Polymerization Reaction Dynamics of Ethylene-Glycol Methacrylates and Dimethacrylates by Calorimetry
Profiles of reaction rate as a function of time were obtained for free radical crosslinking polymerizations of ethylene glycol methacrylates and dimethacrylates using differential scanning calorimetry. Copolymerizations of ethylene glycol monomethacrylates with small amounts of dimethacrylate crosslinking agents were studied in addition to homopolymerizations of dimethacrylates. In the former case, the effects of the crosslinking agent, initiator, solvent, and the pendent ethylene glycol chain length were investigated. Typically, a sharp increase in the reaction rate was observed which was attributed to autoacceleration. The time period before the onset of autoacceleration increased and the maximum reaction rate decreased as the solvent concentration or the pendent chain length were increased or the crosslinking agent concentration was decreased. These results were explained by an increase in the mobility of the growing polymer leading to a decrease in the magnitude of the gel effect. Studies of dimethacrylates yielded similar results for the effect of solvent. However, the maximum reaction rate increased when the number of repeating units between the methacrylate functionalities was increased from one to four, but decreased when the number of repeating units was increased from four to nine. Photopolymerization experiments indicated that radicals with significantly different lifetimes might be present in dimethacrylate homopolymerizations.
Published Article/Book Citation
Polymer, 33:8 (1992) pp.1683-1689.