Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. ³¹P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.

Current challenges highlight the need for polymer research using renewable natural sources as a substitute for petroleum-based polymers. The use of polyols obtained from renewable sources combined with the reuse of industrial residues such as lignin is an important agent in this process. Different compositions of polyurethane-type materials were prepared by combining technical Kraft lignin (TKL) with castor oil (CO) or modified castor oil (MCO1 and MCO2) to increase their reactivity towards diphenylmethane diisocyanate (MDI). The results indicate that lignin increases the glass transition temperature, the crosslinking density and improves the ultimate stress especially for those prepared from MCO2 and 30% lignin content from 8.2 MPa (lignin free) to 23.5 MPa. Scanning electron microscopy (SEM) micrographs of rupture surface after uniaxial tensile tests show ductile-to-brittle transition. The results show the possibility to develop polyurethane-type materials, varying technical grade Kraft lignin content, which cover a wide range of mechanical properties (from large elastic/low Young modulus to brittle/high Young modulus polyurethanes)

Owing to its chemical structure, wide availability and renewable nature, lignin is a promising candidate for the partial replacement of fossil-based raw material in the synthesis of epoxy resins. Its poor compatibility has been reported to be one of the main drawbacks in this domain. On the other hand, a well-established modification method for lignin epoxidation has been used for many years for the improvement of lignin compatibility. However, the extent of the effect of lignin epoxidation on the improvement of bio-based epoxy mechanical properties, applied as adhesives, is still an open question in the literature. In this context, a pristine and industrial grade kraft lignin (AKL) was reacted with epichlorohydrin to yield epoxidized lignin (E-AKL) in this work. Afterwards, AKL or E-AKL were separately blended with petroleum-based epoxy resin at 15 and 30 wt% and cured with a commercial amine. The adhesive curing kinetic was evaluated using a novel technique for thermal transition characterization, Temperature Modulated Optical Refractometry (TMOR); the results showed that the incorporation of AKL reduces the crosslinking rate, and that this effect is overcome by lignin modification. Mechanical tests revealed an improvement of impact and practical adhesion strength for samples containing 15 wt% of E-AKL. These results elucidate the effect of lignin epoxidation on the application of lignin-based epoxy adhesives, and might support the further development and application of these bio-based materials.

Low surface energy and poor adhesion are well-known characteristics of polypropylene (PP). Surface treatments such as plasma, corona, and laser are usually applied to overcome these limitations. However, current studies highlight the incorporation of hydrophilic or amphiphilic polymers into hydrophobic low-surface-energy polymers as an alternative for increasing surface energy and thus improving adhesion. Lignin could be a promising amphiphilic polymer for use in increasing surface energy. In this work, PP/kraft lignin composites were obtained by incorporating up to 5 wt% of kraft lignin (KL) into a PP matrix. Corona treatment was applied to pristine PP and composites surfaces. Contact angle measurements and peeling tests were carried out to investigate the effects of KL incorporation and corona treatment on the surface energy and the mechanical strength of adhesion. Differential scanning calorimetry (DSC) was used to evaluate the PP’s crystallinity index and recrystallization temperature and to dismiss their effects on the surface energy changes. Scanning electron microscopy (SEM) was applied to investigate the lignin dispersion. The results show that KL incorporation has potential as a method to improve the surface energy of PP, improve its poor adhesion, and enhance the effects of corona treatment.

During the last years, several efforts were dedicated to the development of lignin-based polyurethane adhesives, in which phase separation and brittleness were the most significant reported limitations. Hydroxypropylation emerged as a feasible method to overcome their restricted performance, since this method generates lignin with higher reactivity and branched molecular structure, at different extends. However, the effect of lignin hydroxypropylation on properties of lignin-based PU adhesives remains unclear. In this work, mixtures of lignins and castor oil were used as renewable raw material polyol in the PU synthesis. First, a pristine kraft lignin (KL) was used as reference, followed by incorporation of two hydroxypropylated lignins: highT_HPL – obtained under high temperature and pressure (150°C, 18 bar) and lowT_HPL – synthesized under milder conditions (40°C, atm). Temperature modulated optical refractometry (TMOR) revealed a slower curing process for than highT_HPL-containing PU. LowT_HPL lignin improved the PU modulus of elasticity and ultimate tensile stress. KL and lowT_HPL incorporation resulted in higher strength of wooden adhesively bonded joints (single lap shear tests – 4.5 MPa). The results elucidated the main effects of hydropropylation on PU and its application on adhesively bonded joints, supporting the development of further lignin-based adhesives.