Photoinduced Initiation of Olefin Polymerization: Enabling Spatial Control with Light

Polyolefins constitute the majority of plastics produced worldwide. Despite the variety of precatalyst activation mechanisms known in the literature, the development of spatially controlled olefin polymerizations remains relatively unknown. If successful, control over the olefin polymerization process could provide unprecedented synthetic control and potentially broaden industrial applications. Herein, we demonstrate a simple olefin polymerization methodology termed photoinduced initiation of olefin polymerization (PIOP), wherein photoacid generators are used in conjunction with controlled irradiation to achieve precatalyst activation and olefin polymerization. These results demonstrate that PIOP can be used for solution-based polymerizations of ethylene and alpha-olefins and may be extended to heterogeneous polymerizations of gaseous ethylene and propylene, thereby achieving spatial control over the olefin polymerization process.