The design and synthesis of highly functional materials is required to meet the demands of numerous applications in polymer science; where the introduction of functionality can allow precise control over polymer properties and architecture. To expand the range of accessible functional polymers, new design strategies are needed. In want of particular attention is the design of functional degradable polymers, <i>e.g.</i> poly(ester)s and poly(carbonate)s, where the introduction of functionality is limited to functionalities compatible with ring-opening polymerization (ROP) and the preparation of functional monomers is often arduous and low yielding. Herein, we report several strategies designed to expand the range of accessible functional degradable poly(carbonate)s and allow the preparation of poly(carbonate)s of varying architecture. The combination of disparate polymerization techniques, namely ROP and reversible addition-fragmentation chain transfer (RAFT) polymerization, was utilized to prepare highly functional poly(carbonate)s as a consequence of the high functional group tolerance of the RAFT polymerization methodology. Incorporation of RAFT chain transfer agents (CTAs) into the poly(carbonate) backbone allowed the preparation of both linear and cyclic graft copolymers. Furthermore, the growth of hydrophilic polymer arms from the RAFT CTA sites and self-assembly of the resulting amphiphilic graft copolymers provided a convenient route to degradable nanoparticles. In a separate approach, a library of functional and multifunctional poly(carbonate)s were prepared <i>via</i> post-polymerization modification of a norbornene-functional poly(carbonate). In contrast to previous examples of post-polymerization modification, the norbornene-functionality was demonstrated to undergo multiple orthogonal modification reactions, including norbornene-thiol additions, norbornene-azide cycloadditions and the inverse electron demand Diels-Alder reaction with tetrazines, either individually or sequentially to yield multifunctional poly(carbonate), thus greatly expanding the scope of post-polymerization functionalization approaches.

Functional degradable poly(carbonate)s: Design, synthesis, and self-assembly

249th National Meeting (2015)

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