Mechanistic Studies on Template Polymerization in Porous Isotactic Poly(methyl methacrylate) Thin Films by Radical Polymerization and Postpolymerization of Methacrylate Derivatives

The postpolymerization of various vinyl monomers was applied for mechanistic studies of the template polymerization of methacrylic acid (MAA) in porous isotactic (it-) poly(methyl methacrylate) (PMMA) thin films on quartz crystal microbalance (QCM) substrates and on silica gels, which were prepared by the alternative layer-by-layer (LbL) assembly of it-PMMA/syndiotactic- (st-) poly(methacrylic acid) (PMAA). In this study, QCM analyses, FT-IR/ATR spectra, 1H NMR spectra, and SEC were employed to investigate the polymerization mechanism, and they highlighted the following points: (1) the livingness of polymer radicals by postpolymerization on a QCM, (2) substituent effects on the polymerizability in porous it-PMMA thin films, and (3) partial stereocomplex formations of polymerized MMA with host it-PMMAs. Stabilities of porous it-PMMA thin films on QCM substrates and on silica gels are also discussed herein.