Abstract <p>A kinetic model is used to theoretically describe the relationship between the curing rate of methyl methacrylate adhesive and the mole fraction of syndiotactic triads in polymethyl methacrylate formed during adhesive curing with the synthesis conditions and the composition of macroinitiator used for curing. A macroinitiator was obtained by radical coordination polymerization in the presence of a peroxide or hydroperoxide initiator and zirconocene dichloride. It is shown that an increase in the initial concentration ratio of zirconocene dichloride to the initiator’s initial concentration during the macroinitiator synthesis [<i>Mc</i>]<sub>0</sub>/[<i>I</i>]<sub>0</sub> in the range from 0.1 to 10 (at [<i>I</i>]<sub>0</sub> = 1 mmol/L) increases the concentration of coordination active centers in the macroinitiator by at least an order of magnitude, which increases the adhesive curing rate. At the same time, the mole fraction of syndiotactic triads in the polymethyl methacrylate formed during adhesive curing decreases. An increase in the macroinitiator synthesis’s temperature in the range of 323–343 K has a significantly weaker effect on the concentrations of active centers than a change in [<i>Mc</i>]<sub>0</sub>/[<i>I</i>]<sub>0</sub> in the range of 0.1–10, which results in a weaker effect of temperature of the macroinitiator synthesis on the adhesive’s curing rate and the molar fraction of syndiotactic triads in the composition of polymethyl methacrylate.</p>

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Kinetics of Curing of Methyl Methacrylate Adhesive under the Action of a Macroinitiator Obtained by Radically Initiated Polymerization in the Presence of Zirconocene Dichloride

  • D. A. Shiyan,
  • K. A. Tereshchenko,
  • A. A. Osipov,
  • V. P. Bondarenko,
  • N. V. Ulitin,
  • A. O. Kaidarova,
  • H. E. Harlampidi,
  • S. V. Kolesov,
  • O. V. Stoyanov

摘要

Abstract

A kinetic model is used to theoretically describe the relationship between the curing rate of methyl methacrylate adhesive and the mole fraction of syndiotactic triads in polymethyl methacrylate formed during adhesive curing with the synthesis conditions and the composition of macroinitiator used for curing. A macroinitiator was obtained by radical coordination polymerization in the presence of a peroxide or hydroperoxide initiator and zirconocene dichloride. It is shown that an increase in the initial concentration ratio of zirconocene dichloride to the initiator’s initial concentration during the macroinitiator synthesis [Mc]0/[I]0 in the range from 0.1 to 10 (at [I]0 = 1 mmol/L) increases the concentration of coordination active centers in the macroinitiator by at least an order of magnitude, which increases the adhesive curing rate. At the same time, the mole fraction of syndiotactic triads in the polymethyl methacrylate formed during adhesive curing decreases. An increase in the macroinitiator synthesis’s temperature in the range of 323–343 K has a significantly weaker effect on the concentrations of active centers than a change in [Mc]0/[I]0 in the range of 0.1–10, which results in a weaker effect of temperature of the macroinitiator synthesis on the adhesive’s curing rate and the molar fraction of syndiotactic triads in the composition of polymethyl methacrylate.