Synthesis,free-radical polymerization,and stereochemical configuration of methyl α-p-cyanobenzylacrylate

Methyl α-p-cyanobenzylacrylate was synthesized from dimethyl malonate following well-known organic reactions. The purified monomer was polymerized by a free-radical mechanism in benzene solution, using AIBN as initiator in the interval 50–90°C. The kinetic results seem to indicate an apparent ceiling temperature near 90°C. The analysis by ¹³C-NMR of polymers obtained indicates that the macromolecular chains are predominantly syndiotactic and the tacticity is independent of the polymerization temperature in the experimental interval studied. However, the determination of conditional probabilities for iso- and syndiotactic additions and the persistence ratios indicate that the propagation mechanism for the radical polymerization of methyl α-p-cyanobenzylacrylate does not follow a typical Bernoullian statistics.