Javier Read de Alaniz

Hydroxyl‐terminated polybutadiene (HTPB) is found in many applications due to its ease of manufacturing, useful mechanical properties over a wide temperature range, and reactive hydroxyl chain ends. Typically, HTPB is crosslinked with isocyanates to form polyurethane thermosets. Limitations of this approach include the use of toxic isocyanates and the oxidative instability of backbone alkenes. In this work, saturated HTPB is used to form reprocessable covalent adaptable networks that are capable of stress relaxation and reprocessing, without relying on isocyanates or unstable alkenes. This approach introduces dynamic chemistry to the HTPB network via chain extension and subsequent crosslinking with 4‐methyl caprolactone (4mCL) and a novel bislactone crosslinker. Using benzenesulfonic acid (BSA) as a transesterification catalyst, stress relaxation times range from 150 to 8 min at temperatures of 70 to 100 °C. Despite crosslinking, these networks behave elastically, as evidenced by strain‐at‐break values of 93% for pristine samples, and dynamically, as shown by a strain‐at‐break of 72% after reprocessing the damaged samples. Shape reprogramming is also demonstrated by straining the crosslinked networks and heating to elevated temperatures where bond exchange occurs. These findings illustrate the advantageous properties that can be achieved by using cheap commodity building blocks to achieve dynamic properties. We anticipate that valorizing commodity polymers into reprocessable thermosets will be of utility in applications that lack other viable recycling pathways.