A bio-based tetrafunctional epoxy monomer containing
a dicyclo
diacetal linkage was successfully synthesized via acetalization of
protocatechualdehyde (PCA) with erythritol, followed by a reaction
with bioderived epichlorohydrin. The epoxy monomer exhibits good reactivity
with glutaric anhydride in the presence of a zinc(II) acetylacetonate
(ZAA) catalyst and can be cured using a medium-temperature procedure.
The prepared epoxy vitrimer (DGZ) systems exhibit excellent mechanical
and thermal properties resulting from the rigid dicyclo diacetal and
aromatic structures and the high conversion of epoxy groups (αepoxy group). When the ZAA content is 2.5%, DGZ has optimal
integrated mechanical properties, and its impact strength, tensile
strength, and flexural strength can reach 20 kJ/m2, 60
MPa, and 119 MPa, respectively, which can be compared with those of
the commercial bisphenol A epoxy resin cured with a high-temperature
procedure. DGZ systems have a good glass-transition temperature (T
g) of 111–117 °C. The broad glass
transition endows DGZ with a good shape memory effect. The introduction
of dynamic ester bonds in DGZ brings good self-healing ability, welding
ability, and rapid stress relaxation. The self-healing efficiency
of the scratches on the surface of DGZ can reach ∼100% at 200
°C. Owing to the existence of dicyclo diacetal linkages, DGZ
can be completely degraded in 0.1 and 1 M HCl solutions at 25–80
°C. DGZ also has good dielectric properties due to the rigid
dicyclo diacetal and aromatic structures, as well as a high αepoxy group.