Over the past twenty years, stable radical polymers, such as poly(TEMPO-methacrylate) (PTMA), have been largely associated with active cathode material in organic rechargeable batteries. PTMA has shown to be an advantageous polymer that offers improvement in power density compared to lithium-ion batteries due to its fast redox kinetics. However, its redox behavior has been greatly aided by the use of electrolyte solutions for electron transport. Emerging work has now found applications of stable radical polymers in solid-state devices ranging from layered memory devices to OPVs. Recently, the electrical conductivity in solid state thin films has been explored and PTMA has been found to be an electronic insulator. However, when TEMPO is attached to a mobile, low Tg backbone, charge transport between pendant group to pendant group is observed at room temperature. New solid-state applications are still emerging, and in order for PTMA to be a viable material in organic electronic systems, patterning and controlling the long-range order of PTMA at the nanoscale should be fully explored. In this work, we develop a novel synthetic technique to obtain PTMA containing block copolymers with easily UV-degradable secondary blocks such as poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) via anionic polymerization. Various structures at the nanoscale are developed in thin polymer films via solvent vapor annealing. The long-range ordering of these phase morphologies has been characterized using atomic force microscopy (AFM) and grazing-incidence small angle x-ray scattering (GISAXS). Our work on stable radical block copolymers shows the potential for controlling the long-range ordering of the stable radical block, suggesting potential applications in nanopatterning of PTMA for future charge transporting solid-state devices.

Block copolymers containing stable radical and fluorinated blocks with long-range ordered morphologies prepared by anionic polymerization

2019 Fall National Meeting

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