Benzoyl Peroxide- and Azobisisobutyronitrile-Initiated Polymerization of Acrylic Acid and Methyl Acrylate in the Temperature Range Close to Room Temperature

The kinetics and mechanism of benzoyl peroxide- and azobisisobutyronitrile-initiated polymerization of acrylic acid and methyl acrylate in the temperature range of 20–40°C have been investigated. In the case of evacuation of the monomer + initiator system, the polymerization proceeds without heating or other energetic impacts on the system. The polymer yield depends on the initiator concentration and the temperature and time of sample thermostating. It has been shown by EPR that the monomers affect the rate of initiator decomposition into radicals. The structures of intermediate complexes formed in the acrylic acid + azobisisobutyronitrile system have been determined by quantum-chemical calculations, and the activation energies of the relevant processes have been calculated.