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 tuneable thermal response, end-group reactive sites, low toxicity and controlled main-chain degradability has not been realised, yet would represent a significant advance. We report the versatile new poly(oligo(ethylene glycol) vinyl acetate)s 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.