Furfuryl alcohol/tung oil matrix-based composites reinforced with bacterial cellulose fibres.

Polymeric materials have drastically changed the society in the last century. However, their non-renewable origin, together with their indiscriminate use and disposal, resulted in a huge accumulation of waste in the environment and raised a wide discussion about the emission of greenhouse gases, which must be considerably reduced to minimize global warming. Thus, the establishment of a consolidated production of polymers prioritizing the use of renewable sources of raw materials became a hot research topic. Vegetable oils are protagonists of this initiative, and their carbon-carbon double bonds are convenient reactive sites for chain growth polymerization reactions. However, typical vegetable oil-based homopolymers often do not display competitive thermo-mechanical properties, and the preparation of the corresponding copolymers and composites is therefore an interesting alternative strategy. Herein, the preparation of composites based on a tung oil/furfuryl alcohol co-continuous network reinforced with bacterial cellulose fibers is described. For this purpose, the cellulose nanofibers were suspended in furfuryl alcohol, and different amounts of the ensuing suspension were mixed with tung oil in the presence of trifluoroacetic acid as cationic initiator. Fourier-transform infrared spectroscopy analysis of all samples indicated the association of both tung oil and furfuryl alcohol in the final materials, with peaks belonging to cellulose superposed at the fingerprint regions of composites. Differential scanning calorimetry and thermogravimetry demonstrated an interesting relationship between the composition and the corresponding thermal properties, and the morphology of the materials was assessed by scanning electron microscopy (SEM), which revealed a homogeneous distribution of cellulosic fibers at lower concentrations. The results gathered here contribute to the development of original macromolecular materials exclusively based on the renewable platform.

Recent advances in the production of biomedical systems based on polyhydroxyalkanoates and exopolysaccharides.

In recent years, growing attention has been devoted to naturally occurring biological macromolecules and their ensuing application in agriculture, cosmetics, food and pharmaceutical industries. They inherently have antigenicity, low immunogenicity, excellent biocompatibility and cytocompatibility, which are ideal properties for the design of biomedical devices, especially for the controlled delivery of active ingredients in the most diverse contexts. Furthermore, these properties can be modulated by chemical modification via the incorporation of other (macro)molecules in a random or controlled way, aiming at improving their functionality for each specific application. Among the wide variety of natural polymers, microbial polyhydroxyalkanoates (PHAs) and exopolysaccharides (EPS) are often considered for the development of original biomaterials due to their unique physicochemical and biological features. Here, we aim to fullfil a gap on the present associated literature, bringing an up-to-date overview of ongoing research strategies that make use of PHAs (poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxyoctanoate), poly(3-hydroxypropionate), poly (3-hydroxyhexanoate-co-3-hydroxyoctanoate), and poly (3-hydroxybutyrate-co-3-hydroxyhexanoate)) and EPS (bacterial cellulose, alginates, curdlan, pullulan, xanthan gum, dextran, hyaluronan, and schizophyllan) as sources of interesting and versatile biomaterials. For the first time, a monograph addressing the properties, pros and cons, status, challenges, and recent progresses regarding the application of these two important classes of biopolymers in biomedicine is presented.

Copolymers of xylan-derived furfuryl alcohol and natural oligomeric tung oil derivatives.

The utilization of vegetable oils as biological oligomers for the synthesis of macromolecular materials has considerably evolved in the last decades, opening the way for the preparation of sophisticated materials based on synthetic processes for the design of polymers with very specific applications. Tung oil (TO), easily obtained from the seeds of the Asian tung tree (Vernicia fordii), is a relatively cheap commodity that has as its main constituent (~85%) a peculiar natural oligomeric triglyceride structure in which each chain bears three conjugated unsaturations corresponding to α-eleostearic acid. Following a previous study based on the association of TO with furans for the preparation of linear and cross-linked structures based on the Diels-Alder click reaction, the present study deals with the cationic (co) polymerization of xylan-derived furfuryl alcohol (FA) with TO, in order to combine the high intrinsic flexibility of the crosslinked TO polymers with the stiffness of the FA resin, which should lead to fully bio-based crosslinked materials with a tunable glass transition. Three approaches were investigated using trifluoroacetic acid (TFA) in chloroform, viz. (i) combining crude TO and furfuryl alcohol, (ii) combining methyl α-eleostearate and furfuryl alcohol, and (iii) polymerizing furfuryl α-eleostearate itself. The polymerization reactions with varying TFA concentrations were followed by 1H NMR spectroscopy, and it was possible to get valuable information on mechanistic aspects. Also, higher concentrations of TFA were used to synthesize and isolate polymer networks, in order to understand their molecular characteristic as well as access their main thermal properties.

Synthesis of amphiphilic pullulan-graft-poly(ε-caprolactone) via click chemistry.

Chemical modification of natural polymers has been commonly employed for the development of new bio-based materials, aiming at adjusting specific properties such as solubility, biodegradability, thermal stability and mechanical behavior. Among all natural polymers, polysaccharides are promising materials, in which biodegradability, processability and bioreactivity make them suitable for biomedical applications. In this context, this work describes the synthesis and characterization of a novel amphiphilic pullulan-g-poly(ε-caprolactone) (Pull-g-PCL) graft copolymer. In a first step, pullulan was chemically modified with 2-bromopropionyl bromide to obtain bromo-functionalized pullulan (PullBr). Then, this precursor was modified with sodium azide, leading to azide pullulan (PullN3). In parallel, propargyl-terminated poly(ε-caprolactone) was prepared via ring-opening polymerization (ROP). These preliminary steps involved the synthesis of azide and alkyne compounds, capable of being linked together via alkyne-azide cycloaddition reaction catalyzed by copper (Cu (I)), which leads to Pull-g-PCL. The chemical structures of the polymers were assessed by Proton Nuclear Magnetic Resonance (1H NMR) and Fourier Transform Infrared (FTIR).

Recycling tires? Reversible crosslinking of poly(butadiene).

Furan-modified poly(butadiene) prepared by the thiol-ene click reaction is crosslinked with bismaleimides through the Diels-Alder reaction, giving rise to a novel recyclable elastomer. This is possible because of the thermal reversibility of the adducts responsible for the formation of the network. The use of this strategy provides the possibility to produce recyclable tires.

Effect of acid concentration and pulp properties on hydrolysis reactions of mercerized sisal.

The influence of sulfuric acid concentration (H2SO4 5-25%, 100°C), crystallinity and fibers size on the hydrolysis reaction of sisal pulps were investigated, with the goal of evaluating both the liquor composition, as an important step in the production of bioethanol, and the residual non-hydrolyzed pulp, to determine its potential application as materials. Aliquots were withdrawn from the reaction media, and the liquor composition was analyzed by HPLC. The residual non-hydrolyzed pulps were characterized by SEM, their average molar mass and crystallinity index, and their size distribution was determined using a fiber analyzer. Sulfuric acid 25% led to the highest glucose content (approximately 10gL(-1)), and this acid concentration was chosen to evaluate the influence of both the fiber size and crystallinity of the starting pulp on hydrolysis. The results showed that fibers with higher length and lower crystallinity favored glucose production in approximately 12%, with respect to the highly crystalline shorter fibers.