Polybenzoxazines
(PBzs) are emerging as a highly promising and
superior class of thermoset polymers for a variety of applications.
However, it remains a significant challenge to substantially lower
the ring-opening polymerization (ROP) temperature with an ease in
processability. On the other hand, biomacromolecule chitosan (CS)
is explored extensively, but its practical applications have been
precluded by poor thermal and mechanical properties. Here, we developed
a fully biobased copolymer of vanillin benzoxazine (V-fa) monomer
with CS, which is effective in providing mutual benefits, effective
lowering in ROP temperature of benzoxazine (70 °C), and an enhanced
thermal stability of CS (by 85 °C, and with char yield of ∼32%).
To understand this unusual lowering in ROP temperature, we investigated
the structural interaction mechanism between solvated CS and V-fa
using in situ NMR studies. The analysis of fully intercalated co-structure
demonstrated that there is a strong preference for ROP over Schiff
base reaction. It is anticipated that benzoxazine molecules move within
the interplanar distance of CS as supported by powder X-ray diffraction
studies. An increase in V-fa content in feed ratio led to a placement
of V-fa units from random to a systematic and hierarchical arrangement
within the CS framework followed by its subsequent polymerization.
The synergistic interactions were further supported by Fourier transform
infrared, differential scanning calorimetry, scanning electron micrsocopy,
thermogravimetric analysis, and tensile studies. Current work represents
preparation of CS benzoxazine copolymers using a low-cost, efficient,
and sustainable approach to assist metal-free ROP reaction of Bz to
afford low curable temperature processable films. A new strategy is
devised for the utility of CS-PBzs copolymers, enabling their extension
to innovative applications in cross-domains.