Nitroxide radicals such as TEMPO have been thoroughly studied in the context of electrochemistry and magnetic labeling. More recently, polymers bearing TEMPO side groups, such as poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate), also denoted as poly-TEMPO-methacrylate (PTMA), have been used as alternative materials in energy storage systems, such as rechargeable organic radical batteries. Although devices have been created using stable radical polymers, the charge transport mechanism has not been thoroughly studied, and many of these devices fail after a few cycles. In order to improve current advances in the field, the charge transport in nitroxides must be further studied. Currently, there are various inconsistencies in the literature pertaining to the electrical conductivity of PTMA. In this work, we focus on understanding the effects of three different synthetic methods on the electrical conductivity of PTMA, which improves our understanding of the current state of the field.<br/><br/>Due to the importance of PTMA in organic energy storage devices, this work also focuses on creating platforms in which to create nanopatterns of PTMA using block copolymers containing PTMA and fluorinated secondary blocks. Poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) serves as a block to increase the phase separation between the two blocks. PTFEMA is also known to be easily degradable by deep-UV and other lithographic methods. Combining both of these properties, we have created materials that can be used to pattern PTMA via phase segregation.<br/><br/>Various morphologies may be developed in thin polymer films via solvent vapor annealing. The studied block copolymers have been synthesized via anionic polymerization, and their phase morphologies have been observed using Atomic Force Microscopy (AFM) and Grazing-Incidence Small Angle X-Ray Scattering (GISAXS). Investigating phase behavior in these block copolymers allows PTMA to be patterned in new ways, resulting in further improvement and understanding of stable radical polymers.

Stable radical polymers for charge transport studies

256th National Meeting (2018)

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