Organic−inorganic UV-curing of organosilanes containing epoxy and trialkoxysilyl functional groups in the same monomer was implemented using a diaryl iodonium salt as cationic photoinitiator. UV-generated Brönsted acids through photolytic degradation were found to be effective in catalyzing both epoxy ring-opening polymerization and alkoxysilane sol−gel polycondensation reactions. Competition between the formation of inorganic and organic phases was kinetically studied using real-time Fourier transform infrared spectroscopy (RT-FTIR). The nature of the hybrid monomer, the effect of changing the film thickness, the type of substrate and the influence of laminated conditions on the polymerization kinetics were assessed. 29Si and 13C solid state NMR measurements were also performed to investigate the structure of the UV-cured hybrid materials.

Triphenylphosphine (TPP) was used in free‐radical UV‐curable resins to reduce oxygen inhibition effect. The relative influence of concentration, monomer viscosity, light intensity and sample thickness on TPP efficiency was investigated by real time infrared spectroscopy. It is shown that TPP is an effective oxygen scavenger. The mechanism was investigated by means of Laser Flash Photolysis. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2462–2469, 2010

Si NMR spectra of the photocured films F1-F3 (Fig. S1). CP-MAS 13 C NMR spectra of the photocured films F1-F3 (Fig. S2). In situ photographs of the moving tip during a scratch experiment for F1 and F3 films when applying an increasing normal load (Fig. S3).