ABSTRACT
Recent studies have shown that the largest employed thermoset family, polyurethanes (PUs), has great potential to be reprocessed due to the dynamic behavior of carbamate linkage. However, it requires high temperatures, especially in the case of aliphatic PUs, which causes side reactions besides the desired exchange reaction. To facilitate the reprocessing of aliphatic PUs, in this work, we have explored the dynamic potential of alkoxyamine bonds in PU networks to facilitate the reprocessing under mild conditions considering their fast recombination ability. Taking advantage of the structural effect of the nitroxide and alkyl radicals on the dissociation energy, two different alkoxyamine-based diols have been designed and synthesized to generate PU networks. Our study shows that replacing 50 mol % of a nondynamic diol chain extender with these dynamic blocks boosts the relaxation times of the networks, enabling reprocessing at temperatures as low as 80 °C.
ABSTRACT
Oxime chemistry has emerged as a versatile tool for use in a wide range of applications. In particular, the combination of oximes with esters and urethanes has enabled the realisation of Covalent Adaptable Networks (CANs) with improved and tunable dynamic properties. Nevertheless, an exclusively oxime-based chemistry has not yet been explored in the fabrication of CANs. In this work, we investigate the mechanism of the acid-catalysed dynamic exchange of oximes. We propose a metathesis mechanism that is well supported by both experimental and computational studies, which highlight the importance of the substituent effect on the exchange reaction kinetics. Then, as a proof of concept, we incorporate oxime groups into a cross-linked polymeric material and demonstrate the ability of oxime-based polymers to be reprocessed under acid catalysis while maintaining their structural integrity.
ABSTRACT
The transition towards safer and more sustainable production of polymers has led to a growing body of academic research into non-isocyanate polyurethanes (NIPUs) as potential replacements for conventional, isocyanate-based polyurethane materials. This perspective article focuses on the opportunities and current limitations of NIPUs produced by the reaction between biobased cyclic carbonates with amines, which offers an interesting pathway to renewable NIPUs. While it was initially thought that due to the similarities in the chemical structure, NIPUs could be used to directly replace conventional polyurethanes (PU), this has proven to be more challenging to achieve in practice. As a result, and in spite of the vast amount of academic research into this topic, the market size of NIPUs remains negligible. In this perspective, we will emphasize the main limitations of NIPUs in comparison to conventional PUs and the most significant advances made by others and us to overcome these limitations. Finally, we provide our personal view of where research should be directed to promote the transition from the academic to the industrial sector.
