Multimaterial Thermoset Synthesis: Switching Polymerization Mechanism with Light Dosage

The synthesis of polymeric thermoset materials with spatially controlled physical properties using readily available resins is a grand challenge. To address this challenge, we developed a photoinitiated polymerization method that enables the spatial switching of radical and cationic polymerizations by controlling the dosage of monochromatic light. This method, which we call Switching Polymerizations by Light Titration (SPLiT), leverages the use of substoichiometric amounts of a photobuffer in combination with traditional photoacid generators. Upon exposure to a low dose of light, the photobuffer inhibits the cationic polymerization, while radical polymerization is initiated. With an increased light dosage, the buffer system saturates, leading to the formation of a strong acid that initiates a cationic polymerization of the dormant monomer. Applying this strategy, patterning is achieved by spatially varying light dosage via irradiation time or intensity allowing for simple construction of multimaterial thermosets. Importantly, by the addition of an inexpensive photobuffer, such as tetrabutylammonium chloride, commercially available resins can be implemented in grayscale vat photopolymerization 3D printing to prepare sophisticated multimodulus constructs.