This presentation will describe two classes of radical-initiator adsorbates designed for growing surface-grafted polymer thin films on gold surfaces. The adsorbates feature a distinct structural characteristic: a bidentate dithiol headgroup that provides enhanced thermal and radical stability to self-assembled monolayers (SAMs) derived from the adsorbates. In the first example, a series of azo-based adsorbates are designed to possess an <i>α</i>,<i>ω</i>-difunctional architecture for immobilizing 100% (rather than 50%) of the initial AIBN-like radical initiator sites on the metal surfaces. In the second example (see Figure 1), a unique bromoisobutyrate-terminated bidentate dithiol-based adsorbate is utilized for thermally enhanced atom-transfer radical polymerization (ATRP). This presentation will compare the stability and polymerization efficiency of the newly designed bidentate adsorbates to those generated from analogous monodentate adsorbates in the surface-grafted growth of thick brushes of poly(methyl methacrylate) and polystyrene, demonstrating the advantages afforded by the "chelate effect" of the bidentate headgroup incorporated into the new adsorbates. The findings that will be described here can be applied to the growth of thin polymer films in a variety of applications, including those relevant to the aerospace industry.

Robust and thick polymer brushes grafted from gold surfaces using bidentate thiol-based initiators

256th National Meeting (2018)

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