Reactivities of methacrylate derivatives in radical polymerization as evaluated by mercury method

Reactivities of methyl methacrylate derivatives bearing substituents on the ester methyl group have been investigated by competitively adding a cyclohexyl radical generated by a reaction of cyclohexylmercuric chloride with sodium borohydride (mercury method) to these substituted methacrylates and methyl methacrylate or styrene. The relative rate constants of the cyclohexyl radical addition have been found to be nicely correlated with parameters such as Traft α* constants of alkyl esters, Q–e values, lowest unoccupied molecular orbital energies, β‐carbon chemical shifts, and relative reactivities toward a polystyryl radical, indicating that the mercury method is a simple and useful technique for evaluation of the relationship between structure and reactivity of vinyl monomers in their radical polymerization, even when the structural modification is small. Copyright © 1988 John Wiley & Sons, Inc.