Command-destruct thermosets via photoinduced thiol-catalyzed β-scission of acyclic benzylidene acetals

Photoinduced thiol-catalyzed hydrogen abstraction and β-scission of acyclic benzylidene acetals is demonstrated as a new route to “command-destruct” polymer thermosets. Using this approach, we show that poly(thioether acetal) networks synthesized via thiol–ene photopolymerization rapidly degrade to alkyl benzoate byproducts when triggered with light, transitioning from solid to liquid within seconds. The light-driven construction and destruction processes, accessible via distinct differences in kinetics, are readily amenable for photopatterning, additive/subtractive manufacturing and wavelength-selective applications.