2018
DOI: 10.1021/acs.accounts.8b00250
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The Fate of the Peroxyl Radical in Autoxidation: How Does Polymer Degradation Really Occur?

Abstract: Bolland and Gee's basic autoxidation scheme (BAS) for lipids and rubbers has long been accepted as a general scheme for the autoxidation of all polymers. This scheme describes a chain process of initiation, propagation, and termination to describe the degradation of polymers in the presence of O. Central to this scheme is the conjecture that propagation of damage to the next polymer chain occurs via hydrogen atom transfer with a peroxyl radical. However, this reaction is strongly thermodynamically disfavored f… Show more

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Cited by 82 publications
(70 citation statements)
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“…Note that the lower final hardness is a common feature of the alkyd coatings treated with cobalt alternatives [29]. Furthermore, the long-term stability of the active species, originating from cobalt carboxylates, has also some negative aspects, such as a tendency to early embrittlement and aging as the polymer degradation processes, which are also based on autoxidation and can be promoted by primary driers [30].…”
Section: Performance In Solvent-borne Alkyd Bindersmentioning
confidence: 99%
See 1 more Smart Citation
“…Note that the lower final hardness is a common feature of the alkyd coatings treated with cobalt alternatives [29]. Furthermore, the long-term stability of the active species, originating from cobalt carboxylates, has also some negative aspects, such as a tendency to early embrittlement and aging as the polymer degradation processes, which are also based on autoxidation and can be promoted by primary driers [30].…”
Section: Performance In Solvent-borne Alkyd Bindersmentioning
confidence: 99%
“…The C-H stretching band at 3008 cm −1 is very suitable for the investigation of autoxidation kinetics as it follows consumption of the active substrate (Figure 2a). Based on our previous studies [6,30], the autoxidation of a thin layer of alkyd resins behaves as a reaction of pseudo-first-order until~50% conversion, which is related with sufficient mobility of the system. In later phases of the process, the system becomes solid and the autoxidation slows down more rapidly than the pseudo-first order reactions as it no longer satisfy the rule of a stirred liquid, which becomes evident as deviation from linearity in the logarithmic plots.…”
Section: Kinetics Of Autoxidation Process In Alkyd Filmmentioning
confidence: 99%
“…Due to light, heat, humidity, air, or a combination of those, many polymers undergo degradation [ 313 , 314 , 315 , 316 , 317 , 318 , 319 , 320 , 321 ], as also shown in Figure 7 . It can be either an undesirable process that alters the polymer processing and causes the decrease in the (average) molar mass, or it can be a targeted process if polymer recycling through depolymerization is considered.…”
Section: Case Studies For Connection Of Computational Chemistry and Kinetic Modelingmentioning
confidence: 99%
“…This small discrepancy might have several reasons as described in the publication introducing the oxygen partial pressure method 10. Additionally, the formation of volatile oxygen bearing species, for example water, is conceivable11 and might be responsible for underestimating the oxygen consumption obtained from mass balancing. Samples prepared with Span 80 as the surfactant showed a similar reactivity against oxygen (Figure S10, Supporting Information).…”
mentioning
confidence: 99%
“…Further, ≈25 ppm Ru species are present which might act as the initial radical source. Once polymer centered radicals are formed the classical autoxidation mechanism11 is followed: Oxygen reacts with the (polymer centered) radicals forming peroxyl radicals which rapidly propagates via energetically easily feasible hydrogen atom abstractions from double allylic tertiary carbon centers in pNBD leading eventually to products similar to that formed during oxidation of pDCPD 3,4…”
mentioning
confidence: 99%