Homolytic decompositions of hydroperoxides. I. Summary and implications for autoxidation

Hiatt, R.; Mill, Theodore; Mayo, Frank R.

doi:10.1021/jo01268a022

Cited by 127 publications

(52 citation statements)

References 3 publications

(6 reference statements)

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“…It refers to the activation energy of the free‐radical polymerization initiated by the redox decomposition of the initiator at low temperature. For a reduction–oxidation type of initiation, peroxide can be decomposed rapidly by metal ions at ambient temperature, generating free radicals as follows [32, 33]: where ROOH is the initiator, Co 2+ (Co 3+ ) is the promoter, RO • and ROO • are the free radicals, and L is the ligand octoate or naphthenate.…”

Section: Resultsmentioning

confidence: 99%

Kinetic modeling of nanoclay‐reinforced unsaturated polyester resin

2011

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Curing behavior of an unsaturated polyester (UP) resin containing 1 wt% organically modified clay (OMC) catalyzed with methyl ethyl ketone peroxide (MEKP) initiator and promoted by cobalt naphthenate accelerator was investigated by dynamic differential scanning calorimetry (DSC) at five different heating rates of 5, 10, 15, 20, and 25°C/min. X‐ray diffraction and transmission electron microscopy were used to evaluate the morphology of UP/OMC composites. Results showed a mixture of intercalated and exfoliated morphology. The dynamic DSC curing curves showed a bimodal exothermic peak; therefore, two independent reactions, namely, redox and thermal copolymerizations were assumed. Kinetic parameters were calculated by using autocatalytic model and using Down hill simplex method and Runge–Kutta algorithm for each reaction. The addition of nanoclay resulted in decrease of the activation energy of the redox reaction compared to that of the neat UP resin. Also, the pre‐exponential factor of the first reaction for UP/OMC was less than that of the neat UP. Two factors including decreasing the activation energy and decreasing the number ofcollisions of reactionary components finally resulted in increasing the reaction rate of the first reaction out of the whole reaction in the system containing nanoclay compared to the neat UP resin. It is interesting that nanoclay has no effect on the thermal decomposition reaction. POLYM. COMPOS., © 2011 Society of Plastics Engineers.

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Section: Resultsmentioning

confidence: 99%

Kinetic modeling of nanoclay‐reinforced unsaturated polyester resin

2011

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“…Lipid radicals are highly reactive species and they can readily undergo propagation reactions either by abstraction of a hydrogen atom (10,12) or by reaction with an oxygen molecule in its ground state (11).…”

Section: Propagation and Termination Of Autoxidationmentioning

confidence: 99%

“…The radical formed by reaction of a phenol with a lipid radical is stabilised by delocalisation of the unpaired electron around the aromatic ring as indicated by the valence bond isomers (20). (20) The stability of the phenoxyl radical (A') reduces the rate of propagation of the autoxidation chain reaction since propagation reactions such as (21)- (23) are very slow compared with (10), (11) and (12),…”

Section: Primary (Chain-breaking) Antioxidantsmentioning

confidence: 99%

The Mechanism of Antioxidant Action in Vitro

1990

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“…This reaction was accelerated in the presence of light and suggests a radical pathway similar to the decomposition of organic peroxide analogues like tert-butyl hydroperoxide to tert-butyl alcohol and O 2 . [17] Together, these data support a mechanism involving either coordination of O 2 In conclusion, oxygenation of Pd 0 and direct insertion of O 2 into a Pd II À hydride bond have both been shown to be possible pathways for the reaction between O 2 and Pd complexes. Experimental and theoretical evidence support the viability of both mechanisms, but further experimental work will be required to elucidate the details of these pathways in which ligand and additives will most likely have a profound influence.…”

mentioning

confidence: 65%