Novel X-type polyurethane 5 containing 4-(2′,2′-dicyanovinyl)-6-nitroresorcinoxy groups as nonlinear optical (NLO) chromophores, which constitute parts of the polymer backbone, was prepared and characterized. Polyurethane 5 is soluble in common organic solvents such as acetone and N,N-dimethylformamide. It shows thermal stability up to 280 °C from thermogravimetric analysis with a glass transition temperature (Tg) obtained from differential scanning calorimetry thermogram of around 120 °C. The second harmonic generation (SHG) coefficient (d33) of poled polymer film at 1064-nm fundamental wavelength is around 6.12 × 10−9 esu. The dipole alignment exhibits a thermal stability even at 5 °C higher than Tg, and there was no SHG decay below 125 °C due to the partial main chain character of the polymer structure, which is acceptable for NLO device applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013
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