Surface functionalization of cellulose by grafting oligoether chains

Two cellulosic substrates (Whatman paper and wood fibres) were chemically modified using different oligoether chains; poly(ethylene) (POE), poly(propylene) (PPG) and poly(tetrahydrofuran) (PTHF) glycols with different lengths were first converted into mono-NCO-terminating macromolecules to allow direct grafting to the cellulose substrates. This step was achieved by reacting the chosen oligoether with 2,4-toluene diisocyanate. The prepared macromolecular grafts were then coupled with the cellulose surface and the resulting treated substrates were fully characterized by contact angle measurements, elemental analysis, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Thus, all the techniques implemented showed clear evidence of successful grafting, namely: (i) when using PPG grafts, the polar contribution to the surface energy decreased from approximately 25 to virtually 0 mJ m−2 and the wettability by water decreased, as the water contact angle shifted from around 40 to above 90°; (ii) nitrogen atoms were detected by elemental analysis and XPS; (iii) the aliphatic carbon contents increased from 11 to about 39–50%, depending on the oligoether used; and (iv) small spheres having about 100 nm diameter were detected by SEM. Moreover, the grafted fibres were submitted to biodegradation tests which showed that they conserved their biodegradable character, although with a slower biodegradation rate. The novelty of the present paper is the direct grafting of the polymeric matrix onto the fibre surface thanks to a new modification strategy involving the use of a diisocyanate as a mediator between the matrix and the reinforcing elements. The covalently linked polymeric chains constituting the matrix could melt under heating, thus, yielding the interdiffusion of the macromolecular grafts and forming the composite.