Modular Approach to Degradable Acetal Polymers Using Cascade Enyne Metathesis Polymerization

: A modular synthetic approach to degradable metathesis polymers is presented using acetal-containing enyne monomers. The monomers are prepared in a short and divergent synthetic sequence that features two points of modification to tune polymerization behavior and introduce molecular cargo. Steric and stereochemical elements are critical in the monomer design in order to provide rapid and living polymerizations capable of generating block polymers. The developed polyacetal materials readily undergo pH-dependent degradation in aqueous mixtures, and the rate of hydrolysis can be tuned through post-polymerization modification with triazolinedione click chemistry. This presents a new scaffold for responsive metathesis polymers that may find use in applications that requires controllable breakdown and release of small molecules.