Photoswitching Cationic and Radical Polymerizations: Spatiotemporal Control of Thermoset Properties.

The ability to fabricate polymeric materials with spatially controlled physical properties has been a challenge in thermoset manufacturing. To address this challenge, this work takes advantage of a photoswitchable polymerization that selectively incorporates different monomers at a growing chain by converting from cationic to radical polymerizations through modulation of the wavelength of irradiation. By regulating the dosage and wavelength of light applied to the system, the mechanical properties of the crosslinked material can be temporally and spatially tuned. Furthermore, photopatterning can be achieved both on the macroscale and the microscale, enabling precise spatial control of crosslink density that results in high-resolution control over mechanical properties.