Polyurethane Adhesives Based on Oxyalkylated Kraft Lignin.

Lignin-based polyol was obtained via oxyalkylation reaction with propylene carbonate using eucalyptus kraft lignin isolated from the industrial cooking liquor by the Lignoboost® procedure. This lignin-based polyol (LBP) was used without purification in the preparation of polyurethane (PU) adhesives combined with polymeric 4,4'-methylenediphenyl diisocyanate (pMDI). A series of adhesives were obtained by varying the NCO/OH ratio of PU counterparts (pMDI and LBPs) and their performance was evaluated by gluing wood pieces under predefined conditions. The adhesion properties of the novel PU adhesive were compared with those of a commercial PU adhesive (CPA). The occurrence and extent of curing reactions and changes in the polymeric network of PA were monitored by Fourier transform infrared spectroscopy (FTIR) and dynamic mechanical analysis. Although the lap shear strength and glass transition temperature of the lignin-based PU adhesives have increased steadily with the NCO/OH ratio ranging from 1.1-2.2, chemical aging resistance can be compromised when the NCO/OH is very low. It was found that the lignin-based PU adhesive with an NCO/OH ratio of 1.3 showed better chemical resistance and adhesion efficiency than CPA possibly because the NCO/OH in the latter is too high as revealed by FTIR spectroscopy. Despite some lower thermal stability and shorter gelation time of lignin-based PU than CPA, the former revealed great potential to reduce the use of petroleum-derived polyols and isocyanates with potential application in the furniture industry as wood bonding adhesive.

Modification of Paper Surface by All-Lignin Coating Formulations.

All-lignin coating formulations were prepared while combining water-soluble cationic kraft lignin (quaternized LignoBoost®, CL) and anionic lignosulphonate (LS). The electrostatic attraction between positively charged CL and negatively charged LS led to the formation of insoluble self-organized macromolecule aggregates that align to films. The structures of the formed layers were evaluated by atomic force microscopy (AFM), firstly on glass lamina using dip-coating deposition and then on handsheets and industrial uncoated paper using roll-to-roll coating in a layer-by-layer mode. Coated samples were also characterized by optical microscopy, scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (SEM/EDS), and contact angle measurements. It was suggested that the structure of all-lignin aggregates is the result of the interaction of amphiphilic water-soluble lignin molecules leading to their specifically ordered mutual arrangement depending on the order and the mode of their application on the surface. The all-lignin coating of cellulosic fiber imparts lower air permeability and lower free surface energy to paper, mainly due to a decrease in surface polarity, thus promoting the paper's hydrophobic properties. Moderate loading of lignin coating formulations (5-6 g m-2) did not affect the mechanical strength of the paper.

Lignin as a Renewable Building Block for Sustainable Polyurethanes.

Currently, the pulp and paper industry generates around 50-70 million tons of lignin annually, which is mainly burned for energy recovery. Lignin, being a natural aromatic polymer rich in functional hydroxyl groups, has been drawing the interest of academia and industry for its valorization, especially for the development of polymeric materials. Among the different types of polymers that can be derived from lignin, polyurethanes (PUs) are amid the most important ones, especially due to their wide range of applications. This review encompasses available technologies to isolate lignin from pulping processes, the main approaches to convert solid lignin into a liquid polyol to produce bio-based polyurethanes, the challenges involving its characterization, and the current technology assessment. Despite the fact that PUs derived from bio-based polyols, such as lignin, are important in contributing to the circular economy, the use of isocyanate is a major environmental hot spot. Therefore, the main strategies that have been used to replace isocyanates to produce non-isocyanate polyurethanes (NIPUs) derived from lignin are also discussed.

Cationization of Eucalyptus Kraft LignoBoost Lignin: Preparation, Properties, and Potential Applications.

Current changes toward a more biobased economy have recently created tremendous renewed interest in using lignin as a valuable source for chemicals and materials. Here, we present a facile cationization approach aiming to impart kraft lignin water-solubility, with similar good features as lignosulfonates. Eucalyptus globulus kraft lignin obtained from a paper mill black liquor by applying the LignoBoost process was used as the substrate. Its reaction with 3-chloro-2-hydroxypropyl-trimethylammonium chloride (CHPTAC) in an aqueous alkaline medium was studied to assess the impact of different reaction conditions (temperature, time, educt concentration, molar CHPTAC-to-lignin ratio) on the degree of cationization. It has been shown that at pH 13, 10 wt % lignin content, 70 °C, and 3 h reaction time, a CHPTAC-to-lignin minimum molar ratio of 1.3 is required to obtain fully water-soluble products. Elemental analysis (4.2% N), size-exclusion chromatography (M w 2180 Da), and quantitative 13C NMR spectroscopy of the product obtained at this limit reactant concentration suggest introduction of 1.2 quaternary ammonium groups per C9 unit and substitution of 75% of the initially available phenolic OH groups. The possible contribution of benzylic hydroxyls to the introduction of quaternary ammonium moieties through a quinone methide mechanism has been proposed. Since both molecular characteristics and degree of substitution, and hence solubility or count of surface charge, of colloidal particles can be adjusted within a wide range, cationic kraft lignins are promising materials for a wide range of applications, as exemplarily demonstrated for flocculation of anionic dyes.

Synthesis of Lignosulfonate-Based Dispersants for Application in Concrete Formulations.

Lignosulfonates (LS) are products from the sulfite pulping process that could be applied as renewable environmentally-friendly polymeric surfactants. Being widely used as plasticizers and water-reducing admixtures in concrete formulations LS compete in the market with petroleum-based superplasticizers, such as naphthalene sulfonate formaldehyde polycondensate (NSF) and copolymer polycarboxylate ethers (PCE). In this work, different chemical modification strategies were used to improve LS performance as dispersants for concrete formulations. One strategy consisted in increasing the molecular weight of LS through different approaches, such as laccase and polyoxometalate-mediated polymerization, glyoxalation, and reversible addition-fragmentation chain transfer (RAFT) polymerization. The other strategy consisted of preparing LS-based non-ionic polymeric dispersants using two different epoxidized oligomer derivatives of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG). Modified LS were used to prepare cement pastes, which were examined for their fluidity. Results revealed that the most promising products are PPG-modified LS due to the introduction of PPG chains by reaction with phenolic moieties in LS. The enhanced dispersant efficiency of the ensuing products is probably related not only to electrostatic repulsion caused by the sulfonic ionizable groups in LS but also to steric hindrance phenomena due to the grafted bulky PPG chains.

Lignosulfonate-Based Polyurethane Adhesives.

The feasibility of using lignosulfonate (LS) from acid sulphite pulping of eucalyptus wood as an unmodified polyol in the formulation of polyurethane (PU) adhesives was evaluated. Purified LS was dissolved in water to simulate its concentration in sulphite spent liquor and then reacted with 4,4'-diphenylmethane diisocyanate (pMDI) in the presence or absence of poly(ethylene glycol) with Mw 200 (PEG200) as soft crosslinking segment. The ensuing LS-based PU adhesives were characterized by infrared spectroscopy and thermal analysis techniques. The adhesion strength of new adhesives was assessed using Automated Bonding Evaluation System (ABES) employing wood strips as a testing material. The results showed that the addition of PEG200 contributed positively both to the homogenization of the reaction mixture and better crosslinking of the polymeric network, as well as to the interface interactions and adhesive strength. The latter was comparable to the adhesive strength recorded for a commercial white glue with shear stress values of almost 3 MPa. The optimized LS-based PU adhesive formulation was examined for the curing kinetics following the Kissinger and the Ozawa methods by non-isothermal differential scanning calorimetry, which revealed the curing activation energy of about 70 kJ·mol-1.

Lignosulfonate-Based Conducting Flexible Polymeric Membranes for Liquid Sensing Applications.

In this study, lignosulfonate (LS) from the acid sulfite pulping of eucalypt wood was used to synthesize LS-based polyurethanes (PUs) doped with multiwalled carbon nanotubes (MWCNTs) within the range of 0.1-1.4% w/w, yielding a unique conducting copolymer composite, which was employed as a sensitive material for all-solid-state potentiometric chemical sensors. LS-based PUs doped with 1.0% w/w MWCNTs exhibited relevant electrical conductivity suitable for sensor applications. The LS-based potentiometric sensor displayed a near-Nernstian or super-Nernstian response to a wide range of transition metals, including Cu(II), Zn(II), Cd(II), Cr(III), Cr(VI), Hg(II), and Ag(I) at pH 7 and Cr(VI) at pH 2. It also exhibited a redox response to the Fe(II)/(III) redox pair at pH 2. Unlike other lignin-based potentiometric sensors in similar composite materials, this LS-based flexible polymeric membrane did not show irreversible complexation with Hg(II). Only a weak response toward ionic liquids, [C2mim]Cl and ChCl, was registered. Unlike LS-based composites comprising MWCNTs, those doped with graphene oxide (GO), reduced GO (rGO), and graphite (Gr) did not reveal the same electrical conductivity, even with loads up to 10% (w/w), in the polymer composite. This fact is associated, at least partially, with the different filler dispersion abilities within the polymeric matrix.

Evaluating the hazardous impact of ionic liquids - Challenges and opportunities.

Ionic liquids (ILs), being related to the design of new environmentally friendly solvents, are widely considered for applications within the "green chemistry" concept. Due to their unique properties and wide diversity, ILs allow tailoring new separation procedures and producing new materials for advanced applications. However, despite the promising technical performance, environmental concerns highlighted in recent studies focused on the toxicity and biodegradability of ILs and their metabolites have revealed that ILs safety labels are not as benign as previously claimed. This review refers to the fundamentals about the properties and applications of ILs also in the context of their potential environmental effect. Toxicological issues and harmful effects related to the use of ILs are discussed, including the evaluation of their biodegradability and ecological impact on diverse organisms and ecosystems, also with respect to bacteria, fungi, and cell cultures. In addition, this review covers the tools used to assess the toxicity of ILs, including the predictive computational models and the results of studies involving cell membrane models and molecular simulations. Summing up the knowledge available so far, there are still no reliable criteria for unequivocal attribution of toxicity and environmental impact credentials for ILs, which is a challenging research task.

Recent Advances in the Production and Applications of Ellagic Acid and Its Derivatives. A Review.

Ellagitannins (ETs), characterized by their diversity and chemical complexity, belong to the class of hydrolysable tannins that, via hydrolysis under acidic or alkaline conditions, can yield ellagic acid (EA). They are mostly found as a part of extractives in angiosperms. As known antioxidants and chelators, EA and EA derivatives are drawing an increasing interest towards extensive technical and biomedical applications. The latter ones include possible antibacterial, antifungal, antiviral, anti-inflammatory, hepato- and cardioprotective, chemopreventive, neuroprotective, anti-diabetic, gastroprotective, antihyperlipidemic, and antidepressant-like activities, among others. EA's synthesis and production challenges prompt further research on new methods and alternative sources. Conventional and prospective methods and raw materials for the production of EA and its derivatives are reviewed. Among the potential sources of EA, the residues and industrial streams of the pulp industry have been highlighted and considered as an alluring alternative in terms of commercial exploitation.

High Pressure Laminates with Antimicrobial Properties.

High-pressure laminates (HPLs) are durable, resistant to environmental effects and good cost-benefit decorative surface composite materials with special properties tailored to meet market demand. In the present work, polyhexamethylene biguanide (PHMB) was incorporated for the first time into melamine-formaldehyde resin (MF) matrix on the outer layer of HPLs to provide them antimicrobial properties. Chemical binding of PHMB to resin matrix was detected on the surface of produced HPLs by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). Antimicrobial evaluation tests were carried out on the ensuing HPLs doped with PHMB against gram-positive Listeria innocua and gram-negative Escherichia coli bacteria. The results revealed that laminates prepared with 1.0 wt % PHMB in MF resin were bacteriostatic (i.e., inhibited the growth of microorganisms), whereas those prepared with 2.4 wt % PHMB in MF resin exhibited bactericidal activity (i.e., inactivated the inoculated microorganisms). The results herein reported disclose a promising strategy for the production of HPLs with antimicrobial activity without affecting basic intrinsic quality parameters of composite material.