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

Abstract

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 1H NMR and gel permeation chromatography. The effects on the polymerization of ligand, initiator, solvent, CuCl2 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 Mn of the polymer and low polydispersity (Mw/Mn < 1.3). © 2013 Society of Chemical Industry