Enzymatic synthesis of kraft lignin-acrylate copolymers using an alkaline tolerant laccase.

Softwood kraft lignin is a major bioresource relevant to the production of sustainable bio-based products. Continued challenges to lignin valorization, however, include poor solubility in organic solvents and in aqueous solutions at neutral pH. Herein, an alkaline tolerant laccase was used to graft acrylate functionalities onto softwood kraft lignin, which is expected to enhance the reactivity of lignin with isocyanate when producing bio-based polyurethanes. Proton nuclear magnetic resonance, Fourier-transform infrared spectroscopy, and high-performance liquid chromatography were used to confirm successful grafting of the acrylate monomer onto lignin and verify the importance of including tert-butyl hydroperoxide as an initiator in the grafting reaction. Laccase-mediated grafting of softwood kraft lignin under alkaline conditions produced lignin products with approximately 30% higher hydroxyl value and higher reactivity toward isocyanate. The reported enzymatic and aqueous process presents an opportunity for the sustainable valorization of softwood kraft lignin. KEY POINTS: • Softwood kraft lignin displayed high phenolic hydroxyl content, polydispersity index and average molecular weight • Grafting hydroxyethyl acrylate (HEA) monomer onto kraft lignin by laccase was successful at 60 °C and alkaline conditions • Lignin-HEA grafted copolymer showed an increase in total OH value and an increase in average molecular weight.

Choosing the Right Lignin to Fully Replace Bisphenol A in Epoxy Resin Formulation.

Thirteen unmodified lignin samples from different biomass sources and isolation processes were characterized and used to entirely replace bisphenol A (BPA) in the formulation of solubilized epoxy resins using a developed novel method. The objective was to measure the reactivity of different lignins toward bio-based epichlorohydrin (ECH). The epoxy contents of various bio-based epoxidized lignins were measured by titration and 1 H NMR spectroscopy methods. A partial least square regression (PLS-R) model with 92 % fitting accuracy and 90 % prediction ability was developed to find correlations between lignin properties and their epoxy contents. The results showed that lignins with higher phenolic hydroxy content and lower molecular weights were more suitable for replacing 100 % of toxic BPA in the formulation of epoxy resins. Additionally, two epoxidized lignin samples (highest epoxy contents) cured by using a bio-based hardener (Cardolite GX-3090) were found to show comparable thermomechanical performances and thermal stabilities to a petroleum-based (DGEBA) epoxy system.

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.

The Effects of UV Light on the Chemical and Mechanical Properties of a Transparent Epoxy-Diamine System in the Presence of an Organic UV Absorber.

Despite several excellent properties including low shrinkage, good chemical resistance, curable at low temperatures and the absence of byproducts or volatiles, epoxy resins are susceptible to ultra violet (UV) damage and their durability is reduced substantially when exposed to outdoor environments. To overcome this drawback, UV absorbers have been usually used to decrease the rate of UV degradation. In this present study, the effects of UV light on the chemical, mechanical and physical properties of cured epoxy structure, as well as the effect of an organic UV absorber, Tinuvin 1130, on the epoxy properties were investigated. Chemical changes in a cured epoxy system as a result of the presence and absence of Tinuvin 1130 were determined using Fourier transform infrared spectroscopy (FT-IR) analyses. The effect of Tinuvin 1130 on the surface morphology of the epoxy systems was also investigated by scanning electron microscopy (SEM) imaging. Additionally, the glass transition temperatures (Tg) before and during UV radiation were measured. After an 800 h UV radiation, mechanical test results revealed that the lack of the UV absorber can lead to a ~30% reduction in tensile strength. However, in the presence of Tinuvin 1130, the tensile strength was reduced only by ~11%. It was hypothesized that the use of Tinuvin 1130, as an organic UV absorber in the epoxy-amine system, could decrease the undesirable effects, arising from exposure to UV light.

Collision-induced activation: Towards industrially scalable approach to graphite nanoplatelets functionalization for superior polymer nanocomposites.

Scale-up manufacturing of engineered graphene-like nanomaterials to deliver the industry needs for development of high-performance polymer nanocomposites still remains a challenge. Herein, we introduce a quick and cost-effective approach to scalable production of functionalized graphite nanoplatelets using "kitchen blender" approach and Diels-Alder chemistry. We have shown that, in a solvent-free process and through a cycloaddition mechanism, maleic anhydride can be grafted onto the edge-localized electron rich active sites of graphite nanoplatelets (GNP) resulting from high collision force, called "graphite collision-induced activation". The mechanical impact was modelled by applying the point charge method using density functional theory (DFT). The functionalization of GNP with maleic anhydride (m-GNP) was characterized using various spectroscopy techniques. In the next step, we used a recyclable process to convert m-GNP to the highly-reactive GNP (f-GNP) which exhibits a strong affinity towards the epoxy polymer matrix. It was found that at a low content of f-GNP e.g., 0.5 wt%, significant enhancements of ~54% and ~65% in tensile and flexural strengths of epoxy nanocomposite can be achieved, respectively. It is believed that this new protocol for functionalization of graphene nanomaterials will pave the way for relatively simple industrial scale fabrication of high performance graphene based nanocomposites.

Catalyzed Synthesis and Characterization of a Novel Lignin-Based Curing Agent for the Curing of High-Performance Epoxy Resin.

In this study, lignin, an aromatic compound from the forestry industry, was used as a renewable material to synthesize a new aromatic amine curing agent for epoxy resin. Firstly, lignin was separated from black liquor and hydroxyl groups were converted to tosyl groups as leaving groups. Then, primary amination was conducted using an ammonia solution at high pressure and temperature, in the presence of a nano-alumina-based catalyst. The structure of the nanocatalyst was confirmed by FT-IR, ICP, SEM, and XPS analyses. According to the FT-IR spectra, a demethylation reaction, the substitution of hydroxyl groups with tosyl groups, and then an amination reaction were successfully performed on lignin, which was further confirmed by the 13C NMR and CHNS analyses. The active hydrogen equivalent of aminated lignin was determined and three samples with 9.9 wt %, 12.9 wt %, and 15.9 wt % of aminated lignin, as curing agents, were prepared for curing the diglycidyl ether of bisphenol A (DGEBA). The thermal characteristics of the curing process of these epoxy samples were determined by DSC and TGA analyses. Moreover, the mechanical performance of the cured epoxy systems, e.g., the tensile strength and Izod impact strength, were measured, showing that in the presence of 12.9 wt % aminated lignin, the mechanical properties of the aminated lignin-epoxy system exhibited the best performance, which was competitive, compared to the epoxy systems cured by commercial aromatic curing agents.