Oxidation of Unsaturated Compounds. II. Reactions of Styrene Peroxide¹

Reversible addition–fragmentation chain transfer (RAFT) polymerization of styrene in the presence of oxygen

“…1 and 2, the presence of oxygen could slightly accelerate the polymerization; it was supposed that the oxygen might be involved in the initiation process. It had been reported that the interaction of St with oxygen could yield PS peroxide (PSP) under the similar experimental conditions with this work, and the rate of absorption of oxygen by St increased with temperature [32,33]. The PSP was also reported to be used as thermal [34] or UV [35] initiator for the polymerization of MMA and St. To confirm it, an iodometric method [29] was used to measure the concentration of PSP in the polymerization.…”

The real radical generator other than main‐product hydroperoxide in lipid autoxidation

“…Such formation of a peroxy bridge is known to occur in the autoxidation of conjugated olefins, giving relatively unstable olefin-oxygen copolymers; and their instability is explained in terms of concerted decomposition of their repeated α,β-diperoxide structures as shown in Scheme 2 (12,13). The formation of aldehydes is thought to be energetically favorable for the reaction.…”

para-Substituted Poly(styrene peroxide)s: Synthesis, Characterization, Thermal Reactivities, and Chain Dynamics Studies in Solution

“…Small amounts of products other than formaldehyde and p-substituted benzaldehyde (PSB), could be formed via disproportionation, which is also operative in PSP. [27] The above mechanism indicates that the exotherm observed in the DSC is due to the primary degradation of the polymer. This finds support from the thermochemical calculations.…”

“…The thermal stability of the three polyperoxides could be compared from the E d values: the lower the E d values, the higher is the rate of thermal degradation. On the basis of the degradation product analysis and the E d values for the degradation process (corresponding to the cleavage of the O1O bond), a radical chain scission mechanism, similar to that for PSP, [27] could be proposed for the degradation (Scheme 1). Small amounts of products other than formaldehyde and p-substituted benzaldehyde (PSB), could be formed via disproportionation, which is also operative in PSP.…”