Thermal initiator decomposition diacyl peroxides

Aryl migrations are promoted by steric crowding in the initial radical site. This trend is illustrated by data from the thermal decomposition of a series of diacyl peroxides. The amount of product derived from rearrangement increases with the size and number of substituents ... 

Chidsey and coworkers made pioneering works in preparing covalently bonded monolayer films on silicon surfaces by the radical-initiated reaction of 1-alkenes with the H-Si(lll) surfaces. Reactions were carried out in neat deoxygenated alkenes using thermal decomposition of diacyl peroxides as the... 

Some characteristics of initiators used for thermal initiation arc summarized in Table 3.1. These provide some general guidelines for initiator selection. In general, initiators which afford carbon-ccntcrcd radicals e.g. dialkyldiazcncs, aliphatic diacyl peroxides) have lower efficiencies for initiation of polymerization than those that produce oxygen-centered radicals. Exact values of efficiency depend on the particular initiators, monomers, and reaction conditions. Further details of initiator chemistry are summarized in Sections 3.3.1 (azo-compounds) and 3.3.2 (peroxides) as indicated in Table 3,1. In these sections, we detail the factors which influence the rate of decomposition i.e. initiator structure, solvent, complexing agents), the nature of the radicals formed, the susceptibility of the initiator to induced decomposition, and the importance of transfer to initiator and other side reactions of the initiator or initiation system. The reactions of radicals produced from the initiator arc given detailed treatment in Section 3.4. 

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