The role of peroxyl radicals in polyester degradation – a mass spectrometric product and kinetic study using the distonic radical ion approach

文献情報

出版日 2015-03-05

DOI 10.1039/C4CP06056C

インパクトファクター 3.676

著者

B. D. Gervasoni, G. N. Khairallah, R. A. J. O'Hair, U. Wille

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要旨

Mass spectrometric techniques were used to obtain detailed insight into the reactions of peroxyl radicals with model systems of (damaged) polyesters. Using a distonic radical ion approach, it was shown that N-methylpyridinium peroxyl radical cations, Pyr+OO˙, do not react with non-activated C–H bonds typically present in polyesters that resist degradation. Structural damage in the polymer, for example small amounts of alkene moieties formed during the manufacturing process, is required to enable reaction with Pyr+OO˙, which proceeds with high preference through addition to the π system rather than via allylic hydrogen atom abstraction (kadd/kHAT > 20 for internal alkenes). This is due to the very fast and strongly exothermic subsequent fragmentation of the peroxyl–alkene radical adduct to epoxides and highly reactive Pyr+O˙, which both could promote further degradation of the polymer through non-radical and radical pathways. This work provides essential experimental support that the basic autoxidation mechanism is a too simplistic model to rationalize radical mediated degradation of polymers under ambient conditions.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

The role of peroxyl radicals in polyester degradation – a mass spectrometric product and kinetic study using the distonic radical ion approach

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Physical Chemistry Chemical Physics

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