Facile Preparation Route for Nanostructured Composites: Surface-Initiated Ring-Opening Polymerization of ε-Caprolactone from High-Surface-Area Nanopaper

In this work, highly porous nanopaper, i.e., sheets of papers made from non-aggregated nanofibrillated cellulose (NFC), have been surface-grafted with poly(ε-caprolactone) (PCL) by surface-initiated ring-opening polymerization (SI-ROP). The nanopaper has exceptionally high surface area (∼300 m(2)/g). The "grafting from" of the nanopapers was compared to "grafting from" of cellulose in the form of filter paper, and in both cases either titanium n-butoxide (Ti(On-Bu)4) or tin octoate (Sn(Oct)2) was utilized as a catalyst. It was found that a high surface area leads to significantly higher amount of grafted PCL in the substrates when Sn(Oct)2 was utilized as a catalyst. Up to 79 wt % PCL was successfully grafted onto the nanopapers as compared to filter paper where only 2-3 wt % PCL was grafted. However, utilizing Ti(On-Bu)4 this effect was not seen and the grafted amount was essentially similar, irrespectively of surface area. The mechanical properties of the grafted nanopaper proved to be superior to those of pure PCL films, especially at elevated temperatures. The present bottom-up preparation route of NFC-based composites allows high NFC content and provides excellent nanostructural control. This is an important advantage compared with some existing preparation routes where dispersion of the filler in the matrix is challenging.