MONOMERS, POLYMERS AND CHARGE-TRANSFER COMPLEXES OF DITHIAFULVENES AND POLYMERS FROM 4,4'-SULFONYL DIPHENOL (2-BENZYLIDENE, 1,3-DITHIOLES, 1,3-DITHIOLIUM).

Abstract

Monomers, polymers, charge-transfer complexes of 2-benzylidene-1,3-dithioles (Dithiafulvenes), and 1,3-dithiolium (Dithiafulvenium) salts of dithioesters and poly(dithioesters) were synthesized. The infrared, nuclear magnetic resonance (NMR) and ultra violet spectra of these materials were also reported. Condensation polymerization of piperidinium tetrathio terephthalate with α-halocarbonyl compounds using phase-transfer techniques yielded poly(dithioesters) that upon dehydrative cyclization with sulfuric acid gave poly(1,3-dithiafulvenium) salts. Polymerization of substituted dithiafulvenes with diacid chlorides, p-phenylene diisocyanate or terephthalaldehyde yielded polymers with inherent viscosities of 0.10 dL/g to 0.21 dL/g. The electric resistivity of the charge-transfer complexes of several dithiafulvenes and the electron donors TCNQ and TNF measured by the two-probe method was found to be >10⁶ Ω.cm at room temperature, hence behaving like insulators. Polyesters and polyesterimides of 4,4'-sulfonyl diphenol were synthesized. The low molecular weight polymers had viscosities of 0.12 to 0.20 dL/g. The polymers formed brittle films and their IR and NMR spectra were reported.