Abstract
AbstractThe “living” radical polymerization of methyl methacrylate with the aged Cr2+ plus benzoyl peroxide (BPO) system in the presence of various amines as ligand has been studied in N,N′‐dimethylformamide. Aliphatic amines such as ethylenediamine diminished the rate of polymerization, while dipyridyl (dipy) and o‐phenanthroline (phen) accelerated the polymerization rate as follows: phen > dipy > pyridine ≃ none. Specifically, the rate of polymerization in the presence of phen had a maximum value at [phen]/[Cr2+] = 0.5. The retardation of polymerization by aliphatic amines was explained by the interaction of BPO with free and coordinated amines. The latter result may support the mechanism involving the complexed radical proposed for the living radical polymerization with the aged Cr2+ + BPO system. In the presence of phen the effects of aging period and aging temperature as well as polymerization temperature were studied and the nature of complexed radicals is discussed.
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