Molecular design, synthesis and electro-optic properties of novel Y-type polyurethanes with high thermal stability of second harmonic generation

2,4-Di-2′-hydroxyethoxy)benzylidenemalononitrile (3) was prepared and condensed with 2,4-toluenediisocyanate and 3,3′-dimethoxy-4,4′-biphenylenediisocyanate to yield unprecedented novel Y-type polyurethanes (4–5) containing 2,4-dioxybenzylidenemalononitrile group as a nonlinear optical (NLO) chromophore, which constitutes a part of the polymer backbone. The resulting polyurethanes 4–5 were soluble in common organic solvents such as acetone and DMF. Polymers 4–5 showed a thermal stability up to 260 °C from thermogravimetric analysis (TGA) with differential scanning calorimetry (DSC) giving Tg values around 143–156 °C. The approximate lengths of aligned NLO-chromophores estimated from AFM images of poled polymer films were about 10 nm. The SHG coefficients (d33) of poled polymer films were around 7.4 × 10−9 esu. These Poled polymers exhibited a greater thermal stability of dipole alignment even at 10 °C higher than Tg, and no SHG decay was observed below 155 °C due to the partial main chain character of the polymer structure and extensive hydrogen bonds between urethane linkage, which is acceptable for NLO device applications.