The radical polymerization of polar monomers initiated by the air3-benzoyl peroxide system

The Chemistry of Organomettallic and Organometalloid Peroxides

“…Grignard (83), Sabatier (176), and Hesse (89) converted other Grignard reagents with molecular oxygen to the corresponding hydroxy derivatives. In 1909, Wuyts (209) proposed that these reactions proceed via peroxide intermediates which are reduced by the unreacted Grignard reagent to yield the hydroxy derivatives (95,130,135,146).…”

“…Triisobutylaluminum, diisobutylisobutoxyaluminum, tri ethylaluminum, diethylethoxyaluminum, or diisobutylaluminum chloride in the presence of oxygen in xylene initiate free radical polymerization of vinyl monomers (79,132). Similarly, a mixture of triethylaluminum and cumyl hydroperoxide in octane initiates the polymerization of vinyl monomers.…”

Problems of control of the reactivity of macroradicals and the growth of polymer chains

“…This interaction occurs either directly at the reaction centre (with participation of the unpaired electron), or at the functional group (where X is a functional group, Y is the hydrogen atom or a methyl group), or simultaneously at both sites with delocalisation of the unpaired electron On the basis of studies of copolymerisation of MMA with electron-donating monomers involving binary trialkylborane ± OEP initiators, 11,14 it was suggested that the Lewis acid might be involved in the coordination interaction with the poly(methyl methacrylate) (PMMA) radical; this hypotheisis was proved by EPR spectroscopy 28,46 and confirmed by quantum-chemical calculations. 47 In addition, it was shown by quantum-chemical calculations 48 that in the case of radicals containing a C=O group in the a-position to the reaction centre, the reaction centre is delocalised over three atoms.…”