Synthesis and nonlinear optical properties of novel Y-type polyurethanes with high thermal stability of dipole alignment

2,3-Di-(2′-hydroxyethoxy)benzylidenemalononitrile (3) was prepared and condensed with 2,4-toluenediisocyanate and 3,3′-dimethoxy-4,4′-biphenylenediisocyanate to yield novel Y-type polyurethanes 4–5 containing 2,3-dioxy benzylidenemalononitrile group as a nonlinear optical (NLO)-chromophore, which constituted parts of the polymer backbones. Polyurethanes 4–5 were soluble in common organic solvents such as acetone and N,N-dimethylformamide. They showed a thermal stability up to 270 °C in thermogravimetric analysis thermograms and the glass-transition temperatures (Tg) obtained from differential scanning calorimetry thermograms were around 116–135 °C. The second harmonic generation (SHG) coefficients (d33) of poled polymer films at 106.4 mm−1 fundamental wavelength were around 9.07 × 10−19 C (2.72 × 10−9 esu). The dipole alignment exhibited high thermal stability up to 10 °C higher than Tg, and there was no SHG decay below 145 °C due to the partial main-chain character of the polymer structure, which was acceptable for nonlinear optical device applications.