Fabrication of Three-Dimensional Polymer-Brush Gradients within Elastomeric Supports by Cu-Mediated Surface-Initiated ATRP.

Cu-mediated surface-initiated ATRP (Cu SI-ATRP) emerges as a versatile, oxygen-tolerant process to functionalize three-dimensional (3D), microporous supports forming single and multiple polymer-brush gradients with a fully tunable composition. When polymerization mixtures are dispensed on a Cu-coated plate, this acts as oxygen scavenger and source of active catalyst. In the presence of an ATRP initiator-bearing microporous elastomer placed in contact with the metallic plate, the reaction solution infiltrates by capillarity through the support, simultaneously triggering the controlled growth of polymer brushes.