Synthesis and non-isothermal crystallization behavior of poly(ethylene-co-1,4-butylene terephthalate)s

A series of random poly(ethylene-co-1,4-butylene terephthalate)s (PEBTs), as well as poly(ethylene terephthalate) (PET) and poly(1,4-butylene terephthalate) (PBT), were synthesized by the bulk polycondensation. Their composition, molecular weight, and thermal properties were determined. All the copolymers are crystallizable, regardless of the compositions, which may originate from both even-atomic-numbered ethylene terephthalate and butylenes terephthalate units that undergo inherently crystallization. Non-isothermal crystallization exotherms were measured over the cooling rate of 2.5-20.0 K/min by calorimetry and then analyzed reasonably by the modified Avrami method rather than the Ozawa method. The results suggest that the primary crystallizations in the copolymers and the homopolymers follow a heterogeneous nucleation and spherulitic growth mechanism. However, when the cooling rate increases and the content of comonomer unit (ethylene glycol or 1,4-butylene glycol) increases, the crystallization behavior still becomes deviated slightly from the prediction of the modified Avrami analysis, which is due to the involvement of secondary crystallization and the formation of relatively low crystallinity. Overall, the crystallization rate is accelerated by increasing cooling rate but still depended on the composition. In addition, the activation energy in the non-isothermal crystallization was estimated.