Sustainable Synthesis of CO2‐Based Polyols via Pentaerythritol Derivatives for High‐Performance Rigid Polyurethane Foams

ABSTRACT CO 2 ‐based polyols represent a significant advancement in carbon capture and utilization technologies, offering an innovative solution to mitigate greenhouse gas emissions while producing value‐added polymeric materials. This study investigates their synthesis using double metal cyanide (DMC) catalysts and their application in rigid polyurethane foams (RPUFs). To address challenges in conventional CO 2 incorporation, novel initiators, including pentaerythritol propoxylate (PE‐PO) and pentaerythritol ethoxylate (PE‐EO), are evaluated. DMC catalysts are synthesized with tetrahydrofurfuryl alcohol (THFA) as a complexing agent. Among the tested initiators, PE‐PO demonstrated the highest efficiency, achieving a CO 2 incorporation of 20.4 mol% at an optimal monomer‐to‐initiator molar ratio of 50. The resulting CO 2 ‐based polyols are effectively utilized in RPUFs, which exhibit enhanced mechanical properties, uniform cell morphology, and stable thermal performance. The enhanced mechanical properties of the RPUFs correlate with an increase in carbonate linkages within the polymer backbone, leading to greater intermolecular interactions and improved structural integrity, as confirmed by FT‐IR and compression tests. Beyond enhancing material performance, this approach contributes to sustainability by replacing conventional petroleum‐based polyols. This work introduces a novel strategy for CO 2 integration into polyols, advancing the sustainable synthesis of high‐performance RPUFs. The findings highlight the potential of novel initiators and DMC catalysts to overcome existing limitations, representing a significant step forward in eco‐friendly polymer development. image