Process for the preparation of an electrically conductive composition of polyheteroaromatic compounds and polymeric sulfates

Claim 2

A process for preparing a conductive film or filament, which comprises increasing the electrical conductivity of said film or filament by drawing said film or filament, at a temperature below the melting and decomposition temperatures of said film or filament, sufficiently to increase the electrical conductivity of said film or filament, said film or filament having 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 of the formula ##STR42## in repeating structural units.

Claim 3

A process according to claim 1, wherein drawing is effected at a temperature which is in the range of 20° C. below or above the glass transition temperature.

Claim 4

A process according to claim 1 wherein the electrical conductivity is increased by a factor of greater than 1.5 relative to the starting composition.

Claim 5

A process according to claim 1, wherein the drawing operation is carried out to an extent of 20 to 100% of the original length.

Claim 6

A process according to claim 1, wherein the film-forming thermoplastic polymer containing sulfated alcohol groups is selected from the group consisting of polyesters, polyester amides, polyurethanes, polyamides, polycarbonates and polyimides obtained from hydroxy-containing monomers; saponified polymers of vinyl esters and ethers; hydroxylated polybutadiene, polyisoprene and chloroprene; polyacrylates and polymethacrylates containing hydroxyl groups in the ester moiety; polysiloxanes containing hydroxyalkyl groups or reduced polyketones and copolymers thereof; copolymers of vinyl alcohol; acrylates or methacrylates or diolefins with comonomers selected from acrylonitrile, olefins, diolefins, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene, α-methylstyrene, maleic anhydride, maleimide, vinyl ethers and vinyl esters; polyadducts of glycidyl compounds containing on average more than one epoxy group with a diol, and polyimides of hydrogenated ketotetracarboxylic acids.

Claim 7

A process according to claim 5, wherein the film-forming thermoplastic polymer containing sulfated alcohol groups is selected from the group consisting of hydroxylated polybutadiene, polyisoprene and chloroprene.

Claim 8

A process according to 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, the carbon atoms of which are unsubstituted or substituted by C 1 -C 6 alkyl.

Claim 9

A process according to claim 7, wherein the 5- 6-membered ring is selected from the group consisting of pyrrole, thiophene, furan, 2,2'-bipyrrole, 2,2'-bithiophene, 2,2'-bifuran, thiazole, oxazole, thiadiazole and imidazole.

Claim 10

A process according to claim 7, wherein the polyheteroaromatic compound is formed from a pyrrole of the formula ##STR43## wherein R 1 and R 2 are each independently of the other hydrogen or C 1 -C 16 alkyl.

Claim 11

A process according to claim 1, wherein the thermoplastic polymer contains 0.1 to 0.5 structural units containing sulfated alcohol groups ##STR44## per structural unit of the polyheteroaromatic compound.

Claim 12

A process according to claim 10, wherein the thermoplastic polymer contains 0.2 to 0.4 structural units containing sulfated alcohol groups.

Claim 13

A process according to claim 1, wherein the thermoplastic polymer containing sulfated alcohol groups ##STR45## in salt form has a Tg of -100° to +350° C., and M.sup.⊕ is an alkali metal cation or an ammonium cation.

Claim 14

A process according to claim 12, wherein the Tg is -50° to +250° C.

Claim 15

A process according to claim 1, wherein the ratio of free alcohol groups to sulfated alcohol groups ##STR46## in the thermoplastic polymer is 50:1 to 1:50.

Claim 16

A process according to claim 14, wherein the ratio is 10:1 to 1:10.

Claim 17

A process according to claim 1, wherein the thermoplastic 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 ##STR47## groups in the polymer chain.

Claim 18

A process according to claim 16, wherein the polyadduct contains a) 100 to 5 mol % of identical or different structural units of formula I ##STR48## and b) 95 to 0 mol % of identical or different structural units of formula II ##STR49## 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.

Claim 19

A process according to claim 17, wherein R 3 and R 4 are each independently of the other a radical of formula III ##STR50## 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.

Claim 20

A process according to claim 17, wherein R 3 and R 4 are the radical ##STR51##

Claim 21

A process according to claim 1, wherein the thermoplastic polymer is an at least partially sulfated homopolymer or copolymer of acrylates or methacrylates containing a ##STR52##

Claim 22

A process according to claim 20, wherein the polymer contains a) 100 to 5 mol % of identical or different structural units of formula IV ##STR53## and b) 95 to 0 mol % of identical or different structural units of formula V ##STR54## based on said 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 ##STR55## where Y is --O--, --OCO-- 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.sup.⊖, 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.sup.⊖, --COOR 12 , --COOR 8 --OH, --OCO--R 12 or phenyl, where R 8 and R 12 have the given meanings.

Claim 23

A process according to claim 21, 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.