Electro-optic side-chain polymers have been synthesized by the post-functionalization of methacrylate isocyanate polymers with novel phenyl vinylene thiophene vinylene bridge (FTC) nonlinear optical chromophores. For this application, FTC-based chromophores were modified in their electronic donor structure, exhibiting much larger molecular hyperpolarizabilities compared with the benchmark FTC. Of these new chromophores, absorption spectra, hyper-Rayleigh scattering experiment, and thermal analysis were carried out to confirm availability as effective nonlinear optical units for electro-optic side-chain polymers. The electro-optic coefficients (r33) of obtained polymers were investigated in the process of in situ poling by monitoring the temperature, current flow, poling field, and electro-optic signal. Compared with the nonsubstituted analogue, benxyloxy modified FTC chromophore significantly achieved higher nonlinear optical property, exhibiting molecular hyperpolarizability at 1.9 μm of 4600 × 10−30 esu and an r33 value of 150 pm/V at the wavelength of 1.31 μm. Synthesized electro-optic polymers showed high glass transition temperature (Tg), so that the temporal stability examination exhibited >78% of the electro-optic intensity remaining at 85℃ over 500 h. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

doi:10.1002/pola.24410