<p>The
present study utilized chitosan obtained from crab shell and transition metal
salts as precursors to synthesize chitosan-metal coordination biopolymers of
Mn(II), Fe(III), Co(II) and Ni(II) [i.e Chit-Mn(II), Chit-Fe(III), Chit-Co(II)
and Chit-NI(II) respectively]. The synthesized coordination biopolymers have
been characterized using different instrumental techniques such as
spectroscopic (UV-visible, FT-IR, XRD, EDS, and ICP-OES), thermal analysis (TGA
and DTA), surface analysis (SEM), and hydrogen-temperature programmed reduction
(H<sub>2</sub>-TPR) analysis. Spectroscopic studies confirmed the successful
incorporation of the metals into the biopolymer matrix. Thermal analysis and H<sub>2</sub>-TPR
revealed the reducibility of the Chit-Fe(III) at 120 ℃. While Chit-Fe(III) and
Chit-Ni(II) were inactive, Chit-Co(II) and Chit-Mn(II) were found to be active
towards vinyl acetate polymerization in the presence of aqueous Na<sub>2</sub>SO<sub>3</sub>.
Furthermore, the polyvinyl acetate (PVAc) produced from Chit-Co(II) compared
perfectly with a commercial PVAc and was in higher yield than PVAc produced
from Chit-Mn(II). The polymerization has been shown to proceed via
surface-initiated atom transfer radical polymerization (SI-ATRP), and the viscosity
average molecular weight of PVAc produced has been measured as 25, 078. The density
functional theory approach has been used to ascertain the coordination
orientation of the Chit-Co(II) and explain its high efficiency towards vinyl
acetate polymerization. The catalyst reusability test revealed an insignificant
loss of activity for the Chit-Co(II) after seven cycles of polymerization.
Kinetic studies show that the vinyl acetate polymerization suits the
second-order kinetic model at ambient temperature. Thermodynamic studies also
revealed that chain initiation is an endothermic process while chain
propagation is an exothermic process. The result of this work also suggests an
investigation of chitosan-metal coordination biopolymer via low-ppm ATRP
approach for possible biomedical application.</p>