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Epoxy Homopolymerization as a Tool to Tune the Thermo-Mechanical Properties and Fracture Toughness of Vitrimers

Cite this: Macromolecules 2021, 54, 18, 8393–8406
Publication Date (Web):September 15, 2021
Copyright © 2021 American Chemical Society

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    Epoxy/dicarboxylic acid vitrimer was prepared by the solvent-free reaction of diglycidyl ether of bisphenol A (DGEBA) and 1,4-cyclohexane dicarboxylic acid (CHDA) with the addition of monobutyltin oxide (Sn) as a catalyst. By tailoring the catalyst content (≥5 mol %), an effective conversion of functional groups during cure demonstrated the network polymerization mechanisms and a sequence of the side reactions. Indeed, the manufactured vitrimers exhibit creep and full stress relaxation thanks to catalytic transesterifications. By changing the epoxy/diacid ratio, the thermo-mechanical properties and mechanical behavior of the epoxy/acid vitrimers can be tuned while keeping self-healing ability. At high epoxy excess, both glass-transition temperature (Tg) and solid–liquid viscoelastic transition temperature (Tv) shift to a higher temperature. At vitrimer formulations 1:0.6 and 1:0.5 (epoxy/acyl), a remarkable improvement of fracture toughness (KIc) is observed, indicating the transition from stiff to relatively ductile materials at 1:0.6. This is attributed to the altered network structures due to etherification and epoxy homopolymerization. The rough fracture surface suggests more energy dissipation during crack propagation in vitrimer with a high excess epoxy. After healing, welded vitrimers still exhibit good fracture toughness with only a slight reduction (<10%) in KIc. We believe that these vitrimer formulations are promising as matrices in the composite fields.

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    • Calculation of swelling ratio and % soluble fraction, calculation of fracture toughness (KIc) and fracture energy (GIc), fracture toughness specimen, FTIR analysis including experimental procedure, spectra analysis method, spectra of raw materials, spectra of CHDA100_Sn5 at all reaction time, table of FTIR frequency band, deconvolution area and evolution of species upon reaction time in log scale, comparison of catalyst oxidation in CHDA100 sample, thermal stability of all samples, supplementary data of creep experiment for all samples, supplementary data of stress relaxation experiment for all samples, fracture surface of epoxy/amine, and self-healing experiment (DOCX)

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