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Vitrimers represent dynamic polymer networks with unique viscoelastic behavior, combining the best attributes of thermosets and thermoplastics. In this work, we report the concept of polyampholyte physical networks that go far beyond the merits of vitrimer-like materials by combining elevated creep resistance and fast dynamic exchanges. By contrast with most vitrimeric systems requiring out-of-stoichiometric approaches or external catalysts, we simply design polyampholyte physical networks of charge-balanced ionic methacrylates via free radical copolymerization combining poly(ethylene glycol) methyl ether methacrylate (PEGMA). The high ion concentration (i.e., from 33 to 67 mol %) enabled the formation of a physical network containing ionic cross-links acting as both sacrificial and permanent bonds mitigated by the presence of neutral PEGMA. In addition to their vitrimer-like behavior demonstrated using thermomechanical and rheological tools, these physical networks show exceptionally short relaxation times and high creep resistance. Conceptually, these polyampholyte physical networks due to extensive dynamic ion exchange open the door to more circular vitrimer-like systems toward more sustainable plastic materials.

Since the 1940s, bisphenol A (BPA) has been used in the plastic industry, reaching production of 10 Mt in 2022. More than 30% of the produced BPA is used in the production of epoxy resins. Decades of research has now provided enough evidence that BPA has endocrine-disrupting activity. Hence, it is an urgent matter to replace BPA in the production of epoxy resins. In the past years, considerable efforts have been put into finding alternatives to the toxic BPA. However, not only does the diglycidyl ether of BPA exhibit high polymerization reactivity, but also the presence of aromatic rings confers interesting thermomechanical resistance to epoxy networks therefrom. Hence, these properties are also expected from potential alternatives to BPA. In this review, first, the elements leading to toxicity of BPA are explained and then thorough accounts of possible bio-sourced aromatic alternatives to BPA are gathered. The reported synthetic routes for each of these alternatives and their toxicity are described. Also, their use in synthesis of epoxy resins and how the new alternatives influence the mechanical properties are discussed. This is a concise summary of the structure–property and structure–toxicity relationship for possible bio-sourced substitutes of BPA in synthesis of epoxy resins.

We report the synthesis and ring-opening polymerization of new formaldehyde-free benzoxazines. The polybenzoxazines obtained displayed high thermal stability and high char yields. Data from the literature combined with our analyses by differential scanning calorimetry and thermogravimetric analyses gave deeper understanding about the use of aromatic aldehydes instead of formaldehyde for the generation of polybenzoxazines. Using pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS) at different temperatures, we provided qualitative data to propose some polymerization and degradation mechanisms associated with these new structures. A dialdehyde was also used for the first time in order to obtain difunctional monomers, instead of using diamines or bisphenols. Interestingly, we demonstrated that formaldehyde, which is a CMR (carcinogenic, mutagenic, and/or reprotoxic) substance, could be avoided for the synthesis of polybenzoxazines without any loss of thermal performance. Finally, some interesting structure–properties relationships are herein discussed. In particular, the use of benzyl amines, rather than aromatic amines, was found to significantly increase the char yields.