JPS61502261A - Copolymers and polymer blends of polymers with π-conjugated systems - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] "Copolymers and polymer blends of polymers with π-conjugated systems" The present invention relates to copolymers and polymer blends having π-conjugated systems, methods for their production, and their applications.

Polymers with π-conjugated systems that become conductive after doping, i.e. oxidation or reduction can also be considered redox-active polymers. In these things, Oxidation or reduction means the removal of electrons or the donation of electrons in the π-electron system of the main chain.

The resulting charge is localized over a wide region of π-conjugation. these charges can move, i.e. jump around, both along and between the main chains, and therefore Electronically speaking, it is a doping agent that acts to cause charge transport and conduction when an electric field is applied. The semiconductor or insulator band structure of the unpinned polymer is We move on to the band structure of the metal, which is expanded at the Lumi limit and the band is partially filled. Structure Structurally speaking, in this case they align to form hard microcrystalline regions; It is detrimental to the mechanical and processing properties typical of all artificial resins.

This type of intrinsically conductive polymer does not dissolve or melt, but remains in the form it assumes after doping. It is applied in Therefore.

To obtain mechanically useful and processable conductive polymers, polymers with π-conjugated systems is cut with an ordinary macromolecule with movable soft segments to create a block copolymer. - or graft copolymers or polymer blends. Good electrical conductivity combined with mechanical properties and processability make common polymer matrix It is always obtained when the conductive component is distributed as uniformly as possible in the this kind of Copolymers and polymer blends of polyacetylene are already known (Ca lvin and Wnek, J, ar Polym-Set, Pol ym.

Chew, EC, 21, 2727 (1983); Lee and Jopgo n, MakromCbem, Rapid Commun, 4, 375 (1 983)), these contain only 5% of pure polyacetylene at most. A conductivity value that is one or two orders of magnitude smaller than that of . However, oxidative The conductive polyacetylene doped with It has the disadvantage of decomposing and thereby losing its conductivity.

The problem underlying the present invention is to create an intrinsically conductive polymer that is stable and has as good processability as possible. In manufacturing.

This problem has been solved by the present invention, which includes a polymeric component (A) without a π-conjugated system and a π-conjugated system. consisting essentially of a polymeric component (B), in which component A is oxidized or reduced. It must have a sufficient activation potential for oxidation or reduction of component B in its original state. and copolymers and polymer blends.

In the inventive method of producing such copolybodies and polymer blends, refers to redox-active compounds with polymerizable substituents, which are not known per se. be homopolymerized or copolymerized by a method that They are combined by a chemical reaction. With the poly thus obtained, the component A is itself or with the monomers forming component B. , chemically or electrochemically oxidize or reduce. Dependent claims No. 14 to Section 24 describes a preferred variant of this method.

The copolymers and polymer blends of the invention can be used in particular as conductors or semiconductors. In photovoltaic cells, the antistatic finish of artificial resins has a low surface resistance suitable for capacitive scanning. As an electromagnetic barrier material, as a battery electrode, as an electrode material. , and as membranes for electrochemical and fuel cells.

According to the invention, polypyrroles, polythiophenes and substituted polypyrroles, substituted derivatives thereof such as substituted polythiophenes, aromatic rings and pyrrole structural units and or For polymers made from thiophene structural units and oxidative polymerization of aniline. The polyaniline thus obtained can be mixed with a wide range of non-conductive polymers (σ≦I O-8 8ac) and can be processed into copolymers or polymer blends. Almost All common polymers, especially those with flexible and highly mobile chain structures can be processed into conductive artificial resin as a copolymer with polypyrrole. . A prerequisite for this is the presence of a redox-active group, which has a side chain It may be attached as a substituent, or it may itself be difunctional. - may be polymerized and incorporated into the main chain as a redox-active group. is oxidized and reduced again with a high degree of reversibility, and its oxidation potential is that of a π-conjugated system. Of particular interest are those that are slightly above the oxidation potential of polymers with . polypyro polyaniline, and polymers composed of alternating aromatic and pyrrole rings. For Rimmer, this condition means dicyclopentadienyliron, or ferrocene. It is satisfied by the complex. The ferrocene complex has a voltage of about 0.4 to 0.5 V with respect to SCH. is reversibly oxidized and in that form has the aforementioned π-conjugated system as a 7-erithenium salt. Polymers can be oxidized to make them conductive.

For example, polypyrrole has a score of 10 for SCE. Polyaniline with an oxidation potential of 2v is 100, the reaction with a ferricenium salt bound to a polymer has an oxidation potential of IV. In the reaction, electrons are transferred to ferrocene and anions are transferred to the polymer containing the π-conjugated system.

Similarly, ferrocene as a redox-active group In a polymer blend consisting of lineaphthalene pyrrole, electricity is also applied to a non-conductive part. It allows for molecular and ionic movement and is bonded to freely accessible parts of the conductive component. It works to quickly and uniformly dope uncontained conjugated polymers.

For the present invention, ferrocene is added to the side chain of a common polymer via or by a 5M substituent. It is important that it is directly bonded to the cyclopentadienyl ring as a substituent.

Alternatively, disubstituted ferrocene monomers can be synthesized by polycondensation, polyaddition reactions, or Polymers attached in the main chain by aromatic substitution on the cyclopentadienyl ring It is important that The bond as a side chain substituent is 1, for example, polyvinyl chloride, Polybutadiene, polyacrylic ester, polymethacrylic ester, anhydrous polymer Leic acid and styrene copolymer, butadiene and styrene copolymer, chloro Methylated polystyrene, etc., and AfLCl. and unsubstituted ferrocene were reacted. This is possible by setting Percentage of ferrocene, A20 sentence. Addition amount, temperature, reaction Depending on the processing method, a lightly substituted non-crosslinked polymer or a highly substituted A crosslinked polymer is obtained. The ferrocene bond is attached to the polymer p-aminostyrene. was diazotized and then reacted with 7-erocene or ferricenium salt to produce For example, polyvinyl alcohol and partially hydrolyzed polyvinyl acetate or polyvinyl butyral, as well as poly(l-hydroxy Propene-(2)), polyhydroxyethyl acrylate or polyacrylic acid hydro Xypropyl or equivalent polymethacrylic acid esters and their co-products Polymer, poly(l-amino-propene-(2)), poly(α-7 minostyrene ), poly(p-amino-styrene), poly(p-amino-α-methylstyrene) , polyvinylamine and their copolymers, and aminopropyl-triethyl -NH2 or -OH functional polymers such as toxysilane and cyclohexane O oligomers. This is also possible by reaction of a reamer with a ferrocene carboxylic acid chloride.

Copolymers with substituents that are carboxylic acid chlorides, sulfonic acid chlorides or anhydrides It is also possible to combine hydroxyalkylferrocenes into copolymers of acrylic acid. Esterification with hydroxyalkylferrocenes is also possible.

Introduction of ferrocene molecules into the side chains of polymers containing bound polymerizable substituents Homopolymerization or copolymerization of the monomers is also successful. What is used for this is For example, vinylferrocene, divinylferrocene, ferrocenylmethacrylate ferrocenyl methyl acrylate, ferrocenyl methyl acrylamide, ethyl Nylferrocene, p-ferrocenylstyrene, p-7 erocenylphenylacetylene Ren et al.

The attachment of ferrocene into the main chain can be achieved, for example, by polycondensation or polyaddition of suitable substituents. It can be caused by a reaction.

For example, monomers or prepolymer terminals substituted with diamino or dihydroxy groups. Limer, ferrocene dicarboxylic acid, ferrocene dicarboxylic acid ester, ferrocene dicarboxylic acid, ferrocene dicarboxylic acid ester, ferrocene dicarboxylic acid, Sendicarboxylic acid chloride, ferrocene diincyanate, or ferrocendial Possible by reaction with kyloxirane.

On the contrary, dihydroxyalkylferrocene can be combined with monomers that are dicarboxylic acids or Reacts with oligomers that are diisocyanates or prepolymers that are epoxy resins This creates a polymer with a ferrocene complex in its main chain.

Like ferrocene, it binds to the polymer button via a ligand and exhibits reversible redox behavior. transition metal complexes such as Fem/■, Co■/■, and Ru■/■ can be used in the present invention.

This includes, for example, poly(4)-(or -2-)-vinylpyridine or polyvinylpyridine. There are iron salts, cobalt salts, and ruthenium salts complexed with bipyridine. binds to the polymer combined salicylic acid metal salts, metal salicylaldehyde complexes, metal salicylaldehyde Hydroimine complexes, Pfeiffer complexes complexed with amino acids, etc. are also used according to the present invention. It can be suitably used. Polymer-bound metal oxinate, glyoximic acid Metal salts, porphyrin metal complexes, and metal phthalocyanine complexes are preferably used.

In this context, anodic polymerization products of virol and tetrasulfonated Phthalocyanine iron complexes are known (R, A, Bull, F, A, F an, A, J, Bard, J, Electrochem, Sac, ABG 1838.1983), but in these complexes, the redox The active complex is incorporated into a linear polypyrrole and attached to another ordinary polymer. It is not combined with -.

According to the invention, polymers with organic groups that can be reversibly oxidized and reduced can also be copolymerized. 9 which can be used to make remers or polymer blends, e.g. hexamethylene Reacted with diamine to produce benzoquinone main chain polymer, Tokuto H61-502261 (5) or react with poly-p-7 minostyrene to form a benzoquinone side chain polymer. in the main chain or side chain, such as polybenzoquinone tetracarboxylic anhydride, which is converted into Polymers with chimade systems are particularly used.

To combine the redox-active polymer with a polymer having a π-conjugated electron system, Adjustment of oxidation potential and reduction potential is important.

The electroactive state of polymers with isolated redox-active groups is If the oxidation potential of the polymer is lower than that of the copolymer, or if its reduction potential is It is only used if it is higher than that of copolymers.

Polymers with redox-active groups can form conjugated polymers in their oxidized state. It must be able to oxidize and therefore become electronically conductive, but in its reduced state It must be able to reduce polymers with π-conjugated systems.

Therefore, ferrocene bound to a polymer can be Copolymers or polymer blends for polypyrrole that can be made electrically conductive It can be ideally used as The preparation of this kind of polypyrrole polymer blend is 1 In the present invention, the dissolved or swollen ferrocene polymer throat roll is uniformly This occurs by 7-node or chemical oxidation of the mixture. Electrochemically , first, the heptadrocene structural unit receives a positive charge at a potential of +4 to 0.6 V with respect to SCH. It is oxidized to the ferricene structural unit. On the other hand, 0.9 to 1. In IV Polymerization of virol occurs. When polypyrrole reaches a certain conjugated length, Immediately oxidized by ferricene to conductive form under electron and ion transfer . The uniform distribution of ferrocene in the matrix of common polymers This is also a precondition for a uniform distribution of rules. About 4 to 8 mol% of polypyrrole To obtain an intestinal conductivity of 10-2 to 1 s/c with a similar distribution, about 5% by weight A 7-erocene content of 1 to 2 mol % is thus sufficient.

In the present invention, the content of redox active ingredient and portion of conductive polymer ranges from about 1 to It can vary within wide limits of 9 mol%. For electrochemical production, water-soluble tetraalkyl Acetonitrile, propylene with a small amount of water containing ammonium or lithium salts Ren carbonate, nitromethane, dioxane, 1. ? -dimethoxyethane, N -Solvents such as methylpyrrolidone, EMPT and others are suitable. Even from acidic aqueous solutions, Roll polymerization and polymer blend production can be carried out. anion is acid It must be stable under natural conditions, and cannot be smaller than a certain size. , what can be used.

For example, BF, C sentence 0. AsF-5SbF, PF-1Sb(4, No-1ReO -1T　a　F　e, H5O, also benzenesulfonic acid anion or alkali According to the present invention, the ferrocene polymer and the polypyrochloride anion are Polymer blends of polymers are also produced by chemical oxidation. Chemical oxidation is pure Occurs in organic solutions or dispersions, or in aqueous-organic solutions or dispersions. this FeC1 or Fe(C1O)-9H20 is suitable for this purpose, but dichromate Or other oxidizing agents such as H2O2 solutions are also suitable.

The chemical reaction of the ferrocene polymer pyrrole mixture is carried out in acetonitrile or in methyl chloride. Preferably it proceeds in a two-phase ren-water system.

A particular variant of the invention is that during the oxidation, the charge of the oxidized ferrocene and the polypyrrole The charge of ferrocenyl can be offset by the acid anion of the polymer When using a copolymer having a substituent and a carboxylic acid substituent or a sulfonic acid substituent, According to the present invention, this offset is achieved by oxidation with iron acetylacetone (I[I) or is achieved by electrochemical oxidation. In that case, proton and electron respectively is extracted from the polymer.

Poly-bonded ferrocene is for polypyrrole and polyaniline has a sufficiently high oxidation potential, but has a higher electrochemical potential for polythiophenes. iron (III) complex, cobal) (III) M form or ruthenium (m) complex is necessary. The same <, N-substituted virols can be satisfactorily co-coated for the first time with these complexes. Finished as a polymer or polymer blend. For processing method, in this case The same is true for the production of polymer blends of polypyrrole and 7-erocene polymers. The copolymers and polymer blends of the present invention have good mechanical properties and It has a practical nature. They can also be processed when produced from solution or thermoplastic. It can also be shaped into various shapes by plasticity. Adjust the copolymer and ferrocene content. With proper selection, it is possible to produce molded bodies with smooth, highly conductive surfaces. I can do it. Therefore, the molded article according to the present invention can be used electrically, optically, or electrically It can be used for quantitatively scanning surface structures. In addition, carbon fiber Covered with artificial resin filled with rack or metal.

Another important application is the use of copolymers according to the invention as electrodes in batteries or fuel cells. It is to use it. These are highly reversible redox systems and conductive polyesters. It is obtained by combining mer. Oxidation cycle of redox active ingredients and reduction cycles can be ideally used for electrochemical storage purposes. . Electrochemical catalysis can be used in fuel cells, but on the other hand, it is The possibility of use as a chemical catalyst also holds true; other possible applications include Antistatic finishing of electrical conductors or semiconductors, electromagnetic shielding materials, solar cells 2 and artificial resins It is ge.

Example 1 a) Preparation of ferrocenyl butadiene Dissolve 8.5 g of ACl in 200 m of dichloroethane and then Put 48.5g of ferrocene into the container and dissolve in 200m, JL dichloroethane. 54 g of Lithene PM (manufactured by metallgesellschaft) paid in full. After stirring for 2 hours at room temperature, the reaction mixture was dissolved in )ICi methanol solution 6 Injected into 00 mJl. The obtained polymer was filtered, washed and dried. At first The crude polymer was oxidized with FeCl3 in nitromethane, washed and then Used for blend production.

b) Reaction with virol Oxidized ferrocenyl butadiene was swollen with virol in dichloroethane. , followed by a two-phase reaction with a small amount of an aqueous solution of iron perchlorate (m). obtained The polymer blend was precipitated with methanol, washed and dried. The product is thermoplastic It showed moldability and elastic behavior due to plasticity. Electrical conductivity: 10-2sac■a] Hue Preparation of rosenyl polystyrene 6 g of poly-p-aminostyrene suspended in 100 ml of 10% sulfuric acid aqueous solution and mixed with 4.2 g of an aqueous solution of sodium nitrite. Obtained dianium salt A reddish brown aqueous solution of It was poured into a solution of 300ml of water while stirring. Next, stir at room temperature for 6 hours and filter with suction. Separated, washed and dried. Yield: 9.1g b) Reaction with virol 3 g of ferrocenyl polystyrene was mixed with 1.1 g of virol in acetonitrile. 17.2 g of iron (III) perchlorate was dissolved in 25 ml of acetonitrile. The oxidized solution was added to the full amount and oxidized.

The product was introduced into 500 ml of methanol and filtered off with suction until the filtrate became colorless. I washed it with

Yield after drying: 4.4 g, conductivity: 1 s/cm Example 3 3 g of poly-(4-vinylpyridine) iron chloride ([II) complex was added to 1.28 g of filtrate. Mix in acetonitrile with lithium chlorate and 1.07 g throat roll. , by the full amount of 5.2 g of iron chloride (m) dissolved in 20 mjL of acetonitrile. The precipitated polymer product was filtered off with suction and treated with acetone and 2fL of CHC. Washed and dried. Yield 3.85g, conductive @: 8 x 10-”s/am fruit Example 4 1.2 g of 7-erocene is dissolved in dichloroethane with 1 g (1) AlCl2. , mixed with 6 g of polymethacrylic acid ethyl ester in dichloroethane for 1 hour. Heated under reflux. After cooling, pour into ice water and acidify with 4 dilute hydrochloric acid, then separate and filter. The organic phase was separated with a funnel and concentrated by evaporation. Polymer by injection into methanol was precipitated, washed with methanol, and dried.

6 g of ethyl ferrocenyl methacrylate with 1 g of virol in acetonitrile Dissolve in F e (Cl 04) 310% acetonitrile solution, and Mix until there is no visible reaction. Polymer by injection into methanol The product was precipitated, washed and dried.

Yield near, 2g, conductivity: 0.2g/cm, this material can be elastically deformed, thermoplastic Processing based on gender was possible.

and the seal 5% vinyl ferrocene, 90% acrylic acid ethyl ester, and 5% acetic acid. Acrylic acid was copolymerized with 0.5% AIBN at 82°C. The obtained polymer Iron perchlorate (m) dissolved in acetonitrile and mixed with 10% by weight of virol 10% acetonitrile solution. Injecting the product into methanol It was precipitated by Washed with water and ethanol and dried. Conductivity: 0.2s/c m Example 6 4 g of polyvinyl alcohol-vinyl acetal copolymer was added to 40 g of methylene chloride. -CHCl 210 dissolved in a mixture of m, l and 2 g of anhydrous pyridine After addition of 2 g of ferrocenecarboxylic acid chloride dissolved in mλ, at room temperature for 1 h. Stirred. The mixture was then introduced into water and extracted with methylene chloride. f! acid Dry over sodium chloride, filter and remove the solvent to give an amber polymer. It was.

This polymer was dissolved in 250 mu of methylene chloride-acetonitrile 1:1 mixture. While stirring, first mix with 0.5 g of throat roll, then add 10 mJ1 of acetate. Mixed with 38 g of Fe(cxO4) dissolved in nitrile.

A black solution was obtained from which the copolymer gradually precipitated. Excluding CHC12 The precipitation was completed when the residue was poured into water. Black polymer - wash the product several times , dried I7. The product polymer is elastic and can be molded and processed by thermoplastics. We were able to.

Electrical conductivity:, 0.85/C international search report

Claims (25)

[Claims] 1. Substantially, a polymer component (A) that does not have a π-conjugated system and a polymer component that has a π-conjugated system component (B), and component A is composed of component B in an oxidized or reduced state. A copolymer containing redox-active groups with sufficient activation potential for oxidation or reduction. polymers and polymer blends. 2. Component A is bonded as a redox active group in the main chain and/or in the side chain. characterized in that it contains a sigma complex, a π complex or a chelate, preferably of a transition metal. , copolymers and polymer blends according to claim 1. 3. As transition metal complexes, FeIII/n complexes, CoIII/II complexes, and or RuIII/II complex, according to claim 1 or 2. copolymers and polymer blends. 4. Claim No. 1, characterized in that it contains a ferrocene complex as the transition metal complex. Copolymers and polymer blends according to one of items 1 to 3. 5. Metal complexes include salicylic acid metal salts, metal salicylaldehyde complexes, and metal salts. ritylaldehyde imine complex, Buffifer complex recomplexed with amino acids, Preferably, Kanaya oxinate, glyoximate metal salt, metal porphyrin complex, gold Claims 1 to 3 are characterized in that they contain a phthalocyanine complex of the genus phthalocyanine complex Copolymers and polymer blends according to one of clauses 3. 6. Component A is present as a redox-active group in the main chain and/or in the side chain and/or as a redox-active group. is characterized in that it contains a quinoid system, preferably benzoquinone, bonded in the side chain. A copolymer and polymer blend according to claim 1. 7. Component A is an anion-forming group, preferably a carboxylic acid group and/or a sulfonate group. Claim No. Copolymers and polymer blends according to one of clauses 1 to 6. 8. As component B substituted or unsubstituted virol, thiophene and or aniline Claims characterized in that homopolymers and copolymers of Copolymers and polymer blends according to one of paragraphs 1 to 7. 9. Component B is -C=C- structural unit, one C≡C- structural unit, -N=N- structural unit , -C=N- structural unit, monocyclic or polycyclic aromatic group, and substituted or unsubstituted biro characterized by being composed of a ring, a thiophene ring and/or an aniline ring. copolymers and polymer blends according to one of claims 1 to 8, Do. 10. As component B, unsubstituted pyrrole polymerized by oxidation is used. Copolymers and polymers according to one of claims 1 to 8, characterized in that Reser blend. 11. As component B, substituted polypyrrole or substituted pyrrole and unsubstituted pyrrole Claims 1 to 8, characterized in that a copolymer of Copolymers and polymer blends as described in one. 12. Pyrrole is an alkyl group, an alkynyl group, and or a 3-position in the N position. an alkyl group, an alkynyl group, an alkoxy group, and a halogen; Substituted with an alkyl group, alkynyl group, alkoxy group, or halogen group at the 3 or 4 position The alkyl group, alkynyl group, and alkoxy group are Claim characterized in that it has 6, preferably 1 to 3 C atoms. Copolymers and polymer blends according to item 11. 13. Redox-active compounds with polymerizable substituents are known as such. homopolymerization or copolymerization using a specific method to obtain a polymer without a π-conjugated system The polymer component A obtained in this way is bonded by a chemical reaction, and The polymeric component B or the substance that forms component B can be mixed with the polymeric component B in a known manner. characterized by mixing with a polymer and then chemically or electrochemically oxidizing or reducing it. Copolymers and polymer blocks according to one of claims 1 to 12, How to make rend. 14. Using a transition metal complex, preferably ferrocene, as redox-active compound 14. The method according to claim 13, characterized in that: 15. As polymeric component B, substituted or unsubstituted polypyrrole, polythiophene or polyaniline, or a copolymer thereof. The method according to claim 13 or 14. 16. In order to produce polymeric component A, unsubstituted ferrocene is combined with a π-conjugated system. Polymers that do not contain polyvinylchloride, polybutadiene, polyacrylic Acid esters, polymethacrylic esters, maleic anhydride and styrene copolymers -, copolymers of butadiene and styrene, or chloromethylated polystyrene according to one of claims 13 to 15, characterized in that the How to put it on. 17. To produce polymeric component A, ferrocene or ferricenium is The claimed invention is characterized in that it is reacted with azotized poly-p-aminostyrene. A method according to one of ranges 13 to 15. 18. To produce polymeric component A, ferrocenecarboxylic acid or ferrocenecarboxylic acid carboxylic acid anhydride or ferrocene carboxylic acid chloride or ferrocene alkyl carboxylic acid anhydride or ferrocene carboxylic acid chloride Rubonic acid or ferrocenealkylcarboxylic acid anhydride or ferrocenealkylcarboxylic acid The carbonic acid chloride is added to a polymer having -NH2 or OH functional groups, preferably polyvinyl chloride. alcohol or copolymers such as partially hydrolyzed polyvinyl acetate or Claim 13, characterized in that it is reacted with polyvinyl butyral. The method described in one of paragraphs 15. 19. To produce polymeric component A, ferrocene with polymerizable substituents , preferably vinylferrocene, divinylferrocene, ferrocenyl acrylic acid ester. Stell, ferrocenyl methacrylate, alkylferrocenyl acrylate ester, alkyl methacrylate ferrocenyl ester, ferrocenyl methyl acetate Acrylamide, ethynylferrocene, p-ferrocenylstyrene, P-ferroce Nylphenylacetylene is converted into ordinary vinyl molybdenum by a method known in the art. According to one of claims 13 to 15, characterized in that the polymer is polymerized with a polymer. Method described. 20. To produce polymeric component A, dihydroxyalkylferrocene is , diisocyanates that are monomers or oligomers or epoxy polymers that are monomers or oligomers. with a dicarboxylic acid monomer or a carboxyl group at the end. Claims 13 to 1 characterized in that the polyester is reacted with a polyester having The method described in one of paragraphs 5. 21. In order to produce polymeric component A, diamino-terminated or dihydrogen-terminated The doxy-substituted monomer or brepolymer is added to ferrocene dicarboxylic acid, Ferrocene dicarboxylic acid ester, ferrocene dicarboxylic acid chloride or other active Ferrocene dicarboxylic acid derivative, ferrocene diisocyanate, or ferrocene Claims 13 to 12 are characterized in that they are reacted with dialkyloxirane. A method according to one of paragraphs 15. 22. Pyrrole, thiophene or aniline is combined with dissolved or swollen component A. Claim No. A method according to one of paragraphs 13 to 15. 23. Polymeric component A is oxidized to form carboxylic acid ions and/or sulfonic acids. Carboxylic acid groups and/or sulfonic acid groups that convert into ions and their acid anhydride groups. 23. Method according to one of claims 13 to 22, characterized in that it comprises: 24. Polymeric component A is oxidized before being combined with polymeric component B. 24. Method according to one of claims 13 to 23, characterized in that: 25. Copolymers and polymer blocks according to one of claims 1 to 12 conductors or semiconductors for antistatic finishing in lenses, solar cells and artificial resins electromagnetic material as a material with low surface resistance suitable for capacitive scanning. As a shielding material, as a battery electrode, as an electrode material, and as an electrical Application as membrane for chemical and fuel cells.