A sustainable, eugenol-derived epoxy resin with high biobased content, modulus, hardness and low flammability: Synthesis, curing kinetics and structure–property relationship

Exploring renewable biobased epoxy resins possessing intrinsic fire retardancy and high mechanical and thermal properties will greatly advance their potential to satisfy sustainability demands. Herein we develop a biobased route to synthesize a novel eugenol-based difunctional epoxy resin (TPEU-EP) with a full aromatic ester backbone. With 3,3′-diaminodiphenyl sulfone (33DDS) as the curing agent, TPEU-EP is compared with a standard bisphenol A epoxy resin (DGEBA) regarding their cure reactions and ultimate properties. The results show that TPEU-EP/33DDS expresses a higher reaction activation energy and a slower curing rate than DGEBA/33DDS. The isothermal cure reaction of TPEU-EP/33DDS is found to be autocatalytic. We accurately model the curing kinetics and elaborate on the related mechanisms based on the isoconversional analysis. The structure–property study reveals that TPEU-EP/33DDS manifests a 27%, 20% and 17% higher storage modulus (30 °C), Young's modulus and hardness than DGEBA/33DDS, respectively. TPEU-EP/33DDS displays a high glass temperature (168.4 °C) and thermal stability (up to 300 °C), and shows a much higher damping than DGEBA/33DDS in the glassy state. Moreover, compared with DGEBA/33DDS, TPEU-EP/33DDS shows a 130% and 3.3 increase in char yield (in N2) and limiting oxygen index and a 68% and 40% decrease in the heat release rate and total heat release (microscale combustion test), respectively. Impressively, TPEU-EP/33DDS can self-extinguish in a vertical burning test, and the cone calorimeter test further confirms that TPEU-EP/33DDS has a much improved flame retardancy with a notably lowered smoke production. In brief, TPEU-EP possesses good intrinsic flame retardancy, low smoke production, and excellent mechanical properties, showing high promise for application. Our contribution will open a new avenue to develop sustainable high-performance flame-retardant epoxy resins.

A novel biobased epoxy resin with high mechanical stiffness and low flammability: synthesis, characterization and properties

https://research-information.bris.ac.uk/ws/files/85196910/Revised_manuscript_3.pdf

Modern advances in bismaleimide resin technology: A 21st century perspective on the chemistry of addition polyimides

Preparing a biobased (biomass-based) high performance epoxy resin with extremely large biomass content is of great importance for sustainable development. Herein, a new epoxy resin with a precise structure, bis(2-methoxy-4-(oxiran-2-ylmethyl)phenyl)furan-2,5-dicarboxylate (EUFU-EP), was synthesized from two biobased green and low toxic compounds (2,5-furandicarboxylic acid and eugenol) and the biomass content of EUFU-EP is as large as 93.3%. In addition, a new biobased epoxy resin, EUFU-EP/MHHPA, was prepared by using methyl hexahydrophthalic anhydride (MHHPA) as the curing agent and 2-ethyl-4-methylimidazole as the curing accelerator. The curing reactivity and integrated performances including thermal and mechanical properties as well as flame retardancy of the cured resin were systematically researched and compared with those of petrochemical resource-based epoxy resin (DGEBA/MHHPA) consisting of commercial diglycidyl ether of bisphenol A (DGEBA), MHHPA and 2-ethyl-4-methylimidazole. Results show that E...

Biobased Heat Resistant Epoxy Resin with Extremely High Biomass Content from 2,5-Furandicarboxylic Acid and Eugenol

A solventless method was adopted to synthesize two benzoxazine monomers from naturally occurring sources, i.e., eugenol (an extraction from clove), furfurylamine, stearylamine, and paraformaldehyde. The structure of the extracted eugenol and synthesized monomers were supported by FT-IR, 1H NMR, 13C NMR, and mass spectral analysis. The monomers were polymerized/copolymerized via ring-opening polymerization by heating as shown by FT-IR (disappearance of the peak due to oxazine ring at 920 cm–1) and differential scanning colorimetry (DSC). The exothermic peak associated with curing was observed between 198–254 °C. DSC analysis shows that the onset of curing temperature for the copolymers decreased linearly from 207–202 °C on increasing the content of F-Bz. The results from TGA analysis indicate that PF-Bz shows the maximum thermal stability when compared with PS-Bz and their copolymers. In the case of the copolymers, as the F-Bz content is increased, the thermal stability also increases. All the polymers als...

Synthesis and Copolymerization of Fully Biobased Benzoxazines from Renewable Resources

5,5′-Bieugenol (BEG) and eugenol novolac (EGN) were synthesized by the oxidative coupling reaction of eugenol (EG) and the addition–condensation reaction of EG with formaldehyde, respectively. The EG, BEG and EGN were prepolymerized with 4,4′-bismaleimidediphenylmethane (BMI) at 180 °C and then compression-molded at finally 250 °C for 6 h to produce cured EG/BMI (EB), BEG/BMI (BB) and EGN/BMI (NB) resins with eugenol/maleimide unit ratios of 1/1, 1/2 and 1/3. The FT-IR analysis of EBs and 13C NMR analysis of the model reaction product of EG/N-phenylmaleimide (PMI) 1/3 at 200 °C for 12 h suggested that the ene reaction and subsequent Diels-Alder/ene reactions mainly occurred for EBs. The FT-IR analyses of BBs and NBs supported the occurrence of ene reaction and subsequent thermal addition copolymerization in a similar manner to the well-known curing reaction of 2,2′-diallylbisphenol A and BMI. The glass transition temperature (Tg) and 5% weight loss temperature (T5) of the cured resin increased with increasing BMI content, and EB 1/3 showed the highest Tg 377 °C and T5 475 °C. The flexural strengths and moduli of EBs and NBs were higher than those of BBs, and EB 1/2 showed the most balanced flexural strength and modulus (84.5 MPa and 2.75 GPa). The FE-SEM analysis revealed that there is no phase separation for all the cured resins.

Bio-based thermosetting bismaleimide resins using eugenol, bieugenol and eugenol novolac

High-performance bio-based thermosetting resins based on bismaleimide and allyl-etherified eugenol derivatives

Bio-based bismaleimide (2MPD), trismaleimide (3MGC) and tetramaleimide (4MDG) were synthesized by reactions of 4-isocyanatophenylmaleimide with 1,3-propanediol, glycerol and α,α′-diglycerol, respectively. Although 2MPD did not melt until the temperature where thermal decomposition starts, 3MGC and 4MDG exhibited broad melting temperatures with onset points at 165 °C and 124 °C, respectively. 3MGC and 4MDG were homogeneously prepolymerized at 170 °C with 2,4-diallyl-6-methoxyphenol (rAEG) which was prepared by the Claisen rearrangement of allyl-etherified eugenol (AEG). The prepolymers were compression-molded at 250 °C to produce cured rAEG/3MGC (A3Mxy) and rAEG/4MDG (A4Mxy) with the allyl/maleimide ratio of x/y = 1/1, 1/2 or 1/3. The FT-IR analysis revealed that the ene reaction of allyl and maleimide groups and subsequent addition copolymerization occurred for the cured resins. The thermal and mechanical properties of the cured resins were compared with those of the cured rAEG/4,4′-bismaleimidodiphenylmethane (BMI) (ABMxy) with the same allyl/maleimide ratio. A3M13 and A4M13 showed no inflection point of thermal expansion due to glass transition until 300 °C, which is a little lower than the thermo-degradation temperature. Flexural strengths and flexural strains at break for A3Ms and A4Ms increased with the polymaleimide contents, and those of A3M13 and A4M13 were much higher than those of ABM13.

Makiyo Neda

Papers

Bio-based thermosetting bismaleimide resins using eugenol, bieugenol and eugenol novolac

High-performance bio-based thermosetting resins based on bismaleimide and allyl-etherified eugenol derivatives

Bio-based thermosetting resins composed of aliphatic polyol-derived polymaleimides and allyleugenol