Sodium tetrazodiphenyl naphthionate and pyromellitic dianhydride were polycondensed under microwave irradiation and oil-bath heating. The resultant poly(amic acid) was imidized in the solid phase by microwave irradiation and oil-bath heating. The effects of the reaction temperature, the concentration of monomers, the monomer ratio, and the microwave irradiation time on the conversion, intrinsic viscosity, and third-order nonlinear optical (NLO) coefficient of the polymer were investigated. The results showed that the polycondensates had high third-order NLO coefficients (χ(3) = 1.476 × 10−12esu) and very fast time responses (15.79 ps). The χ(3) values of the polycondensates under microwave irradiation were higher than those of conventional thermopolymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1121–1128, 2003
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