This review paper gathers almost one hundred recent publications devoted to the synthesis and the free radical (co)polymerization of phosphonate vinyl monomers. Different synthetic approaches are discussed to introduce the phosphonate moieties into vinyl monomers, focusing especially on recent advances. Allyl-type, vinyl-type, styrenic-type and (meth)acrylic-type monomers bearing phosphonate groups (i.e. either mono or bisphosphonate) are considered with a special care about their reactivity in free radical (co)polymerization. It is shown that depending on the position of the phosphonate moieties the reactivity of the vinyl monomers is thus modified. For instance, free radical polymerization of vinyl phosphonate monomers is mainly dominated by transfer reactions, whereas the propagation rate of para-vinylbenzyl phosphonate monomers is enhanced by the phosphonate group. According to the structure of the phosphonate-bearing (co)polymers, the resulting properties are also investigated.
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