| Autor: |
Gazzola G; Laboratory for Macromolecular and Organic Chemistry, Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy., Filipucci I; Laboratory for Macromolecular and Organic Chemistry, Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy., Rossa A; Laboratory for Macromolecular and Organic Chemistry, Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy., Matyjaszewski K; Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States., Lorandi F; Laboratory for Macromolecular and Organic Chemistry, Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy., Benetti EM; Laboratory for Macromolecular and Organic Chemistry, Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131 Padova, Italy. |
| Abstrakt: |
Achieving tolerance toward oxygen during surface-initiated reversible deactivation radical polymerization (SI-RDRP) holds the potential to translate the fabrication of polymer brush-coatings into upscalable and technologically relevant processes for functionalizing materials. While focusing on surface-initiated photoinduced atom transfer radical polymerization (SI-photoATRP), we demonstrate that a judicious tuning of the composition of reaction mixtures and the adjustment of the polymerization setup enable to maximize the compatibility of this grafting technique toward environmental conditions. Typically, the presence of O 2 in the polymerization medium limits the attainable thickness of polymer brushes and causes the occurrence of "edge effects", i.e. , areas at the substrates' edges where continuous oxygen diffusion from the surrounding environment inhibits brush growth. However, the concentrations of the Cu-based catalyst and "free" alkyl halide initiator in solution emerge as key parameters to achieve a more efficient consumption of oxygen and yield uniform and thick brushes, even for polymerization mixtures that are more exposed to air. Precise variation of reaction conditions thus allows us to identify those variables that become determinants for making the synthesis of brushes more tolerant toward oxygen, and consequently more practical and upscalable. |
