Synthesis of new ferrocene-containing polymers

Abstract

Six new polymers based on ferrocene and its derivatives have been synthesized and their electrophysical properties investigated. The polymers were prepared by various methods. In polymerization of acetylferrocene oxime and difulvene of 1,1′-diacetyl-ferrocene the yield of polymers was 90%. In the direct interaction of ferrocene and hexamethylene diisocyanate, poly(ferrocenylene polyamide) resulted in 73% yield. The polycondensation of ferrocene both with phthalic anhydride and with carbamyl chloride, and that of acetylferrocene with ammonium bicarbonate, in the presence of zinc chloride gave new ferrocenic polymers with a system of conjugated bonds. All produced polymers were coloured powders partly soluble in organic solvents. In the direct interaction of ferrocene and carbamyl chloride (in the form of a complex with zinc chloride) (poly-(ferrocenyl nitrile), not described previously, has been obtained. By polycondensation of acetylferrocene and ammonium bicarbonate the insoluble polymers and oligomer of molecular weight 480 and m.p. 145-150°C. containing two hydroxy groups have been prepared. The presence of CN bonds in poly(ferrocenyl nitrile) and the products of polycondensation of acetyl- and 1,1,-diacetylferrocene with ammonium bicarbonate has been confirmed by the complexing effect of CN bonds with a silver salt. Silver extraction due to the complex formation has been 0.62 g./g. of the polymer. The prepared polymers produced a narrow one-component signal in the ESR spectrum at spin concentration of 10−7–1019 spins/g. which confirms the presence of conjugated double bonds in the polymers. The electrical conductivity temperature plot obeyed the exponential law. The values of conductivities were 11−12 to 10−8 ohm−1-cm.−1, and activation energies—0.72-0.049 e.v.