Intermolecular effects in macromolecular reactions—1. Decomposition of poly(t-butyl acrylate_

✍ Scribed by A.D. Litmanovich; V.O. Cherkezyan

• Publisher: Elsevier Science
• Year: 1984
• Tongue: English
• Weight: 346 KB
• Volume: 20
• Category: Article
• ISSN: 0014-3057
• DOI: 10.1016/0014-3057(84)90125-3

✦ Synopsis

Decomposition of poly(t.-butyl acrylate) (PTBA) at 165-200 < proceeds with strongly pronounced acceleration. A comparison of initial rates of PTBA decomposition in the pure state and in a composition with polyacrylic acid reveals a substantial contribution of intermolecular interactions to the acceleration. The proposed mechanism of the acceleration includes an interaction of a t.-butyl acrylate group with two carboxylic groups simultaneously, provided at least one of these COOH groups is not the nearest neighbour of the ester group. On the basis of a theory published previously, a mathematical model of the macromolecular reaction in a polymer melt is developed. The model permits quantitative description of the kinetics of PTBA decomposition. Rate constants and activation energies of the thermal and autocatalytic stages of the reaction have been estimated. The results show the intermolecular interactions to be a decisive factor in PTBA decomposition.