Synthesis and Characterization of High-Performance, Bio-Based Epoxy–Amine Networks Derived from Resveratrol

Abstract

Resveratrol is a sustainable and versatile bio-derived phenolic compound that has shown promise as a high glass-transition temperature (T g), flame-resistant building block for thermoset networks. In this study, three components of epoxy thermoset resins were synthesized from resveratrol: trans-resveratrol trisepoxy (1), dihydroresveratrol trisepoxy (2), and a trifunctional amine, 4,4′-((5-(4-(4-aminophenoxy)­phenethyl)-1,3-phenylene)­bis­(oxy))­dianiline (4). The epoxy monomers were low melting solids (mp < 80 °C) or thick oils consisting of primarily monomeric trisepoxides. Toxicity testing of 4 revealed that it was not mutagenic and had a low LD50 of 560 mg/kg, an aquatic toxicity of >2000 mg/L, and no cytotoxicity up to its solubility limit. The epoxy monomers were cured with 4,4′-methylenedianiline (3) and 4 to produce four epoxy–amine networks (A–D). Networks C and D, prepared with the resveratrol-derived aniline, contained up to 52.6% bio-based material. The moisture uptake, thermal stability, and dry/wet thermomechanical properties of the networks were measured. The networks had T g’s as high as 285 °C, approximately 110 °C higher than networks based on petroleum-derived bisphenol A (BPA). In addition, the resveratrol networks had char yields as high as 51 and 46% in nitrogen and air, respectively, compared to ca. 15 and 5%, respectively, for BPA-based networks. Overall, this study shows the advantages of resveratrol-based epoxy and amine monomers as components of sustainable, low-toxicity, high-temperature resin systems.

Recent development on bio‐based thermosetting resins

“…60,61 Other plant extracts, such as catechol, cinnamic acid and resveratrol, also prove to be the suitable materials for epoxy resin. [62][63][64][65][66][67] Through some treatment, the bio-based platform compounds can be transformed into amine derivatives, which could be designed to a green epoxy curing agent. Combining with the bio-derived epoxy resin, a resin with more bio-based content will be obtained, which could be divided into fully bio-based system as well.…”

“…68 By Michael addition, three amines were integrated into acrylic epoxy soybean oil, which can be used for simply regulating the properties of polymers. 69 In addition, utilizing the curing system with amine derivatives containing aliphatic ring, 39 hetero ring, 21 and aromatic ring, 67 could improve the performance of mixture.…”

“…The similar structure of genistein and naringin was successfully adopted for preparing high performance epoxy resin as well 60,61 . Other plant extracts, such as catechol, cinnamic acid and resveratrol, also prove to be the suitable materials for epoxy resin 62–67 …”

Design of controllable degradable epoxy resin: High performance and feasible upcycling

“…Vanillin, an aromatic compound derived from lignin, has been regarded as an ideal platform chemical in the synthesis of bio‐based thermoset resins 30–32 . Starting from the aromatic aldehyde group, Vanillin can prepare the cyclic acetal structure 18 and also react with amine groups rapidly in mild condition to form Schiff‐base structure 13 . The spior diacetal unit, as one of the cyclic acetal structure, is generally used for high performance applications 33 .…”

Synthesis and application of poly (cyclotriphosphazene‐resveratrol) microspheres for enhancing flame retardancy of poly (ethylene terephthalate)

“…Resveratrol, known as “French paradox,” a natural polyphenol organic compound that can be extracted from grape leaves or skins, is generally applied in cosmetics, 29 degradation, 30,31 food, 32 and medicine 33 by virtue of its diverse biological activities 34 . Furthermore, the polyphenol structure makes it as an exceptional candidate for carbonization agent 35,36 and reaction crosslinking agent 37 . Tian et al fabricated a resveratrol‐based epoxy resin with high glass transition temperature ( T g ) and considerable mechanical properties, which showed low flammability and compact char yield, indicating that bio‐based flame retardents, especially those containing the polyphenol groups have broad applications prospects for the fire safety 38 .…”