This review article aims to summarize the potential of using renewable natural resources, such as lignin and tannin, in the preparation of NIPUs for wood adhesives. Polyurethanes (PUs) are extremely versatile polymeric materials, which have been widely used in numerous applications, e.g., packaging, footwear, construction, the automotive industry, the lighting industry, insulation panels, bedding, furniture, metallurgy, sealants, coatings, foams, and wood adhesives. The isocyanate-based PUs exhibit strong adhesion properties, excellent flexibility, and durability, but they lack renewability. Therefore, this study focused on the development of non-isocyanate polyurethane lignin and tannin resins for wood adhesives. PUs are commercially synthesized using polyols and polyisocyanates. Isocyanates are toxic, costly, and not renewable; thus, a search of suitable alternatives in the synthesis of polyurethane resins is needed. The reaction with diamine compounds could result in NIPUs based on lignin and tannin. The research on bio-based components for PU synthesis confirmed that they have good characteristics as an alternative for the petroleum-based adhesives. The advantages of improved strength, low curing temperatures, shorter pressing times, and isocyanate-free properties were demonstrated by lignin- and tannin-based NIPUs. The elimination of isocyanate, associated with environmental and human health hazards, NIPU synthesis, and its properties and applications, including wood adhesives, are reported comprehensively in this paper. The future perspectives of NIPUs’ production and application were also outlined.

Biocomposites reinforced with natural fibers represent an eco-friendly and inexpensive alternative to conventional petroleum-based materials and have been increasingly utilized in a wide variety of industrial applications due to their numerous advantages, such as their good mechanical properties, low production costs, renewability, and biodegradability. However, these engineered composite materials have inherent downsides, such as their increased flammability when subjected to heat flux or flame initiators, which can limit their range of applications. As a result, certain attempts are still being made to reduce the flammability of biocomposites. The combustion of biobased composites can potentially create life-threatening conditions in buildings, resulting in substantial human and material losses. Additives known as flame-retardants (FRs) have been commonly used to improve the fire protection of wood and biocomposite materials, textiles, and other fields for the purpose of widening their application areas. At present, this practice is very common in the construction sector due to stringent fire safety regulations on residential and public buildings. The aim of this study was to present and discuss recent advances in the development of fire-resistant biocomposites. The flammability of wood and natural fibers as material resources to produce biocomposites was researched to build a holistic picture. Furthermore, the potential of lignin as an eco-friendly and low-cost FR additive to produce high-performance biocomposites with improved technological and fire properties was also discussed in detail. The development of sustainable FR systems, based on renewable raw materials, represents a viable and promising approach to manufacturing biocomposites with improved fire resistance, lower environmental footprint, and enhanced health and safety performance.

In this study, technical lignin from black liquor was used as a pre-polymer for the preparation of bio-polyurethane (Bio-PU) resins. Briefly, the isolated lignin was fractionated using ethyl acetate (EtAc) and methanol (MeOH). The liquid fractions of lignin, such as lignin-EtAc (L-EtAc) and lignin-methanol (L-MeOH), were mixed with 10% of polymeric isocyanate (based on the weight of liquid fractions) to obtain Bio-PU resins. The isolated lignin, fractionated lignin, and lignin-derived Bio-PU resins were characterized using several techniques. The obtained Bio-PU resins were then used to modify ramie fibers using vacuum impregnation method. Fourier Transform Infrared (FTIR) spectroscopy, Differential Scanning Calorimetry (DSC), and Thermogravimetric Analysis (TGA) revealed that the isolated lignin had quite similar characteristics to the lignin standard. Fractionation of lignin with EtAc and MeOH altered its characteristics. FTIR, DSC, and TGA showed that solid fractions of lignin had similar characteristics to lignin standard and isolated lignin, while the liquid fractions had characteristics from lignin and the solvents. The absorption band of isocyanate (−N=C=O) groups was shifted to 2285 cm−1 from 2240 cm−1 owing to the reaction with the −OH groups in lignin, forming urethane (R−NH−C=O−R) groups at 1605 cm−1 in Bio-PU resins. Thermal properties of Bio-PU resins derived from L-EtAc exhibited greater endothermic reaction compared to Bio-PU-L-MeOH. As a result, the free −N=C=O groups in Bio-PU resins have reacted with –OH groups on the surface of ramie fibers and improved its thermal properties. Modification of ramie fibers with Bio-PU resins improved the fibers’ thermal stability by 15% using Bio-PU-LEtAc for 60 min of impregnation.Keywords: Bio-polyurethane resins, Impregnation, Lignin fractions, Ramie fibers, Thermal stability

Tannins are soluble, astringent secondary phenolic metabolites generally obtained from renewable natural resources, and can be found in many plant parts, such as fruits, stems, leaves, seeds, roots, buds, and tree barks, where they have a protective function against bacterial, fungal, and insect attacks. In general, tannins can be extracted using hot water or organic solvents from the bark, leaves, and stems of plants. Industrially, tannins are applied to produce adhesives, wood coatings, and other applications in the wood and polymer industries. In addition, tannins can also be used as a renewable and environmentally friendly material to manufacture bio-based polyurethanes (bio-PUs) to reduce or eliminate the toxicity of isocyanates used in their manufacture. Tannin-based bio-PUs can improve the mechanical and thermal properties of polymers used in the automotive, wood, and construction industries. The various uses of tannins need to be put into perspective with regards to possible further advances and future potential for value-added applications. Tannins are employed in a wide range of industrial applications, including the production of leather and wood adhesives, accounting for almost 90% of the global commercial tannin output. The shortage of natural resources, as well as the growing environmental concerns related to the reduction of harmful emissions of formaldehyde or isocyanates used in the production of polyurethanes, have driven the industrial and academic interest towards the development of tannin-based bio-PUs as sustainable alternative materials with satisfactory characteristics. The aim of the present review is to comprehensively summarize the current state of research in the field of development, characterization, and application of tannin-derived, bio-based polyurethane resins. The successful synthesis process of the tannin-based bio-PUs was characterized by Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), MALDI-TOF mass spectrometry, and gel permeation chromatography (GPC) analyses.