polymer was made electroactive by applying a potential of about -1.8 volts to SCE in the presence of an electrolyte solution capable of providing charge-compensating ionic dope agents.

Example .'XIX ..

Electrochemical doping of poly-2, é- (4 (4'-nonhoxyphenyl) -quinoline).

A 12.5 cm platinum wire was coated with a thin film of the polymer of Example XIIIId by dipping the wire in a 5% solution of the polymer in a mixture of m-cresol and PgO2. the coated wire was neutralized by dipping in a 10% triethylamine-90% ethanol solution and dried in a vacuum oven at 60 ° C.

The polymer coated wire was attached to the one in Example X.

described device and immersed in a 0.1 molar solution of tetrabutyl ammonium bromide in acetonitrile. A linear potential, ranging from 0 to -2.3 volts relative to SCE, was applied to the platinum wire. The output current was substantially zero until the potential reached about -1.5 volts.

8202016 - 31 -

At this point, the cathode current increased at a peak at -2.1 volts. After potential reversal, an anode current with a peak at -1.5 volts was observed. When the original potential of -1.5 volts was applied, the polymer adhering to the wire changed to a dark metal color. This color disappeared after increasing the voltage to more than -1.5 volts.

Bit behavior indicates an initial resistance to current followed by a rapid uptake of electrons, resulting in a charged polymer, containing tetraethylammonium ion as the charge compensating ionic dopant. In fact, the polymer was made electroactive by applying a voltage of about -2.1 volts to SCE in the presence of an electrolyte solution capable of providing charge-compensating ionic dopants.

15 Example XX.

Boping and conductivity measurement of poly-2,6- (4-phenyl-quinoline).

The polymer poly-2,6- (4-phenylquinoline) was dipped and made electroactive according to Examples III and IT. However, the conductivity modifier was 0.5 molar sodium anthracenide THE. The conductivity of the electroactive polymer -1 -1 was 20 ohm cm Yoa image XXI.

Boping and conductivity measurement of poly ~ 2,6- (4- (4'-chloro-25-phenyl) quinoline),

The polymer of Example IX was dipped and electroactive according to Examples III and IT. However, the conductivity modifier was 0.5 mdair sodium anthracenide in THE. The conductivity of the electroactive polymer was -1 -1 30 1.25 ohm cm

Example XXII.

Boping and conductivity measurement of poly-2,6- (4-phenyl-quinoline).

The polymer poly-2,6- (4-phenylquinoline) was dipped and made electroactive according to Examples III 'and IT. However, the conductivity modifier was 0.1 molar sodium anthracenide THE. The conductivity of the electro-active polymer was 15 ohm / cm 2.

Example XXIII.

40 Boping and conductivity measurement of poly-2,6- (4-phenyl-8202016- 32-quinoline).

The polymer poly-2,6- (4-phenylquinoline) was dipped and electroactive following Examples III and IY.

However, the conductivity modifier was 0.01 molar sodium anthracenide in THE. The conductivity of the electroactive -1 -1 polymer was 15 ohms in Example XXIY.

Doping and conductivity measurement of poly-2,6- (4-phenyl-quinoline).

The polymer poly-2,6- (4-phenylquinoline was baptized and electroactive according to Examples III and IY. However, the conductivity modifier was 0.005 molar sodium anthracenide THE. The conductivity of the electroactive -1 -1 polymer was 2.75 ohm cm 8202016

Claims (57)

An electroactive polymer, containing a charged polymer backbone of repeating units of a fused, nitrogen-containing, unsaturated heterocyclic ring system and associated charge-compensating ionic dopants. The electroactive polymer according to claim 1, characterized in that the recurring units of the charged polymer backbone are diradicals of fused nitrogen containing six-rings. Electroactive polymer according to claim 1 or 2, characterized in that the diradicals contain 1 to 6 nitrogen atoms distributed in and over the fused six-rings, each ring containing three or fewer nitrogen atoms in successive bond. 15 Electroactive polymer according to claims 1 to 3, characterized in that the fused rings contain 1 nitrogen atom and are positional diradicals of quinoline, isoquinolime, 9a2-chirioline and quinoliainium. Electroactive polymer according to claims 1 to 3> 20, characterized in that the fused rings contain 2 nitrogen atoms 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. Electroactive polymer according to claims 1 to 3> characterized in that the fused rings contain 3 nitrogen atoms and are positional diradicals of 1,2,3-benzotriazine, 1,2,4-benzotriazine, pyridoT3> 2-d] pyrimidine, pyrido f4 »3-d] pyrimidine, pyrido [3,4-d] pyrimidine, pyrido [2,3- <1] -30 pyrimidine, pyrido [2,3-pyridazine, pyrido |" 3> 4-pyridazine , pyrido-2,3-d] pyridazine and pyrido [3,4- <1] pyridazine. Electroactive polymer according to claims 1 to 3, characterized in that the fused rings contain 4 nitrogen atoms and are positional diradicals of pyridazino [4,5- pyridazine, pyrimidor5> 4- <3-] pyriniide, pteridine, pyrimido ("4> 5-d) pyridazine, pyrimidof4> 5-d] pyrlmidine, pyrazino ,32,3-b Jpyraziney pyrazino [2,3-d] pyridazine, pyridazinoΓ4> 5-cl] pyrodazine, pyrimido [4) 5- c] pyridazine, pyrazino [2,3-c] pyridazine, pyrido [3,2-d] -v-trizine and pyridor2,3-e] -ras-triazine. 8202016 -34-. Electroactive polymer according to claims 1 to 3, characterized in that the fused rings contain 5 nitrogen atoms and are positional diradicals of pyrimido [4,5-e] as-triazine and pyrimido [5,4- <1 ~ ] -v-triazine. 5 Electroactive polymer according to claims 1 to 3, characterized in that the fused rings contain 6 nitrogen atoms and are positional diradicals of as-triazino [6,5-d] -v-triazine and s-tetrazino [1,2 -a] -s-tetrazine. Electroactive polymer according to claims 1 to 3, 10, characterized in that said repeating units of diradicals are selected from the group consisting of quinolizinium, 9aH-quinoline, pyridazino ["1,2-a] pyridazine, 2H-pyrido [1,2-a] pyrazine, pyrido [1,2-a] pyrimidin-5-ium, pyrimido [1,2-a] pyrimidin-5-ium and pyrazino [1,2-a] pyrazine. Electroactive polymer according to claim 1 or 2, characterized in that the repeating units are positional diradicals of quinoline, isoquinoline, substituted derivatives or mixtures thereof. 12. The electroactive polymer according to claim 11, characterized in that the quinoline and substituted quinoline are recurring units of diradicals attached at the 2,6 * and 3,6 positions and mixtures of these diradicals. Electroactive polymer according to claim 11, characterized in that the isoquinoline and substituted isoquinoline are recurring units of diradicals bonded at the 2,6 and 3,6 positions and mixture of these diradicals. The electroactive polymer according to claim 11, characterized in that the repeating units are selected from the group consisting of quinoline diradicals or quinoline diradicals with a substituent on the 4-plate. Electroactive polymer according to claim 14, characterized in that the quinoline and substituted quinoline are recurring units of diradicals bonded at the 2,6 and 3,6 positions and mixtures of these diradicals. Electroactive polymer according to claim 2, characterized in that the repeating units are selected from the group consisting of isoquinoline diradicals or isoquinoline diradicals having a substituent in the 4-position. 40 Electroactive polymer according to claim 16, characterized in that the diradical units are bonded at the 2,6 and 3> 6 positions and mixtures thereof. Electroactive polymer according to claim 2, characterized in that the repeating units are quino-5 line diradicals and substituted quinolin-diradicals, in which the diradicals are dispersed with a linking unit and the diradicals at 2,6- and 3> 6 - sites connected to the side and mixtures thereof. Electroactive polymer according to claim 2, characterized in that the repeating units are isoquinoline diradicals and substituted diradicals, the diradicals being connected at the 2,6 and 3> 6 positions and mixtures thereof. 20. Electroactive polymer full gas claim 2, characterized in that the repeating units of diradiene are selected from the group consisting of quinoline, substituted quinoline, isoquinoline, substituted isoquinoline and mixtures thereof, the diradicals being connected to the 2 , 6 and 3 »6 positions and mixtures thereof. Electroactive polymer according to claim 20, characterized in that the repeating units quinoline and isoquinoline are diradicals. Electroactive polymer according to claim 20, characterized in that the repeating units are substituted quinoline and isoquinoline diradicals. Electroactive polymer according to claim 20, characterized in that the repeating units quinoline and substituted isoquinoline are diradicals. Electroactive polymer according to claim 20, characterized in that the repeating units are substituted quinoline and substituted isoquinoline diradicals. Electroactive polymer according to claim 3, characterized in that the repeating unit has the for-y / mule 34. Electroactive polymer according to claims 1, 3, 11, 18, 20 or 23, characterized in that the charge-compensating ionogenedope agent is a cation selected from the group consisting of the alkali metal ions, alkaline earth metal ions, 40 metal ions of group III of the periodic table, the cations 8202016 - 35 - XX of formulas 4> 5 and 6, wherein R is a straight or branched chain alkyl group of 1 to 6 carbon atoms or mixtures of these cations. 27 · Electroactive polymer, characterized in that the polymer contains a charged polymer backbone and 5 charge compensating ionogenic dopants associated therewith with the formula 7 ", in which formula a is 0 or 1, b is 0 or 1, c 0 or 1, n is an integer from 2 to 20,000, d is an integer from 1 to 40,000, s is 1, 2 or 3, R is a fused, nitrogen-containing, unsaturated diradical heterocyclic ring • | 0 system , R · has the same meaning as R or any other fused, unsaturated heterocyclic ring system, X is a linking unit, Y is the same linking unit as X or another linking unit, and M charge compensating ionic dopant of opposite electric charge than the charge of the poly- 15 is multiple main chain. An electroactive polymer according to claim 27, characterized in that R and R 'are diradicals of an anylated, nitrogen-containing six-ring units. The electroactive polymer of claim 28, wherein R 2 and R 1 contain 1 to 6 nitrogen atoms distributed in and across the fused six-rings, each ring containing three or fewer nitrogen atoms sequentially attached. Electroactive polymer according to claim 29, characterized in that R and R 'are substituted. 25 Electroactive polymer according to claim 30, characterized in that R and R 'are quinoxaline or substituted quinoxaline. 32. An electroactive polymer according to claim 30, characterized in that R and R are quinoline, isoquinoline di-zq radical and substituted derivatives thereof, and X and YR and R at 2,6- and 3> 5- connecting places. Electroactive polymer according to claim 32, characterized in that R and R 'are 2,6-quinoline of formula 20, wherein R 1, R 1, R 1 and R 1 substituent groups are selected from 55 hydrogen, hydroxy, carboxy, amino, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, a cycloaliphatic group of 5 or 6 carbon atoms, alkenyl of 2 to 4 carbon atoms, aryl of 6 to 10 carbon atoms, aryl of 6 to 10 carbon atoms substituted with 40 1 to 3 alkyl groupaa with 1 to 4 carbon atoms, alkenyl groups with 8202016 * - 37 - 1 to 4 carbon atoms, alkynyl groups with 1 to 4 carbon atoms, alkoxy groups in 1 to 4 carbon atoms, 1 to 3 cyano groups , 1 to 5 halogen atoms, dialkylamino groups of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, and a nitrogen-5 containing, unsaturated 5 "or 6-ring heterocycle. Electroactive polymer according to Claim 33, with II IV characterized in that R and R are hydrogen. Electroactive polymer according to claim 34, with II IV characterized in that R and R are hydrogen, a is 1, 10 is b 0, c is 0, X is the group of formula 17 and the repeating unit is of formula 46 possession. 36. An electroactive polymer according to claim 34? characterized in that R is -C00H, a is 0, b and c are 1, Y is the group of formula 15 and the repeating unit has formula 47. The electroactive polymer according to claim 34, characterized in that R is hydrogen, a is 0, b and c are 1, Y is a fifenyl radical and the repeating unit has the formula 48. 20 Electroactive polymer according to claim 34, characterized in that R is methyl, a is 0, b and c are 1, Y is the group of formula 29 and Z is a linking unit and the repeating unit is formula 49 possession. Electroactive polymer according to claim 34, characterized in that Rx is hydroxy, b is 0, a and c are 1, X is the group of formula 12 and the repeating unit has formula 50. 40. An electroactive polymer according to claim 34? characterized in that R 1 is phenyl and the repeating unit has formula 51. 41. The electroactive polymer according to claim 40, characterized in that R 1 '' is phenyl, substituted in the 4-position with a halogen atom and the repeating unit has the formula 52. 55 Electroactive polymer according to claim 40? characterized in that R is phenyl substituted in the 4-position with a methoxy group and the repeating unit has the formula 55. The electroactive polymer according to claim 40, characterized in that X-0-, a is 1, b · 1 is, c is 1, Y 8202016 - 58 - is a p-phenyldiradical and the repeating unit is the formula 54. 44 * Electroactive polymer according to claim 40, characterized in that a is 1, X is a biphenyl diradical, 5 is b 0, c is 1 and the repeating unit has the formula 55. 45 * An electroactive polymer according to claim 40, characterized in that the nitrogen atom in E and E 'is substituted with a CH 2 + ion and a and b are 0 and the repeating unit has the formula 56. An electroactive polymer according to claim 40, characterized in that a is zero, b and c are 1, E and 1 'are phenylquinoxaline and Y is a group of formula 10 and the repeating unit has formula 34. Electroactive polymer according to claims 27, 35, 15, 34, 40, 41 or 42, characterized in that the linking units X and Y are selected from the group consisting of -0-, -S-, -CH = CH-, -C: C-, and the groups of formulas 9 to 17, V VI VU wherein R, R and R are hydrogen or methyl and mixtures of these compound units. The electroactive polymer according to claim 47, characterized in that c is zero and n is 10 to 20,000. 49 * An electroactive polymer according to claim 48, characterized in that n is from 50 to 50000. 50. The electroactive polymer according to claim 27, characterized in that R and R 'are isoquinoline having the Vinix X formula 33j wherein R, R and R are a substituted group selected from hydrogen, hydroxy, carboxy, amino, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, a cycloaliphatic group with 5 or 8 carbon atoms, alkenyl with 2 to 4 carbon atoms, aryl with 6 to 10 carbon atoms, aryl with 6 to 10 carbon atoms substituted with 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-35 groups, 1 to 3 halogen atoms, dialkylamino groups of 1 to 4 4 carbon atoms, alkylthiol of 1 to 4 carbon atoms and a nitrogen-containing 5- or 6-ring heterocycle, The electroactive polymer according to claim 50, characterized in that the linking units X and Y are selected 40 from a group consisting of -0-, -S-, -CH = CH-, -CsC-, and the 8202016 - 39 - -. y groups of formulas 9 to 17 wherein R, R and R are hydrogen or methyl and mixtures of these linkers. 52. An electroactive polymer according to claims 27, 30, 31, 32, 50 or 51, characterized in that a is 1, 5. and c are 0 and the repeating unit has the formula £R- (X) ^ . 53 * Electro-active polymer according to claims 27, 30, 31 »32, 50 or 51», characterized in that a, b and c are 0 and the repeating unit has the formula fR ^}. 10 Electroactive polymer according to claims 50 and 52, characterized in that c is 0 and n is 10 to 20,000. Electroactive polymer according to claim 54, characterized in that n is from 50 to 5000. 56. The electroactive polymer according to claims 27, 30, 15, 31, 32, 46 or 50, characterized in that the charge-compensating ionogen doping agent is a cation selected from the group consisting of the alkali metal ions, alkaline earth metal ions, metal ions of group IIE of the periodic table and the XI cations of formulas 4, 5 and 6, wherein R is a straight or branched chain alkyl group of 1 to 6 carbon atoms, or mixtures of these cations. 57 · Polymer containing recurring units of formula 57, wherein R is alkoxy of 1 to 4 carbon atoms or a halogen atom. 25 8202016