Free Radical Generation by Olefins
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This chapter includes the following topics: Reactions of Retrodisproportionation Chain Initiation in Thermal Radical PolymerizationAtmospheric chemistry
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Structures of Sulphur - Centered Radicals (D. Armstrong & D. Chipman). Thermochemistry of Sulfur Radicals (D. Armstrong). SOx Radical Monoanions - Reactions in Solution and in the Gas Phase (R. Huie & L. Sieck). The Chemistry of Gas Phase Organic Sulfur - Centered Radicals (S. Urbanski & P. Wine). Sulfur Centered Reactive Intermediates as Studied by Radiation Chemical and Complementary Techniques (K. Asmus & M. Bonifacic). Reactions of Aromatic Thiyl Radicals (O. Ito). Reactions of Thiyl Radicals in the Solid Phase (Y. Razskazovskii & M. Mel'nikov). The Sulfoxyl Radicals: Formation, Structure and Kinetics (Y. Razskazovskii, et al.). Organic Sulfuranyl Radicals (P. Margeretha). Thiyl Radicals in Biology: Their Role as a Molecular Switch Central to Cellular Oxidative Stress (P. Wardman). Sulfur Centered Radicals in Organic Synthesis (C. Chatgilialoglu, et al.).
Thermochemistry
Radical disproportionation
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Polypropylene
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This chapter contains sections titled: Introduction Free radical rearrangements Other routes to triphenylmethyl radicals The persistent radical effect Properties of triphenylmethyl radicals Steric effects and persistent radicals Substituted triphenylmethyl radicals and dimers Tris(heteroaryl)methyl and related triarylmethyl radicals Delocalized persistent radicals: analogues of triarylmethyl radicals Tetrathiatriarylmethyl (TAM) and related triarylmethyl radicals Perchlorinated triarylmethyl radicals Other triarylmethyl radicals Diradicals and polyradicals related to triphenylmethyl Outlook Acknowledgements References
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Peroxide
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This chapter contains sections titled: C-, N-, and O-centered Radicals Si-, P-, and S-centered Radicals CC-, NN-, and OO-centered Radicals NO- and NO2-centered Radicals PO-, PP-, SO-, SS-, and SO2-centered Radicals
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Abstract O and OH radicals are the most important reactive oxygen species (ROS) in the plasma treatment of polymer surfaces. In our previous studies, we found that the modification efficiency of polypropylene (PP) surface by O radicals was approximately four times higher than that by OH radicals. This observation contrasts with the well-established fact that the chemical reactivity of O radicals with saturated hydrocarbons (CnH2(n+1)) is 50–60 times lower than that of OH radicals. In this study, molecular dynamics (MD) simulations with a reactive force field (ReaxFF) were used to explain this contradiction. The results showed that both O and OH radicals penetrated into the bulk of PP, namely physical adsorption occurred. The surface penetration depth of O radicals was greater than that of OH radicals. Compared to the case of OH radicals, alkoxy radicals (RO·) are more readily formed on the interactions of the PP surface with O radicals. Furthermore, the β-scission (splitting the C–C bonds) of alkoxy radicals can be accelerated by the physically adsorbed O radicals, leading to earlier breakage of PP chains. The improved efficacy of surface modification of PP upon exposure to O radicals, in contrast to OH radicals, can be attributed to the distinctions observed in the above three crucial processes.
ReaxFF
Reactivity
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Free radicals are produced by the reaction of hydroxyl radicals and amino-radicals with alkenes or halogenated alkenes. In each case the e.s.r. spectra are attributable to radicals formed by primary addition of an OH or NH2 fragment to the olefinic double bond.
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Introduction. Generation of Free Radicals. Elementary Reactions of Free Radicals. Reactivity of Free Radicals. Nonchain Radical Reaction. Nonbranched Chain Reactions. Branched Chain Reactions. Oscillating Reactions. Chemical Lasers. Free Radicals and Biochemistry. Radicals in the Cosmos and in the Atmosphere. Index. c. 304 pp., 7x10, due January 1989, ISBN 0-8493-5387-4. Illustrated by:
Chain reaction
Reactivity
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