A reactive molecular dynamics model of thermal ...（活性分子动力学模型的热）.pdf

Polymer 44 (2003) 883–894 /locate/polymer A reactive molecular dynamics model of thermal decomposition in polymers: I. Poly(methyl methacrylate) a a b, * b Stanislav I. Stoliarov , Phillip R. Westmoreland , Marc R. Nyden , Glenn P. Forney aDepartment of Chemical Engineering, University of Massachusetts Amherst, Amherst, MA 01003-9303, USA bBuilding and Fire Research Laboratory, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 208998665, USA Received 31 August 2002; received in revised form 18 October 2002; accepted 19 October 2002 Abstract The theory and implementation of reactive molecular dynamics (RMD) are presented. The capabilities of RMD and its potential use as a tool for investigating the mechanisms of thermal transformations in materials are demonstrated by presenting results from simulations of the thermal degradation of poly(methyl methacrylate) (PMMA). While it is known that depolymerization must be the major decomposition channel for PMMA, there are unanswered questions about the nature of the initiation reaction and the relative reactivities of the tertiary and primary radicals formed in the degradation process. The results of our RMD simulations, performed directly in the condensed phase, are consistent with available experimental information. They also provide new insights into the mechanism of the thermally induced conversion of this polymer into its constituent monomers. q 2002 Elsevier Science Ltd. All rights reserved. Keywords: Reactive mole