Oxanorbornene (ONB) derivatives with carboxylic anhydride (ONBA) or carboximide (ONBI) side chains, when polymerized through ring-opening metathesis polymerization (ROMP) with Grubbs 3rd generation catalyst (G3), offer a platform for the creation of functional polymer films with applications in separation processes and surface coatings. The presence of anhydride and carboximide groups in the side chains provides opportunities for pre- and post-polymerization functionalization, allowing the introduction of both hydrophilic and hydrophobic components, tailoring material properties for specific applications. This talk presents the successful synthesis of continuous, surface-covering polymer films from pristine ONBA and ONBI monomers using spin coating ROMP (scROMP). The scROMP method combines polymer synthesis and deposition into one process, generating films of up to 36 cm2 in under 3 min with orders-of-magnitude reduction in solvent usage (<1 mL), providing a rapid, low-solvent method for synthesizing polymer films. Additionally, polymer films from various cyclic olefin monomers have been generated using scROMP, with films possessing high molecular weights (MW > 200 kDa) and low polydispersities (PDI <1.2). Further functionalization of pONBA or pONBI films was achieved by exposing the polymer to base, acid, or amine-containing molecules, modifying the side chains to contain hydrophilic or hydrophobic moieties through anhydride cleavage or N-substitution respectively. The pristine and modified films were characterized to determine critical structure-property relationships, including glass transition temperature, surface energy, impedance, and mechanical properties. Furthermore, comparisons of these properties were made between scROMP-generated polymers and polymers made in solution. Lastly, a select number of modified pONBA and pONBI were evaluated as membranes for the dehydration of polar solvents. The systemic modification of polymer side chain functionality provides a route for designing polymeric materials with tailored surface properties and bulk characteristics. These findings contribute to a deeper understanding of structure-property relationships in scROMP-generated polymer films and their implementation in separation processes and surface coatings.
