Formation and Structure of Well-Defined Reactive Polymer Brushes Based On “Clickable” Poly 2-Vinyl-4,4,-Dimethylazlactone (PVDMA)

End-tethered interfacial layers based on poly(vinyl-dimethylazlactone) (pVDMA) are of considerable interest from conceptual and technological perspectives due to the facile nature in which they can be modified with biomolecules or converted into polyelectrolyte brushes. Azide-terminated pVDMA chains were “clicked” onto a “primer” layer comprised of a random copolymer of glycidylmethacrylate (GMA), which contains pendent epoxy groups to covalently anchor the polymeric scaffold to the substrate, and propargylmethacrylate (PMA), which provides alkynes for 1,3 dipolar cycloaddition reactions. Spectroscopic ellipsometry, neutron reflectivity measurements, and atomic force microscopy were used to examine the surface morphology and structure of the p(GMA-co-PMA) primer layer and the subsequent pVDMA brush layer. The p(GMA-co-PMA) copolymer composition was varied in order to elucidate its impact on brush formation and swelling behavior of the pVDMA brushes in various solvent environments. Neutron reflectivity measurements of the dry layers show excellent agreement with the ellipsometric data, providing evidence of well-defined p(GMA-co-PMA) base layers. Efforts to characterize the nanoscale structure and swelling of pVDMA brushes after surface attachment using neutron reflectivity are currently underway and will provide further insight into structure-property relationships of the reactive polymer brushes. The flexibility of using “clickable” base layers and end-functionalized polymers offers considerable potential for creating interesting biomaterial coatings, (bio)sensors and functionalized membranes.