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J Phys Chem A. 2009 Jul 30;113(30):8765-80. doi: 10.1021/jp904250r.

Synthesis, characterization, and study of photoinduced optical anisotropy in polyimides containing side azobenzene units.

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Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Sklodowska 34, 41-819 Zabrze, Poland.


In this paper, novel processable aromatic polymers with imide rings and attached as side-chain azobenzene units are presented. Polymers differ in the chemical structures of chromophores and polymer backbones. Azopolymers were obtained by a two-step synthetic approach. This includes the preparation of a precursor poly(esterimide) and poly(etherimide) with pendant phenolic hydroxyl groups, followed by the covalent bonding of NLO chromophores onto the polyimide backbone by the Mitsunobu reaction. The degree of functionalization of polymers was estimated by UV-vis spectroscopy. Polymers were characterized and evaluated by FT-IR, (1)H NMR, X-ray, UV-vis, DSC, and TGA methods. The synthesized polymers exhibited glass transition temperatures in the range of 167-228 degrees C, thermal stability with decomposition temperatures in the range of 275-446 degrees C, and excellent solubilities in common organic solvents. The light-induced optical anisotropy was studied in obtained azopolymers with the help of a holographic grating recording technique. Two polarization geometries were applied for the grating inscription s-s and p-p. The influence of the polarization geometry on the diffraction efficiency dynamics and on the depth of the surface modulation was not observed, which is different from results reported in the literature. Surface relief gratings, which appeared after the light exposure, were observed by atomic force microscopy. Additionally, the optical anisotropy in poly(esterimide)s was investigated by photoinduced birefringence measurements. For the first time, in polyimide with covalently bonded azobenzene derivatives, the high photoinduced birefringence (Delta n = 0.01) was measured.

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