The gelation process in chainwise crosslinking polymerisation of methacrylate resins with average functionalities of 2.1–50 (1.05–25 methacrylate groups/molecule) was investigated using dynamic mechanical analysis. For all systems a crossover in tan d (tan d independent of frequency) was observed at gelation. The gel time was found to decrease with increasing functionality of the system. Within the measured frequency ranges, power law behaviour for the dynamic modulus was observed at the gel point in all systems. A value of the power law exponent n of 0.4 ^ 0.2 to 0.6 ^ 0.1 (increasing with increasing functionality of the system) was determined for gelation during reactions at T $ Tg∞. This trend suggests that the differences in screening between the systems dominate over the difference in fractal dimension. For reaction temperatures below Tg∞ a value of n 0.3 ^ 01 was obtained, which was attributed to the influence of micro-vitrification.
Посилання на статтю:
Gelation behaviour during chainwise crosslinking polymerisation of methacrylate resins / Jakob Lange, Mats Johansson, Camilla T. Kelly, Peter J. Halley // Polymer. – 1999. – N 40. – P. 5699–5707.