Kinetics of atom transfer radical polymerization of crosslinkable terpolymer P(MMA‐BA‐HEMA)

A crosslinkable terpolymer P( MMA‐BA‐HEMA ) was prepared by atom transfer radical copolymerization of 2‐hydroxyethyl methacrylate, methyl methacrylate and butyl acrylate. The structure of the terpolymer was characterized by 1 H NMR and gel permeation chromatography. The effects on the polymerization of ligand, initiator, solvent, CuCl 2 added in the initial stage and reaction temperature were investigated. The optimal reaction conditions were ethyl 2‐bromopropionate as initiator, CuCl / PMDETA as catalyst, cyclohexanone as solvent, catalyst/ligand = 1:1.5, [M] 0 :[I] 0 = 200:1 and temperature 70 °C. The reaction followed first‐order kinetics with respect to monomer concentration, indicating the best control over the polymerization process, a constant concentration of the propagating radical during the polymerization, efficient control over M n of the polymer and low polydispersity ( M w / M n < 1.3). © 2013 Society of Chemical Industry