Kinetics of the nonstationary photopolymerization of diacrylates

Bratus, A.; Turovki, A.; Medvedevskikh, Yu. G.; Zagladko, E.; Заиков, Г. Е.

doi:10.1002/app.2317.abs

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“…In this interfacial phase, because of the sharply decreas-ing translational and segmental mobility of the macroradicals, the chain termination is monomolecular, so chain propagation leads to macroradical trapping by the polymeric matrix or its freezing. 3,5 Studying the postpolymerization kinetics of dimethacrylates, 8,[10][11][12] that is, the polymerization process after the UV illumination is ended, is needed to determine that the monomolecular chain termination is ordered according to Kohlrausch's stretched exponential law and allows us to numerically evaluate the rate constant of monomolecular chain termination (k t ) in the range of 1 Â 10 À5 to 5 Â 10 À5 m 3 /mol s for different dimethacrylates. The theoretical inference 8,13 of the stretched exponential law also permits us to explain the fractal dependence of k t on the molecular weight of dimethacrylates or the molar volume concentration.…”

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confidence: 99%

Kinetics of bimolecular radical decay in different polymeric matrices

Medvedevskikh

Kytsya

Holdak

et al. 2007

J of Applied Polymer Sci

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Using electron spin resonance spectroscopy, we have studied the kinetics of the bimolecular decay of methacrylic macroradicals in networked and unnetworked polymeric matrices. We have determined that macroradical decay in the entire range of temperatures (20-708C) is definitely ordered to a second-order kinetic reaction equation. We have estimated the activation parameters of the process. Using Smolukhovsky's and Einstein's equations and the fractal dependence of the conformation radius of the macroradical on its polymerization degree, we have obtained an equation for the constant of bimolecular radical decay under diffusion conditions. This equation is in good agreement with all the experimental data and possesses a commonness permitting its use in the analysis of bimolecular chain termination in different reaction zones via polymerization processes until high conversions.

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