Enthalpy-Entropy Compensation in Polyester Degradation Reactions

[摘要] In an earlier work the author had studied the degradation kinetics of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate (PBT) under nonisothermal conditions in air and N2at heating rates of 5, 10, 15, and 20°C/min. In this paper the kinetic degradation parameters of PET, PTT, and PBT were estimated using the Coats-Redfern method for two different weight loss regions ranging from 2–8% (Zone I) and 8–40% (Zone II). A comparative analysis of the enthalpy-entropy compensation effect for these polyesters in air and N2is presented. A linear relationship was found to exist between entropy and enthalpy values. The following criteria were applied to establish an enthalpy-entropy compensation effect and to check the presence of an isokinetic temperature: (a) Exner’s plot of logk3T1versus logk3T2, and (b) Krug et al. linear regression of ΔHversus ΔG.By the use of the latter two methods, varying isokinetic temperatures were obtained. These temperatures were not in the range of the experimental work conducted, indicating that these systems do not display compensation phenomena.

[学科分类] 工业化学