Simultaneous Spin Coating and Ring-Opening Metathesis Polymerization for the Rapid Synthesis of Polymer Films

We report a highly controlled technique for the synthesis of polymer films atop a substrate by combining spin coating with ring-opening metathesis polymerization (ROMP), herein termed spin coating ROMP (scROMP). The scROMP approach combines polymer synthesis and deposition into one process, fabricating films of up to 36 cm² in under 3 min with orders-of-magnitude reduction in solvent usage. This method can convert numerous norbornene-type molecules into homopolymers and random copolymers as uniform films on both porous and nonporous substrates. Film thickness can be varied from a few hundred nanometers to a few tens of micrometers based on spin speed and monomer concentration. The resulting polymers possess high M_W (>100 kDa) and low polydispersity (PDI) (<1.2) values that are similar to ROMP polymers made in solution. We also devise a model to investigate the balance between convective monomer spin-off and polymer growth from the surface, which allows the determination of critical kinetic parameters for scROMP. Finally, translation of scROMP to porous supports enables the synthesis of thin film composite membranes that demonstrate the ability to dehydrate ethanol by pervaporation.