Synthesis and isodimorphic cocrystallization behavior of poly(1,4-cyclohexylenedimethylene terephthalate-co-1,4-cyclohexylenedimethylene 2,6-naphthalate) copolymers

Abstract

A series of poly(1,4-cyclohexylenedimethylene terephthalate-co-1,4-cyclohexylenedimethylene 2,6-naphthalate) [P(CT-co-CN)] copolymers were synthesized, and their cocrystallization behavior was investigated using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). Although the P(CT-co-CN) copolymers synthesized have statistical random distribution of CT and CN units, all the copolymers show clear melting and crystallization peaks in DSC thermograms over entire copolymer composition, and have an eutectic melting temperature in the plot of melting temperature versus copolymer composition. WAXD patterns of all the samples show sharp diffraction peaks, and are largely divided into two classes according to the copolymer composition, that is, PCT-type and PCN-type diffraction patterns. These facts lead us to conclude that P(CT-co-CN) copolymers show isodimorphic cocrystallization. The eutectic composition at which the crystal transition from PCT-type to PCN-type crystal occurs was estimated ca. 40 mol % CN content. When the defect Gibbs free energy was estimated by using the equilibrium inclusion model proposed by Wendling and Suter, the value (7.18 kJ/mol) in the case of incorporation of CT units in the PCN crystals were larger than the case (3.32 kJ/mol) of incorporation of CN units in the PCT crystals. (C) 2003 Wiley Periodicals, Inc. J Polym Sci Part 13: Polym Phys 42: 177-187, 2004.