Kinetics of UV curable alkyl 3-mercaptopropionate-vinyl silizane

Photopolymerization of vinyl-containing liquid silizane preceramic monomers copolymerized with thiol monomers, based on a step-growth radical polymerization mechanism, is a novel, rapid, inexpensive and simple technique for producing preceramic structures from liquid precursors. The kinetics of alkyl 3-mercptopropionate-vinyl silizane under UV irradiation is investigated by using real-time Fourier transform infrared (FT-IR) and photo-differential scanning calorimetry (photo-DSC). The experimental results show preliminarily that: (1) about 80% conversion of vinyl group has been achieved in the presence of a low concentration photoinitiator under UV irradiation; (2) by increasing the functionalities of the thiol group, the peak rate of copolymerization increases and the final conversion of the vinyl group decreases; (3) the copolymerization is primarily a bimolecular radical termination process; (4) the copolymerization is first-order, i.e., its rate is proportional to the vinyl group concentration and independent of the concentration of thiol group.