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• W2022342208 abstract "Abstract Mechanisms for pyrolysis of poly(α-methylstyrene) must rationalize high selectivity for monomer formation, negligible formation of volatile oligomers, and notably slow decrease in molecular weight compared with the rate of weight loss, i.e., unzipping dominates both back-biting and transfer. Backbone homolysis should form both a tert -benzylic radical R tb and a prim radical R p , with formation of the latter potentially supplemented in chain propagation steps emanating from the former. Hence product-forming pathways characteristic of each are expected to compete. Simulations of initial product distributions based on assigned rate constants for chain propagation steps indicate that R tb is indeed predicted to efficiently unzip with minimal transfer or back-biting. However, R p is predicted to give comparable amounts of transfer and back-biting with minimal unzipping, behavior inconsistent with experimental data. The proposed escape from this impasse is a previously unrecognized pathway, 1,2-phenyl shift in R p to form a tert radical. If it undergoes β-scission, the net result is an inter-conversion of R p to R tb . Quantitative simulations suggest that this sequence is indeed highly competitive with other reactions of R p and thus efficiently subverts the otherwise expected propagation of chains emanating from R p ." @default.
• W2022342208 created "2016-06-24" @default.
• W2022342208 creator A5061285821 @default.
• W2022342208 date "2007-10-01" @default.
• W2022342208 modified "2023-09-27" @default.
• W2022342208 title "Mechanistic analysis and thermochemical kinetic simulation of the products from pyrolysis of poly(α-methylstyrene), especially the unrecognized role of phenyl shift" @default.
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• W2022342208 doi "https://doi.org/10.1016/j.jaap.2007.05.005" @default.
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