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Melt grafting of polymethyl methacrylate onto poly(ethylene‐co‐1‐octene) by reactive extrusion: Model compound approach

“…This reaction is characteristic to tertiary peroxides, which undergo a unimolecular reorganization of the primary alcoxyl radical into an alkyl radical (usually a methyl radical). It is also strongly sensitive to temperature as its driving force is entropic 33. With a half life time of ˜ 3.7 min at 150 °C,34 the 2‐ethyl‐hexylcarbonate of tertiobutylperoxy (Luperox TBEC, from Arkema) has a decomposition scheme slightly more complex than DCP.…”

Reactivity of Polyolefins toward Cumyloxy Radical: Yields and Regioselectivity of Hydrogen Atom Transfer

“…The H atom atom transfer reactions of present interest are, in principle, amenable to gas-phase quantum chemical calculations, and several attempts to determine the structures and free energies of relevant transition states have been reported. An early attempt to calculate the overall thermodynamic and thermokinetic parameters for t -BuO • reactivity confirmed that H atom abstraction from unhindered C–H bonds is under enthalpic control . However, calculated activation enthalpies were significantly different from accepted experimental values.…”

Selective Alkane Transformations via Radicals and Radical Cations: Insights into the Activation Step from Experiment and Theory

“…In general, the solvent has only a moderate influence on the kinetic parameters of these reactions. 395,[398][399][400][401] The C-H selectivities reported for t-BuO • in the reactions with a number of linear as well as branched 402 alkanes are k 2°/ k 1°) 12 403 and k 3°/ k 1°) 50, 404 i.e., these are quite high relative to those of OH, Cl, and Br radicals. The chlorination of adamantane with t-BuOOBu-t in CHCl 3 gave a 1-AdCl/2-AdCl ratio of 10:1.5.…”

“…The most recent kinetics 397 gave rate constants of 9.8 × 10 5 and 7.2 × 10 5 M -1 s -1 for cyclohexane ( E a = 3.49 kcal mol -1 ) and cyclopentane ( E a = 3.54 kcal mol -1 ) for the reaction with t -BuO • in PhF. In general, the solvent has only a moderate influence on the kinetic parameters of these reactions. ,− The C−H selectivities reported for t -BuO • in the reactions with a number of linear as well as branched alkanes are k 2 ° / k 1 ° = 12 and k 3 ° / k 1 ° = 50, i.e . , these are quite high relative to those of OH, Cl, and Br radicals.…”