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.

Rigid polyurethane foams (RPUFs) were synthesized using exclusively lignin-based polyol (LBP) obtained via the oxyalkylation of kraft lignin with propylene carbonate (PC). Using the design of experiments methodology combined with statistical analysis, the formulations were optimized to obtain a bio-based RPUF with low thermal conductivity and low apparent density to be used as a lightweight insulating material. The thermo-mechanical properties of the ensuing foams were compared with those of a commercial RPUF and a RPUF (RPUF-conv) produced using a conventional polyol. The bio-based RPUF obtained using the optimized formulation exhibited low thermal conductivity (0.0289 W/m·K), low density (33.2 kg/m³), and reasonable cell morphology. Although the bio-based RPUF has slightly lower thermo-oxidative stability and mechanical properties than RPUF-conv, it is still suitable for thermal insulation applications. In addition, the fire resistance of this bio-based foam has been improved, with its average heat release rate (HRR) reduced by 18.5% and its burn time extended by 25% compared to RPUF-conv. Overall, this bio-based RPUF has shown potential to replace petroleum-based RPUF as an insulating material. This is the first report regarding the use of 100% unpurified LBP obtained via the oxyalkylation of LignoBoost kraft lignin in the production of RPUFs.

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.

Oxyalkylation with propylene carbonate (PC) is a safe process to convert lignin into a reactive liquid polyol to be used in polyurethane formulations. In this study, the effect of operating conditions of oxyalkylation (temperature, time and quantify of PC) on the quality of lignin-based polyol in terms hydroxyl number (I_OH) and viscosity was studied. Full factorial modeling and response surface methodology (RSM) were applied to study the effect and interaction of process variables on the I_OH and viscosity of lignin-based polyols. The results revealed that the I_OH is highly affected by the reaction time, while the viscosity is affected by the amount of PC. Validation experiments confirmed the model is reliable. Furthermore, RSM optimization allowed to reduce the amount of PC by about 50% and to increase the lignin content in the polyol from 12.5% to 25% (w/w) depending on the temperature and time of the process and also on the purpose of the polyol produced (i.e., application in rigid foams or adhesives).

This study aimed to develop new rigid polyurethane foams (RPUFs) for thermal insulation based on kraft lignin, the main by-product of the pulp and paper industry. Crude lignin-based polyol (LBP) was obtained via the oxyalkylation of kraft lignin using propylene carbonate (PC). A design of experiments (DoE) was used to evaluate the effect of the isocyanate (NCO)-to-hydroxyl (OH)-group’s ratio, the content of crude LBP, the blowing agent (BA), and catalyst on the thermal conductivity and density of RPUFs. Statistical analysis revealed that the increase in crude LBP and BA content in the formulation decreases the thermal conductivity and density of the foams. In addition, the fact that LBP is a viscous polyol containing PC-oligomers appears to affect the cellular structure of RPUFs, and consequently reduces their mechanical and thermal properties. The main novelty of this study consisted in the careful optimization of the formulation, namely, with regard to the type of blowing agent and with the high content of crude LBP obtained from the oxyalkylation of LignoBoost kraft lignin without purification to obtain good quality RPUF that meets market requirements for insulation materials.