Enhancement of nonlinear optical and thermal properties of polyurethanes by modifying the chromophores with fused heterocyclic and pyrimidine rings

This article describes the synthesis of substituted triazolo[3,4‐b]‐thiadiazole heterocycles based nonlinear optical (NLO) responsive chromophores. To enhance the NLO properties of the chromophores, the pyrimidine ring was introduced with an appropriate π‐bonding. With these chromophores, different series of polyurethanes were prepared by condensation with tolylene‐2,4‐diisocyanate and 3,3′‐dimethoxy‐4,4′‐biphenylene diisocyanate. The structure of the resulting chromophores and polyurethanes was confirmed using Fourier transform infrared, proton nuclear magnetic resonance, and Carbon Hydrogen Nitrogen (CHN) analyzer. The inherent viscosities (η_inh) of the polyurethanes measured by Ubbelohde viscometer were in the range of 0.2324–0.2760 dl/g. Thermal behavior of the polyurethanes was investigated using differential scanning calorimetry and thermogravimetric analysis. The molecular orientation in polyurethane films was induced by a corona poling, and this was ascertained using ultraviolet‐visible spectrophotometer and atomic force microscope. The thicknesses and refractive indices of thin films were determined by an Ellipsometer. Polyurethanes exhibited excellent solubility in most of the common organic solvents. The second harmonic generation (SHG) coefficients (d₃₃) of the poled polyurethanes ranged from 63.20 and 95.32 pm/V at 532 nm. None of the polyurethanes showed SHG decay below 100°C, and retained 95% of the signal even up to 500 h. The resulting enhanced NLO efficiency and longer temporal stability make these polyurethanes as promising candidates for photonic devices. POLYM. ENG. SCI., 59:500–509, 2019. © 2018 Society of Plastics Engineers