Recyclable Dynamic Covalent Networks Derived From Isocyanate Chemistry: the Critical Role of Electronic and Steric Effects in Reversibility

The dynamic covalent networks (DCNs), featuring dynamic covalent bonds (DCBs) formed through isocyanate‐involved chemistry, potentially contributes to a circular economy in polyurea and polyurethane industries, due to the inherent recyclability of DCNs. Over the past decade, remarkable progress has been made in the development of isocyanate‐derived DCBs (IdDCBs) for the synthesis of recyclable DCNs, aiming to substitute conventional, non‐recyclable materials. Here, we delve into the fundamental aspect of the IdDCB‐related chemistries reported to date, and find that their reversibility is governed by electronic and steric effects. This discovery encourages us to structure the review into three sections. The first section examines the reversibility of various IdDCBs through the lens of electronic and steric influences. Our findings show that the reversibility of some IdDCBs is driven by a single chemical effect, with the examples of steric effect contributing to the dynamic behavior of thiourethanes and hindered ureas, while other cases of reversibility arise from a combination of two or more chemical effects. The knowledge thus established allows to categorize and discuss the technologically relevant DCNs, with particular emphasis on how these chemical effects influence their recyclability. Finally, the review concludes by highlighting several potentially impactful research directions that merit further exploration.