Transcarbamoylation in Polyurethanes: Underestimated Exchange Reactions?

While transesterification has been largely explored by chemists, only a few studies comparatively dealt with its "sluggish cousin", transcarbamoylation. Originally suggested 70 years ago to explain the stress decay observed at high temperature in polyurethane chemical networks, transcarbamoylation─also called transurethanization or urethane exchange─is still underexploited in both organic and polymer chemistry. This is mainly related to the use of toxic reactants such as isocyanates and tin-based catalysts involved during the preparation of molecular carbamates or polyurethanes (PUs) as well as harsh conditions required to observe such exchanges in molecular transformations. Many studies have focused their interest in alternatives to the use of isocyanates, underestimating the potential of transcarbamoylation to produce, recycle, or reprocess PUs (wastes). This Perspective presents the latest developments and plausible future directions to prepare sustainable PU-based materials by using transcarbamoylation with a focus on covalent dynamic networks.