Studying the Suitability of Nineteen Lignins as Partial Polyol Replacement in Rigid Polyurethane/Polyisocyanurate Foam.

In this study, nineteen unmodified lignins from various sources (hardwood, softwood, wheat straw, and corn stover) and isolation processes (kraft, soda, organosolv, sulfite, and enzymatic hydrolysis) were used to replace 30 wt.% of petroleum-based polyol in rigid polyurethane/polyisocyanurate (PUR/PIR) foam formulations. Lignin samples were characterized by measuring their ash content, hydroxyl content (Phosphorus Nuclear Magnetic Resonance Spectroscopy), impurities (Inductively Coupled Plasma), and pH. After foam formulation, properties of lignin-based foams were evaluated and compared with a control foam (with no lignin) via cell morphology, closed-cell content, compression strength, apparent density, thermal conductivity, and color analysis. Lignin-based foams passed all measured standard specifications required by ASTM International C1029-15 for type 1 rigid insulation foams, except for three foams. These three foams had poor compressive strengths, significantly larger cell sizes, darker color, lower closed-cell contents, and slower foaming times. The foam made with corn stover enzymatic hydrolysis lignin showed no significant difference from the control foam in terms of compressive strength and outperformed all other lignin-based foams due to its higher aliphatic and p-hydroxyphenyl hydroxyl contents. Lignin-based foams that passed all required performance testing were made with lignins having higher pH, potassium, sodium, calcium, magnesium, and aliphatic/p-hydroxyphenyl hydroxyl group contents than those that failed.

Lignin as a Partial Polyol Replacement in Polyurethane Flexible Foam.

This study was focused on evaluating the suitability of a wide range of lignins, a natural polymer isolated from different plant sources and chemical extractions, in replacing 20 wt.% of petroleum-based polyol in the formulation of PU flexible foams. The main goal was to investigate the effect of unmodified lignin incorporation on the foam's structural, mechanical, and thermal properties. The hydroxyl contents of the commercial lignins were measured using phosphorus nuclear magnetic resonance (31P NMR) spectroscopy, molar mass distributions with gel permeation chromatography (GPC), and thermal properties with differential scanning calorimetry (DSC) techniques. The results showed that incorporating 20 wt.% lignin increased tensile, compression, tear propagation strengths, thermal stability, and the support factor of the developed PU flexible foams. Additionally, statistical analysis of the results showed that foam properties such as density and compression force deflection were positively correlated with lignin's total hydroxyl content. Studying correlations between lignin properties and the performance of the developed lignin-based PU foams showed that lignins with low hydroxyl content, high flexibility (low Tg), and high solubility in the co-polyol are better candidates for partially substituting petroleum-based polyols in the formulation of flexible PU foams intended for the automotive applications.

Kraft Lignin with Improved Homogeneity Recovered Directly from Black Liquor and Its Application in Flexible Polyurethane Foams.

An effective method that can produce a large amount of Kraft lignin with improved homogeneity is strongly desired for Kraft lignin's high-value applications and scientific advancements. Herein, a one-pot acid-catalyzed liquefaction method was developed to recover Kraft lignin directly from black liquor. The recovery rate and properties of the recovered lignin were affected by the reaction time, reaction temperature, moisture content (MC), pH, and acid categories. The highest lignin recovery rate of 75% was achieved when the concentrated black liquor (MC = 25%) reacted with methanol at pH = 7 and 160 °C for 10 min using acetic acid as the catalyst. Most of the recovered lignin from this method showed an average molecular weight (Mw) value less than 2000 Da and a polydispersity (PDI) value less than 2.0. Such a PDI value was lower than that of current acid precipitated lignin (around 2.2-5.4). The recovered lignin was directly used to replace 20% of the petroleum-based polyol in the formula of a flexible polyurethane (PU) foam, and it was found that the molecular weight characteristics of the lignin affected the physical and mechanical properties of the flexible PU foams. The recovered lignin with the Mw value of 1600 Da and the PDI value of 1.8 was able to maintain the major physical and mechanical properties of the flexible PU foams. This study provided a promising way to recover lignin with improved homogeneity from black liquor with the potential to customize lignin properties to meet the requirements of downstream processes.

Comparative study of ultrasonic pretreatment and ultrasound assisted three phase partitioning for extraction of custard apple seed oil.

Custard apple seed oil is a marketable product extracted from custard apple seed which is a potential agriculture waste. The present work aims to elucidate simultaneous extraction of the custard apple seed oil and proteins using three phase partitioning (TPP). The efficient oil extraction was executed by optimization of parameters including time, slurry ratio, salt concentration, and slurry to t-butanol ratio. Additionally, the application of ultrasound as process intensification tool for TPP was studied that reduces the time of conventional TPP and increases the yield by 2.53%. The work also comprises a comparative study of two modes of ultrasound application, namely ultrasound pre-treatment and simultaneous ultrasound assisted TPP. This work proves ultrasonic pre-treatment followed by TPP as a superior mode of ultrasound application that attributes 33.6 ±â€¯0.56% (w/w) oil extraction with optimized pre-treatment time of 150 s, 30 W ultrasound power and 75% duty cycle. Extraction kinetics studied for conventional, Ultrasound assisted Three Phase Partitioning (UTPP), and Ultrasound Pre-treatment assisted Three Phase Partitioning (UPTPP) were observed to fit Peleg's model.

Lignin-Based Polyurethanes: Opportunities for Bio-Based Foams, Elastomers, Coatings and Adhesives.

Polyurethane chemistry can yield diverse sets of polymeric materials exhibiting a wide range of properties for various applications and market segments. Utilizing lignin as a polyol presents an opportunity to incorporate a currently underutilized renewable aromatic polymer into these products. In this work, we will review the current state of technology for utilizing lignin as a polyol replacement in different polyurethane products. This will include a discussion of lignin structure, diversity, and modification during chemical pulping and cellulosic biofuels processes, approaches for lignin extraction, recovery, fractionation, and modification/functionalization. We will discuss the potential of incorporation of lignins into polyurethane products that include rigid and flexible foams, adhesives, coatings, and elastomers. Finally, we will discuss challenges in incorporating lignin in polyurethane formulations, potential solutions and approaches that have been taken to resolve those issues.