The compositions of a series of poly (ethylene/trimethylene terephthalate) copolyesters were identified by 1H-NMR and 13C-NMR. The ethylene terephthalate (ET) units are 8.9, 33.7, 37.9, 50.1, 72.5, 77.8, and 90.8% in the copolyesters with sample codes of C2, C3, C4, C5, C6, C7, and C8, respectively. The triad sequence probabilities were determined from the normalized areas of aromatic quaternary carbons. The calculated average-number sequence lengths of ethylene- and trimethylene- terephthalate units range from 1.0 to 10.2 that depends on the relative ratio of both units in the copolymer. The values of randomness parameter for all of these copolyesters are between 0.96 and 1.1. Both values of sequence length and randomness parameter indicate that these copolyesters are random copolymers. Differential scanning calorimeter (DSC) was used to study the isothermal crystallization kinetics and the melting behaviors at heating rates of 10 and 50¢XC/min. The average enthalpy of isothermal crystallization (DH) decreased from 47 to 28 J/g when the ET units in the copolymer increased from 8.9% (C2) to 72.5% (C6), and then the enthalpy increased up to 42 J/g for the C8 copolymer with 90.8% of ET units. The results of Avrami analysis yielded one (n1) or two exponents. The n1 values of all of these copolymers were between 2.03 and 2.98. It suggests that the primary crystallization followed a heterogeneous nucleation with two-three dimensional form of growth. While investigating the isothermal crystallization, DSC specimens were crystallized for 9-14 times of the peak time to ensure the completion of crystallization. Both heating curves at 10 and 50¢XC/min showed multiple endothermic peaks. Triple-melting peaks were detected at lower crystallization temperature (Tc), then the medium and the highest temperature peaks merged gradually to form double-melting peaks with increase in Tc, finally, all three peaks merged together to become a single peak at higher Tc. The low temperature melting peak was associated with the last step of secondary crystallization. The middle temperature melting peak was considered to be characteristic of the melting of the crystals formed in the primary crystallization. The highest temperature melting peak may be due to the melting of crystallite formed by melting and recrystallization during the DSC heating scans. From the results of multiple melting behaviors at a heating rate of 50¢XC/min, the melting peak temperatures of primary crystals were plotted versus the crystallization temperature, Tc. The Hoffman-Weeks plot gave an equilibrium melting temperature, . Using the half-time of crystallization (t1/2) for analysis, regime II¡÷III transition was found for each copolyester. The pairs of ( , ) in unit of ¢XC are (237.1, 193.6), (198.9, 147.3), (187.9, 140.4), (226.6, 164.8), (230.1, 172.0), and (261.1, 208.4) for C2, C3, C4, C6, C7, and C8, respectively. Finally, the overall crystallization rates (1/ t1/2) were compared at equivalent supercooling, DT ( - Tc). The C2 copolyester crystallized the fastest and at lower supercooling. C3 and C4 copolyesters had very similar rates. The C6 copolyester crystallized the slowest and at higher supercooling. At DT = 50~60¢XC, the rates of C7 were close to those of C3 and C4 copolyesters, then the C7 copolyester crystallized faster at higher supercooling. The average value of DH or crystallinity decreased from ¡V47 to ¡V32 J/g when the minor component, ET unit, increasesd from 8.9% (C2) to 37.9% (C4), and then the crystallinity increased from ¡V28 to ¡V42 J/g as the ET unit increases from 72.5% (C6) to 90.8% (C8). It indicated that the number and the distribution of minor component in the main chain should affect the nucleation rate, the growth rate and the final crystallinity of the copolyesters.

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