Fully degradable polymer networks from conventional radical polymerization of vinyl monomers enabled by thionolactone addition

We report the preparation of degradable polymer networks by conventional free radical copolymerization of n-butyl acrylate with a crosslinker (1 mol%) and dibenzo[c,e]oxepane-5-thione (DOT) as a strand-cleaving comonomer. Addition of only 4 mol% of DOT imparts the synthesized networks with full degradability by aminolysis, whereas gels with less DOT (2-3 mol%) cannot be degraded, in excellent agreement with the recently proposed reverse gel-point model. Importantly, even though DOT significantly slows down the polymerization and delays gelation, it has a minimal effect on physical properties of the networks such as shear storage modulus, equilibrium swelling ratio, glass transition temperature or thermal stability.