Recycling development and shaping of a thermo-reversible epoxy resin with partial contents of Diels-Alder bonds

Abstract

Thermo-mechanical recycling and reshaping of dynamic covalent networks is a promising field under development that could help to increase thermoset sustainability. Herein, the reprocessing of a partially reversible epoxy resin with a 0.6 Diels-Alder crosslink ratio, which has a relatively high Tg and a simplified manufacturing route, is studied to determine the optimal conditions for its thermomechanical recycling through milling and hot-pressing, and reshaping. Thus, in this work, we have studied the influence of compaction time, pressure, and temperature on recycled bulk properties. Meanwhile, different heating temperatures and times are also tested to evaluate the cured resin shaping to fix a new geometry and to observe its shape-recovering capability. Their characterization reveals that the recycling method generates dense thermosetting polymers with similar crosslinking structure and behavior, comparable to the virgin resin, inducing light post-curing that increases their glass transition temperature (Tg). The most efficient thermo-mechanical recycling conditions consist of the application of isothermal compaction at 130 °C and 150 bar for 30 min, which leads to resin bulks with comparable properties to the neat resin even after 3 cycles of milling and hot-pressing. On the other hand, the synthesized resin has shown excellent shaping due to the structural relaxation induced by the initiation of retro Diels-Alder reaction, adopting new geometries easily when the samples are heated above their Tg (91 °C) and preserving them after cooling to ambient temperature. Moreover, the samples also show high shape-recovering after heating again up to Tg. This reshaping and recovery have been maintained for several cycles without observing an irreversible lack of shape fixing or shape recovery.