Characterization of unidirectional photopolymerization in poly(vinyl cinnamate) by surface optical second-harmonic generation

Surface optical second-harmonic generation measurements were used to determine the change in the surface density and the surface orientational order parameter of the trans-cinnamoyl side groups of unidirectionally photopolymerized poly(vinyl cinnamate) (PVCN) films. The observed surface features were compared to the bulk properties of the films, which were probed by their UV absorption spectra and birefringence measurements. We found that the surface and the bulk photoreaction kinetics of the trans cinnamoyl side groups of the PVCN are very similar. The two photoreaction processes (trans-cis photoisomerization and photo-induced cross linking) appear to affect the linear and nonlinear optical properties of the polymer differently. This may explain the discrepancy between the birefringence and the azimuthal anchoring force of the unidirectionally photopolymerized PVCN.