Synthetic polymer compositions containing charge transfer complexes, their preparation and the use thereof

A process for the preparation of a electrically-conductive polymer composition which polymer composition comprises (a) a thermosetting, thermoplastic or structurally crosslinked polymer and (b) a charge transfer complex of formula I in the form of a network of crystal needles in the polymer matrix

• [A].sup..crclbar. .multidot.B.sup..sym. (I),
• wherein A is a compound of formula II or a mixture of compounds of formula II ##STR8## wherein the R substituents are identical and are H or C.sub.1 -C.sub.4 alkyl, the adjacent R substituents, taken together, are --(CH.sub.2).sub.3 -- or --(CH.sub.2).sub.4 --;
• R.sub.1 is H or C.sub.1 -C.sub.4 alkyl;
• and X.sub.1 is .dbd.N--CN, and X.sub.2, X.sub.3 and X.sub.4 are .dbd.O or .dbd.N--CN, and B is a compound of formula III or IIIa ##STR9## wherein R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently of one another H, linear or branched C.sub.1 -C.sub.18 alkyl-(Z.sub.1).sub.n --, phenyl-(Z.sub.1).sub.n -- or benzyl-(Z.sub.1).sub.n -- which are unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkylthio, R.sub.2 and R.sub.3 as well as R.sub.4 and R.sub.5 are together, each independently of the other, trimethylene, tetramethylene, --Z.sub.2 --(CH.sub.2)--Z.sub.2 --, --Z.sub.2 --(CH.sub.2).sub.2 --, --Z.sub.1 --CH.dbd.CH--Z.sub.1 -- or --CH.dbd.CH--CH.dbd.CH--, each unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkylthio, n is 0 or 1, Y.sub.1 and Y.sub.2 are each independently of the other --S-- or --Se--, Z.sub.1 is --S-- or --Se--, Z.sub.2 is --O--, --S-- or --Se--, Z is --S--, --Se-- or NR.sub.7, and R.sub.7 is H, C.sub.1 -C.sub.6 alkyl, phenyl or benzyl, and R.sub.6 is H, C.sub.1 -C.sub.4 alkyl, phenyl or benzyl, which process comprises:
• (a) blending a CT complex of formula I into a thermoplastic polymer,
• (b) blending a CT complex of formula I with at least one component of a thermosetting or structurally crosslinkable polymer and then polymerising the blend to a thermosetting or structurally crosslinked polymer, or
• (c) dissolving either a compound of formula II or a fulvalene derivative of formula III or IIIa and a thermoplastic polymer or at least one component of a thermosetting or structurally crosslinkable polymer in an organic solvent to form a first solution, dissolving the other of either a fulvalene derivative of formula III or IIIa or a compound of formula II in an organic solvent to form a second solution, mixing the first and second solutions, and removing the organic solvent to yield either the electrically-conductive polymer composition or a curable mixture, which curable mixture is then cured to yield the electrically-conductive polymer composition.