Journal of Applied Polymer Science, Vol.100, No.6, 5066-5086, 2006
Analysis of the epoxy polymerization process with pineridine as the initiator
Measurements of the rate of heating from a polymerization reaction of a popular Epoxy compound, EPON 828, with piperidine as the initiator were made until no further heat output was detectable. The results were obtained using a microcalorimeter at a temperature of 27.5 degrees C. Three experiments were run where the amine equivalents relative to the epoxy equivalents were 0.034, 0.100, and 0.170. At these ratios, the amine was insufficient to bond with all the epoxide rings. Each amine bond produces an oxide ion, which in turn reacts with other epoxide rings creating another oxide ion. This propagation reaction continues until all the epoxy groups are opened and bonded. The heat rate from the epoxy reaction started at a value proportional to the amine content but then it accelerated rapidly by over an order of magnitude and then decelerated after about 50% completion. The heat rate profiles were found to fit a combination of three mechanisms operating during the polymerization. The first stage is generation of an oxide ion by amine reaction and by a hydrogen ion exchange between the unreacted amine and a hydroxyl group present in the EPON 828 molecule. The second stage is the rapid acceleration in heat rate due to a build up of an ether bond from the reaction of the oxide ion with an epoxy group. The peak heating rate occurred when the epoxy rings and ether bonds were equal. The last stage is a classic diffusion process, which is the only mechanism left to allow reaction after the other mechanisms have dissipated. The paper generates rate equations and discusses specific issues arising from the heat rate database. (c) 2006 Wiley Periodicals, Inc.