Eugenol-based thermally stable thermosets by Alder-ene reaction: From synthesis to thermal degradation

Abstract

Performing thermostable materials such as phenolic or epoxy networks are classically obtained from petrobased and harmful monomers. In this study, alternative solutions based on renewable eugenol trifunctional monomer (TEP) are proposed. Thus, innovative biobased Alder-ene thermosets are prepared by reacting TEP with two different bismaleimides : N,N'-1,3-phenylene bismaleimide (PhBMI) and polydimethylsiloxane bismaleimide (SiBMI) leading to different crosslinked aromatic networks. These materials exhibit various mechanical properties with very different T g values of-113°C and 247°C for SiBMI and PhBMI materials respectively. However, both thermosets exhibit excellent thermal properties with elevated degradation temperature and high char yield. The degradation behavior was studied using thermogravimetric analysis-Fourier transformed infrared spectroscopy (TGA-FTIR): only 2 silicon compounds were observed for SiBMI, whereas phosphorus and carbonaceous products had specific signatures in degradation gases for PhBMI. Kinetic analysis of degradation confirmed those different behaviors. Our contribution with two original Alder-ene thermosets is an innovative way to develop sustainable versatile high-performant materials.

Synthesis of eugenol‐based monomers for sustainable epoxy thermoplastic polymers

“…To improve the thermomechanical properties of bismaleimide thermosets, which are brittle materials due to their high aromaticity and their high crosslink density, Caillol and his collaborators 83 selected a trifunctional eugenol monomer, trieugenol phosphate (39) (TEu-P), previously synthesized via a nucleophilic substitution reaction of eugenol (10) and phosphorus oxychloride (POCl 3 ) (38) (in molar ratio 3:1) in the presence of Et 3 N, 84 to study the advantages of curable TEu-P/bismaleimide polymer networks (Scheme 11).…”

“…Notably, some chlorides come from renewable acids, such as succinic (77), adipic (78), suberic (79), itaconic (80), and 2,5-furandicarboxylic (81) acids. Both these renewable acids and petroleumderived acids (terephthalic (82), isophthalic (83), and 1,3,5-benzenetricarboxylic (84) acids) are transformed into their respective dichlorides 85-92, which react smoothly with the phenolic group of eugenol molecules through an esterification reaction, providing biseugenol esters 93-100. Then, the oxidation of their allylic groups (m-CPBA, CH 2 Cl 2 , or AcOE) allows the preparation of the corresponding diepoxide eugenol monomers 101-107 and triepoxy derivative 108 (Scheme 23).…”

Lignin-Inspired Polymers with High Glass Transition Temperature and Solvent Resistance from 4-Hydroxybenzonitrile, Vanillonitrile, and Syringonitrile Methacrylates

“… 25 These polymethacrylates, as well as similar ones based on phenol, syringol, and syringaldehyde, respectively, have been produced and investigated for various coating applications. 26 , 27 Lignin-derived building blocks, such as eugenol, 28 have also been employed to produce densely cross-linked thermosets with high T g values.…”

Bio‐based hydroxymethylated eugenol modified bismaleimide resin and its high‐temperature composites

“…[4][5][6][7] Therefore, the development of bio-based thermosetting resins is of far-reaching significance. [8,9] Bismaleimide (BMI) resins are important high performance thermosetting resins with a range of outstanding performance including superior mechanical and electrical properties, low flammability, excellent chemical resistance, and good thermal stability, [10][11][12][13][14] which makes BMI resins widely used for many high-tech fields such as aviation, aerospace, and electromechanical. [15,16] Most BMI resins are modified by petrochemical resources.…”

“…[21,22] Eugenol (EG, 4-allyl-2-methoxyphenol), an allyl natural phenol easily extracted from cloves, is considered to be a cost-effective material for the synthesis of bio-based substitute of DABPA to modify BMI due to its low price and renewability. [12,23,24] In this study, EG was reacted with BMI (eugenol/maleimide ratios was 1/1) to synthesize EG-BMI 1/1 (EB-1) resins, and the composite based on EB-1 was prepared. However, there are many unsatisfactory issues that need to be addressed for EB-1.…”