Thermo-responsive bottlebrush polymers are synthesized by a novel grafting-to, radical coupling method with no small molecule synthesis involved. With this method, we demonstrate that bottlebrush polymers with molecular weight in the millions of g/mol can be easily prepared using either homopolymer or block copolymer side chains. More importantly, the dynamic bonds resulting from our radical coupling reactions, which link side chains and backbones of bottlebrush polymers synthesized by our method, are thermo-reversible at elevated temperature. Exploiting this dynamic feature via a simple annealing process with no extra synthetic step involved, the grafting density of bottlebrush polymers can be tuned post-synthesis with the bottlebrush regime going from loose bottlebrush to dense comb and potentially to loose comb with increased annealing. Such materials provide the opportunity to study grafting density-property relationships in bottlebrush polymers with other factors held constant. Thus, besides a facile synthetic pathway, our method also provides a platform for advancing the scientific understanding and technological applications of bottlebrush polymers through incorporated dynamic chemistry. Characterization of bulk and confined properties of our resulting bottlebrush polymers will be described, and implications for achievement of novel nanostructures will be given.

Simple grafting-to, radical coupling strategy yields post-synthesis tuning of grafting density in bottlebrush polymers: Synthesis and characterization of bulk and confined properties

2019 Spring National Meeting

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