Organic Catalysis for the Ring-Opening Graft Polymerization of p-Dioxanone with Xylan in Ionic Liquid

Recently, organic catalysis has become a powerful alternative to the use of more traditional metal-based catalysts. In this study, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were applied to mediate the ring-opening graft polymerization (ROGP) of p-dioxanone (PDO) with xylan-based hemicelluloses in ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim]Cl). Excellent control of the molar ratio of the catalyst to anhydroxylose units (AXU) in xylan was found for a good tuning of the weight percent gain (WPG) of xylan-graft-poly(p-dioxanone) (xylan-g-PPDO) copolymers. As a result, the maximum WPG of xylan-g-PPDO copolymers was 431.07% (DMAP/AXU of 2/1), 316.72% (DBU/AXU of 0.2/1), and 323.15% (TBD/AXU of 0.2/1), respectively. The structure of xylan-g-PPDO copolymers was characterized with FT-IR and NMR. The thermal properties of copolymers were investigated using thermogravimetric analysis (TGA/DTG) and differential scanning calorimetry (DSC), and a significant difference was observed regarding the transition temperature (T-g), melting temperature (T-m), and crystallization temperature (T-c).