Accessible and sustainable Cu(0)-mediated radical polymerisation for the functionalisation of surfaces

Abstract

Polymer brushes have great potential for use in functionalising surfaces due to their chemical and mechanical robustness, and wide variety of useful properties including antibacterial and antifouling behaviour. One such grafted polymer of interest is poly[2-(methacryloyloxy)ethyl]trimethylammonium chloride (PMETAC), shown to have excellent antibacterial behaviour due to the presence of quaternary ammonium chloride groups (QACs). Previous studies have shown that increasing the density of QACs increases the efficacy of these surfaces, therefore the production of thick PMETAC brushes is highly desirable. Cu(0)-mediated radical polymerisation (CuRP) offers a simple route to the production of these surfaces. A movement towards more sustainable chemistry has led to research into polymerisations in environmentally benign solvent, with focus placed on recycled and easily accessible catalysts. In this study, the growth of PMETAC brushes up to 300 nm dry thickness (∼ 425 nm water-swollen thickness) is demonstrated, thicker than any previous report we have found for this polymer brush. Furthermore, tap water is used as a cheap and readily available solvent, with a catalyst derived from copper wire. The use of copper wire, compared to the commonly used CuBr₂ catalyst, leads to thicker coatings which also display a lower swelling ratio, implying an increased grafting density. The protocol can be continuously cycled over a 7-day period without changing the monomer solution or catalyst, with numerous wafers being functionalised over the time period with no significant reduction in grafted amount. In addition, the polymerisation can be carried out in ambient (non-inert) conditions with no degassing steps, again without with significant detriment to grafting.