Synthesis and nonlinear optical properties of a novel polyurethane containing cyanovinylthiophene with enhanced thermal stability of dipole alignment for electro‐optic applications

Stabilization of electrically induced dipole alignment is one of the important criteria in the development of nonlinear optical (NLO) polymers for electro-optic device applications. Polyurethanes for NLO applications have attracted attention because of their high thermal stability due to hydrogen bonding. In the work reported here, we designed and synthesized a new type of NLO polyurethane, in which the pendant NLO chromophores are part of the polymer backbone. This mid-type NLO polymer is expected to have the merits of both main-chain and side-chain NLO polymers, namely stable dipole alignment and good solubility. 1-[3,4-Di-(2-hydroxyethoxy)phenyl]-2-(2-thienyl)ethene was prepared and condensed with 3,3′-dimethoxy-4,4′-biphenylenediisocyanate to yield a polyurethane. This polyurethane was reacted with tetracyanoethylene to give a novel Y-type polyurethane (7) containing 1-(3,4-dioxyphenyl)-2-[5-(1,2,2-tricyanovinyl)-2-thienyl]ethenes as NLO chromophores, which constitute part of the polymer backbone. Polyurethane 7 is soluble in common organic solvents such as N,N-dimethylformamide and dimethylsulfoxide. It shows a thermal stability up to 280 °C from thermogravimetric analysis with a glass transition temperature obtained from differential scanning calorimetry of ca 162 °C. The second harmonic generation (SHG) coefficient (d33) of a poled polymer film of he polyurethane at 1560 nm fundamental wavelength is ca 1.11 × 10−18 C. Polymer 7 exhibits an enhanced thermal stability and no significant SHG decay is observed below 150 °C, which is acceptable for NLO device applications. Copyright © 2009 Society of Chemical Industry