Electrically conductive composition of polyheteroaromatic compounds and polymeric sulfates

Abstract

A composition comprising (a) at least one oxidized polycationic polyheteroaromatic compound and (b) at least one polyanion of a film-forming thermoplastic polymer containing sulfated alcohol groups ##STR1## in repeating structural units. The composition has high electrical conductivity and good mechanical properties, especially after drawing at temperatures below the melt/decomposition temperature. The material may be used as electrodes, electrically conductive filaments or components for electromagnetic screening.

What is claimed is: 
     
       1. .[.A.]. .Iadd.An electrically conductive polymer .Iaddend.composition comprising .[.(a).]. at least one .[.oxidized.]. polycationic .Iadd.polymer and at least one polyanionic polymer, wherein the polycationic polymer is prepared by electropolymerizing, in a solution with the polyanionic polymer, a monomer selected from the group consisting of aniline, a 3-C 1  -C 12  alkyl-substituted aniline and a .Iaddend.polyheteroaromatic compound which has 5- or 6-membered rings containing 1-3 heteroatoms selected from the group consisting of --O--, --S-- and --N---.Iadd., which rings are either unsubstituted or substituted on the carbon atoms with C 1  -C 16  alkyl .[.or at least one oxidized polycationic aniline or a 3-C 1  -C 12  alkyl-substituted oxidized polycationic aniline.]..Iadd.; .Iaddend.and   .[.(b) at least one polyanion of.]. .Iadd.the polyanionic polymer is .Iaddend.a film-forming thermoplastic polymer containing sulfated alcohol groups ##STR43## in repeating structural units.Iadd., .Iaddend.having a glass transition temperature of -100 to +350° C. and a tensile strength of 5 MPa to 1000 MPa.Iadd., the polyanionic polymer being selected from the group consisting of polyesters, polyester amides, polyurethanes, polyamides, polycarbonates, polyimides obtained from hydroxyl-containing monomers, saponified polymers of vinyl esters and ethers, hydroxylated polybutadiene, polyisoprene or polychloroprene, polyacrylates or polymethacrylates containing hydroxyl groups in the ester moiety, polysiloxanes containing hydroxyalkyl groups or reduced polyketones, polyadducts of glycidyl compounds containing on average more than one epoxy group with a diol, and copolymers thereof.Iaddend..   
     
     
       2. A composition according claim 1, wherein the polyheteroaromatic compound is formed from 5- or 6-membered rings which contain 1 to 3 hetero atoms selected from the group consisting of O, S and N, and the carbon atoms of which are unsubstituted or substituted by C 1  -C 16  alkyl. 
     
     
       3. A composition according to claim 2, wherein the 5- 6-membered ring is selected from the group consisting of pyrrole, thiophene, furan, 2,2'-bipyrrole, 2,2'-bithiophene, 2,2'-bifurane, thiazole, oxazole, thiadiazole and imidazole. 
     
     
       4. A composition according to claim 2, wherein the polyheteroaromatic compound is formed from a pyrrole of formula ##STR44## wherein R 1  and R 2  are each independently of the other hydrogen or C 1  -C 6  alkyl. 
     
     
       5. A composition according to claim 1, which contains 0.1 to 0.5 structural units containing sulfated alcohol groups ##STR45## per structural unit of the polyheteroaromatic compound. 
     
     
       6. A composition according to claim 5, which contains 0.2 to 0.4 structural units containing sulfated alcohol groups. 
     
     
       7. A composition according to claim 1, wherein the thermoplastic polymer containing sulfated alcohol groups ##STR46## salt form has a Tg of -100 to +350° C., and M⊕ is an alkali metal cation or an ammonium cation. 
     
     
       8. A composition according to claim 7, wherein the Tg if -50° to +250° C. 
     
     
       9. A composition according to claim 1, wherein the ratio of free alcohol groups to sulfated alcohol group ##STR47## in the thermoplastic polymer is 50:1 to 1:50. 
     
     
       10. A composition according to claim 9, wherein the ratio is 10:1 to 1:10. 
     
     
       11. A composition according to claim 1, wherein the .[.thermoplastic.]. .Iadd.polyanionic .Iaddend.polymer is an at least partially sulfated polyadduct of a) a glycidyl compound containing on average more than one epoxy group and b) a diol which contains ##STR48## groups in the polymer chain. 
     
     
       12. A composition according to claim 11, wherein the polyadduct contains a) 100 to 5 mol % of identical or different structural units of formula I ##STR49##  and b) 95 to 9 mol % of identical or different structural units of formula II ##STR50##  based on said polyadduct in which formulae (I) and (II) above R 3  and R 4  are each independently of the other the radical of a diol containing aliphatic or aromatic diol groups which radical is diminished by two hydroxyl groups, and R' is hydrogen, C 1  -C 20  alkyl, C 1  -C 20  acyl or aminocarbonyl which is substituted by a C 1  -C 20  hydrocarbon atom.   
     
     
       13. A composition according to claim 12. wherein R 3  and R 4  are each independently of the other a radical of formula III ##STR51## wherein X is a direct bond, C 1  -C 4  alkylene, C 2  -C 12  alkylidene, C 5  -C 8  cycloalkylidene, --O--, --S--, --SO--, SO 2  --, --CO--, --CO 2 , --N(C 1  -C 4  alkyl) or --Si(CH 3 ) 2 , R 5  and R 6  are each independently of the other hydrogen, halogen, C 1  -C 4  alkyl, or C 1  -C 4  alkoxy, and x is 1 or 2 and y is 0 or 1. 
     
     
       14. A composition according to claim 12, wherein R 3  and R 4  are the radical ##STR52## 
     
     
       15. A composition according to claim 1, wherein the .[.thermoplastic.]. .Iadd.polyanionic .Iaddend.polymer is an at least partially sulfated homopolymer or copolymer of acrylates or methacrylates containing a ##STR53## group in the ester moiety. 
     
     
       16. A composition according to claim 15, wherein the .Iadd.polyanionic .Iaddend.polymer contains a) 100 to 5 mol % of identical or different structural units of formula IV ##STR54##  and b) 95 to 0 mol % of identical or different structural units of formula V ##STR55##  based on .[.said.]. .Iadd.the polyanionic .Iaddend.polymer, in which formulae (IV) and (V) R 7  is hydrogen or methyl, R 8  is linear or branched C 2  -C 18  -alkylene, poly(C 2  -C 6  oxaalkylene) containing 2 to 6 oxaalkylene units, C 5  -C 8  cycloalkylene, phenylene, benzylene or xylylene or is the group ##STR56##  Y is --O--, ##STR57##  or --N(C 1  -C 4  alkyl) and R 12  is C 1  -C 18  alkyl, C 5  -C 7  -cycloalkyl, (C 1  -C 12  alkyl)-C 5  -C 7  cycloalkyl, phenyl, (C 1  -C 12  alkyl)phenyl, benzyl or (C 1  -C 12  alkyl)benzyl, R 9  is hydrogen, C 1  -C 6  alkyl, --COOR 12  or --COO⊖, R 10  is hydrogen, fluoro, chloro, cyano or C 1  -C 6  alkyl, and R 11  is hydrogen, fluoro chloro, cyano, R 12  is --O--, C 1  -C 12  alkyl, --COO⊖, --COOR 12 , --COOR 8  --OH, --OCO--R 12  or phenyl, where R 9  and R 12  have the given meanings.   
     
     
       17. A composition according to claim 16, wherein the polymer contains structural units of formula IV in which R 7  is hydrogen or CH 3 , and R 8  is linear or branched C 2  -C 6  alkylene, cyclopentylene or cyclohexylene, and structural units of formula V wherein R 9  is hydrogen, R 10  is hydrogen or methyl, and R 11  is --COOR 12  or --COOR 8  --OH. .Iadd. 
     
     
       18.  A composition as set forth in claim 1 wherein said polymer is a copolymer containing moieties which are residues of saponified vinyl esters or ethers, acrylates or methacrylates containing hydroxyl groups in the ester moiety, or hydroxylated butadiene, isoprene or chloroprene; wherein the monomer has been further copolymerized with a different comonomer selected from the group consisting of acrylonitrile, olefins, diolefins, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene, α-methylstyrene, maleic anhydride, maleimide, vinyl ethers and vinyl esters. .Iaddend. .Iadd. 
     
     
       19.  A composition as set forth in claim 1 wherein the polyimide contains residues from hydrogenated ketotetracarboxylic acids. .Iaddend.