Cellulose from cotton fibers was functionalized through a dissolution–regeneration process with phosphonate-based ionic liquids (ILs): 1,3-dimethylimidazolium methylphosphonate [DIMIM][(MeO)(H)PO₂] and 1-ethyl-3-methylimidazolium methylphoshonate [EMIM][(MeO)(H)PO₂]. The chemical modification of cellulose occurred through a transesterification reaction between the methyl phosphonate function of ILs and the primary alcohol functions of cellulose. The resulting cellulose structure and the amount of grafted phosphorus were then investigated by X-ray diffraction, ICP-AES, and ¹³C and ³¹P NMR spectroscopy. Depending on the IL type and initial cotton / IL ratio in the solution, regenerated cellulose contained up to 4.5% of phosphorus. The rheological behavior of cotton cellulose/ILs solutions and the microscale fire performances of modified cellulose were studied in order to ultimately prepare flame retardant cellulosic materials. Significant improvement in the flame retardancy of regenerated cellulose was obtained with a reduction of THR values down to about 5–6 kJ/g and an increase of char up to about 35 wt%.

The asymmetry of halloysite surface chemistry was used to perform a selective modification of its inner surface via grafting of a synthesized styrene/(methacryloyloxy)methyl phosphonic acid copolymer. Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA) and pyrolysis gas chromatography/mass spectrometry were used to evidence and quantify the grafting. Then, raw and hybrid nanoparticles were incorporated in polystyrene (PS)/polyamide‐11 (PA11) blends (80/20 and 60/40 wt%). Scanning electron micrographs showed differences in localization of the halloysite nanotubes (HNTs), since raw halloysite is concentrated in the PA11 phase while modified halloysite is also located at the PS/PA11 interface, leading to a better interfacial adhesion between PS and PA11. An inhibiting effect of modified halloysite on PA11 coalescence was evidenced by measuring the particle size distribution of the extracted nodules. Moreover, the presence of modified halloysite at the interface shows an improvement in terms of thermal stability as observed by TGA, but with no significant effects on PA11 crystallization behaviour as shown by differential scanning calorimetry results. Rheological measurements were carried out to study the influence of the surface modification of halloysite on the blend morphology. A gel‐like behaviour was observed for the (60/40 wt%) HNTs reinforced composition that was enhanced in the case of 10% functionalized halloysite. © 2016 Society of Chemical Industry

Hexagonal boron nitride (h-BN) has recently gained much attention due to its high thermal conductivity and low electrical conductivity. In this study, we proposed to evaluate the impact of the modification of h-BN for use in a polymethylmethacrylate/polyamide 6 (PMMA/PA6) polymer blend. Different methods to modify h-BN particles and improve their affinity with polymers were proposed. The modification was performed in two steps: (1) a hydroxylation step for which three different routes were used: calcination, acidic treatment, and ball milling using gallic acid; (2) a grafting step for which four different silane agents were used, carrying different molecular or macromolecular groups: the octadecyl group (Si-C18), propyl amine group (Si-NH2), polystyrene chain (Si-PS), and PMMA chain (Si-PMMA). The modified h-BN samples after hydroxylation and functionalization were characterized by FTIR and TGA. Py-GC/MS was also used to prove the successful graft with Si-C18 groups. Sedimentation tests and multiple light scattering were performed to assess the surface modification of h-BN. Granulometry and SEM observations were performed to evaluate the particle size distribution after hydroxylation. After the addition of Si-PMMA modified h-BN into a PMMA/PA6 co-continuous blend, the morphology of the polymer blend nanocomposites was characterized using SEM. The calculation of the wetting parameter based on the surface tension measurement using the liquid drop model showed that h-BN dispersed in the PA6 phase. Grafting PMMA chains onto hydroxylated h-BN particles combined with an adequate sequence mixing led to a successful localization of the grafted h-BN particles at the interface of the PMMA/PA6 blend.