Rigid Polyurethane Foams' Development and Optimization from Polyols Based on Depolymerized Suberin and Tall Oil Fatty Acids.

The utilization of polyols derived from renewable sources presents an opportunity to enhance the sustainability of rigid polyurethane (PUR) foams, thereby contributing to the advancement of a circular bioeconomy. This study explores the development of PUR rigid foams exclusively using polyols sourced from second-generation renewable biomass feedstocks, specifically depolymerized birch bark suberin (suberinic acids) and tall oil fatty acids. The polyols achieved a total renewable material content as high as 74%, with a suberinic acid content of 37%. Response surface modeling was employed to determine the optimal bio-polyol, blowing agents, and catalyst content, hence, optimizing the bio-based foam formulations. In addition, response surface modeling was applied to rigid PUR foam formulations based on commercially available petroleum-based polyols for comparison. The results, including apparent density (~40-44 kg/m3), closed cell content (~95%), compression strength (>0.2 MPa, parallel to the foaming direction), and thermal conductivity (~0.019 W/(m·K)), demonstrated that the suberinic acids-based rigid PUR foam exhibited competitive qualities in comparison to petroleum-based polyols. Remarkably, the bio-based rigid PUR foams comprised up to 29% renewable materials. These findings highlight the potential of suberinic acid-tall oil polyols as effective candidates for developing rigid PUR foams, offering promising solutions for sustainable insulation applications.

Innovative Approach to Enhance Bioavailability of Birch Bark Extracts: Novel Method of Oleogel Development Contrasted with Other Dispersed Systems.

Birch outer bark extract (BBE), containing pentacyclic triterpenes such as betulin, lupeol, and betulinic acid, is a widely recognized natural product renowned for its diverse pharmacological effects. However, its limited water solubility restricts its bioavailability. Therefore, the main objective is to enhance the bioavailability of BBE for pharmaceutical use. In this study, we aimed to develop a dispersion system utilizing a unique oleogel-producing method through the recrystallization of BBE from an ethanol solution in the oil phase. We generated an oleogel that demonstrates a notable 42-80-fold improvement in betulin and lupeol peroral bioavailability from BBE in Wistar rats, respectively. A physical paste-like BBE hydrogel developed with antisolvent precipitation showed a 16-56-fold increase in the bioavailability of betulin and lupeol from BBE in rat blood plasma, respectively. We also observed that the repeated administration of the BBE oleogel did not exhibit any toxicity at the tested dose (38.5 mg/kg betulin, 5.2 mg/kg lupeol, 1.5 mg/kg betulinic acid daily for 7 days). Betulin and betulinic acid were not detected in rat heart, liver, kidney, or brain tissues after the peroral administration of the oleogel daily for 7 days. Lupeol was found in rat heart, liver, and kidney tissues.

Rigid Polyurethane Foams as Thermal Insulation Material from Novel Suberinic Acid-Based Polyols.

Developing polyols from biomass sources contributes to a more circular economy by replacing petroleum-based polyols in the vast production of polyurethanes (PUR). One such potential biomass source could be leftover birch bark from which suberinic acids (SA) can be obtained. The purpose of this study was to identify the best synthesis routes for novel SA-based polyols, obtain rigid PUR foams, and evaluate their competitiveness and potential suitability as thermal insulation material. Novel polyols were synthesized from depolymerized SA by esterification with various functionality and molecular weight alcohols in several molar ratios. The moisture content, hydroxyl and acid values, and apparent viscosity were tested. Free-rise rigid PUR foams from the most suitable SA-based polyol and tall oil-based polyol were successfully prepared, reaching ~20 wt.% total renewable material content in the foam. The obtained rigid PUR foams' morphological, mechanical, and thermal properties were investigated and compared to present foam materials, including commercial foams. The apparent density (~33 kg/m3), as well as the closed cell content (~94%), compression strength (0.25 MPa, parallel to the foaming direction), and thermal conductivity (~0.019 W/(m·K)), approved the competitiveness and potential ability of SA-based rigid PUR foam production as thermal insulation material.

Thermomechanical and Alkaline Peroxide Mechanical Pulping of Lignocellulose Residue Obtained from the 2-Furaldehyde Production Process.

The necessity for the reduction in greenhouse gas emissions, the growing demand for the improvement of biorefinery technologies, and the development of new biorefining concepts oblige us as a society, and particularly us, as scientists, to develop novel biorefinery approaches. The purpose of this study is to thoroughly evaluate the leftover lignocellulosic (LC) biomass obtained after the manufacture of 2-furaldehyde, with the intention of further valorizing this resource. This study demonstrates that by using thermomechanical and alkaline peroxide mechanical pulping techniques, birch wood chips can be used in the new biorefinery processing chain for the production of 2-furaraldehyde, acetic acid, and cellulose pulp. In addition, the obtained lignocellulosic residue is also characterized. To produce a lignocellulosic material without pentoses and with the greatest amount of cellulose fiber preserved for future use, a novel bench-scale reactor technology is used. Studies were conducted utilizing orthophosphoric acid as a catalyst to deacetylate and dehydrate pentose monosaccharides found in birch wood, converting them to 2-furaldehyde and acetic acid. The results showed that, with the least amount of admixtures, the yields of the initial feedstock's oven-dried mass (o.d.m.) of 2-furaldehyde, acetic acid, and lignocellulose residue ranged from 0.04 to 10.84%, 0.51 to 6.50%, and 68.13 to 98.07%, respectively, depending on the pretreatment conditions utilized. The ideal 2-furaldehyde production conditions with reference to the purity and usability of cellulose in residual lignocellulosic material were also discovered through experimental testing. The experiment that produced the best results in terms of 2-furaldehyde yield and purity of residual lignocellulose used a catalyst concentration of 70%, a catalyst quantity of 4%, a reaction temperature of 175 °C, and a treatment period of 60 min. It was possible to create pulp with a tensile index similar to standard printing paper by mechanically pulping the necessary LC residue with alkaline peroxide, proving that stepwise 2-furaldehyde production may be carried out with subsequent pulping to provide a variety of value-added goods.

Utilization of Suberinic Acids Containing Residue as an Adhesive for Particle Boards.

The birch (Betula spp.) outer bark is a valuable product rich in betulin. After removal of betulin extractives, suberin containing tissues are left. Suberin is a biopolyester built from α,ω-bifunctional fatty acids (suberinic acids), which after depolymerization together with lignocarbohydrate complex is a potential adhesive as a side-stream product (residue) from obtaining suberinic acids for polyol synthesis. In this work, we studied the utilization possibilities in particleboards of the said residue obtained by depolymerization in four different solvents (methanol, ethanol, isopropanol and 1-butanol). The adhesives were characterised by chemical (acid number, solubility in tetrahydrofuran, epoxy and ash content) and instrumental analytical methods (SEC-RID, DSC, TGA and FTIR). Based on the results of mechanical characteristics, ethanol was chosen as the most suitable depolymerization medium. The optimal hot-pressing parameters for particleboards were determined using the design of experiments approach: adhesive content 20 wt%; hot-pressing temperature 248 °C, and hot-pressing time 6.55 min.

Characterization of Birch Wood Residue after 2-Furaldehyde Obtaining, for Further Integration in Biorefinery Processing.

Latvia is a large manufacturer of plywood in Eastern Europe, with an annual production of 250,000 m3. In Latvia's climatic conditions, birch (Betula pendula) is the main tree species that is mainly used for plywood production. A significant part of the processed wood makes up residues like veneer shorts, cores, and cut-offs (up to 30%), which have a high potential for value-added products. The aim of this research was to comprehensively characterize lignocellulosic (LC) biomass that was obtained after 2-furaldehyde production in terms of further valorization of this resource. The polymeric cellulose-enriched material can be used in the new biorefinery concept for the production of 2-furaldehyde, acetic acid, cellulose pulp, thermomechanical (TMP) and an alkaline peroxide mechanical (APMP) pulping process. In addition, we experimentally developed the best 2-furaldehyde production conditions to optimize the purity and usability of cellulose in the leftovers of the LC material. The best experimental results in terms of both 2-furaldehyde yield and the purity of residual lignocellulose were obtained if the catalyst concentration was 70%, the catalyst amount was 4 wt.%, the reaction temperature was 175 °C,and the treatment time was 60 min. After process optimization with DesignExpert11, we concluded that the best conditions for maximal glucose content (as cellulose fibers) was a catalyst concentration of 85%, a catalyst amount of 5 wt.%, a temperature of 164 °C, and a treatment time of 52 min.

Suberinic Acids as a Potential Feedstock for Polyol Synthesis: Separation and Characterization.

Global sustainability challenges prompt the world to modify its strategies and shift from a fossil-fuel-based economy to a bio-resources-based one and to the production of renewable biomass chemicals. Depolymerized suberinic acids (SA) were considered as an alternative resource to develop bio-polyols that can be further used in polyurethane (PU) material production. Birch (Betula pendula) outer bark was used as a raw material to obtain the SA, extracted with ethanol, and depolymerized with potassium hydroxide ethanol solution. By acidifying the filtrate to pH 5.0, 3.0, and 1.0 and drying it at 50 °C and 130 °C, 12 different SA potential feedstocks were obtained and characterized using chemical (total phenolics content, solubility in DMSO, acid, hydroxyl, and saponification number) and instrumental analytical methods (GC-MS, SEC-RID, DSC, and FTIR). Several bio-polyols were synthesized from the SA sample acidified to pH 1 and dried at 130 °C. Acid number and hydroxyl number values, the apparent viscosity and moisture content were measured. It was concluded that SA have a high enough saponification and acid value to investigate the polyol synthesis route via the esterification reaction. Moreover, SA had OH groups in their structure, which can be exploited for PU material development. The majority of SA compounds had relatively low molecular weight with <1300 Da that are suited for bio-polyol synthesis applied for rigid PU foam development. The synthesized bio-polyols had high hydroxyl number values necessary for bio-polyols to be used for rigid PU foam production.

Residual Birch Wood Lignocellulose after 2-Furaldehyde Production as a Potential Feedstock for Obtaining Fiber.

From birch wood, it is possible to obtain both acetic acid and 2-furaldehyde as valuable value-added products. The main objective of this study was to develop a new wasteless technology for obtaining 2-furaldehyde, acetic acid, and lignocellulose (LC) residue usable as feedstock in further processing such as thermomechanical (TMP), alkaline peroxide mechanical (APMP), and sulfate pulping processes. To achieve this objective several screening tests were performed, and a further experimental plan was developed using DesignExpert11. Process yields were analyzed both in terms of total yield and at individual time increments. In addition, the obtained LC residue was also characterized. A unique bench-scale reactor system was used to obtain an LC material without pentoses and with maximum preservation of cellulose fiber for further research. Studies on the deacetylation and dehydration of birch wood hemicelluloses of pentose monosaccharides to 2-furaldehyde and acetic acid using orthophosphoric acid as a catalyst were carried out. Results showed that, depending on the used pre-treatment conditions, the 2-furaldehyde yield was from 0.04% to 10.84% oven dry mass (o.d.m.), the acetic acid yield was from 0.51% to 6.50% o.d.m., and the LC residue yield was from 68.13% to 98.07% o.d.m. with minimal content of admixtures. Process optimization using DesignExpert11 revealed that the main pre-treatment process parameters that influenced the yield of 2-furaldehyde in the pre-treatment process were process temperature (53.3%) and process duration (29.8%).

Weathering Stability and Durability of Birch Plywood Modified with Different Molecular Weight Phenol-Formaldehyde Oligomers.

This study investigated the effect of phenol-formaldehyde (PF) resin treatment on the weathering stability and biological durability of birch plywood. Silver birch (Betula pendula) veneers were vacuum-pressure impregnated with four different PF resins with average molecular weights (Mw) of 292 (resin A), 528 (resin B), 703 (resin C), and 884 g/mol (resin D). The aging properties of PF resin modified birch plywood were analyzed using artificial weathering with ultraviolet (UV) light, UV and water spray, and weathering under outdoor conditions. The same combinations of PF-treated plywood specimens were then tested in soil-bed tests to determine their resistance against soft-rot wood decay. It was not possible to compare weathering processes under artificial conditions to processes under outdoor conditions. However, the weathering stability of birch plywood treated with PF resins A, B, and C, scored better than plywood treated with commercial resin D (regardless of solid content concentration [%]). Results from unsterile soil bed tests showed improvements in resistance to soft-rot wood decay compared to untreated plywood and solid wood. Mass loss [%] was lowest for birch plywood specimens treated with resin of highest solid content concentration (resin D, 20%). Provisional durability ratings delivered durability class (DC) ratings of 2-3, considerably improved over untreated solid wood and untreated birch plywood (DC 5).