Simple synthetic strategies that enable the design of precise and complex polymeric architectures are a central element to developing advanced soft-materials with application-relevant properties. Two new approaches to macromolecular design are through robust reversible deactivation radical polymerizations with alkylborane initiation and in-situ block copolymer self-assembly using post-polymerization functionalization. As a first approach to macromolecular design, AI-RAFT (alkylborane initiated reversible addition-fragmentation chain transfer) is discussed as a novel initiation platform for synthesizing well-defined polymers at room-temperature while in the presence of oxygen. The mechanism and structure-reactivity relationships of the initiation system are explored using a range of alkylborane Lewis acid-base pairs, chemical deblockers, and reaction conditions for establishing optimal polymerization conditions. As a second approach to macromolecular design, FISA (functionalization induced self-assembly) is discussed as a unique strategy to self-assemble block copolymers through two highly-efficient reactions. Key parameters governing the FISA process are explored to elucidate the process of self-assembly and the impact of functionality on nanostructure properties by using a range of structurally-diverse chemical functionalities.

Synthesizing precise macromolecules through new pathways: Alkylborane initiation and functionalization-induced self-assembly

2019 Fall National Meeting

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