The combination of exceptional thermal and chemical stability and high mechanical strength over a broad range of temperatures make polyamides (PAs) attractive candidates in a plethora of applications spanning from the automotive and electronics industry to films and fibers used in packaging and as textiles respectively. From a synthetic perspective, PAs’ conventional production routes are energy demanding as high temperature and low pressure are needed as well as the use of solvents and/or auxiliaries. An essential prerequisite for more sustainable materials is finding greener synthetic alternatives and the aforementioned requirements are in contrary to this ever-increasing need. We therefore sought to develop a strategy, with respect to the principles of green chemistry, that would eliminate the aforementioned drawbacks and would enable the synthesis of more sustainable and functional PAs. Finding a difunctional, cyclic monomer, derived from renewable resources was a crucial parameter to realize the feasibility and potential of the method. Ethylene brassylate fulfilled the above criteria and provided an excellent opportunity to establish a solvent-free, base-catalyzed ring-opening aminolysis-crosslinking reaction that enabled the synthesis of biobased thermoset PAs under mild conditions. The reaction conditions were optimized, the structure of the thermosets was elucidated and the structure-property-function relationship was investigated. The PA thermosets exhibited solidification times as short as 10 min under the optimized conditions and yielded flexible, transparent films. The thermal and mechanical properties were studied as a function of monomers’ structure and stoichiometry and correlated to short oligoester segments identified within the polymer network as a result of ring-opening polymerization. Such segments formed crystalline domains and were found to have a profound impact on the mechanical behavior of the final thermoset as they provided superior strength compared to similar PA thermosets without them. Notably, the crystalline domains gave rise to a shape-memory effect making the thermosets interesting candidates for applications where such a function in combination with toughness and thermal stability is needed.

Biobased thermoset polyamides with tuneable properties through a one-Step ring-opening aminolysis-crosslinking reaction

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.