The surface composition of a polymer thin film determines the interactions of the film with its environment and equips the film for specific applications, such as a coating, sensor, adhesive, anti-foulant, or membrane. We report a new method to reduce the waste of expensive monomer in polymer film synthesis by growing functional outer blocks on top of inexpensive lower blocks through sequential depositions of different monomer solutions onto a catalyst-laden surface. The method, called spin coating ring-opening metathesis polymerization (scROMP), efficiently integrates polymer film synthesis and deposition into one rapid process, converting the sequential monomers into layered polymer films in < 3 min with < 1 mL of solvent for a 36 cm2 film. The scROMP approach is shown here to produce films composed of polymers with > 550 kDa molecular weights and < 1.15 polydispersities and to effectively stack two or more layers of distinct functionalities that constitute the bulk and surface regions of the film. Layer thicknesses are controlled via the selected spin speeds upon the addition of the respective monomers. As potential applications, we demonstrate the syntheses of unique block-like copolymer films with specialized properties such as polar solvent dehydration selectivity, omniphobicity, protein resistance, and bacteria resistance, based on the outer composition of the block.
