A new phosphonated methacrylate, namely dimethyl(methacryloyloxy)methyl phosphonate (MAPC1), has been synthesized using paraformaldehyde and potassium carbonate according to the Pudovik reaction. The quantitative synthesis of MAPC1 was followed by selective hydrolysis of the ester group with sodium bromide to replace NaI (imparting non‐negligible ecological impact). Pure MAPC1(OH) was obtained in high yield and efficiently copolymerized with MMA. The r1 for MAPC1(OH)) and r2 (for MMA) values are 0.99 and 1.02, respectively, which indicates that the monophosphonic groups are statistically linked to the methacrylate backbone. When blended with PVDF, MMA/MAPC1(OH) copolymers show very good adhesion promoters in both dry and wet conditions and subsequently provide good anticorrosive properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4794–4803, 2008

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.