ABSTRACT
We prepared chitosan (CHI) hydrogels reinforced with highly charged cellulose nanofibrils (CNF) by the desalting method. To this end, the screening of electrostatic interactions between CHI polycation and CNF polyanion was performed by adding NaCl at 0.4 mol/L to the chitosan acetate solution and to the cellulose nanofibrils suspension. The polyelectrolyte complexation between CHI polycation and CNF polyanion was then triggered by desalting the CHI/CNF aqueous mixture by multistep dialysis, in large excess of chitosan. Further gelation of non-complexed CHI was performed by alkaline neutralization of the polymer, yielding high reinforcement effects as probed by the viscoelastic properties of the final hydrogel. The results showed that polyelectrolyte association by desalting can be achieved with a polyanionic nanoparticle partner. Beyond obtaining hydrogel with improved mechanical performance, these composite hydrogels may serve as precursor for dried solid forms with high mechanical properties.
ABSTRACT
Rubber materials with well-dispersed fillers and large mechanical reinforcement have been obtained by melt-processing a diene elastomer matrix and tailored nanocellulose powders having both a high specific surface area and a modified interface. Such filler powders with a specific surface area of 180 m2 g-1 and 100 m2 g-1 have been obtained by freeze-drying suspensions of short needle-like cellulose nanocrystals (CNCs) and entangled networks of microfibrillated cellulose (MFC) in tert-butanol/water, respectively. A quantitative and toposelective filler surface esterification was performed using a gas-phase protocol either with palmitoyl chloride (PCl) to obtain a hydrophobic but non-reactive nanocellulose interface, or with 3,3'-dithiopropionic acid chloride (DTACl) to introduce reactive groups that can covalently bind the nanocellulose interface to the dienic matrix in a subsequent vulcanization process. A set of filled materials was prepared varying the filler morphology, interface and volume fraction. Transmission electron microscopy images of ultrathin cryo-sections showed that modified nanocellulose fillers presented a relatively homogeneous distribution up to a volume fraction of 20%. The materials also exhibited a significant modulus increase, while keeping an extensibility in the same range as that of the neat matrix. Strikingly, in the case of the reactive interface, a strong stress-stiffening behavior was evidenced from the upward curvature of the tensile curve, leading to a large increase of the ultimate stress (up to 7 times that of the neat matrix). Taken together, these properties, which have never been previously reported for nanocellulose-filled elastomers, match well the mechanical characteristics of industrial carbon black or silica-loaded elastomers.
ABSTRACT
Supramolecular polymer networks have been designed on the basis of a π-electron donor/acceptor complex: naphthalene (N)/cyclobis(paraquat-p-phenylene) (CBPQT4+ = B). For this purpose, a copolymer of N,N-dimethylacrylamide P(DMA-N1), lightly decorated with 1 mol% of naphthalene pendant groups, has been studied in semi-dilute un-entangled solution in the presence of di-CBPQT4+ (BB) crosslinker type molecules. While calorimetric experiments demonstrate the quantitative binding between N and B groups up to 60 °C, the introduction of BB crosslinkers into the polymer solution gives rise to gel formation above the overlap concentration. From a comprehensive investigation of viscoelastic properties, performed at different concentrations, host/guest stoichiometric ratios and temperatures, the supramolecular hydrogels are shown to follow a Maxwellian behavior with a strong correlation of the plateau modulus and the relaxation time with the effective amount of interchain cross-linkers and their dissociation dynamics, respectively. The calculation of the dissociation rate constant of the supramolecular complex, by extrapolation of the relaxation time of the network back to the beginning of the gel regime, is discussed in the framework of theoretical and experimental works on associating polymers.
ABSTRACT
Most polymeric thermoresponsive hydrogels contract upon heating beyond the lower critical solution temperature (LCST) of the polymers used. Herein, we report a supramolecular hydrogel system that shows the opposite temperature dependence. When the non-thermosesponsive hydrogel NaphtGel, containing dialkoxynaphthalene guest molecules, becomes complexed with the tetra cationic macrocyclic host CBPQT4+ , swelling occurred as a result of host-guest complex formation leading to charge repulsion between the host units, as well as an osmotic contribution of chloride counter-ions embedded in the network. The immersion of NaphtGel in a solution of poly(N-isopropylacrylamide) with tetrathiafulvalene (TTF) end groups complexed with CBPQT4+ induced positive thermoresponsive behaviour. The LCST-induced dethreading of the polymer-based pseudorotaxane upon heating led to transfer of the CBPQT4+ host and a concomitant swelling of NaphtGel. Subsequent cooling led to reformation of the TTF-based host-guest complexes in solution and contraction of the hydrogel.
ABSTRACT
Aqueous suspensions of microfibrillated cellulose obtained by a high pressure homogenization process were freeze-dried after solvent exchange into tert-butanol. The resulting aerogels, which displayed a remarkable open morphology with a surface area reaching 100 m(2)/g, were subjected to a gas-phase esterification with palmitoyl chloride. Under these conditions, variations of the reaction temperature from 100 to 200 °C, of the reaction time from 0.5 to 2 h, and of the initial quantity of reagent, led to the preparation of a library of cellulose palmitates with DS varying from zero to 2.36. These products were characterized by gravimetry, FTIR, and (13)C solid-state NMR spectroscopy. Of special interest were the cellulose palmitate samples of low DS in the range of 0.1-0.4, which corresponded to hydrophobic cellulose microfibrils exclusively esterified at their surface while keeping intact their inner structure.
