Recent
advances in the area of biomass-derived C6-furanic platform
chemicals for sustainable biomass processing are analyzed focusing
on chemical reactions important for development of practical applications
and materials science. Among the chemical processes currently being
studied, tuning the amount of oxygen-containing functional groups
remains the most active research direction. Production of efficient
fuels requires the removal of oxygen atoms (reduction reactions),
whereas utilization of biomass-derived furanic derivatives in material
science points out the importance of oxidation in order to form dicarboxylic
derivatives. Stimulated by this driving force, oxidation and reduction
of 5-(hydroxymethyl)furfural (HMF) are nowadays massively studied.
Moreover, these fundamental transformations are often used as model
reactions to test new catalysts, and HMF transformations guide the
development of new catalytic systems. From the viewpoint of organic
synthesis, highly diverse chemical reactivity is explored and a number
of bioderived synthetic building blocks with different functional
groups are now accessible. This Perspective covers the most recent
literature (since Jan 2017) to highlight the emerging research trends.
Acetylene, HC≡CH, is one of the primary building blocks in synthetic organic and industrial chemistry. Several highly valuable processes have been developed based on this simplest alkyne and the development of acetylene chemistry has had a paramount impact on chemical science over the last few decades. However, in spite of numerous useful possible reactions, the application of gaseous acetylene in everyday research practice is rather limited. Moreover, the practical implementation of high-pressure acetylene chemistry can be very challenging, owing to the risk of explosion and the requirement for complex equipment; special safety precautions need to be taken to store and handle acetylene under high pressure, which limit its routine use in a standard laboratory setup. Amazingly, recent studies have revealed that calcium carbide, CaC2 , can be used as an easy-to-handle and efficient source of acetylene for in situ chemical transformations. Thus, calcium carbide is a stable and inexpensive acetylene precursor that is available on the ton scale and it can be handled with standard laboratory equipment. The application of calcium carbide in organic synthesis will bring a new dimension to the powerful acetylene chemistry.
Rapid development in the area of cellulose biomass conversion to furanic platform chemicals has led to expectations of their valuable practical use. Impressive research progress in this direction has resulted in several achievements but at the same time identified a key challengethe necessity to produce aromatic compounds. In this perspective, we analyze the current stage of development of the furanics-tobenzene conversion process (F2B process) in connection with a bioderived route to aromatic compounds. Cycloaddition reactions between bioderived C 6 -furans as diene components and alkene/alkyne units are discussed in detail, followed by considering the subsequent aromatization reaction. Progress in the development of the F2B process and future challenges are outlined in this perspective. The key role of the F2B process in the overall biomass to aromatics transformation is discussed in view of the implementation of carbon neutral sustainable technologies in practice.
Biomass-derived poly(ethylene-2,5-furandicarboxylate) (PEF) has been used for fused deposition modeling (FDM) 3D printing. A complete cycle from cellulose to the printed object has been performed. The printed PEF objects created in the present study show higher chemical resistance than objects printed with commonly available materials (acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), glycol-modified poly(ethylene terephthalate) (PETG)). The studied PEF polymer has shown key advantages for 3D printing: optimal adhesion, thermoplasticity, lack of delamination and low heat shrinkage. The high thermal stability of PEF and relatively low temperature that is necessary for extrusion are optimal for recycling printed objects and minimizing waste. Several successive cycles of 3D printing and recycling were successfully shown. The suggested approach for extending additive manufacturing to carbon-neutral materials opens a new direction in the field of sustainable development.
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