Open AccessFirst-Principles Model to Evaluate Quantitatively the Long-Life Behavior of Cellulose Acetate Polymers
Author(s) -
Abeer Al Mohtar,
S. L. Nunes,
Joana Silva,
A.M. Ramos,
José Lopes,
Moisés L. Pinto
Publication year - 2021
Publication title -
acs omega
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.779
H-Index - 40
ISSN - 2470-1343
DOI - 10.1021/acsomega.0c05438
Subject(s) - polymer , degradation (telecommunications) , acetic acid , cellulose acetate , sorption , density functional theory , cellulose , chemistry , hydrolysis , thermodynamics , kinetics , materials science , computational chemistry , organic chemistry , computer science , physics , telecommunications , adsorption , quantum mechanics
A deep understanding of the degradation of cellulose diacetate (CDA) polymer is crucial in finding the appropriate long-term stability solution. This work presents an investigation of the reaction mechanism of hydrolysis using electronic density functional theory calculations with the B3LYP/6-31++G** level of theory to determine the energetics of the degradation reactions. This information was coupled with the transition-state theory to establish the kinetics of degradation for both the acid-catalyzed and noncatalyzed degradation pathways. In this model, the dependence on water concentration of the polymer as a function of pH and the evaporation of acetic acid from the polymer is explicitly accounted for. For the latter, the dependence of the concentration of acetic acid inside the films with the partial pressure on the surrounding environment was measured by sorption isotherms, where Henry's law constant was measured as a function of temperature. The accuracy of this approach was validated through comparison with experimental results of CDA-accelerated aging experiments. This model provides a step forward for the estimation of CDA degradation dependence on environmental conditions. From a broader perspective, this method can be translated to establish degradation models to predict the aging of other types of polymeric materials from first-principles calculations.