This article describes the homopolymerization of isocyanatoethyl methacrylate (IEM) and its copolymerization with methyl methacrylate (MMA) in acetonitrile in the presence of 2,2′‐azobisisobutyronitrile. The constant characteristic of IEM polymerizability (kp2/kte = 128 × 10−3 L mol−1 s−1, where kp is the propagation constant and kte is the termination constant) was determined. The study of IEM reactivity toward MMA gave ratios of 0.88 and 1.20 for IEM and MMA, respectively. The physicochemical properties of the IEM homopolymer and IEM/MMA copolymers were also studied. The glass‐transition temperature of poly(isocyanatoethyl methacrylate) was found to be 47 °C. From the thermogravimetric analysis of the weight‐loss percentage corresponding to the first wave of the thermogram, it was shown that the degradation mechanism of the IEM/MMA copolymers started from the isocyanate group. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4762–4768, 2006

This article describes the use of isocyanatoethyl methacrylate (IEM) as a monomer in telomerization and cotelomerization reactions. First, the selectivity of benzenethiol addition to the unsaturation of IEM is proven. Even with an equimolar amount of reactants, benzenethiol reacts almost selectively with the ethylenic double bonds. The radical telomerization of IEM and its cotelomerization with MMA, in the presence of benzenethiol, has been achieved and shows that control of molecular weight is possible. Finally, the addition of a phosphonated alcohol to these telomers, followed by ester cleavage reactions, leads selectively to families of mono or diphosphonate products. The study of the thermal properties of the cotelomers shows that the degradation starts at 180 °C on the isocyanate group of IEM, and then on the ester group of MMA, and the decomposition is complete at 450 °C. The introduction of the phosphonated ester group decreases the glass transition temperature of the cotelomers, but after hydrolysis these values increase.