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This paper describes the thermally enhanced in-plane alignment and other properties of liquid crystalline (LC) copolymers (1, 2, and 3) consisting of a methacrylate with a 2-styrylpyridine side group as a photocyclodimerizable group and a methacrylate with a methoxy biphenyl side group as a mesogenic group. 1H NMR spectroscopy indicated that the contents of the photoreactive monomer unit in copolymers 1, 2, and 3 were 0.65, 0.46 and 0.19(mole fraction), respectively. The copolymers in the film showed a transmittance of 92% at wavelengths > 450 nm,even at 100 oC, as well as thermal stability up to approximately 360 oC. Copolymers 1 and 2 gave a nematic texture at 155 and 150 oC, respectively, while copolymer 3 showed a smectic texture at 130 oC. The copolymer films aligned parallel to the linearly polarized UV(LPUV) light after LPUV light irradiation and subsequent thermal annealing. The respective in-plane order parameters of copolymers 1, 2, and 3 in the film at 315 nm were 0.65 at 0.001 J/cm2,0.59 at 0.01 J/cm2, and 0.48 at 0.025 J/cm2 by the same treatment in the LC temperature ranges. This suggests that the photoreactive LC copolymers not only have high optical transparency and good thermal stability but also have controllable, high in-plane alignment with the contents of the photoreactive monomer unit.
This paper describes the out-of-plane order of a liquid crystalline (LC) methacrylate copolymer (3) comprised of a methacrylate (1) with a 4-styrylpyridine moiety as the photo-cyclodimerizable group and a benzoate moiety as the mesogenic group in the side chain, and another methacrylate (2) with a 4-(4-methoxyphenyl)benzoate moiety as the mesogenic group. The composition of 1 and 2 units in 3 was estimated to have a molar ratio of 54.2:45.8 by 1H NMR spectroscopy. The X-ray diffraction study revealed that the copolymer forms a partial bilayer smectic structure. The copolymer gave rise to a high out-of-plane order parameter of about 0.74 in a wide LC temperature range of 110~160 oC after linearly polarized, UV light irradiation and subsequent annealing. Moreover, the external reflection IR analysis indicated that excess UV-light irradiation makes the out-of-plane LC structure of the copolymer appear in a higher and wider temperature range.