DE3218762A1 - ELECTRONIC POLYMER - Google Patents

Description

«« T ·· «· trl« ■ # I "»

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description

The invention relates to electroactive organic polymeric materials and is particularly concerned with the incorporation of electroactivating agents known as dopants.
5

Research has already been carried out on organic polymeric materials to make their electrical Modify conductivity at room temperature by reacting these materials with electron donor or acceptor molecules. The electron donor or acceptor molecules that act as n- and p-type dopants, respectively are known, are able to convert the organic polymeric materials in such a way that these modified organic polymeric materials have semiconducting properties as well as electrical metal conduction properties at room temperature own. Polyacetylene is an example of an organic polymeric material whose electrical conductivity can be modified by several orders of magnitude beyond its insulator state at room temperature the incorporation of dopant molecules (see US Pat. No. 4,222,903). Other examples of organic polymers Materials whose electrical conductivity at room temperature is several orders of magnitude compared to their state of insulation can be increased by the incorporation of dopant molecules are poly-p-phenylene, polypyrrole, Poly-1,6-heptadiyn and polyphenylenevinylene. All examples given above apply to organic polymeric materials, which are completely insoluble or infusible and therefore absolutely unworkable.

Other examples of organic polymers whose electrical conductivity at room temperature with the help of dopants can be modified are polyphenylene

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sulfide and poly-m-phenylene. The ones given above Although materials can be processed in their original state, they do, however, do so with dopants irreversible chemical reactions that modify their electrical conductivity at room temperature will. These irreversible reactions make these dopant modified organic polymeric materials no longer processable. After the dopants are removed, these materials no longer take the chemical structure that they originally had before modification with the dopants. The inorganic Material polysulfur nitride is also considered to be a polymeric conductor. As in the case of the previously mentioned Polymeric materials, polysulfur nitride is also completely unprocessable.

It is desirable to have available organic polymeric electrically conductive materials for many electronic purposes, which have a predetermined conductivity at room temperature, this temperature being within a wide range Range can be varied. This area should preferably differ from the isolation status of the unmodified organic polymeric material over the semiconducting range up to the highly conductive metallic state extend. It is also desirable that these organic polymeric electrically conductive materials be processable so that valuable objects of any desired shape and size can be made from them. Processable organic polymers are those that easily turn into desired objects from a liquid state, d. H. either from a melt, a fluid-to-glassy state or from a solution after the end of the polymerization reaction of the organic polymeric material can be shaped, molded, pressed, cast, etc.

By the invention will t - .:!. 3218762 - ·· t electroactive • 20th polymeric a

material made available, which consists of an organic polymer modified with a dopant, its electrical conductivity at room temperature can be controlled in a highly selective and reversible manner is. An electroactive polymer is defined as a polymer with a conductivity that is associated with electron acceptor or donor dopants can be modified in such a way that the is greater than the conductivity of the original polymers. The electroactive organic polymeric material is made from a fresh polymer, which itself is very easy to process and shows excellent mechanical and thermal properties and is also very stable to oxidative degradation by modifying the polymer with a die Conductivity modifying agents, d. H. an electron donor dopant or electron acceptor dopants. The electroactive organic polymeric material consists of repeating units of a condensed nitrogen-containing unsaturated heterocyclic Ring system and a conductivity modifier. In particular, the electroactive polymer is a charged, either positive or negative, polymer backbone, incorporated into the charge compensating ionic dopant have been, d. H. Ions with opposite charge with respect to the charge of the polymer backbone. the repeating units are diradicals. The Diradika-Ie are directly connected to each other or can be connected to each other be linked via connection units. A connecting unit is called any atom or group of atoms defines, which is able to link the specified dirests together in a polymer chain.

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An electroactive organic polymer of the η-type is made by reacting the fresh original polymer with reducing or electron donating dopants produced. Induce electron donating dopants an n-type conductivity in the polymer by donating an electron to the polymer and reducing it the same to a polyanion, the dopant is oxidized to a cation. Similarly, j

a p-type electroactive organic polymer is obtained by reacting the original polymer with oxidizing electron acceptor dopants. Electron acceptor dopants induce p-type conductivity in the polymer by oxidizing the polymer to a polycation, reducing the dopant to an anion. The desired level of electrical conductivity at room temperature of the electroactive organic polymer modified with the dopant is determined in advance by controlling the degree of incorporation of the dopants into the fresh polymer. Optionally, the desired value of the electrical conductivity at room temperature of the electroactive organic polymer modified with the dopant can be determined in advance in such a way that the length of the reaction time between the fresh polymer and the dopants is controlled . Furthermore, the extremely selective and reversible modification of the electrical conductivity at room temperature of the fresh polymer can take place either by chemical or electrochemical measures. The extremely selective and reversible modification of the electrical conductivity of the dopant-containing organic polymeric material together with the processability of the original polymer is extremely desirable in this respect / as the production of

_IV · f ··· · I'll

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valuable items such as primary and secondary batteries, photo elements, Schottky devices, etc. is. Furthermore, the materials according to the invention can be used as active components in certain devices and articles be used, for example in electro-color representations and for performing photolithographic Procedure.

Electroactive organic polymers are made by modifying original polymers that can be processed of repeating units of conjugated nitrogen-containing unsaturated heterocyclic ring systems exist by suitable conductivity modifiers manufactured. The polymers consist of repeating diradical units that are condensed on six-membered nitrogen-containing ring systems decline, with each ring not having more than three nitrogen atoms contains that are sequentially bound. A diradical is defined as a molecule that has two unsaturated ones Has positions available for linkage to the polymer chain. If applicable, are the diradicals in the polymer chain are separated by connecting units.

The condensed rings contain 1 to 6 nitrogen atoms. The nitrogen atoms are between the fused rings distributed, with three or fewer nitrogen atoms sequentially bonded in a ring. Suitable examples for a single nitrogen-containing fused ring system are the diradicals of quinoline and isoquinoline. Suitable examples of fused ring systems containing two nitrogen are the diradicals of quinoline, Quinazoline, quinoxaline, 2-phenylquinoxaline, phthalazine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, 1,8-

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Naphthyridine, 2,6-naphthyridine, Coyprin or the like. Suitable examples of condensed ring systems containing three nitrogens are the diradicals of 1,2,3-benzotriazine, 1,2,4-benzotriazine, pyrido / 3,2-d7pyrimidine, pyrido / 4,3-d7-pyrimidine, pyrido / .* 3,4-d7pyrimidine, pyrido / 2, 3-dypyrimidine, pyrido £ 2,3-b7pyridazine, pyrido ^ 3,4-b7pyrxdazine, pyrido / "2,3-d7 -pyridazine, pyrido / 3,4-d7pyridazine or the like.Suitable examples of four nitrogen-containing fused ring systems are the diradicals of Pyrida <: ino / 4,5-d7pyridazine, pyrimido / 5 _r 4-d7pyrimidine, pteridine, pyrimido / f4, 5-d7-pyridazine, pyrimido £ 4,5-d7pyrimidine, pyrazino ^, 3-b7pyrazin _f pyrazino / 2 _r 3-d7pyridazine, pyridazino ^ l ^ S-dypyridazine, pyrimido #, 5-c7pyridazine, pyrazinoZ2,3-c7pyridazine _f Pyrido ^ '3,2-d / -v-triazine, pyrido / 2 _f 3-e / -as-triazine or the like.Suitable examples of five nitrogen-containing condensed ring systems are the diradicals of pyrimido / * 4,5-e7- astriazine, pyrimido / 5,4-d7-v-triazine or the like. Suitable examples The condensed ring systems containing six nitrogen atoms are the diradicals of As-triazinoZ "6,5 ~ d / -vtridzin, s-tetrazino £" 1,2-a / -s-tetrazine or the like. All of the above-mentioned condensed nitrogen ring systems are known and are described in "The Ring Index" 2nd Edition and Supplements I, Ii, and III to Patterson et al, American Chemical Society. The molecules are synthesized by known methods, for example by treatment with ZnCl ₂ or FeCl ₃ and an alkyl iodide, or by dichlorination and subsequent reaction with appropriately disubstituted molecules, such as disodium sulfide, the disodium salt of ethylene glycol or the like.

radicals can be modified with substituents which modify the polymer properties, for example with electron donating or withdrawing groups according to known methods.

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Suitable compounds in which one or more of the nitrogens are saturated with hydrogen in the condensed Are bound in the ring or are in ionic form, the diradicals of quinolizinium, 9aH-quinoline, Pyridazino £ 1, 2-a7pyridazine, 2H-pyrldo / * 1,2-a7-pyrazine, Pyrido £ 'i, 2-a7-pyrimidin-5-ium, Pyrimido ^ i, 2-a7-pyrimidin-5-ium as well as 2H-pyrazino / "1,2-a ^ pyrazine. The compounds are known and are described in "The Ring Index" as well as supplements I, II and III. The polymers are produced according to known methods.

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For example, an electroactive polymer with repeating units from positional diradicals made of quinoline, substituted quinoline, isoquinoline, substituted isoquinoline, and mixtures thereof will. The diradicals can be in 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- as well as in the 6,8-position be linked, links in the 2,6- and 3,6-position in the polymer are preferred. The quinoline ring system is numbered as follows:

The isoquinoline ring system is numbered as follows:

30th

35

For example, the 2,6 diradical corresponds to quinoline

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the formula;

A preferred diradical of quinoline or isoquinoline is substituted in the 4-position. Preferably that is Diradically substituted with a phenyl group.

The diradicals can be separated by one or more linking units. Preferred connecting entities are biphenyl, -CH = CH- and -CsC-. The connecting units can be the same or different and between be adjacent diradicals are present in the polymer chain.

The polymer can be a homopolymer of the diradicals of quinoline, isoquinoline and the substituted derivatives thereof or a copolymer of the diradicals. A homopolymer is defined as a polymer that is present in the It has been made so that it has the same repeating diradicals. A copolymer becomes defined as a polymer that has various diradicals shows. In addition, the polymer is a copolymer if identical or different repeating diradicals are present separated by connecting units.

The polymer is electro- made active. In particular, the polymer is made electroactive by adding electrons to the original one Polymer backbone (reduction) or by removing electrons from the original polymer backbone (oxidation). This can be done in such a way that in the original

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initial polymers a conductivity modifier is incorporated which is either an electron donor dopant or an electron acceptor dopant. An electron donor dopant is there donates an electron to the polymer, the polymer is reduced to a polyanion, and the dopant becomes a Cation oxidizes. An electron acceptor dopant removes an electron from the polymer that becomes polymer oxidized to a polycation and the dopant is reduced to an anion. Optionally, the polymer can be made electroactive by electrochemical oxidation or reduction. In this case it becomes an electron withdrawn from the polymer from an electrode or added from an electrode, the charge compensating Anions or cations are incorporated into the polymer from the electrolyte solution.

In both cases the resultant oleoactive polymer exists from a charged polymer backbone into the charge-compensating one ionic dopants are incorporated. A suitable positively charged compensating dopant may be a cation such as an alkali metal ion, an alkaline earth metal ion, a metal ion a Group III metal or an organic cation such as

R ^ -N ⁺ , R ^xi - ⁺ N ^ 0)! or

wherein R is a straight or branched Cj-Cg-alkyl group is. Mixtures of these charge compensation dopants can be used. These ionic dopants produce n-type conductivity when they associate with a reduced or negatively charged polymer polyanion.

ι If ti M '<K ··

27 -

A suitable negatively charged compensating dopant, ie an anionic dopant, can be an anion, such as a halogen ion, and other ions such as AsP ", and in particular ions such as AsF ₆ ", ClO ₄ ", PF ₆ ", SO ₃ CF are possible ₃ ", BF ₄ ", NO ₃ ", POF ₄ ", CN ", SiF ₅ ", SbCIg ", SbFg", HSO ₄ ", organic anions such as CH ₃ CH ₂ " (acetate), CgH ₅ CO ₂ "( Benzoate), CH ₃ Cg H ₄ SO ₃ "(tosylate) or the like. Mixtures of the charge compensating dopants can be used. These ionic dopants produce p-type conductivity when they associate with an oxidized or positively charged polymer polycation.

The electroactive polymer modified with a dopant has a charge that corresponds to the charge of the conductivity modifier, d. H. of the ionic dopant, is opposite. The charges on the one with one Dopant modified electroactive polymers and the ionic dopant are balanced so that the electroactive polymer modified with a dopant is an electrically neutral system. The association of the original polymer with electron donor dopants produces an electroactive polymer that exhibits n-type conductivity. In particular, the reduction produces the original polymer and the incorporation of the cationic charge compensation dopants into a polymer, showing n-type conductivity. The association of the original polymer with electron acceptor dopants creates an electroactive polymer with a p-type conductivity. In particular, it produces oxidation of the polymer and the incorporation of an anionic charge compensating dopant a polymer with p-type conductivity.

The electroactive polymers of the present invention correspond to the following formula:

··· j? : · · «· ^< 3oip7co,:. * .. '.r ... ·. <··· οά Ιο / Oc

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■ Ε

R-HX R '' ""

where a is O or 1, b is either O or 1, c is either O or 1, η is an integer between 1 and 20,000
means that d is an integer between 1 and 40,000,
s represents an integer of 1, 2 or 3, R either
an unsubstituted or substituted condensed one
Nitrogen-containing heterocyclic diradical ring

system means that R 'is identical to or different from R, X is a connecting unit from a single one
Atom or a group of atoms means, Y is a connecting unit that is identical to or different from X, and M is an atom or a group of atoms

is used as charge compensating ion dopants
act, the electric charge being opposite to it
the charge is those repeating units

USd)
20th

comes to. fs '.'

The repeating units form the polyanion or i Polycation of the electroactive polymer. ί

The diradical group R is a substituted or non-; | substituted fused six-membered nitrogen

containing ring. The diradicals contain 1 to 6 stick- '

substances between the condensed six-membered Rin- ^

genes are distributed, with each ring no more than 3 at a time

otherwise contains bound nitrogen. Suitable |

Groups R are diradicals of molecules as they were previously ^

have been named, which contain 1 to 6 nitrogens. I.

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Preferred fused ring systems containing two nitrogen atoms consist of substituted or unsubstituted ones Quinoxaline diradicals.

In particular, R and R ¹ are unsubstituted or substituted quinoline or isoquinoline diradicals or mixtures of diradicals which are connected to one another either directly or via the connecting units X and Y with the formation of bridges. Preferably the bridges are formed at the 2,6 and 3,6 positions.

The connecting units X and Y can be selected from the group consisting of the following components:

-O-; -S-; -CH = CH-; -CHC-;

where R ^v , R ^V1 and R ^{V11 are} H or methyl, mixtures of these units also being possible. Biphenyl, vinyl and acetylene are preferred as linking groups.

The size of η determines the physical properties of the electroactive polymer. Preferably η is 10 to 10,000 when c is 0. In particular, η is 50 to 5,000 when c O is. Processable films are made using electroactive Polymers produced in which η exceeds a value of 50. A preferred molecular weight is at 10,000 or above.

The increase in the conductivity of the electroactive polymer over the value of the conductivity of the polymer in the original

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state is also determined by d. The conductivity is increased and adjusted as d is increased. For example, the original polymer of 2,6- (4-phenylquinoline has a conductivity of approximately 10 " ¹⁵ 5 ohms-cm. then the conductivity

2-1-1

increased to about 10 ohm cm. Preferred electroactive polymers are doped polymers, the conductivities of more than about 1 χ 10 ohm "cm, in particular

- 4 - 1 - 1

those more than 1 χ 10 ohm cm. Conductivities in the field of semiconductors can be obtained when d is about 10 to about 1,000. Larger concentrations on the charge-compensating ionic dopant M increase the conductivity up to the range of metallic conductivity. The charge compensating cationic or anionic dopant M is made from the above specified dopants and the like. Selected. M remains the same for all of the preferred ones given below Polymers.

The groups R and R ¹ are identical or different. If a stands for 1, then b and c are 0, R ¹ and Y fall out and the polymer corresponds to the following formula:

(+ Sd)

, US)

if a, b and c are O, R ', X, Y fall out and that Polymers corresponds to the formula

USd)

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10

A preferred substituent R or R ¹ is selected from the group consisting of quinoline diradicals, substituted quinoline, isoquinoline and substituted isoquinoline. A preferred diradical is a 2,6-substituted quinoline of the formula

, iii

> iv

15 20 25 30

wherein R ¹¹ ,

R and R ^{v are} substituent groups from

selected from H, 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 6 carbon atoms, an alkenyl group with 2 to 4 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, substituted by 1 to 3 alkyl groups with 1 to 4 carbon atoms, an alkonyl group with 2 to 4 carbon atoms, an alkynyl group with 2 to 4 carbon atoms, an alkoxy group with 1 to 4 Carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms, dialkylamino groups having 1 to 4 carbon atoms, an alkylthiol having 1 to 4 carbon atoms, or a 5- or 6-membered nitrogen-containing unsaturated heterocyclic group. The nitrogen atoms in the above polymers can be quaternized by reaction with quaternizing agents, for example dimethyl sulfate.

nt <■ ····> »·. · Ι · Wt I ν / Ü4 ι «

The term "alkyl" applies to both straight chain and jj

branched alkyl groups. Suitable examples are methyl, f>

Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and |

t-butyl. I.

I.

The term "alkoxy" relates to the group R ¹ O-, in which R ¹ * l

stands for alkyl. Suitable examples are methoxy, ethoxy, | " Propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy as well

t-butoxy. }:;

?? The term "alkylthio" includes, for example, methylthio,

Ethylthio, propylthio, isopropylthio, butylthio, isobutyl-JT thio, t-butylthio and s-butylthio.

Suitable examples of cycloaliphatic groups are cyclo pentyl, cyclohexyl, 3-methylcyclopentyl or the like.

The term "alkenyl" refers to unsaturated alkyl groups with a double bond (for example CH ₀ CH = CH (CH -) ^) and includes both straight-chain and branched alkenyl groups, such as ethenyl, but-3-enyl, propenyl or the like.

The term "aryl" relates to aromatic hydrocarbon radicals such as phenyl, naphthyl or the like. Suitable examples for aryl which is substituted by an alkyl are 2-tolyl, Mesityl, 3-isopropylphenyl or the like. Suitable examples for aryl substituted by an alkenyl are 3-styryl, 4-isopropenylphenyl or the like. Suitable aryl groups, which are substituted by an alkoxy are 1-methoxy-2-naphthyl, 3-n-Butoxyphenyl or the like. Suitable aryl groups which are substituted with a cyano group, are 4-cyanophenyl, 4-cyano-1-naphthyl or the like. Suitable Examples of aryl with an Hfllogen are 4-fluorophenyl,

• - •• ι »» t · · ·;

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3-chloro-4-bromo-1-naphthyl or the like. Suitable examples of Aryl that is substituted with a dialkylamino are 3-dimethylaminophenyl, 6-diethylamino-2-naphthyl or the like. Suitable examples of an aryl which is associated with an alkylthio is substituted are 4-butylthiophenyl, 3-methylthio-2-naphthyl or the like. Suitable examples of 5- or 6-membered nitrogen-containing heterocyclic groups are 3-pyrrolyl, 4-pyridyl or the like.

Preferred polymers of 2,6-substituted quinoline are present when R and R ^{v are} H. A preferred polymer is obtained when R and R are H and R is phenyl, ie poly-2,6- (4-phenylquinoline).

USd)

Another preferred group of polymers is obtained when R is phenyl and R ¹¹ and R ^{iv are selected} from the group of substituents as mentioned above.

Another preferred polymer is produced from 2,6- (4-phenylquinoline) diradicals in which a CH ₃ ⁺ component is linked directly to the nitrogen of the quinoline diradical, ie when quaternization is present.

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CH

USd)

Another preferred polymer is made from 2,6- (4- (4 · pyridyl) quinoline) and / or its quaternized analog. If R and R ^{1 are the} same and consist of the 2,6-quinoline diradical unit, then the repeating unit of the electroactive polymer modified in the dopant is as follows:

iv

AVt

R ^iU R ^iv

(± Sd)

C-O

where R,

R and R ^{v are} substituents consisting of the groups given above, while X and Y are the connecting units mentioned above. M is a conductivity modifier noted above.

A preferred polymer corresponds to the formula

It ·! · »« Ff · ··

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± Sd)

10

where R * · and R ^{iv is} H, R ^{i: Li is} phenyl, a, b and c are 1, X is an O-diradical and Y is a phenyl diradical.

15 20 25 30 35

Another preferred polymer corresponds to the formula

USd)

wherein R ¹¹ and R ^{iV are} H, R ^{iid is} phenyl, a and c are 1, b is O and X is a biphenyl diradical.

Another preferred polymer corresponds to the formula

USd)

where R ¹¹ and R ^{iv are} H, R ^{Ui is} -COOH, a is O, b and σ are 1 and Y is a biphenyl diradical.

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Another preferred polymer corresponds to the formula:

(+ Sd)

wherein R ¹¹ , R ¹¹¹ and R ^{iv are} H, a is O, b and c
1 and Y is a biphenyl diradical.

Another preferred polymer corresponds to the formula

(± Sd) _k (± S)

wherein R ¹¹ and R ^{lv are} H, R ^{111 is} -CH ₃ , a is O, b and c are 1 and Y

and Z is a link unit composed of the link units for X and Y.

Another preferred polymer corresponds to the formula

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OH

(± Sd)

where R ¹¹ and R ^{iv are} H, R ^{111 is} τΟΗ, a and c are 1, b is O and X is

means.

Another preferred polymer is obtained when R

and R ^{1 are} substituted quinoline diradicals, where R

and R ^{iv are} H, a is 1, b is 1, c is 1, X -CR ^vii =

CR ^V - means and Y is -CR ^vii = CH-. The polymer corresponds

the formula

.η (± sd) _R m _R vii

, 111

(iS)

Another preferred polymer is obtained when R is phenyl and R ^{vii is} H.

If R or R * are substituted isoquinoline diradicals, then a preferred diradical corresponds to the formula

10

15th

I I I I I

• · I

I · · Il

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, VIII

where R ^viii ,
like R ^U ,

R ^ix and R ^x consist of the same substituent groups, R ¹¹¹ and R. Polymers that the previously

are similar to the preferred quinoline polymers given are also preferred for isoquinoline.

A preferred electroactive poly (phenylquinoxaline) polymer corresponds to the formula

where R and R ^{1 are} phenylquinoxaline, a is O, b and c are 1 and Y

means.

The polymers are made as follows!

The starting material for the production of the electroactive polymers according to the invention consists of polymers and copolymers of repeating units from condensed nitrogen-containing unsaturated heterocyclic ring systems. Preferably the repeating units consist of quinoline or isoquinoline or substituted ones Quinoline or isoquinoline. These polymers and copolymers are well-known materials that are

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methods can be produced. For example, quinoline, isoquinoline or substituted derivatives thereof can be prepared in polymers by treatment with zinc chloride or by treatment with FeCl ₃ and an alkyl iodide (Rabinovich et al, Dokl. Akad. Nauk SSSR 1971, 13 (6), 395-6). The process is also suitable for the polymerization of the other diradicals mentioned above.

Other polymers are produced by a synthetic route that involves the conversion of dichloro or dibromo derivatives condensed nitrogen-containing unsaturated heterocyclic units with magnesium in ether, and then Provides contact with a nickel salt. The dihalogen derivatives with halogen in essentially all possible Combinations are known. This route represents a method of making polyquinolines or polyisoquinolines with bridges over any two of seven possible connection points.

Another method of making the polymeric starting materials is a synthesis that involves the final reaction of a corresponding diketone with a corresponding Provides aminodiacylbenzene in the presence of a base or an acidic catalyst (cf. Korshok 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; Silence, 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).

Another method for the preparation of polyquinolines, which are suitable as starting materials for the compounds according to the invention, is the condensation polymer

• ··

• · t

-40 -

sation of corresponding di (aminophenyl) compounds with corresponding Di (alpha, gamma-diketo) compounds (cf. V. Korshak et al, Vysokomol Soedin, Ser. B9 (3), 171, (1967) The polymers obtained have structures of the formula

wherein Z is O or CH ₂ CH ₃

The di (aminophenyl) compounds can contain a variety of Contain substituents, but must have an unsubstituted position ortho to the amino group exhibit. Typical compounds are 4,4'-diaminobiphenyl, 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-arainophenyl) ethane, 1,2-di (4-aminophenyl) ethylene or the like.

The di (alpha, gamma-diketo) compounds consist of compounds in which the diketones are linked at the alpha position by various linking groups. These connections correspond to the structure:

O 000

η η η μ \

CH ₃ -C-CH ₂ -CZC-CH ₂ -C-CH ₃ , j

wherein Z is a linking group. Typical linking groups are linking groups X and Y with two ors more atoms (PR-PS 1 468 677 and J. Polym. Sci. Part C, No. 16 Part 8, 4653 (1968)).

- 41 -

The preferred method of making the polyquinoline polymer starting materials is by the methods of W. H. Beever, et al., Journal of Polymer Science: Polymer Symposium 65, pp. 41-53 1978, p. 0. Norris, et al., Macromolecules, Vol. 9, No. 3, May-June 1976, pages 496-505, J. Pharm. Sci. 57, 784 (1968), and J. Heterocycle Chem. 11 107 (1974)).

Subsequent to the polymerization, objects such as fibers, ribbons or films can be cast from the solution. The solution is formed in such a way that the desired polymer is dissolved in a solvent composed of sulfuric acid, formic acid or a mixture of P ₂ ^O S and m-cresol consists. The solution temperature is approximately 25 and approximately 200 ^° C. and preferably approximately 140 ^° C., in particular 100 ^° C. The polymers are coagulated into solid forms, such as fibers, tapes or films, in a basic coagulation bath. To be used for making films

Solutions used containing about 2 to 25% polymer,

dissolved in the solvent. At concentrations exceeding 10%, the cast films adopt an anisotropic morphology. The anisotropic properties increase the conductivity in the anisotropic direction. A Amine, for example triethylamine, is dissolved in a protonic solvent such as H ₂ O and preferably ethyl alcohol is the coagulation bath. The bath is kept at a temperature which is lower than the dissolution temperature of the polymer in the solvent.

Usually room temperature is selected as the working temperature for the coagulating bath. The manufactured objects are dried. Elevated temperatures, usually 60 ^° C., and reduced pressure, accelerate the drying process. Drying continues until no

; it:. *

- 42 -

further weight loss is more noted.

After making the desired articles from the polycondensed heterocyclic quinoline polymers after In the methods described above, the objects are made electroactive, for example by chemical means or electrochemical methods. The objects can be made electroactive in an atmosphere related to of the polymer and the dopant is inert by contacting the articles with suitable ones Conductivity modifiers, d. H. Dopants. An inert atmosphere is an atmosphere that does not react with the polymer, dopant, or electroactive polymer. For example, can the atmosphere consists of argon, helium and nitrogen or the like. The doping can also be in an inert liquid Medium such as tetrahydrofuran, acetonitrile or the like. Can be carried out. The dopants can be oxidizing or electron accepting molecules or reducing or electron donating molecules. Both types of dopants can be in the form of gases or vapors, pure liquids or liquid solutions. Preferably, oxygen and water moisture are used during or excluded after the doping process because the conductive polymers lead to decomposition, i.e. H. to a loss conductivity when exposed to oxygen or moisture.

For example, the polymer 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 modifier can be between about 0.001 and about 1 mole, and preferably between about 0.01 and about 0.5 moles in THF or other suitable

- 43 -

Solvent lying. Other optionally applicable doping

; | Approximation methods can be found in US Pat. No. 4,204,216.

> | It is not yet fully understood how that

% 5 electron donor or acceptor dopants into the

ν polymers are incorporated. The incorporation of the doping

tel into the polymer can be achieved by a color change in the polymer as well as an increased conductivity

/ | be respected. For example, an original changes

';; {10 polymer film with a yellow or orange color its color ■; be in blue or black with a metallic sheen when

{ Doping, whereby the measured conductivity by many

> Order increases.

Optionally, the polyquinoline polymers can lead into their ■ the molds using electrochemical methods

oxidized or reduced. To carry out these methods, called electrochemical doping, the polymer is immersed in a suitable electrolyte solution and used as an electrode of an electrochemical cell. When an electric current is passed through such a cell, the polymer is reduced (or oxidized, depending on the direction of the current) and charge-compensating cations (or anions) from the electrolyte are incorporated into the polymer. This Do- \ l orientation is carried out with the above-described characteristic color change. In this way, the polymer can be electrochemically doped with a suitably charged ion which is present in the electrolyte solution. Electrolyte solutions consist of a salt,

which is dissolved in a solvent. Suitable solvents are acetonitrile, tetrahydrofuran, 2-methyl- tetrahydrofuran, propylene carbonate, dimethylformamide, dimethyl sulfoxide y or the like. Suitable cations are Li ^+, Na ^+, K ^+,

I · · · · t · ft I

- 44 -

(CH ₃ ) ₄ N ⁺ and (C ₄ H ₉ J ₄ N ⁺

Suitable anions are Cl "

Br

ClO,

and PF ,. '. The extent of the doping leaves

easily controlled by adjusting the charge that is electrochemically introduced into the polymer, either by controlling the amount of current applied (galvanostatic charge) or by control the potential of the polymer electrode with respect to a comparison electrode (potentiostatic charge).

The electrochemical doping method described above is completely reversible. The polymer may "dedoped ¹¹ and returns to its original neutral non-conductive state, simply by applying a current which is opposite to the current that has been used for the doping process. After completion of undoping the color returns the polymer to its For example, a reduced conductive polyquinoline polymer can be fully reoxidized to its neutral non-conductive form, with the charge compensating cations incorporated during the electrochemical reduction being pushed out of the article during the electrochemical reoxidation.

The following examples illustrate the invention without restricting it. Obvious modifications fall into the Scope of the invention.

30 examples

Example 1a Preparation of 2-methyl-2- (4-nltrophenyl) -1,3-dioxolane

ι ι

• · · t

• «'I

- 45 -

1.65 g (10 mmol) of p-nitroacetophenone, 5 ml (89 mmoles) of ethylene glycol, 2.96 g (20 mmol) of triethyl orthophonate and 0.086 g (0.5 mmol) of p-toluenesulphonic acid are combined in 4 ml of methylene chloride. The solution is heated with an oil bath (50 to 70 ⁰ C, 6 h), cooled to room temperature and poured into an excess of a 10% sodium hydroxide solution. The phases are separated and the aqueous phase is extracted twice with methylene chloride. The combined organic phases are washed three times with water and dried with anhydrous sodium sulfate. (- Be 75 ⁰ C, see J. Pharm 57, 784 (1968) literature 73rd.). Evaporation of the solvent, a pale yellow product in an amount of 1.7 g with a remains F. ° C 69-71 back .

Example 1b Production of 5- (2-methyl-1 _/ 3-dioxolan-2-yl) -3-phenyl-

2,1-benzisoxazole

0/84 g (7.2 mmol) of phenylacetonitrile and 1.50 g (7.2 mmol) of 2-methyl-2- (4-nitrophenyl) -1,3-dioxolane (P. 69-71 ⁰ C) a kept at room temperature solution of 1.44 g (36 mmol) of sodium hydroxide in 8 ml of methanol. A slight exothermic reaction is noted and stirring is continued for 16 hours. The mixture is filtered and the collected solid to give a yellow powder in an amount of 1.60 g having a melting point of 137 ⁰ C obtained several times with water and washed once with cold methanol (literature melting point of 137-138 ⁰ C. (see J. Heterocyclic Chem. 11, 107 (1974)).

- 46 -

Example 1c Production of 2-amino-5- (2-methyl-1,3-dioxolan-2-yl) -

benzophenone

1.50 g (5.3 mmol) 5- (2-methyl-1 _# 3-dioxolan-2-yl) -3-phenyl-2,1-benzisoxazole, 0.3 ml triethylamine and 0.15 g 5% - Palladium-on-charcoal are combined in 13 ml of a dry tetrahydrofuran. The device is purged with nitrogen and then with hydrogen. A static hydrogen atmosphere (1 atm) is maintained and the course of the reaction is followed by gas chromatography. The starting material and the product have retention times of 11.15 and 11.33 minutes, respectively, After the conversion is complete, the mixture is filtered through a Gelite filter to give a clear yellow solution. Evaporation of the solution gives a yellow solid in an amount of 1.35 g with a F. of 108 to 111 ^° C.

Example Id Manufacture of 5-acetyl-2-amlnobenzophenone

1.0 g (3.54 mmol) of 2-amino-5- (2-methyl-1,3-dioxolan-2-yl) -benzophenone are dissolved in 30 ml of absolute ethanol .

14 ml of 1M perchloric acid are added to this solution.

The resulting mixture is stirred at room temperature for 18 hours. The mixture is made alkaline with 3N sodium hydroxide solution and then extracted with a few portions of ethylene chloride. The combined methylene chloride extracts are washed with water, dried with anhydrous sodium sulfate and evaporated, a yellow product in an amount of 0.79 g with a mp of 158 to 161 ^° C. being obtained. A portion of the product is recrystallized from a mixture of methylene chloride and hexane to give a material having a melting point of 158 - 162 ⁰ C is obtained.

ti ·· ti · ·

- 47 -

Example 1e Production of poly-2,6- (4-phenylquinoline)

A solution is made from 1.07 g (7.5 mmol) of phosphorus pentoxide and 2.5 ml of a freshly distilled m-cresol Heating to 140 ^° C. for 2.5 hours under nitrogen. The solution is cooled to room temperature, whereupon 0.30 g (1.28 mmol) of 2-aminobenzophenone and 1.3 ml of m-cresol are added. The solution is heated to 120 ⁰ C. heated and held at this value for 48 hours. The resulting solution is mixed into a mixture with stirring 60 ml of 95% ethanol and 6 ml of triethylamine are poured in, a fibrous yellow solid being obtained which is washed twice with ethanol in a Waring-Mi- shear washed. It is then extracted with ethanol for 19 hours in a Soxlet device and dried, being an orange colored product in an amount of 0.26 g (1.28 mmol) is obtained.

Example 2 Production of films from poly-2,6- (4-phenylchinoline)

A solution is prepared from 0.8 g (5.6 mmol) of phosphorus pentoxide and 2.5 ml of distilled m-cresol by heating at 110 -120 ⁰ C under argon. The solution is cooled to room temperature and 0.051 g (0.25 mmol) of poly-2,6- (4-phenylquinoline) are added. The mixture is ^{heated to 140 °} C., a viscous deep red solution being obtained. Films are made in the way that a few drops of this solution are applied to a heated glass plate, whereupon in a bath of 10% Triethylamine and 90% ethanol is quenched. The clear yellow films are between layers of filter paper pressed and dried in a vacuum oven.

- 48 -

Example 3 Doping of poly-2,6- (4-phenylquinoln)

The transparent yellow film obtained according to Example 2 is placed in a vessel which is placed in a drying chamber with a dry argon atmosphere. After 30 minutes, a dimethoxyethane solution is made of sodium naphthalide poured into the jar. The film reacts immediately and its color changes to a dark color, the green-blue in transmitted light and purple-green with a metallic sheen in reflected light is. After exposure to air, the dark color disappears immediately and the polymer takes its original Look back on.

Example 4

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

The method described in Example 3 is repeated, with the exception that the film is first wetted with tetrahydrofuran (THF) and then dissolved with 0.1M sodium naphthalide in THF. After the addition of the sodium naphthalide, the polymer film hits a deep blue with a metallic shine around. The surface of the film is rinsed with THF. The conductivity of the doped film with a thickness of 2.54 χ 10 cm is using was measured on a Signature Co. 4-point sample device. The four points of the device form a single one Line. A DC voltage (VE) is applied across the two outermost points and the voltage (VI) of the Current measured across the inner two points. The conductivity is calculated from these values as follows:

- 49 -

VE - 0.1 volts VI = 0.06 volts (measured) R = 1074 (VE / VI) = 1790 ohms / square

fcho = Rxt - 1790 χ 2.54 χ 1θ " ³ = 4.55 ohm cm

- 1-1 sigma = 1 / rho = 0.22 ohm cm

whereby

VE = applied voltage

t = film thickness

VI = measured voltage

R = resistance on the surface

rho = specific resistance of the object

sigma = conductivity

1074 = instrument and unit conversion factor

The washed but undoped polymer is non-conductive, but rather an insulator with conductivity of 10 ohm cm, measured with the same device (cf. J. Polym. Sci. Poly. Symp. 65, 41 (1978).

-15
This same value (10) is measured on the doped film after it has turned yellow after exposure to air.

The infrared spectra of the original undoped film as well as that exposed to air doped film are the same. The infrared spectrum of the dark sodium naphthalide-doped film is opaque without adsorption between 4000 and 600 cm, which indicates a metallic behavior. This experiment shows that the doped polyquinoline films are surprisingly good electrical Are leaders.

Example 5

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

• · t · • · · I

• · ι

- 50 -

Films are doped as in Example 4, but with potassium naphthalide. After placing these films in a vacuum drying chamber under a pressure of less than 10 ~ mm Hg for 6 days have been maintained, the following conductivity values are determined:

PU = 36 mv

VI = 55 mv

rho = 1.78 ohm cm

t = 2.54 χ 10 ~ ³ cm -1 -1

sigma = 0.56 ohm cm

Values of this order of magnitude show that the doped polymer is electroactive and represents a conductor of electricity.

Example 6a Production of bis-4-nitrophenyl ether

20.0 g (0.142 mol) i-fluoro-4-nitrobenzene, 19.7 g (0.142 mol) 4-nitrophenol and 28.3 g (0.486 mol) of potassium fluoride are combined in 75 ml of dimethyl sulfoxide and for 0.5 h for Heated to reflux. The mixture is cooled and left at room temperature overnight.

The precipitate is collected and washed in water. It is dissolved in warm toluene, from a layer of water separated and dried with magnesium sulfate.

Concentrating and cooling provides 28.8 g of the product (F. 144 to 146 ⁰ C) in two portions.

Example 6b Preparation of 5,5'-oxybis- (3-phenyl-2,1-benzisoxazole)

17.72 g (0.151 mol) phenylacetonitrile and 19.52 g (0.075 mol)

. ] .ου ::

ϊ - 51 -

Bis-4-nitrophenyl ether become one at room temperature held solution of 30.01 g (0.75 mol) of sodium hydroxide in 150 ml of methanol and reflux

, | i heated for 9 h. The reaction mixture is used on carpentry 5 cooled temperature and with 50 ml of a 50% methanol solution diluted in water and then in one

^: Ice bath cooled. The precipitate is collected and

washed with cold methanol. The solid is dissolved in warm toluene, dried with magnesium sulfate, concentrated and cooled to give 7.55 g. Recrystallization from warm toluene gives 5.19 g of a product with a F. of 208 to 209 ^° C. A second, unidentified material with a F. of 158 to 165 ^° C. is also isolated. 15th

Example 6c Preparation of 4,4'-diamino-3,3'-dibenzoyldiphenyl ether

4.92 g (12.0 mmol) 4,4'-oxybis (3-phenyl-2,1-benzisoxazole) and 1.32 mol of triethylamine are in 50 ml of tetrahydrofuran combined under a nitrogen atmosphere. Palladium on carbon (5%, 0.41 g) is added and then hydrogen is slowly bubbled through the system for 15 hours. the Mixture is filtered through gelite and evaporated,

a yellow oil obtained from a mixture is crystallized from toluene and hexane (10: 1). 4.33 g (87%) of the desired product are obtained. This is further purified by recrystallization from methanol, yielding 2.43 g of a material with an F. of 154 to 155 ° C can be obtained.

• ■

<I.

• · 4 · · · • I · II fit

- 52 -

• I · ·

I «I I I I

Example 6d Production of a quinole copolymer from 4/4 '

3,3'-dibenzoy! Diphenyl ether and p-diacetyl benzene

A solution is 5/6 ml of g (39.4 iranol) fresh phosphorus pentoxide and 20 of a freshly distilled m-cresol prepared by heating to 14O ⁰ C. A portion of this solution (7/6 ml) is used to dissolve 0/5005 g (1/225 iranol9 4 / 4'-diamino-3,3 ¹ -dibenzoyl diphenyl ether and 0.1987 g (1.225 mmol) p-diacetylbenzene The solution is kept at 110 to 120 ^° C. for 48 hours, the mixture is cooled and poured into a mixture of 10 ml of triethylamine and 100 ml of a 95% strength ethanol, a white fibrous product being obtained Dissolve 15 ml of chloroform and precipitate with ethanol. This operation is repeated to finally obtain 0.10 g of a white fibrous polymer. A film is obtained by dissolving 25.7 mg in 0.52 g of the above-mentioned phosphorus pentoxide / m-cresol Solution prepared at 60 ^° C., applying a few drops to a warm glass plate and spreading it out with a warm blade. After quenching in a bath of 90% ethanol and 10% triethylamine, a film is obtained. This film has the following structure:

Il t

I · · I.

t : I ■

I I

I I ·

- 53 -

Example 7 Doping and conductivity measurement of the polymer of Example 6

Films made from the polymer of Example 6d are kept in a drying cabinet for 2 weeks with less than 10 ppm water and kept oxygen. The films are then coated with sodium naphthalide according to that described in Example 3 Method endowed. After doping, the films have a deep metallic blue color. The conductivity measurements result in the following values:

VE = 4.5 mV VI = 0.3 mV R = 16110 Ohm / square

rho = 40.92 ohm cm

-1 -1 sigma = 0.024 ohm cm

Example 8a Preparation of 5-bromo-3-phenyl-2,1-benzisoxazole

8.1 g (69 mmol) of phenylacetonitrile are added to a solution, kept at room temperature, of 74 g (1.1 mol) of potassium hydroxide (85%) in 150 ml of methanol. 12.7 g (63 mmol) of 4-bromo-1-nitrobenzene, suspended in 130 ml of methanol, are added to this solution. An exothermic reaction is observed and the reaction was continued at 5O ⁰ C for 5 h. After cooling to room temperature, 400 ml of water are added. The precipitate is collected and washed with water. The crude product (13.15 g) is recrystallized from hot methanol (200 ml) to give yellow needles in an amount of 9.52 g having a melting point 113-116 C are obtained ^e.

Ι ·

- 54 -

Example 8b Manufacture of 2-amino-5-bromobenzophenone

7.5 g (28.6 mmol) of 5-bromo-3-phenyl-2,1-benzisoxazole, 14.6 ml of water and 9.3 g (143 mmol) of zinc dust are combined. 8.6 ml (143 mmol) of acetic acid are added and the mixture stirred and heated at 8O ⁰ C for a period of 90 min. After cooling to room temperature, both the liquid and the solid portion are extracted from the reaction with methylene chloride. The combined methylene chloride solutions are washed once with a sodium hydroxide solution (10%) and a few times with water. After drying (sodium sulfate) and evaporation, the desired product is an amount of 7.42 g in a P. of 92 - 102 ⁰ C obtained.

Example 8c

Preparation of 4,4'-diamino-3,3 · -dibenzoylbiphenyl

0.55 g (2.0 mmol) of 4-bromo-2-aminobenzophenone are dissolved in 10 ml of a dry and deoxygenated dimethylformamide in a chamber with an inert atmosphere. 0.55 g (2.0 mmol) of bis (1,5-cyclooctadiene (nickel (O)) are added in portions to the solution. The reaction mixture is removed from the chamber with the inert atmosphere by means of a Schlenk method to a vacuum / argon manifold connected the reaction mixture for 4 hours at 50 -... heated 55 ⁰ C and at room temperature, allowed to stand overnight the mixture is then poured into 200 ml water which is made slightly basic with sodium hydroxide, the water is several times with ethyl acetate Extra hiert. After drying with sodium sulfate and a

- 55 -

evaporating, a dark brown liquid is obtained in the amount of 0.48 g. Recrystallization from hexane gives 100 mg of a yellow-brown solid with a mp of 180 to 185 ° C.

Example 8d

Preparation of a polymer from 4,4'-diamino-3,3'-dibenzoylbiphenyl and 4,4'-diacetylbiphenyl

80.0 mg (0.204 mmol) of 4,4'-diamino-3,3'-dibenzoylbiphenyl and 48.6 mg (0.204 mmol) of 4,4'-diacetylbiphenyl are combined in a solution which consists of 0.348 g (2.45 mmol) phosphorus pentoxide and 1.2 ml of a freshly distilled m-cresol has been prepared, and ^{heated to 120-130 °} C. for 46 h. The hot reaction mixture is poured into a mixture of 6 ml of triethylamine and 60 ml of 95% ethanol, with stirring. The fibrous red precipitate is stirred in the base bath until its color has turned yellow. It is washed with water and ^{dried at 80 °} C., 120 mg of a yellow powder (mp> 320 ^° C. being obtained. Films of this material are obtained by dissolving 50 mg at 120 ^° C. in m-cresol (0.75 ° C.) A few drops of this solution are spread on a glass plate and quenched in a bath of triethylamine (10%) and ethanol (90%) to give a yellow film. This copolymer has the following structure :

- 56 -

The polymer is then made according to that described in Example 3 Method made guiding. The conductivity is measured according to the method described in Example 4. The conductivity of the doped polymer is 0.024 ohm "cm

-1

Example 9 Production of poly-2 _# 6- (4- (4'-chlorophenyl) chlnoline)

This polymer is prepared essentially by the method described in Example 1, with the exception that 4-chlorophenylacetonitrile is used instead of phenylacetonitrile. The analysis of the polymer gives the following results: Calculated for (C ₁₅ HgNCl): C 75.80%, H 3.39%, N 5.89%, Cl 14.92%. Found: C 76.81%, H 3.64%, N 5.86%, the balance is Cl. The polymer has the following structure:

The polymer is then made according to that described in Example 3 Method made guiding. The conductivity is measured according to the method described in Example 4. the Conductivity of the doped polymer is 0.02 Ohm '

-1

- 57 -

Example 10 Electrochemical doping of quinoline polymers

A 125 mm platinum wire is coated with a thin film of the polymer from Example 1 by immersing the wire in a 5% strength solution of the polymer in a m-cresol / PjO ^ mixture. The wire coated with the film is neutralized by immersion in a solution of 10% triethylamine and 90% ethanol and dried ^{at 60 ° C. in a vacuum oven.}

The wire coated with the polymer is tied with an E.G. and G. Princeton Applied Research Apparatus from one universal programmer and a potentiostat / galvanostat connected to a recording device. The end of the wire coated with the polymer is then inserted into immersed a 0.1 M solution of lithium tetrafluoroborate in acetonitrile. A voltage that contrasts from 0 to -3.0 volts an SCE fluctuates is applied to the platinum wire. The output current is essentially zero to the voltage approximately Has reached -1.5 volts. At this point the cathodic current rises rapidly and reaches its peak at -2.25 volts. After reversing the voltage, an anode current is observed which reaches its maximum at -1.5 volts. If the initial voltage of -1.5 volts is applied, then goes the color of the polymer adhering to the wire changes from light yellow to a dark metallic color. This color disappears when the voltage is increased to more than -1.5 volts.

This behavior shows an initial resistance to the passage of the current, which is subject to rapid absorption of electrons, which results in a charged electroactive polymer, the lithium ions as a charge compensation dopant contains. The polymer is thus produced by applying a voltage of approximately -2 volts in

• ·· · · t ft » « · ι

- 58 -

Presence of an electrolyte solution that is a charge compensation dopant able to make available, made electroactive.

Example 11 Electrochemical doping of quinole polymers

The same experiment as in Example 10 is carried out, with the exception that the lithium tetrafluoroborate is replaced by tetrabutylammonium bromide. Essentially the the same results as in Example 10 are obtained. In this case, it becomes coated with the polymer Wire alternately charged and discharged without loss of activity. The metallic color comes and goes with Loading or unloading the polymer.

This experiment shows that the charged electroactive polymer can be used as an electron source. One application is as the anode of a battery. This experiment also shows that the electroactive Polymers is able to incorporate ionic charge compensation dopants into its structure.

Example 12 Electrochemical doping of a poly (phenyl-chloroxaline)

A 125 mm platinum wire is covered with a thin film of a polymer of the structure

- 59 -

by immersing the wire in a 5% solution of the Polymers coated in a m-cresol / PjOg mixture.

The polymer used is available from Aldrich Chemical Co. and is a product of Scientific Polymer Product, Inc., 6265 Dean Parkway, Ontario, New York Catalog # 330, batch 101. The polymer is 100% solid in m-cresol The wire coated with the film is neutralized by immersion in a solution of 10% triethylamine and 90% ethanol and dried ^{at 60 ° C. in a vacuum oven.}

The wire coated with the polymer is connected to a

E. G. and G. Princeton Applied Research Apparatus consisting of a universal programmer and a potentiostat / galvanostat connected to a recording device. The end of the wire coated with the polymer is then inserted into a 0.1m solution of lithium tetrafluoroborate immersed in acetonitrile. A voltage that contrasts from 0 to -3.0 volts an SCE fluctuates is applied to the platinum wire. The output current is essentially 0 to the voltage has reached approximately -1.5 volts. At this point the cathode current increases rapidly and reaches -2.0 Volt reached its peak. After reversing the voltage, an anode current is observed which is -1.25 volts highest value reached. If the initial voltage of -1.5 volts is applied, then the color of the polymer suggests adhered to the wire, from light yellow to a dark me-

- 60 -

metallic color around. This color disappears when the voltage is increased above -1.5 volts.

This behavior shows an initial resistance to the passage of current, which is followed by a rapid uptake of electrons / which results in a charged polymer that contains lithium ions as a charge compensation dopant. Thus, the polymer is made electroactive by the application of a voltage of about -2 volts in the presence of an electrolyte capable of providing ionic charge compensation dopants.

Example 13a

Preparation of 4-acetyl-2- (4'-methoxy) benzoylanillin monomers

20th

38.2 g of NaOH are dissolved in 200 ml of methanol in a 1 l three-necked flask equipped with a mechanical stirrer, reflux condenser, N ₂ inlet and hot jacket. 28.14 g (0.19 mol) of p-methoxyphenyl acetonitrile are added, followed by the addition of 40 g (0.191 mol) of p-nitroacetophenone ethylene glycol ketol. The reaction mixture is mechanically stirred under reflux for 22 hours.

The product is filtered off, washed with water and recrystallized from methanol.

30 35

The product has the formula

- 61 Analysis calculated for C ₁₈ H ₁ -ON

Calculated Found

% C 69.44 68.16%

H . 5.50 5.41

N 4.50 4.26

Example 13b
Hydrogenation of the product of Example 13a

17.12 g (0.055 moles) of the product of Example 13a will be obtained in 150 ml of tetrahydrofuran and 4 ml of triethylamine in a 500 ml 3-necked flask equipped with a gas inlet tube, reflux condenser, Thermometer and magnetic stirrer is provided, dissolved. 1.2 g of a 5% Pd / carbon catalyst are added.

The flask is purged with nitrogen and then connected to a slow stream of hydrogen.

The reaction mixture becomes magnetic at room temperature

Stirred for 9 h. ^K

Thin layer chromatography indicates a complete reaction.

The reaction mixture is flushed with nitrogen and the catalyst filtered through Celite. 30th

The filtrate is evaporated to an oily residue in an amount of 19.3 g.

The product has the formula
35

- 62 -

Example 13c Hydrolysis of the product from Example 13b

19.1 g of the product from Example 13b are dissolved in 60 ml of tetrahydrofuran and 30 ml of water in a 250 ml round bottom flask. The pH of the solution is brought to about 3 with concentrated HCl adjusted and the reaction mixture was left to stand at room temperature for about 18 h sen.

Thin layer chromatography shows complete hydrolysis.

The reaction mixture is poured into 300 ml of a saturated Na ₂ CO ₃ solution and extracted three times with an equal volume of methylene chloride.

The combined methylene chloride solution is washed with water, dried and evaporated, giving 14.5 one yellow residue are obtained. The product is recrystallized from methylene chloride / hexane. Its temperature is 119 to 123 ° C.

The product has the formula

OCH-

• ·

- 63 -

se, calculated for ι N 36 Found , 33 Calculated 61 71 / 69 % C. 71 20th 5 , 78 % H 5, 5 % N 5, ^C 16 ^H 15 ° 3

Example 1 3d
Preparation of poly / 2,6- (4-p-methoxyphenyl) quinolines

The catalyst solution is made by dissolving 9.44 g (66.5 mmol) of P ₃ O ₅ (weighed in a drying chamber) in 24 ml of m-cresol (Aldrich gold label) in a 50 ml 3-necked round bottom flask equipped with a mechanical stirrer , Reflux condenser and N ₂ inlet is made.

The catalyst solution is stirred mechanically and heated in an oil bath to 105 ^° C. under a nitrogen blanket until the solution has become homogeneous (approximately 2.5 h). 3 g (11.16 mmol) of the monomer from Example 13c are added, followed by the addition of 10 ml of m-cresol. The temperature of the oil bath is raised to 120 ⁰ C and 48 carried out the polymerization reaction at this temperature for hours. The color of the solution changes from gold to deep red, whereby the solution becomes more viscous.

The polymerization solution is slowly poured into 500 ml of a 10% strength solution of triethylamine in ethanol and stirred at room temperature overnight. During the neutralization , the polymer forms a spindle.

The polymer is collected by filtration with ethanol

••• I ··· »/» (

- 64 -

washed and extracted with ethanol in a Soxlet extractor overnight.

Following the extraction is filtered and dried in vacuo at 70 ⁰ C with 2.3 g (88.5%) of the trok- kenen polymers.

The polymer has the formula

10

Analysis:

20th

% C H N

Calculated * 82.38 4.75 6.01

Found 78.52 4.40 5.52

= 0.83 dl / g (measured in

Then the polymer according to the methods described in Example 3 using a 0.5 molar Solution of sodium anthracenide in THF instead of sodium naphthalide made conductive. The conductivity is after the method described in Example 4 measured. That

Polymers have a conductivity of 2.5 ohms * "cm".

• ·· · »till« t ft

- 65 -

Example 14 Manufacture of PolyZS , 6- (i-methyl-4-phenyl) quinolinium7-

metasulfate

10

Platinum wires coated with poly-2,6- (4-phenylquinoline) are placed in a 50 ml round bottom flask and covered with 10 ml of dimethyl sulfate (Aldrich). The piston comes with a Provided reflux condenser and a drying tube within a fume cupboard. The reaction mixture is left at room temperature overnight and then for 6 hours heated to reflux.

15th 20th 25th 30th

After cooling, the dimethyl sulfate solution is decanted off and the wires are quenched with approximately 30 ml of a 10% strength solution of triethylamine in ethanol. Subsequent to the neutralization, the wires are washed thoroughly with ethanol and dried ^{at 80 ° C. in vacuo.}

The polymer has the formula

CH-OSO,! * ^J CH

The polymer is made conductive according to the method described in Example 3. However, the dopant consists of 0.5 molar sodium anthracenide in THF. The conductivity of the polymer is 0.75 ohms " ¹ cm" ¹ , measured according to the method described in Example 4.

- 66 -

Example 15 Electrochemical doping of PolyZ "2,6- (1-methyl-4-

phenyl) quinolnium 7

A 125 mm platinum wire is coated with a thin film of poly-2,6- (4-phenylquinoline) as in Example 10. The polymer is then quaternized as in Example 14.

The polymer-coated wire obtained is with connected to the device described in Example 10 and in a 0.1 M solution of tetraethylammonium tetrafluoroborate immersed in acetonitrile. A linear voltage that ranges from 0.5 to -1.3 volts versus an SCE fluctuates, is applied to the platinum wire. The output current is essentially 0 until the voltage is approximately Has reached 0.8 volts. At this point the cathode current increases rapidly and reaches its maximum at -1.1 volts. After reversing the voltage, an anode current is observed which reaches its maximum at -0.8 volts.

This behavior shows an initial resistance to a flow of current that is rapidly absorbed of electrons to form a reduced polymer. Therefore the polymer becomes electroactive by applying a voltage of approximately -1.1 volts versus an SCE in the presence of an electrolyte solution made.

Example 16 Electrochemical doping of a copolymer of 4,4'-

Dlamino-3,3'-dlbenzoyldiphenyl ether and p-diacetylbenzene

-i

- 67 - ψ

· ■ _ if

A 125 mm platinum wire is coated with a thin film of the polymer according to Example 6d by immersing the wire in a 5% strength solution of the polymer in an m-cresol / P _{2 O 5} mixture. The wire coated with the film is neutralized by immersion in a solution of 10% triethylamine and 90% ethanol and dried ^{at 60 ° C. in a vacuum oven.}

The wire coated with a polymer is connected to the device described in Example 10 and immersed in a 0.1 M solution of tetraethylammonium tetrafluoroborate in acetonitrile. A linear voltage that varies from 0 to -2.5 volts versus an SCE is applied to the platinum wire. The output current is essentially zero until the voltage reaches approximately -1.7 volts. At this point the cathode current rises rapidly to a maximum value of -2.2 volts and shows a double wave with a peak separation of 200 mV. After reversing the voltage, an anode current is detected, which also shows a double wave, namely at -1.8 volts. When the initial voltage of -1.7 volts is applied, the polymer adhering to the wire fluctuates from its near colorless, transparent appearance to a dark metallic color. This color disappears by raising the voltage to greater than -1.5 volts.

This behavior shows an initial resistance to the flow of current, which is followed by a rapid uptake of electrons, which results in a charged polymer containing tetraethylammonium ions as ionic charge compensation dopants. Therefore, by applying a voltage of approximately -2.2 volts to an SCE in the presence of an electrical

- 68 -

lytic solution made electroactive, which ionic charge compensation dopants provide ;;; able. t

; ■

Example 17

Electrochemical doping of a copolymer of 4,4'- i? Diamino-3,3'-dibenzoylbiphenyl and 4,4'-diacetylbiphenyl

A 125 mm platinum wire is coated with a thin film of the polymer from Example 8d by immersing the wire in a 5% strength solution of the polymer in an m-cresol / P _{2 O 5} mixture. The wire covered with the film is neutralized by immersion in a 10% triethylamine / 90% ethanol solution and dried ^{in a vacuum oven at 60 ° C.}

The wire coated with the polymer is connected to the in Example 10 connected device and in a 0.1 M solution of tetraethylammonium tetrafluoroborate immersed in acetonitrile. A linear voltage that varies from 0 to -2.5 volts versus an SCE will applied to the platinum wire. The output current is essentially 0 until the voltage reaches -1.7 volts has reached. At this point the cathode current increases rapidly and peaks at -2.0 volts. After reversing the voltage, an anode current is determined, ■ · :; which reaches its maximum at -1.6 volts. If the initial] voltage of -1.7 volts is applied, the Far- | changes be of the polymer adhering to the wire, from light yellow | to a dark metallic color. This color disappears- $ det when increasing the voltage to more than -1.4 volts. |

This behavior shows an initial resistance to ^% over a flow of current, which is followed by a rapid rise

if ······ I

- 69 -

would take from electrons what a charged polymer connects has the consequence that it contains tetraethylammonium ions as an ionic charge compensation dopant. Hence will the polymer by applying a voltage of approximately -2.0 volts to an SCE in the presence of an electrolyte solution Made electroactive, which ionic charge compensation can provide compensation dopants.

Example 18

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

A 125 mm platinum wire is coated with a thin film of the polymer from Example 9 by dipping the wire in a 5% solution of the polymer in an m-cresol / PjOg mixture. The wire coated with the film is neutralized by immersion in a 10% triethylamine / 90% * ethanol solution and placed in a vacuum oven at | 6O ⁰ C dried. |

The wire coated with the polymer is connected to the device described in Example 10 and immersed in a 0.1 m solution of tetrabutylammonium bromide in acetonitrile. A linear voltage that varies from 0 to -2.3 volts versus an SCE is applied to the platinum wire. The output current is essentially zero until the voltage reaches approximately -1.5 volts. At this point the cathode current increases rapidly and reaches its maximum at -1.8 volts. After the voltage has been reversed, an anode current is detected which reaches its maximum at -1.3 volts. Is the initial voltage applied from -1.5 volts, then the color changes of the polymer that adheres to the wire on "to a dark metallic color to. This color disappears when the voltage is increased to more than

• ·

- 70 -

-1.2 volts.

This behavior shows an initial resistance to a flow of current that is subject to rapid absorption of electrons, which results in a charged polymer, the ionic tetraethylammonium ions Contains charge compensation dopants. Hence will the polymer by applying a voltage of approximately - 1.8 volts made electroactive against an SCE in the presence of an electrolyte solution, which is an ionic Is able to provide charge compensation dopants.

Example 19

Electrochemical doping of poly-2,6- (4- (4'-methoxyphenyl) chlnoline)

A 125 mm platinum wire is coated with a thin film of the polymer from Example 13d by dipping the wire in a 5% solution of the polymer in an m-cresol / P-Oe mixture. The coated wire with the film is neutralized by immersion in a 10% triethylamine / 90% ethanol solution and dried in a vacuum oven at 6O ⁰ C.

The wire coated with the polymer is connected to the device described in Example 10 and immersed in a 0.1 M solution of tetrabutylammonium bromide in acetonitrile. A linear voltage that varies from 0 to -2.3 volts versus an SCE is applied to the platinum wire. The output current is essentially zero until the voltage reaches approximately -1.5 volts. At this point the cathodenetrom rises rapidly and peaks at -2.1 volts. After reversing the

32187G2

- 71 -

Voltage, an anode current is observed which is -1.5 volts reached its maximum. The initial voltage will be -1/5 When a volt is applied, the color of the polymer attached to the wire turns a dark metallic color around. This color disappears when the voltage is increased above -1.3 volts.

This behavior shows an initial resistance to the flow of the current, which is fast-Ie This is followed by the uptake of electrons, which results in a charged polymer known as tetraethylammonium ions contains ionic charge compensation dopant. Therefore, by applying a voltage of about -2.1 volts against an SCE made electroactive in the presence of an electrolyte solution, which is ionic Is able to provide charge compensation dopants.

Example 20

Doping and conductivity measurement of poly-2, (H4-phenyl - quinoline)

The polymer poly-2,6- (4-phenylquinoline) is according to the in the method described in Examples 3 and 4 doped and made electroactive. The conductivity modifier however, is a 0.5 molar solution of sodium anthracenide in THF. The conductivity of the electroactive polymer

30th

is 20 ohms " ¹ cm" ¹

¥ Example 21

$ Doping and conductivity measurement of poly-2,6- (4- (4'-

f chlorophenyl) chlnoline)

'.Il, i ,,,.,: VA IUf U ^ U

The polymer of Example 9 is made according to the examples 3 and 4 described methods doped and electro-

made active. The conductivity modifier is |

but 0.5 molar sodium anthracenide in THF. The conductive %

-1-1 &

speed of the electroactive polymer is 1.25 ohm cm. see>

Example 22

Doping and conductivity measurement of poly-2,6- (4-phenylquinoln)

The polymer poly-2,6- (4-phenylquinoline) is doped according to the method described in Examples 3 and 4 made electroactive. However, the conductivity modifier is a 0.1 molar solution of sodium anthracenide in THF. The conductivity of the electroactive polymer

-1 -1
is 15 ohm cm

Example 23

Doping and conductivity measurement of poly-2,6- (4-phenylquinoline)

The polymer poly-2,6- (4-phenylquinoline) is doped according to the method described in Examples 3 and 4 made electroactive. However, the conductivity modifier is a 0.01 molar solution of sodium anthra

Example 24

Doping and conductivity measurement of Polv-2,6- (4 phenylquinoline)
35

cenid in THF. The conductivity of the electroactive poly- '. {

- 1 - 1 ϊί

meren is 15 ohm cm. ;

I t

• · · I

- 73 -

The polymer poly-2,6- (4-phenylquinoline) is according to the in the method described in Examples 3 and 4 doped and made elektroaktiν. The conductivity modifier however, is a 0/005 molar solution of sodium anthracenide in THF. The conductivity of the electroactive

- 1-1 polymer is 2.75 ohm cm.

10 15

25 30 35

Claims (1)

PATBNTAICWAtTB STJROPXAIT VAXBHS ATTOSHBY LEVER DR. WOLPOANO MÜLLER-BORS (PATENT ADVOCATE FROM 1βΖ7 - 1S75) DR. PAUL DCUFEL .. DIPL. · CHEM. DR. ALTRIID SCHÖN. DIPL.-CHEM. WKRNBR HKRTKL, DIPL.-PHYS. C 3363 Chevron Research Company Market Street
San Francisco, Calif. 94105 / USA Electronic polymer Claims ΛElectroactive polymer from a charged polymer backbone of repeating units from a condensed nitrogen containing unsaturated heterocyclic ring system and charge compensating ionic dopants associated therewith. 10 2. Polymer according to claim 1, characterized in that that the repeating units of the charged polymer backbone consist of direstates of condensed six-membered Molecules containing nitrogen. MUNICH M, SIUKRTSTR. 4 POBM0T20 KABKLl MUKBOPAT TKL. (OM) 47400 · TKLKCOMKN XKROX 400 · TKLKX 3. Polymer according to claim 2, characterized in that the Direste have 1 to 6 nitrogen atoms distributed within the condensed six-membered rings, each ring having 3 or fewer nitrogen atoms, which are sequentially bound contains. 4. Polymer according to claim 3, characterized in that the condensed rings contain a nitrogen and are positive direste from quinoling, isoquinoline, 9aH-quinoline and quinolizinium. 5. Polymer according to claim 3, characterized in that the condensed rings contain 2 nitrogen and positive residues of cinnoline, quinazoline, quinoxaline, 2-phenyl-quinoxaline, phthalizine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, 1,8-naphthyridine, 2,6-naphthyridine or copyrin. 6. Polymer according to claim 3, characterized in that * the condensed rings contain 3 nitrogen substances and positive direste of 1,2,3-benzotriazine, 1,2,4-benzotriazine, Pyrido / 3,2-d / pyrimidine, pyrido / 4,3-d7pyrimidine, Pyrido / f3,4-d / pyrimidine, pyrido £ 2,3-d / pyrimldine, PyridoZ2,3-b7pyridazine, Pyrido £ 3,4-b7pyridazine, Pyrido - / "2,3-d7pyridazine as well as pyrido / 3,4-d7pyridazine. 7. Polymer according to claim 3, characterized in that the condensed rings contain four nitrogen substances and positive direste of pyridazino / 4,5-c7pyridazine, Pyrimido / 5,4-d7pyrimidine, pteridine, pyrimido / 4,5-d / pyridazine, Pyrimido / 4 / 5-7pyrimidine, pyrazino / 2,3-b7pyrazine, Pyrazino / 2,3-d7-pyridazine, pyridazino / 4,5-d7-pyridazln, PyrlmidoZ4,5-q7pyridazine, Pyrazino ^, 3-c7 ~ pyridazine, pyrido £ 3,2-d7-v-triazine and pyrido £ 2,3-e7- as-triazine are. ···· III «* !, ff j «I - 3 - 8. Polymer according to claim 3, characterized in that
that the condensed rings contain 5 nitrogen and are positive direstheses of pyrimido / f4,5-e / -as-triazine and pyrimido £ 5,4-d7-v-triazine. 9. Polymer according to claim 3, characterized /
'■ *' that the condensed rings 6 As-triazino / t>, 5-cl7-v- triazine and s-TetrazinoZ * 1/2-a7-s-tetrazine. 10. Polymer according to claim 3, characterized in that
that the repeating units are Direste selected from the group consisting of quinolizinium, 9aH-quinoline, pyridazino ^ O, 2-a7pyridazine, 2H-pyriod / * 1,2-a7pyrazine, pyrido / Ί ^ -a / pyrimidine -S-ium, pyrimido / i / 2-a7pyrimidin-5-ium and pyrazino / 1/2-a7-pyrazine. 11. Polymer according to claim 2, characterized /
that the repeating units are positive dirs of quinoline, isoquinoline, substituted derivatives thereof, or mixtures thereof. 12. Polymer according to claim 11, characterized / that the repeating quinoline and substituted Quinoline units are direste / which are linked to one another at the 2,6 and 3,6 positions, or consist of mixtures of these direstes. 13. Polymer according to claim 11 / characterized in .30 that the repeating isoquinoline and substituted Isoquinoline units Direste, which are connected at the 2,6- \ xnd 3,6-positions, as well as mixtures of these Direste are. 14. Polymer according to claim 11, characterized in that that the repeating units are selected from the group consisting of quinoline or There are quinolindl residues which have a substituent in the 4-position. 15. Polymer according to claim 14, characterized in that that the repeating quinoline and substituted quinoline units Direste attached to the 2,6- and 3,6-positions are connected, as well as mixtures of these direste are. 16. Polymer according to claim 2, characterized in that that the repeating units are selected from the group consisting of isoquinoline residues or Isoquinoline residues with a substituent in the 4-position. 17. Polymer according to claim 16, characterized in that the direst units in the 2,6- and 3,6-position are connected or consist of mixtures thereof. 18. Polymer according to claim 2, characterized in that that the repeating units are quinoline and substituted quinoline, where the Direste are separated by a connecting unit Functions are mixed, or mixtures thereof. and the direstes in the 2,6 and 3,6 positions sell ■ £ 1.9. Polymer according to claim 2, characterized in that the repeating units are isoquinoline residues and substituted dir residues, the dir residues being connected in the 2,6 and 3,6 positions , and mixtures thereof. I. 20. Polymer according to claim 2, characterized in that the repeating units are direste, selected from the group consisting of quinoline, substituted quinoline, isoquinoline, substituted Isoquinoline and mixtures thereof, with the diresthes being linked in the 2,6- and 3,6-positions. 21. Polymer according to claim 20, characterized in that the repeating units of quinoline and isoquinoline residues. 22. Polymer according to claim 20, characterized in that the repeating units of substituted Quinoline and isoquinoline residues exist. 23. Polymer according to claim 20, characterized in that the repeating units of quinoline and substituted isoquinoline residues. 24. · Polymer according to claim 20, characterized in that the repeating units are substituted Are quinoline and substituted isoquinolindl radicals. 25. Polymer according to claim 3, characterized in that the repeating unit of the formula is equivalent to. 26. A polymer according to claims 1, 3, 11, 18, 20 or 23, characterized in that the charge-compensating ionic dopant is a cation which is selected from the group consisting of the alkali metal ions, alkaline earth metal ions ■ Group III Rj ¹ - H ⁺ , R ^xi + i / o) or <^ - N ⁺ - R ^ ¹ 10
“, Where R ^{xi is} a straight-chain or branched one C.-CgT is an alkyl group, and also mixtures of these cations come into question. 27.Polymer from a charged polymer backbone and charge-compensating ionic dopants, associated with the formula j ~ -] (isd) (± S) '- Y ⁿ where a is 0 or 1, b is 0 or 1, c is 0 or 1, η is an integer from 2 to 20,000, d is an integer from 1 to 40,000, s is the integer 1, 2 or 3 denotes, R denotes a condensed nitrogen-containing unsaturated diradical heterocyclic ring system, R ^{1 has} the same meaning as R or denotes another conjugated unsaturated heterocyclic ring system, X denotes a connecting unit, Ϋ the same connecting unit as X or a different connecting unit Denotes unit, and M is a charge-compensating ionic dopant with opposite electrical charge with respect to the charge of the polymer backbone . -7- 28. Polymer according to claim 27, characterized in that R and R ^{1 are} diradicals from condensed six-membered nitrogen-containing units. 29. Polymer according to claim 28, characterized in that R and R ¹ contain 1 to 6 nitrogen atoms which are distributed within the condensed six-membered rings, each ring containing 3 or fewer nitrogen atoms which are sequentially bonded. 30. Polymer according to claim 29, characterized in that R and R ^{1 are} substituted. 31. Polymer according to claim 30, characterized in that R and R ¹ consist of quinoxaline or substituted quinoxaline. 32. Polymer according to claim 30, characterized in that R and R ¹ stand for isoquinoline, an isoquinoline derivative or substituted derivatives thereof and ^{link X and YR and R 1} in the 2,6- and 3,6-positions. 33. Polymer according to claim 32, characterized in that R and R ^{1 is} a 2,6-quinoline of the formula are, R ", R" · and R ^{iv are} substituent groups that 10 15th 34, 20th 25th 30th from H, hydroxy, carboxy, amino, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, Alkylthio with 1 to 4 carbon atoms, dycloaliphatic groups with 5 or 6 carbon atoms, Alkenyl groups with 2 to 4 carbon atoms, aryl groups with 6 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms substituted with 1 to 3 alkyl groups with 1 to 4 carbon atoms, Alkenyl groups with 1 to 4 carbon atoms, alkynyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms, dialkylamino groups with 1 to 4 carbon atoms, alkylthiol groups with 1 to 4 carbon atoms or a 5- or 6-membered group Nitrogen-containing unsaturated heterocyclic group. Polymer according to Claim 33, characterized in that R "and R ^{iv denote} _H. 35. Polymer according to claim 34 _r characterized in that that R "and R ^{iv are} H, a is 1, b is 0, C is 0, X is -CR ^vii = CR ^ ü and the repeating unit of the following formula is equivalent to. 36. Polymer according to claim 34, characterized in that J-ii 35 that R * stands for -COOH, a is 0, b and C are 1, means and the repeating unit of formula is equivalent to. 37. Polymer according to claim 34, characterized in that R ^{111 is} H, a is O, b and C 1 are, Y is a biphenyl dir radical and the repeating unit of the formula is equivalent to. 38. Polymer according to claim 34, characterized in that R ^{iv is} -CH ₃ , a is 0, b and c are 1, Y • f «tr ** · ff · ff · - 10 - and Z represents a linking unit and the repeating unit of the formula is equivalent to. 39. Polymer according to claim 34, characterized in that R ^{111 is} -OH, b is 0, η and c are 1, X - \ _ y— means and the repeating unit the formula is equivalent to. 40. Polymer according to claim 34, characterized in that R "'is phenyl and the repeating unit the formula - 11 - is equivalent to. 41. Polymer according to claim 40, characterized in that R " ¹ stands for phenyl which is substituted in the 4-position by a halogen, and the repeating unit of the formula (Halogen) is equivalent to. 42. Polymer according to claim 40, characterized in that R ¹ "is phenyl, substituted in the 4-position with an OCHj group, and the repeating unit of the formula - 12 - OCH is equivalent to. 43. Polymer according to claim 40, characterized in that that X is -O-, a is 1, b is 1, c is 1, Y is a para-phenyl dir and the repeating Unit of the formula is equivalent to. 44. Polymer according to claim 40, characterized in that a stands for 1, X is a biphenyl dir radical, b is O 1st, c is 1 and the repeating unit of the formula is equivalent to. • ♦ · · - 13 - 10 45. Polymer according to claim 40, characterized in that the nitrogen in R and R ¹ is substituted by a CH ₃ + ion and a and b are O and the repeating unit of the formula 15th is equivalent to. 20 25 30 35 46. Polymer according to claim 40, characterized in that a is O and b and c = 1, R = R ¹ and phenylquinoxaline and Y is is and the repeating unit of the formula is equivalent to. - 0 - 14 - 10 47. Polymer according to claim 27, 33, 34, 40, 41 or 42, characterized in that the connecting units X and Y are selected from the group consisting of -O-; -S-; -CH = CU-; -CHC-; consists, where R ^v , R ^vi and R ^Vii stand for H or methyl, it also being possible for mixtures of these connecting units to be present. 48. Polymer according to claim 47, characterized in that c is O and η is 10 to 20,000. 20th 30th 49. Polymer according to claim 48, characterized in that η means 50 to 5,000. 50. Polymer according to claim 27, characterized in that R and R ^{1 represent} an isoquinoline of the formula R ^x R ^ix viii wherein R ^viii , R ^ix and R ^{x are} a substituted group selected from H, hydroxy, carboxy, amino, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to carbon atoms, a cycloaliphatic Group with 5 or 6 carbon atoms, an alkeny group 32Ί8762 - 15 - 10 15th 20th 25th 30th having 2 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms substituted with 1 to alkyl groups of 1 to 4 carbon atoms, one Alkenyl group having 1 to 4 carbon atoms, an alkynyl group having 1 to 4 carbon atoms, one Alkoxy group with 1 to 4 carbon atoms, 1 to 3 cyano, 1 to 3 halogen atoms, dialky / amino groups with 1 to 4 carbon atoms, an alkylthiol group with 1 to 4 carbon atoms or a 5- or 6-membered nitrogen-containing heterocyclic Group. 51. Polymer according to claim 50, characterized in that the connecting units X and Y from the Group consisting of -0-, -S-, -CH = CH-, -C = C-, -CR ^vii = CRÜÜ or where R ^v , R ^v and R ^{vil are} H or methyl, mixtures of these connecting units also being possible. 52. Polymer according to claim 27, 30, 31, 32, 50 or 51, characterized in that a is 1, b and c are O and the repeating unit of the formula 35 is equivalent to. • Si ···· - 16 - 53. Polymer according to claim 27, 30, 31, 32/50 or 51 / where a, b and c stand for O and which are repeated lende unit of the formula is equivalent to. 54. Polymer according to claim 50 or 52 / characterized / that c is O and η is 10 to 20,000. 55. Polymer according to claim 54 / characterized / that η is 50 to 5,000. ¹ S 56. Polymer according to claim 27, 30/31, 32, 46 or 50, characterized in that the charge-compensating ionic dopant is a cation selected from the group / consisting of the alkali metal ions, Alkaline earth metal ions, Group III or 20 metal ions R ^ ¹ —N ⁺ , R * i + N ^ c) and ^ 5) —N ⁺ R ^ ¹ xi
where R is a straight-chain or branched Cj-Cg-alkyl group, mixtures of these cations also being possible. 57. Polymer made from repeating units of the formula 30 tit, ι ι f «···» · 'rl » - 17 - OO wherein R is C ₁ -C ₄ -AlkOXy or a halogen.