Green approaches in the synthesis of furan-based diepoxy monomers

Abstract

Two eco-respectful, one-step synthetic routes for the preparation of a bio-based epoxy monomer derived from furan precursors are developed. The diglycidyl ester products are throughly characterized in terms of structure and thermal properties. Gathered results indicate that the two selected approaches allow the preparation of pure, furanic diglycidyl ester, which represents a viable bio-based alternative to its petrochemical aromatic counterpart.Research on bio-based polymers has been rapidly increasing in past years, pushed by growing environmental and economic concerns, as well as by the uncertainty about future availability of nite petrochemical resources.1 Sustainability is a keyword in this process. In this frame, products that are respectful towards the environment, including eco-compatible building blocks and additives, are now researched to replace petroleum-based polymers with those derived from naturally occurring feedstocks.2-4 In the eld of epoxy resins, this trend is related also to the necessity to nd a good candidate to substitute the controversial building block bisphenol A (BPA), a molecule recognized as an endocrine disrupter and reprotoxic substance.5 Epoxy resins are very versatile thermosetting polymers, extremely resistant to corrosion, moisture and chemicals, with good adhesive strength toward most materials (wettability) and low shrinkage upon curing. Due to their high glass transition temperatures and excellent mechanical strength, epoxy resins are widely employed in a broad range of applications, such as electronics, structural adhesives, aerospace composites and protective coatings. In the latter application, the use of BPA results in hazard for customers of food and beverage products packed into containers treated with epoxy resins. The effects of human body contamination caused by BPA are diabetes, cardiovascular diseases, altered liver enzymes and reproductive apparatus damages.5 For these reasons, this molecule has been banned in many countries for the manufacturing of child products, and in France and Canada from all the materials in direct contact with food. Therefore, the necessity to nd non-toxic and sustainable building blocks to replace BPA in the production of epoxy resins results mandatory. If one considers also the decreasing availability of oilderived feedstock, the research of new molecules is logically focusing on bio-derived chemicals. Epoxidized vegetable oils have been widely studied for their use in epoxy resins preparation, thanks to their characteristics, availability and low cost.6-8 Mechanical properties of epoxy resins obtained using these long aliphatic molecules, alone or mixed to aromatic epoxy comonomers, are encouraging.9,10 In order to further improve chemical, thermal and mechanical properties of epoxy resins, the presence of signicant content of aromatic moieties is required. In this frame, lignin derivatives appear to be the natural substitutes of BPA. However, time-and energyconsuming extraction processes make lignin-based epoxies expensive and b...

Recent Research Progress on Lignin-Derived Resins for Natural Fiber Composite Applications

“…The literature combining lignin-derived-based resins such as lignin, VN, and DVN is necessary to explore bio-based resin's value in natural fiber composites application for years to come. Bio-based thermoplastic and thermoset polymers are gaining attraction due to their biodegradability and environmental concern that can replace petroleum feedstock-based products [32,33]. Until now, several studies have described the use of lignin in biothermoplastics, including biocomposites due to its modifications possibility, availability, biodegradability, and good mechanical properties [6,34,35].…”

Heterogeneous additive‐free highly selective synthesis of 2,5‐bis(hydroxymethyl)furan over catalysts with ultra‐low Pt content

“…One of them is 2,5‐ bis(hydroxymethyl)furan (BHMF), the product of selective reduction of the carbonyl group. BHMF is an intermediate for the production of a great number of valuable compounds, from polymers, 5 foams 6 and resins 7 to biofuels 8 and fuel additives 9 . Many publications are devoted to the synthesis of various esters of fatty acids based on BHMF, which can be used as dopants for increasing the fuel cetane number 10,11 .…”

Thermal and Fire Behavior of a Bio-Based Epoxy/Silica Hybrid Cured with Methyl Nadic Anhydride

“…2,5-bis[(oxyran-2-ylmethoxy)methyl]furan (BOMF) is one of the most promising furan-based diepoxy monomers for producing sugar-based furan polymers [20,21]. In a recent work, BOMF and DGEBA were cured with methyl nadic anhydride (MNA) in the presence of 2-methyl imidazole (2-MI) as initiator.…”