Facile Synthesis of Thick Films of Poly(methyl methacrylate), Poly(styrene), and Poly(vinyl pyridine) from Au Surfaces

Atom transfer radical polymerization (ATRP) is commonly used to grow polymer brushes from Au surfaces, but the resulting film thicknesses are usually significantly less than with ATRP from SiO2 substrates. On Au, growth of poly(methyl methacrylate) (PMMA) blocks from poly(tert-butyl acrylate) brushes occurs more rapidly than growth of PMMA from initiator monolayers, suggesting that the disparity between growth rates from Au and SiO2 stems from the Au surface. Radical quenching by electron transfer from Au is probably not the termination mechanism because polymerization from thin, cross-linked initiators gives film thicknesses that are essentially the same as the thicknesses of films grown from SiO2 under the same polymerization conditions. However, this result is consistent with termination through desorption of thiols from noncross-linked films, and reaction of these thiols with growing polymer chains. The enhanced stability of cross-linked initiators allows ATRP at temperatures up to similar to 100 degrees C and enables the growth of thick films of PMMA (350 nm), polystyrene (120 nm) and poly(vinyl pyridine) (200 nm) from Au surfaces in 1 h. At temperatures >100 degrees C, the polymer brush layers delaminate as large area films.