Aqueous free-radical polymerization of PEGMEMA macromer: kinetic studies via an on-line 1H NMR technique

Abstract

Free-radical polymerization of polyethylene glycol methyl ether methacrylate macromer (PEGMEMA) was studied in aqueous media and in the presence of potassium persulfate (KPS) as water soluble initiator. An on-line nuclear magnetic resonance (NMR) method was applied to record the reaction data and determine the monomer conversion at various times during the polymerization reaction progress. 1H NMR spectrum of reaction mixture containing monomer, initiator and resultant polymer was continuously recorded in NMR instrument with the increase of reaction time. By processing the obtained data from NMR spectrum, the rate equation can be derived and reaction order can be determined with regard to monomer and initiator concentration. In other words, to determine the order of polymerization with regard to the concentration of reactants in free-radical polymerization of PEGMEMA, macromer samples with different amounts of monomer and KPS were prepared and polymerized at 50 °C. Orders of reaction with respect to monomer and initiator molar concentrations were equal to 1.025 and 0.480, respectively. The obtained values for reaction orders in this study were consistent with the classical kinetic rate equation in which the dependency of polymerization rate (Rp) on monomer and initiator concentrations was equal to 1 and 0.5, respectively. To measure polymerization activation energy (Ea), the effect of reaction temperature on the polymerization rate was investigated and Ea = 37.08 kJ/mol was obtained at the temperature range of 40–50 °C.