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In response to the environmental impacts of conventional polyurethane adhesives derived from fossil fuels, this study introduces a sustainable alternative utilizing lignin-based polyols extracted from rice straw through a process developed at INESCOP. This research explores the partial substitution of traditional polyols with lignin-based equivalents in the synthesis of reactive hot melt polyurethane adhesives (HMPUR) for the footwear industry. The performance of these eco-friendly adhesives was rigorously assessed through Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), rheological analysis, and T-peel tests to ensure their compliance with relevant industry standards. Preliminary results demonstrate that lignin-based polyols can effectively replace a significant portion of fossil-derived polyols, maintaining essential adhesive properties and marking a significant step towards more sustainable adhesive solutions. This study not only highlights the potential of lignin in the realm of sustainable adhesive production but also emphasises the valorisation of agricultural by-products, thus aligning with the principles of green chemistry and sustainability objectives in the polymer industry. [ABSTRACT FROM AUTHOR]

Valorization of industrial low-value side-streams are of great interest, contributing to boosts in the circular economy. In this context, lignin side-streams of the pulp and paper industry were oxypropylated to produce biobased polyols and tested in the synthesis of rigid polyurethane (RPU) foams. E. globulus lignins, namely a lignin isolated from an industrial Kraft black liquor and depolymerized lignins obtained as by-products of an oxidation process, were used. RPU foams, synthesized with 100% lignin-based polyols and using a 1.1 NCO/OH ratio, were characterized concerning apparent density, morphology, thermal conductivity, thermal stability, and heat release rate (HRR). Foams containing the lignin-based polyols presented densities varying from 44.7 to 112.2 kg/m3 and thermal conductivity in the range of 37.2–49.0 mW/mK. For the reference foam (sample produced with 100% wt. Daltofoam TP 32015 polyol), values of 70.9 kg/m3 and 41.1 mW/mK were obtained, respectively. The achieved results point out the viability of using the generated lignin-based polyols at 100% content in RPU foams, mainly when depolymerized lignins are used. Moreover, fire retardancy was favored when the lignin-based polyols were introduced. The proposed strategies can contribute to establishing the integrated pulp and paper biorefinery concept where material synthesis (polyols and RPU foams) can be combined with chemical production (vanillin and syringaldehyde).

Valorization of industrial low-value side-streams are of great interest, contributing to boosts in the circular economy. In this context, lignin side-streams of the pulp and paper industry were oxypropylated to produce biobased polyols and tested in the synthesis of rigid polyurethane (RPU) foams. E. globulus lignins, namely a lignin isolated from an industrial Kraft black liquor and depolymerized lignins obtained as by-products of an oxidation process, were used. RPU foams, synthesized with 100% lignin-based polyols and using a 1.1 NCO/OH ratio, were characterized concerning apparent density, morphology, thermal conductivity, thermal stability, and heat release rate (HRR). Foams containing the lignin-based polyols presented densities varying from 44.7 to 112.2 kg/m3 and thermal conductivity in the range of 37.2–49.0 mW/mK. For the reference foam (sample produced with 100% wt. Daltofoam TP 32015 polyol), values of 70.9 kg/m3 and 41.1 mW/mK were obtained, respectively. The achieved results point out the viability of using the generated lignin-based polyols at 100% content in RPU foams, mainly when depolymerized lignins are used. Moreover, fire retardancy was favored when the lignin-based polyols were introduced. The proposed strategies can contribute to establishing the integrated pulp and paper biorefinery concept where material synthesis (polyols and RPU foams) can be combined with chemical production (vanillin and syringaldehyde). [ABSTRACT FROM AUTHOR]

Lignin-based polyols (LBPs) with controlled microstructure were obtained by cationic ring opening polymerization (CROP) of oxiranes in an organosolv lignin (OL) tetrahydrofuran (THF) solution. The control on the microstructure and consequently on the properties of the LBPs such as hydroxyl number, average molecular weight, melting, crystallization and decomposition temperatures, are crucial to determine the performance and application of the derived-products. The influence of key parameters, for example, molar ratio between the oxirane and the hydroxyl groups content in OLO, initial OL concentration in THF, temperature, specific flow rate and oxirane nature has been investigated. LBPs with hydroxyl numbers from 35 to 217 mg KOH/g, apparent average Mw between 5517 and 52,900 g/mol and melting temperatures from −8.4 to 18.4 °C were obtained. The CROP procedure allows obtaining of tailor-made LBPs for specific applications in a very simple way, opening the way to introduce LBPs as a solid alternative to substitute currently used fossil-based polyols. [ABSTRACT FROM AUTHOR]