An innovative and eco-friendly one-pot synthesis of bio-based polyurethanes is proposed via the epoxy-ring opening of epoxidized soybean oil (ESO) with methanol, followed by the reaction of methoxy bio-polyols intermediates with 2,6-tolyl-diisocyanate (TDI). Both synthetic steps, methanolysis and polyurethane linkage formation, are promoted by a unique catalyst, molybdenum(VI) dichloride dioxide (MoCl2O2), which makes this procedure an efficient, cost-effective, and environmentally safer method amenable to industrial scale-up.

Unprecedented in the literature, levulinic acid (LA), one of the top value-added intermediates of chemical industry, is obtained from cigarette butts as cellulose feedstock by means of a one-pot hydrothermal process carried out at 200 °C for 2 h and catalysed by phosphoric acid. The protocol avoids the use of more aggressive and toxic H2SO4 and HCl, that are generally employed on several cellulose sources (e.g. sludge paper), thus minimizing corrosion phenomena of plants. Neither chemical pre-treatment of butts nor specific purification procedure of LA are required. Notably, by simply modifying acid catalyst (e.g. using CH3COOH), another top value-added fine chemical such as 5-hydroxymethylfuraldehyde (HMF) is obtained, thus widening the scope of the method. Being cigarette filters a waste available in quantities of megatonnes per year, they represent an unlimited at no cost source of cellulose, thus enabling the up-scale to an industrial level of LA production.

Polyurethane-resin doming is currently one of the fastest growing markets in the field of industrial graphics and product identification. Semi-rigid bio-based polyurethanes were prepared deriving from soybean oil as a valuable alternative to fossil materials for digital doming and applied to digital mosaic technology. Bio-resins produced can favorably compete with the analogous fossil polymers, giving high-quality surface coatings (ascertained by SEM analyses). In addition, polyurethane synthesis was accomplished by using a mercury- and tin-free catalyst (the commercially available zinc derivative K22) bringing significant benefits in terms of cost efficiency and eco-sustainability.

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Background & Objective: A green one-pot synthesis of oleic acid (1) derivatives is promoted by Rare Earth Metal (REM) triflates and commercial Molybdenum dioxo dichloride (MoCl 2 O 2) in the presence hydrogen peroxide as a green oxidant. Results: The protocol permits to govern the oxidation selectivity by simply choosing the proper combination of Mo and Sc catalysts. Conclusion: Methyl oleate epoxide 2a and azelaic acid 6 thus obtained are valuable industrial intermediates for synthesizing bio-compostable plastics, plasticizers of PVC, lubricating oils, cosmetics and pharmaceuticals (bactericides, anti-inflammatories, etc.).