Trapping bond exchange phenomenon revealed for off-stoichiometry cross-linking of phase-separated vitrimer-like materials.

Vitrimer materials combined with nano-phase separated structures have attracted attention, expanding the tuning range of physical properties, such as flow and creep properties. We recently demonstrated a preparation of vitrimer-like materials with phase-separated nanodomains in which dissociative bond exchange -alkylation of quaternized pyridine was operated. In this study, we demonstrate a new finding about the bond exchange mechanism: that is, the trapping bond exchange phenomenon. The component polymer is a poly(acrylate) containing pyridine side groups randomly along the chain, which is cross-linked by diiodo molecules pyridine-iodo quaternization, where the quaternized pyridines are aggregated to form nano-size domains. When the cross-linking reaction is performed at an off-stoichiometric pyridine : iodo ratio (, an excess of pyridine groups), free pyridine groups are located in the matrix phase. Since the bond exchange in the present system progresses in an inter-domain manner, the dissociated unit bearing pendant iodo is trapped by the free pyridine groups in the matrix, which generates other small aggregates. This trapping phenomenon greatly affects the relaxation and creep properties, which are very different from those found in conventional knowledge about vitrimer physics.