Sustainable and scalable synthesis of acetal‐containing polyols as a platform for circular polyurethanes

Polyurethanes (PUs) are highly versatile polymers widely utilized across industries. However, chemical recycling of PU poses significant challenges due to the harsh conditions required and the formation of complex mixtures of oligomers upon depolymerization. Addressing this inherent lack of recyclability, we developed closed‐loop recyclable PU materials by integrating cleavable acetal groups. We present a sustainable and scalable synthesis method for acetal‐containing polyols (APs) through aldehyde‐diol polycondensation, utilizing reusable heterogeneous catalysts. Three APs with different hydrolytic stabilities depending on the structure of acetal groups were synthesized from formaldehyde, acetaldehyde, and propionaldehyde with 1,6‐hexanediol (H16). These APs were employed alongside 4,4′‐methylene diisocyanate (MDI) for preparation of PU materials. The resulting PUs exhibited mechanical properties comparable to or surpassing those of conventional PUs, while demonstrating excellent recyclability under acidic conditions. Notably, hydrolysis of PU materials based on acetaldehyde‐derived APs yielded remarkable monomer recovery rates, with 89 % for H16 and 84 % for 4,4′‐methylenedianiline, a precursor to MDI. Furthermore, we successfully demonstrated closed‐loop recycling by synthesizing APs from recovered H16, resulting in PU materials with identical properties to the original PU. This achievement highlights the potential for establishing a closed‐loop recycling system for acetal‐containing PUs, contributing to the advancement of a sustainable and circular economy.