Imidazole-containing triblock copolymers with a synergy of ether and imidazolium sites

Abstract

Reversible addition–fragmentation chain transfer (RAFT) polymerization enabled the synthesis of well-defined A–BC–A triblock copolymers containing a synergy of pendant ether and imidazolium sites. The soft central BC block comprises low T_g di(ethylene glycol) methyl ether methacrylate (DEGMEMA) and 1-(4-vinylbenzyl) methyl imidazolium units. External polystyrene blocks provide mechanical reinforcement within a nanoscale morphology. Dynamic mechanical analysis (DMA) of the A–BC–A triblock copolymers exhibited a plateau region, which suggested the formation of a microphase-separated morphology. Atomic force microscopy (AFM) and small angle X-ray scattering (SAXS) collectively probed the morphology of the A–BC–A triblock copolymers, revealing long-range order at the nanoscale dimensions. Dielectric relaxation spectroscopy (DRS) examined the ion-transport properties of ionomeric A–BC–A triblock copolymers and random copolymers with different compositions. The role of morphology was demonstrated with block copolymer nanoscale structures providing superior ionic conductivity and mechanical performance compared to random copolymers. Under a 4 V direct current (DC) applied voltage, electromechanical transducers derived from these triblock copolymer membranes with added ionic liquid showed superior actuation performance compared to a benchmark Nafion® membrane, suggesting potential for ionic polymer device applications. This was attributed to optimum modulus, improved ionic conductivity, and microphase-separated morphology of triblock copolymers.