Free‐radical grafting on natural and synthetic polymers is a method widely used to modify these polymers chemically. A number of these chemical systems show an unexpected behaviour of the polymerization rate when the monomer concentration is sufficiently high: it decreases and sometimes it increases afterwards. Here, the effect of varying the monomer concentration on the graft yield when grafting methyl acrylate, vinyl acetate and a mixture of both monomers onto cellulose initiated by ceric ions is discussed, considering a three‐component mechanism of grafting (mechanisms from, onto and from‐to). It is suggested that the unexpected behaviour indicated above is accounted for by the presence of the grafting mechanism from‐to. Some knowledge about the copolymer structure can be reached by using this mechanistic approach.
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I. Casinos (1994) studied this question.