Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts

• Main Authors: Felipe de la Cruz-Martínez, Marc Martínez de Sarasa Buchaca, Almudena del Campo-Balguerías, Juan Fernández-Baeza, Luis F. Sánchez-Barba, Andrés Garcés, Carlos Alonso-Moreno, José A. Castro-Osma, Agustín Lara-Sánchez
• Format: Article
• Language: English
• Published: MDPI AG 2021-05-01
• Series: Polymers
• Subjects: ring-opening copolymerization; epoxides; cyclic anhydrides; polymers; zinc complexes
• Online Access: https://www.mdpi.com/2073-4360/13/10/1651

The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO₂ as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex <b>3</b> with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened. The catalytic system was capable of copolymerizing selectively and efficiently CHO with phthalic, maleic, succinic and naphthalic anhydrides to afford the corresponding polyester materials. The polyesters obtained were characterized by spectroscopic, spectrometric, and calorimetric techniques. Finally, the reaction mechanism of the catalytic system was proposed based on stoichiometric reactions.