To develop functional sustainable epoxy resins, we report a novel epoxy resin (DEU-EP) with high net biobased content (70.2 wt%) derived from renewable eugenol. We comparatively study DEU-EP with a commercial bisphenol A epoxy resin (DGEBA) in the presence of a diamine curing agent, 4,4′-diaminodiphenyl methane (DDM). Differential scanning calorimetry reveals that DEU-EP can be sufficiently cured by DDM at a slower rate than DGEBA. By applying an autocatalytic reaction kinetic model we adequately simulate the curing rate of DEU-EP/DDM, and reveal its detailed kinetic mechanisms from model-free isoconversional analysis. Dynamic mechanical analysis shows that DEU-EP/DDM takes the higher storage modulus up to ∼97 °C than does DGEBA/DDM with the glass temperature of 114 °C. Nanoindentation and thermogravimetric analyses demonstrate that compared with DGEBA/DDM, DEU-EP/DDM exhibits a 20%, 6.7% and 111% increase in Young’s modulus, hardness and char yield, respectively. Microscale combustion calorimetry data show that DEU-EP/DDM expresses 55% and 38% lower heat release rate and total heat release than does DGEBA/DDM, respectively. The horizontal burning test approves DEU-EP/DDM can self-extinguish in a short time. Our results demonstrate that the eugenol building blocks and their arrangement greatly affect the cure behaviors of DEU-EP/DDM, and contribute significantly to its enhanced mechanical properties, high-temperature charring ability and chain motions at the glassy state, as well as the reduced flammability. To summarize, DEU-EP exhibits a high promise as a new sustainable epoxy monomer for fabricating high biobased content, high rigid and low flammable epoxy materials

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.

Aiming at developing highly efficient nano fire retardants and fire retarding epoxy resins, a series of functionalized layered double hydroxides (LDHs) based on a multi-modifier system have been developed. These functionalized LDHs were used as novel nano flame-retardants for bisphenol epoxy resins and compared with unmodified LDHs.