The solid-state polymerization (SSP) of poly (ethylene 2,6-naphthalate) (PEN) was studied and compared with that of poly(ethylene terephthalate) (PET). The SSP of PEN, like that of PET, could be satisfactorily described with a modified second-order kinetic model, which was based on the assumptions that part of the end groups were inactive during SSP and that the overall SSP followed second-order kinetics with respect to the active end-group concentration. The proposed rate equation fit the data of the SSP of PEN quite well under various conditions. PEN prepolymers in pellet and cube forms with intrinsic viscosities (IVs) ranging from 0.375 to 0.515 dL/g, various particle sizes, and various carboxyl concentrations were solid-state polymerized at temperatures ranging from 240 to 260 degrees C to study the effects of various factors. The SSP data obtained in this study could be readily applied to the design of commercial PEN SSP processes. Because PEN and PET share the same SSP mechanism, in general, the SSP behaviors of PEN are similar to those of PET. Thus, the SSP rate of PEN increased with increasing temperature, increasing prepolymer IV, and decreasing prepolymer particle size. However, because of the much higher barrier properties of PEN, the prepolymer particle size and carboxyl concentration had much greater effects on the SSP of PEN than on the SSP of PET. (c) 2006 Wiley Periodicals, Inc.