Polymer brushes are end-tethered polymer chains attached to a substrate which have been studied for their unique surface modification properties. The two main synthetic pathways to deposit polymer brushes include: grafting-to, where an end-functionalized polymer chain is tethered covalently a surface, and grafting-from, where a polymer chain is grown epitaxially from initiator sites present on the surface. To overcome the limitations of these previous methods, the polymer single crystal (PSC) assisted grafting - to approach (PSCAGT) was developed as a pathway to deposit polymer brush layers with tunable grafting densities and surface coverage. The PSCAGT approach offers a robust approach to study various aspects brush layers. In this work, alkoxysilane-functionalized Poly(ε-caprolactone) (PCL) single crystals were grown through a self-seeding process and used to deposit unique homopolymer and segmented brush surfaces of various shape, composition, and grafting density. This study summarizes three different mechanisms to control the morphology of the deposited brush: 1) the control of polymer brush grafting density through varying the degree of undercooling and fold number of the PSC’s lamellae, 2) the use of a PSC as a seed to co-crystallize additional polymer into polymer brush frames and lateral segmented brushes and 3) time-dependent co-crystallization with inert end-groups to develop various gradient polymer brushes with different geometries. The level of control over PCL brush morphology through control of the crystallization process offers a robust method to deposit polymer brushes with various architectures and surface characteristics.

Controlled deposition of poly(ε-caprolactone) brush layers through polymer single crystal templates

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.