Kinetic simulation of the thermal degradation of phenethyl phenyl ether, a model compound for the β-O-4 linkage in lignin

被引：36

作者：

Beste, Ariana ^{[1
]}

Buchanan, A. C., III ^{[2
]}

机构：

[1] Univ Tennessee, Joint Inst Computat Sci, Oak Ridge, TN 37831 USA

[2] Oak Ridge Natl Lab, Div Chem Sci, Oak Ridge, TN 37831 USA

来源：

CHEMICAL PHYSICS LETTERS | 2012年 / 550卷

基金：

美国国家科学基金会;

关键词：

BOND-DISSOCIATION ENTHALPIES; DENSITY-FUNCTIONAL THEORY; ALPHA/BETA-SELECTIVITIES; COMPUTATIONAL PREDICTION; PYROLYSIS; THERMOLYSIS; RADICALS; BIOFUELS; COAL;

D O I：

10.1016/j.cplett.2012.08.040

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070305 [高分子化学与物理];

摘要：

Employing kinetic Monte Carlo, we simulated the radical chain propagation of the pyrolysis of phenethyl phenyl ether (PPE), which serves as a model compound for the beta-O-4 linkage in lignin. The input rate constants were obtained with transition state theory based on density functional calculations. Pre- and post-complexes for hydrogen abstraction and beta-scission reactions were included assuming thermal equilibrium. Individual rate constants compare well with experimental estimates. The calculated overall alpha/beta-product selectivity is qualitatively in agreement with experiment. The simulation revealed that the carbon-carbon phenyl shift reaction for the beta-PPE radical is part of the pyrolysis mechanism. (c) 2012 Elsevier B.V. All rights reserved.

引用

页码：19 / 24

页数：6

共 36 条

[1]

Beste A, 2012, RATE CONSTANT CALCUL, P191

[2]

BESTE A, UNPUB

[3]

Computational prediction of α/β selectivities in the pyrolysis of oxygen-substituted phenethyl phenyl ethers [J].