In 2011, a new type of materials combining both thermoplastic and thermoset properties was invented, vitrimers, now already referred to as the third type of plastics and receiving world-wide industrial and academic attention. The huge enthusiasm in vitrimers originates from the fact that they combine the best of both polymer classes. By incorporation of exchangeable covalent linkages into a polymer network, dynamic cross-links can be formed above a certain temperature. These vitrimers can therefore be thermally processed, reshaped and recycled without losing network integrity. Besides, the design and synthesis of superior polymeric materials with excellent combination of chemical and physical properties has triggered research on fluorinated polymers, leading to immediate acceptance in commercial products for various markets in which no other polymeric materials can really compete: coatings (Teflon), energy storage (batteries), lithography and many others. Although fluorinated materials are indispensable for certain added value applications, the wider uses of fluorine-containing materials are still hampered by their production cost, complexity of synthesis, toxicity and difficult processability. Here, the reported materials are the first example of fluorinated low Tg materials (-100 °C) exhibiting vitrimers properties. A catalyst-free transamination of vinylogous urethane has been successfully used as associative dynamic chemistry platform. A straightforward and one-pot solvent-free network synthesis has been reported. Transparent Perfluoropolyether-based vitrimers can be recycled multiple times at 140°C with extremely short time scale (few seconds), and materials recovered 90 % of the original mechanical properties. Viscoelastic and mechanical properties can also be tuned by the addition of additives and adjusting crosslinking density.

Low Tg fluorinated vitrimers for high performance applications

256th National Meeting (2018)

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