Extraordinary reinforcement effect of three-dimensionally nanoporous cellulose gels in poly(ε-caprolactone) bionanocomposites.

Three-dimensionally nanoporous cellulose gels (NCG) were prepared by dissolution and coagulation of cellulose from aqueous alkali hydroxide-urea solution, and used to fabricate NCG/poly(ε-caprolactone) (PCL) nanocomposites by in situ ring-opening polymerization of ε-CL monomer in the NCG. The NCG content of the NCG/PCL nanocomposite could be controlled between 7 and 38% v/v by changing water content of starting hydrogel by compression dewatering. FT-IR and solid-state (13)C NMR showed that the grafting of PCL onto cellulose are most likely occurred at the C6-OH groups and the grafting percentage of PCL is 25 wt % for the nanocomposite with 7% v/v NCG. (1)H NMR, XRD, and DSC results indicate that the number-average molecular weight and crystal formation of PCL in the nanocomposites are remarkably restricted by the presence of NCG. AFM images confirm that the interconnected nanofibrillar cellulose network structure of NCG are finely distributed and preserved well in the PCL matrix after polymerization. DMA results show remarkable increase in tensile storage modulus of the nanocomposites above glass transition and melting temperatures of the PCL matrix. The percolation model was used to evaluate the mechanical properties of the nanocomposites, in which stress transfer among the interconnected nanofibrillar network is facilitated through strong intermolecular hydrogen bonding and entanglement of cellulose nanofibers.