Polymer, Vol.41, No.12, 4415-4422, 2000
Bergman cyclopolymerization kinetics of bis-ortho-diynylarenes to polynaphthalene networks. A comparison of calorimetric methods
Bis-ortho-diynylarene (BODA) monomers undergo radical mediated Bergman-type cycloaddition polymerization to yield polynaphthalene networks. This report describes the use of conventional and modulated temperature differential scanning calorimetry to compute the cure kinetic parameters of BODA monomers with different spacer groups. Three different kinetic methods employed here utilize non-isothermal dynamic thermal profiles to estimate activation energies (E-a = 28.7-33.5 kcal/mol [120-140 kJ/mol]) and the first order rate constants (k similar to 10(-5) s(-1) at 210 degrees C) of polymerization. The results obtained from these methods show surprisingly good mutual agreement and also reveal that varying the spacer group has marginal effect on the cure kinetics. It has also been shown that the reaction kinetic information obtained from the dynamic methods must be corrected, when applied under isothermal conditions, to account for sample vitrification. The correction factor has been estimated using modulated temperature differential scanning calorimetry which is capable of monitoring the sample heat capacity in real time. (C) 2000 Elsevier Science Ltd. All rights reserved.