Homogeneous ring opening graft polymerization of ɛ-caprolactone onto xylan in dual polar aprotic solvents

Homogeneous ring-opening graft polymerization (ROGP) of ɛ-caprolactone (ɛ-CL) onto xylan was investigated in dual polar aprotic solvents, N,N-dimethylformamide/lithium chloride (DMF/LiCl), N,N-dimethylacetamide/LiCl (DMAc/LiCl), and 1-methyl-2-pyrrolidinone/LiCl (NMP/LiCl). The effects of reaction solvents, temperature, and the molar ratio of ɛ-CL to anhydroxylose units (AXU) on the degree of substitution (DS) of xylan-graft-poly(ɛ-caprolactone) (xylan-g-PCL) copolymers and the degree of polymerization (DP) of the attached PCL side chains were investigated. FT-IR and NMR analyses provided the evidence of the occurrence of ROGP reaction. The thermal stability of xylan increased upon ROGP reaction due to the increased length of PCL side chains. With the increased attachment of PCL side chains, the tensile strength and Young's modulus of the films decreased, whereas the elongation at break increased. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) observations provided the evidences of the increased film properties due to the attachment of PCL side chains.