Polymerization of Methyl Methacrylate by Heat-Catalyst and Gamma-Irradiation Methods


  • F. C. Beall
  • A. E. Witt


Methyl methacrylate (MMA) was bulk-polymerized with 0 to 4% crosslinker (ethylene glycol dimethacrylate, EGDM, and trimethylol propane trimethacrylate, TMPTM), initiated with 0.05 to 5% catalyst (Vazo) at 65-75 C or 0.1 to 1 Mrad/hr gamma radiation at 20 C. Heat-catalyzed MMA conversion to polymer vs. time was obtained directly from polymer mass, which indicated that about 90% conversion had occurred at the exothermic peak temperature. The time to the exothermic peak temperature was used to determine sample polymerization time. The over-all polymerization rate varied with the half-power of initiator concentration. An Arrhenius plot of the initiator-time data gave an activation energy of 18 kcal/mole. A log-log relationship was found between crosslinker concentration and polymerization time over the 65-75 C temperature and 0.1-0.4% initiator range. The crosslinkers were found equally efficient in reducing polymerization time. Peak exothermie temperature varied directly with time, irrespective of the initiator and crosslinker concentrations or bath temperature except as they affected time. In the irradiation tests, the crosslinkers exhibited different data fits: log-log with EGDM and semilog for TMPTM. The time-dose rate equation for uncrosslinked MMA was analogous to that for heat-catalyzed polymerization. Molecular weight of uncrosslinked PMMA was determined as a function of temperature and catalyst concentration, and dose rate. Similar molecular weights were obtained for heat-catalyzed polymerization at 65 C and gamma irradiation at 20 C for numerically the same initiator concentration (%) and does rate (Mrad/hr).


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