Advanced polymeric architectures require techniques that can incorporate diverse monomer classes, which often require different mechanisms of polymerization. Current methods to achieve materials from multiple polymerization mechanisms generally require tedious synthetic manipulations on a multi-functional initiator or the chain end to achieve block polymers, often in multiple stages. This proposal seeks to realize higher-level control over block composition and sequence through the development of a one-pot cationic and anionic polymerization, regulated through orthogonal external stimuli (e.g., light and heat). This switchable system will allow for the synthesis of novel block polymers based on poly(vinyl ethers) and poly(thiiranes). We will study these materials in the context of block polymer self-assembly and by leveraging the unique opportunities presented by the poly(thiirane) block, including oxidation to chiral (sulfoxide) or self-immolative (sulfone) materials and by post-polymerization modification to cationic or zwitterionic states.
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