The living cationic polymerization of p-methoxystyrene using the 1-(4-methoxyphenyl)ethanol/B(C6F5)3 initiating system in solution and in aqueous dispersion is reported. Solution experiments first showed that the molar mass of the obtained polymers increases in direct proportion to the monomer conversion and the molar mass distribution stays narrow in the course of the polymerization (M w/M n ∼ 1.2). The living nature of the growing chains was confirmed by sequential monomer addition experiments, although matrix-assisted laser desorption ionization time-of-flight mass spectroscopy (MALDI-TOF-MS) revealed some hydroxyl elimination under monomer-starved conditions. Aqueous suspension polymerization of p-methoxystyrene using the same initiating system did not show a good control of molar masses, since after polymerization has proceeded at the interface up to critical DP, oligomers terminated by water penetrate inside the particles where they stop propagating. This limitation was leveled off for the first time by polymerizing p-methoxystyrene in an aqueous dispersion, i.e., in a mixture of H2O:CH3CN 3:2 (v/v). Under these conditions, the hydroxyl-terminated poly(p-methoxystyrene)s can be reactivated by B(C6F5)3 located inside the particles to reinitiate the polymerization; molar masses thus increase with conversion, up to 3000 g mol-1, and exhibit a narrow molar mass distribution (M w/M n ∼ 1.3) and an almost pure hydroxylated functionality.

In this study, a novel polymerizable ionic liquid monomer (ILM) based on a bisimidazolium salt was first synthesized in order to substitute bisphenol A diglycidyl ether (DGEBA) as a starting material, avoiding the use of highly toxic and carcinogenic bisphenol A and epichlorohydrin products. From such a new epoxy monomer, an epoxy network was prepared from the copolymerization between the bisimidazolium salt and isophorone diamine (IPD). Subsequently, the properties of this novel ionic liquid based polymer network have been investigated in terms of polyaddition reaction kinetics as well as the architectureproperties, i.e., thermal stability, surface properties, and the mechanical performances. In addition, for the first time, molecular dynamics simulations were combined with experimental measurements in order to confirm the experimental data as well to be able to predict the physical behaviors from their architecture, molecular scale structuration, and thermomechanical properties of the resulting network. Finally, the substitution of DGEBA by this ILM led to a thermosetting polymer with high thermal stability (up to 450 °C), hydrophobic behavior (21 mJ m −2 ), and promising mechanical performances (1.7 GPa) including a shape memory behavior.