In this study, we designed novel methods to prepare a cellulose graft copolymer series (Cell-g-PDLs) with varied graft chain lengths, via direct ring-opening polymerization (ROP) of unmodified cellulose with alkyl-branched lactones. With increasing alkyl-branched graft chain length of the Cell-g-PDLs, the crystalline phase of cellulose became increasingly weakened, while the glass transition temperature significantly decreased. The latter was attributed to the extended free volume derived from the increased chain end-group concentrations of the branched graft chains. These results suggested that the incorporation of a highly alkyl-branched graft chain into unmodified cellulose is an effective way to improve its thermo-plasticity. Notably, the Cell-g-PDL with the longest graft chain (Cell-g-PDL9) was demonstrative of highly sufficient thermo-plasticity, owing to the enhanced molecular mobility resulting from the reduced frictional forces between the cellulose molecules.

Keywords: Alkyl-branched graft copolymers; Crystalline structure; Hydrogen bonding; Microcrystalline cellulose; Thermoplasticity; ε-Decalactone.

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