Abstract
Photoinduced orientational behavior of polymethacrylates with side chains (amorphous polymers, pMAz2 and C2MeO, and liquid crystalline polymers, C6MeO and C12MeO) with different alkylene spacer lengths (n = 2, 6, 12) were investigated by means of polarized Fourier transform infrared (FT-IR) and UV−vis absorption spectroscopy. Being different from pMAz2, C2MeO showed high optical anisotropy due to in-plane orientation and the excellent thermostability even above Tg, which can be explained in terms of potential liquid crystallinity to be able to have a tendency to form a well-ordered domain. We observed marked dependence of photoorientation processes on film temperatures of C6MeO. While in-plane orientation was generated in glassy state as well as at 76 °C, irradiation at 90 °C slightly lower than TSN (transition temperature between smectic and nematic phases) gave rise to the distinct transformation from in-plane orientation at the early stage to successive out-of-plane reorientation, which was accompanied by H-aggregation. This situation enabled ones to record optical images in a C6MeO film on the basis of the difference in birefringences between two orientational modes. The biaxial reorientation occurred also for C12MeO, though both in-plane and out-of-plane photoorientation occurred simultaneously at room temperature as well as elevated film temperatures.
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