  Vitrimers - a class of polymer networks which are covalently crosslinked and
insoluble like thermosets, but flow when heated like thermoplastics - contain
dynamic links and/or crosslinks that undergo an associative exchange reaction.
These dynamic crosslinks enable vitrimers to have interesting
mechanical/rheological behavior, self-healing, adhesive, and shape memory
properties. We demonstrate that vitrimers can self-assemble into complex meso-
and nanostructures when crosslinks and backbone monomers strongly interact.
Vitrimers featuring polyethylene (PE) as the backbone and dioxaborolane
maleimide as the crosslinkable moiety were studied in both the molten and
semi-crystalline states. We observed that PE vitrimers macroscopically phase
separated into dioxaborolane maleimide rich and poor regions, and characterized
the extent of phase separation by optical transmission measurements. This phase
separation can explain the relatively low insoluble fractions and overall
crystallinities of PE vitrimers. Using synchrotron-sourced small-angle X-ray
scattering (SAXS), we discovered that PE vitrimers and their linear precursors
micro-phase separated into hierarchical nanostructures. Fitting of the SAXS
patterns to a scattering model strongly suggests that the nanostructures -
which persist in both the melt and amorphous fraction of the semi-crystalline
state - may be described as dioxaborolane maleimide rich aggregates packed in a
mass fractal arrangement. These findings of hierarchical meso- and
nanostructures point out that incompatibility effects between network
components and resulting self-assembly must be considered for understanding
behavior and the rational design of vitrimer materials.
