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.

This work aimed to evaluate the influence of the aliphatic and aromatic hydroxyl level on the polyurethane adhesive property and chemical structure. This adhesive was obtained through the reaction of technical Kraft lignin (TKL) as polyol with diphenylmethane diisocyanate (MDI). Thus, lignopolyurethane adhesives were obtained with NCO:OH ratios of 0.8:1.0, 0.9:1.0, 1.0:1.0, 1.1:1.0, and 1.2:1.0. Initially only the TKL aliphatic hydroxyl level was taken into consideration in the stoichiometry in order to define the mass ratio between MDI and polyol. Subsequently, lignopolyurethane adhesive was obtained using the same NCO:OH ratios considering TKL total hydroxyls’ level, and aromatic and aliphatic hydroxyls. The chemical structures of the synthesized adhesives were analyzed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (¹³C NMR). The mechanical property of the adhesively bonded joints, comprising wood substrates and synthesized adhesives, was measured using single lap shear tests. Results illustrated that by increasing the NCO:OH ratio, there is an increase in the free isocyanate content leading to higher shear strength values. Higher free isocyanate content leads to MDI dimer formation in the lignopolyurethane structure.

In 2021, global petroleum-based plastic production reached over 400 million metric tons (Mt), and the accumulation of these non-biodegradable plastics in the environment is a worldwide concern. Polyhydroxybutyrate (PHB) offers many advantages over traditional petroleum-based plastics, being biobased, completely biodegradable, and non-toxic. However, its production and use are still challenging due to its low deformation capacity and narrow processing window. In this work, two linear-chain polyester oligomers were used as plasticizers to improve the processability and properties of PHB. Thermal analyses, XRD, and polarized optical microscopy were performed to evaluate the plasticizing effect on the PHB and the reflection on the mechanical behavior. Both oligomers acted as PHB plasticizers, with a reduction in T_g and T_m as a function of the plasticizer concentration, which can make it easier to handle the material in thermal processing and reduce the probability of thermal degradation. Plasticizer 2 proved to be the most promising between the two with an optimized condition of 20%, in which there was a decrease in elastic modulus of up to 72% and an increase in the maximum elongation of 467%.

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.