Mixed (electronic and ionic) conductive solid polymer matrix, 1. Synthesis and properties of poly(2,5,8,11,14,17,20,23‐octaoxapentacosyl methacrylate)‐block‐poly(4‐vinylpyridine)

Poly(2,5,8,11,14,17,20,23‐octaoxapentacosyl methacrylate)‐block‐poly(4‐vinylpyridine) semicomb polymers were synthesized using anionic living polymerization techniques. The polymers are white, powdery materials and were characterized by 1H and 13C nuclear magnetic resonance spectroscopy and gel‐permeation chromatography. The polymers display monomodal molecular weight distributions which are relatively narrow. The block copolymers show microphase separation as indicated by the presence of two glass transition temperatures (Tg), a soft (oxyethylene) phase Tg is observed between −60°C and −45°C and a hard (4‐vinylpyridine) phase Tg is observed between 135°C and 150°C. The soft oxyethylene phase has been doped with LiClO4 to obtain ionic conductors with electrical conductivities around 5 · 10−6 S · cm−1 at 25°C and the hard 4‐vinylpyridine phase has been complexed with 7,7,8,8‐tetracyano‐1,4‐quinodimethane (TCNQ, 2,5‐cyclohexadiene‐1,4‐diylidenedimalonitrile) to obtain electronic conductivities around 10−6 S · cm−1 at 25°C. The mixed (electronic and ionic) conductivities are intermediate between the ionic and electronic conductivities. Higher electronic conductivities (≈ 10−5 S · cm−1 at 30°C) are obtained for the polycation TCNQ−/TCNQ0 complexes.