Period-doubling behavior in frontal polymerization of multifunctional acrylates

J Masere
F Stewart
T Meehan
JA Pojman


Front dynamics in the frontal polymerization of two multifunctional acrylate monomers, 1,6-hexanediol diacrylate (HDDA) and trimethylolpropane ethoxylate triacrylate (TMPTA), with Lupersol 231 [1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane] as the initiator, are studied. In most frontal polymerization systems, the dynamics are associated with a planar front propagating through the sample. However, in some cases, front behavior can be altered: the front becomes nonplanar characterized by complex patterns like spin modes and pulsations. To determine how these periodic and aperiodic modes arise, reactant solutions consisting of HDDA diluted with diethyl phthalate (DEP) and TMPTA diluted with dimethyl sulfoxide (DMSO) were used in the study. In the study we reveal frontal behavior characteristic of period-doubling behavior, a doubling of spin heads that degenerate into an apparently chaotic mode. Also, a pulsating symmetric mode has been observed. These observations have a striking similarity to observations made in studies of self-propagating high-temperature synthesis (SHS) in which the addition of an inert diluent afforded a rich variety of dynamical behavior. The degree of cross-linking has also been found to be a bifurcation parameter. The energy of activation of multifunctional acrylate polymerization is a strong function of the degree of polymerization. By adding a monoacrylate (benzyl acrylate: BzAc), such that the front temperature was invariant, we observed a period-doubling bifurcation sequence through changes in the energy of activation, which has not been previously reported. (C) 1999 American Institute of Physics. [S1054-1500(99)01202-1].