Polymer Brushes through Programmable Polymer Crystal Templates

Polymer brushes are polymer chains which are chemically or physically tethered to an exterior surface. Planar polymer brushes have been primarily deposited through two processes: grafting-to and grafting-from. Recently, our group developed an alternative grafting-to approach which utilizes polymer single crystals as a template for polymerization, which contain chains with an end-functionalized moiety for coupling to a surface. The planar polymer single crystals can then be deposited onto a functionalized surface and immobilized, yielding a polymer brush layer matching the geometry of the parent crystal. This affords unique control over the polymer brush deposition process as dependent brush morphology can be manipulated during the solution-based formation of the host crystals, leading to a versatile method to deposit brushes with various compositions and architectures. In this presentation, we demonstrate the synthesis and characterization of patterned and gradient polymer brushes of homopolymers and copolymers. The morphologies and methods developed in this study provide a robust template to deposit complex brush architectures through programmable solution-based methods.