Synthesis and characterization of copolymaleimides containing 4‐cyanobiphenyl‐based side groups for nonlinear optical applications

We report the synthesis of a nematic copolymer, P(CBMS‐co‐M₃), prepared by free radical polymerization of an equimolecular mixture of p‐(4‐cyanobiphenyl‐4′‐yloxy)methylstyrene (CBMS) and N‐[3‐(4‐cyanobiphenyl‐4′‐yloxy)propyl]maleimide (M₃) and two isotropic alternating copolymers, P(S‐alt‐M_n) (n = 3,6) prepared by chemical modification of poly(styrene‐alt‐maleimide), P(S‐alt‐M), by n‐(4‐cyanobiphenyl‐4′‐yloxy)alkan‐1‐ol. These copolymaleimides were characterized by NMR, DSC, and optical microscopy. Some corona poling experiments were performed and the second harmonic coefficients d₃₁ and d₃₃ were measured. It was shown that one can gain in net polar ordering by starting with a liquid crystalline system. The ratio d₃₃/d₃₁ was much larger than 3, in agreement with the molecular statistical models for electric field poling of liquid crystals. At ambient conditions, changes of d₃₃ and d₃₁ are 15% over 325 days. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 513–524, 1999