Claims
- 1. 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.
- 2. A process of claim 1 wherein the electrically-conductive polymer composition is prepared by a process which comprises 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.
- 3. A process according to claim 1, wherein R and R.sub.1 in formula II are H.
- 4. A process according to claim 1, wherein in formula II X.sub.1 and X.sub.4 are .dbd.N--CN and X.sub.2 X.sub.3 are .dbd.O or .dbd.N--CN, or X.sub.2 and X.sub.3 are .dbd.N--CN and X.sub.1 X.sub.4 are .dbd.O or .dbd.N--CN.
- 5. A process according to claim 1, wherein X.sub.1, X.sub.2, X.sub.3 and X.sub.4 in formula II are .dbd.N--CN.
- 6. A process according to claim 1, wherein R.sub.2 to R.sub.5 in formula III are identical.
- 7. A process according to claim 1, wherein Y.sub.1 and Y.sub.2 in formula III and IIIa are each --S--.
- 8. A process according to claim 1, wherein R.sub.2 to R.sub.5 in formula III defined as alkyl-(Z.sub.1).sub.n -- are C.sub.1 -C.sub.12 alkyl-(Z.sub.1).sub.n --, wherein Z.sub.1 and n are as defined in claim 1.
- 9. A process according to claim 1, wherein alkyl-(Z.sub.1).sub.n -- is methyl, ethyl, n- and isopropyl, n-, iso- and tert-butyl, methylthio, methylseleno, ethylthio and ethylseleno.
- 10. A process according to claim 1, wherein R.sub.6 in formula IIIa is H or C.sub.1 -C.sub.4 alkyl.
- 11. A process according to claim 1, wherein Z.sub.1 is --S-- and Z.sub.2 is --S-- or --O--.
- 12. A process according to claim 1, wherein the CT complex of formula I is one in which, in formula II, R is H, methyl or ethyl, R.sub.1 is H or methyl and X.sub.1 to X.sub.4 are .dbd.N--CN, and, in formulae III and IIIa, R.sub.2 and R.sub.3 as well as R.sub.4 and R.sub.5 or R.sub.2 to R.sub.5 are identical and are H, linear or branched C.sub.1 -C.sub.8 alkyl-(Z.sub.1).sub.n --, unsubstituted or C.sub.1 -C.sub.4 alkyl-substituted phenyl-(Z.sub.1).sub.n -- or benzyl-(Z.sub.1).sub.n --, or R.sub.2 and R.sub.3 as well as R.sub.4 and R.sub.5 are together, each independently of the other, unsubstituted or C.sub.1 -C.sub.4 alkyl-substituted trimethylene, tetramethylene, --Z.sub.2 --(CH.sub.2)--Z.sub.2 --, --Z.sub.2 --(CH.sub.2).sub.2 --Z.sub.2 --, --Z.sub.1 --CH.dbd.CH--Z.sub.1 -- or --CH.dbd.CH--CH.dbd.CH--, n is 0 or 1, Y.sub.1 and Y.sub.2 are --S--, Z.sub.1 is --S--, Z.sub.2 is --O-- or --S--, Z is --S-- or NR.sub.7, and R.sub.7 is H or C.sub.1 -C.sub.4 alkyl, and R.sub.6 is H or C.sub.1 -C.sub.4 alkyl.
- 13. A process according to claim 12, wherein the CT complex of formula I is one in which, in formula II, R and R.sub.1 are H, X.sub.1 to X.sub.4 are .dbd.N--CN, and in formulae III and IIIa R.sub.2 to R.sub.5 are identical and are H, or are linear or branched C.sub.1 -C.sub.4 alkyl-(Z.sub.1).sub.n --, or R.sub.2 and R.sub.3 as well as R.sub.4 and R.sub.5 are each together trimethylene, tetramethylene, --Z.sub.2 --(CH.sub.2)--Z.sub.2 --, --Z.sub.2 -(CH.sub.2).sub.2 --Z.sub.2 --, --Z.sub.1 --CH.dbd.CH--Z.sub.1 -- or --CH.dbd.CH--CH.dbd.--, n is 0 or 1, Y.sub.1 and Y.sub.2 are --S--, Z.sub.1 is --S--, Z.sub.2 is --O-- or --S--, Z is --S-- or NR.sub.7, and R.sub.7 is H or C.sub.1 -C.sub.4 alkyl, and R.sub.6 is H or C.sub.1 -C.sub.4 alkyl.
- 14. A process according to claim 1, wherein the CT complexes of formula I are those in which A is 5,7,12,14-pentacenetetracyanoimine and B is a compound of formula IIIb ##STR10## wherein Y.sub.1 and Y.sub.2 are each --S--, and R.sub.2, R.sub.3, R.sub.4 R.sub.5 are each independently of one another H, C.sub.1 -C.sub.4 alkyl 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 together are --S--CH.sub.2 CH.sub.2 --S--.
- 15. A process according to claim 14, wherein the CT complexes of formula I are those in which A in formula I is 5,7,12,14-pentacenetetracyanoimine, and B is selected from the group consisting of tetrathiofulvalene, tetramethyltetrathiofulvalene, tetraethyltetrathiofulvalene, dimethyldiethyltetrathiofulvalene, tetra-n-propyltetrathiofulvalene, tetra-n-butyltetrathiofulvalene, tetra(methylthio)tetrathiofulvalene, tetra(ethylthio)tetrathiofulvalene, tetra(n-propylthio)tetrathiofulvalene, tetra(n-butylthio)tetrathiofulvalene, dimethyldimethylthiotetrathiofulvalene, diethyldimethylthiotetrathiofulvalene, diethylthiodimethylthiotetrathiofulvalene and tetraselenofulvalene.
- 16. A process according to claim 15, which contains the charge transfer complex in an amount of 0.01 to 30% by weight, based on the weight of the electrically conductive polymer composition.
- 17. A process according to claim 16, which contains the charge transfer complex in an amount of 0.01 to 10% by weight.
- 18. A process according to claim 1, wherein the thermoplastic polymer is selected from the group consisting of polyolefins, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyacrylates, polymethacrylates, polyamides, polyesters, polycarbonates, aromatic polysulfones, aromatic polyethers, aromatic polyether sulfones, polyimides and polyvinyl carbazole.
- 19. A process according to claim 1, wherein the thermosetting polymer is an epoxy resin.
- 20. A process according to claim 1 which is combined with a shaping process.
Priority Claims (1)
Number |
Date |
Country |
Kind |
242/92 |
Jan 1992 |
CHX |
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Parent Case Info
This is a divisional of Ser. No. 08/007,426, filed Jan. 22, 1993, now U.S. Pat. No. 5,378,744.
US Referenced Citations (9)
Foreign Referenced Citations (3)
Number |
Date |
Country |
285564 |
Oct 1988 |
EPX |
344109 |
Nov 1989 |
EPX |
3437814 |
Oct 1983 |
DEX |
Non-Patent Literature Citations (1)
Entry |
Synthetic Metals, 41-43 (1991) pp. 2365-2375 Stanton Rak et al. |
Divisions (1)
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Number |
Date |
Country |
Parent |
7426 |
Jan 1993 |
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