Cure kinetics of a thermosetting liquid dicyanate ester monomer/high‐Tg polycyanurate material
Authors: Simon S. L. , Gillham J. K. 
Published: April 2003

The cure of a liquid dicyanate ester monomer, which reacts to form a high‐Tg (≈200°C) polycyanurate network, has been investigated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and a dynamic mechanical technique, torsional braid analysis (TBA). The monomer is cured with and without catalyst. The same one‐to‐one relationship between fractional conversion and the dimensionless glass transition temperature is found from DSC data for both the uncatalyzed and catalyzed systems, independent of cure temperature, signifying that the same polymeric structure is produced. Tg is the parameter used to monitor the curing reactions since it is uniquely related to conversion, is sensitive, is accurately determined, and is also directly related to the solidification process. The rate of uncatalyzed reaction is found to be much slower than that of the catalyzed reaction. The apparent overall activation energy for the uncatalyzed reaction is found to be greater than that of the catalyzed reaction (22 and 13 kcal/mol, respectively) from time–temperature superposition of experimental isothermal Tg vs. In time data to form kinetically‐controlled master curves for the two systems. Although the time–temperature superposition analysis does not necessitate knowledge of the rate expression, it has limitations, because if the curing process consists of parallel reactions with different activation energies, as is considered to be the case from analysis of the FTIR data, there should not be a kinetically‐controlled master curve. Consequently, a kinetic model, which can be satisfactorily extrapolated, is developed from FTIR isothermal cure studies of the uncatalyzed reaction. The FTIR data for the uncatalyzed system at high cure temperatures, where the material is in the liquid or rubbery states throughout cure, 190 to 220°C, are fitted by a model of two parallel reactions, which are second‐order and second‐order autocatalytic (with activation energies of 11 and 29 kcal/mol), respectively. Using the model parameters determined from the FTIR studies and the relationship between Tg and conversion from DSC studies, Tg, vs. time curves are calculated for the uncatalyzed system and found to agree with DSC experimental results for isothermal cure temperatures from 120 to 200°C to even beyond vitrification. The DSC data for the catalyzed system are also described by the same kinetic model after incorporating changes in the pre‐exponential frequency factors (due to the higher concentration of catalyst) and after incorporating diffusion‐control, which occurs prior to vitrification in the catalyzed system (but well after vitrification in the uncatalyzed system). Time–temperature‐transformation (TTT) isothermal cure diagrams for both systems are calculated from the kinetic model and compared to experimental TBA data. Experimental gelation is found to occur at a conversion of approximately 64% in the catalyzed system by comparison of experimental macroscopic gelation at the various curing temperatures and iso‐Tg (iso‐conversion) curves calculated from the kinetic model. © 1993 John Wiley & Sons, Inc.