Unique effects of microwave heating on polymerization kinetics of poly(methyl methacrylate) composites

•The MWH speeds the MMA material polymerization and changes the kinetics model.•A novel concept of MWH action based on activation complexes formation is presented.•The Selective Energy Transfer model is used to explain the effects of MWH.•The kinetics parameters under MWH are lower than for CH.•The activation energy for both MWH and CH polymerization is quantized.

The effects of heating mode (conventional and microwave) on the kinetics of isothermal polymerization of MMA composite materials were investigated. Isothermal kinetics curves at temperature range from 343 K to 363 K for both conventional (CH) and microwave heating (MWH) were determined. It was found that the polymerization of MMA composite materials was kinetically elementary reaction for both CH and MWH. The kinetics of CH polymerization can be described by the model of phase-boundary controlled process (contracting volume), whereas the kinetics of MWH polymerization can be described by the model of first-order chemical reaction. The kinetics parameters (Ea and ln A) of the polymerization under microwave heating are lower than for conventional heating. The established decreases in the activation energy and pre-exponential factor under the MWH compared to the CH is explained with the increase in the energy of ground vibrational level of the C–O valence vibrations (ν = 987 cm−1) in methyl methacrylate molecule and with the decrease in its anharmonicity factor which is caused with the selective resonant transfer of energy from the energetic reservoir to the oscillators in methyl methacrylate molecules.

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