Poly(oligo(ethylene glycol) vinyl acetate)s: A Versatile Class of Thermoresponsive and Biocompatible Polymers

Polymers with a thermally triggered phase transition are important in the design of materials for biological applications, where their behavior can be used to trigger release or (dis)assembly events. Despite their advantages, a system with tunable thermal response, end‐group reactive sites, low toxicity, and controlled main‐chain degradability has not been realized, yet this would be a significant advance. The versatile new poly(oligo(ethylene glycol) vinyl acetate)s are presented with excellent control over their molecular properties obtained through RAFT/MADIX polymerization. Furthermore, we demonstrate structure‐controlled thermal transitions, conjugation to human lysozyme through the retained end‐group, and moreover show that this class of polymers can uniquely be copolymerized with 2‐methylene‐1,3‐dioxepane (MDO) to generate polymers in which the degradability and cloud point can be independently tuned to create materials that display the same cloud point but degrade differently. Smart acetates: The controlled polymerization of a family of PEGylated vinyl acetates is reported. These polymers display a thermal response that can be tuned by (co)monomer choice and enables the independent tuning of response and degradation behavior. High end‐group retention also enables new opportunities in protein–polymer conjugation.