Preparation of Novel T-type Polyurethanes with High Thermal Stability of Second Harmonic Generation and Their Nonlinear Optical Properties

2,5-Di-(2'-hydroxyethoxy)benzylidenemalononitrile (3) was prepared and polymerized with 2,4-toluenediisocyanate and 3,3'-dimethoxy-4,4'-biphenylenediisocyanate to yield novel T-type polyurethanes 4 and 5 containing 2,5-dioxybenzylidenemalononitrile, nonlinear optical (NLO)-chromophores as part of the polymer backbones. Polyurethanes 4 and 5 were soluble in common organic solvents such as acetone and N,Ndimethylformamide and showed a thermal stability up to $250{^{\circ}C}$ with glass-transition temperatures ($T_g$) in the range $119-146{^{\circ}C}$. The second harmonic generation (SHG) coefficients ($d_{33}$) of poled polymer films at 1064 nm fundamental wavelength were around $5.82{\times}10^{-9}$ esu. The dipole alignment exhibited high thermal stability up to $T_g$, and there was no SHG decay below $140{^{\circ}C}$ due to the partial main-chain character of the polymer structure, which was acceptable for nonlinear optical device applications.