Multistep Kinetic Behavior in the Thermal Degradation of Poly(l‑Lactic Acid): A Physico-Geometrical Kinetic Interpretation

• Published in: The journal of physical chemistry. B Vol. 118; no. 38; pp. 11397 - 11405
• Main Authors: Yoshikawa, Masahiro, Goshi, Yuri, Yamada, Shuto, Koga, Nobuyoshi
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 25.09.2014
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp507247x

A physico-geometrical kinetic interpretation of the thermal degradation of poly(l-lactic acid) (PLLA) is described based on the results of a kinetic study using thermogravimetry (TG) and the microscopic observation of the reaction process. From the physico-geometrical viewpoint, the reaction process is separated into two different stages characterized by a surface reaction of the molten PLLA in the initial reaction stage followed by continuous bubble formation and disappearance in the established reaction stage. The generally reported trend of variation in the apparent activation energy as the reaction advances is explained by the partial overlapping of these two reaction stages. The kinetic rate data obtained using TG were kinetically separated into those for the respective reaction stages by optimizing the kinetic parameters. The significance of the kinetic results is discussed in terms of the physico-geometrical characteristics of the reaction. Such systematic kinetic analyses demonstrate the importance of considering the physico-geometrical perspective when interpreting the kinetic results for the thermal degradation of polymers.