Second-order nonlinear optical hyperbranched polymers via facile ring-opening addition reaction of azetidine-2,4-dione

A new hyperbranched polymeric structure was chosen as a nonlinear optical material. First, a difunctional chromophore, 4-(4′-nitrophenyl-diazenyl) phenyl-1,3-diamine (NDPD) was synthesized, which was then reacted with 4-isocyanato-4′(3,3-dimethyl-2,4-dioxo-azetidino)diphenylmethane (MIA) to form NDPDMIA (A2 type monomer). The azetidin-2,4-dione functional groups exhibit selective reactivity, which can react only with primary amines under mild conditions. The hyperbranched polymers were synthesized via ring-opening addition reaction between azetidine-2,4-dione (A2 type monomer) and primary amine (B3 type monomer). This synthetic scheme comes with easy purification, high yield and rapid synthesis. Chemical structures of the hyperbranched polymers were characterized by FT-IR, 1H NMR, and elemental analysis. The inherent viscosity of hyperbranched polymers in DMSO ranged from 0.15 to 0.22 dLg−1. All of the obtained polymers were soluble in DMF, DMAc, and DMSO. Using in situ contact poling, r33 coefficients of 6–16 pm/V and their temporal stability at 60 °C were obtained. Optical loss measurement was also achieved by a prism coupling setup.