Surface modification of cellulose by PCL grafts

Two cellulosic substrates (microcrystalline cellulose, MCC, and bleached kraft softwood pulps, BSK) were grafted by polycaprolactone (PCL) chains with different molecular weights, following a three-step procedure using non-swelling conditions in order to limit the reaction to their surface. First, one of the two OH PCL ends was blocked by phenyl isocyanate and the reaction product (adduct 1) was subsequently reacted with 2,4-toluene diisocyanate (adduct 2) to provide it with an NCO function, capable of reacting with cellulose. The ensuing PCL-grafted cellulosic materials were characterized by weight gain, elemental analysis, contact angle measurements, attenuated total reflexion–Fourier transform infrared (ATR–FTIR), X-ray photoelectron spectroscopy (XPS) and biodegradation tests. The modification was proven to occur by the presence of nitrogen atoms in the elemental analysis tests and XPS spectra of modified and soxhlet-extracted cellulose. The contact angle measurements have also shown that the surface became as hydrophobic as PCL itself. The polar component of the surface energy of cellulosic substrates before treatment was found to be about 32 and 10 mJ m^?2, for MCC and BSK, respectively. This value vanished to practically zero after grafting with different PCLs. The strategy proposed in the present work is original since, to the best of our knowledge, this paper reports for the first time the chemical “grafting onto” of the cellulose surface by PCL macromolecular structures, with the aim of obtaining fibre–matrix co-continuous fully sustainable and biodegradable composite materials.