Synthesis of Unsaturated (Co)polyesters from Ring-Opening Copolymerization by Aluminum Bipyridine Bisphenolate Complexes with Improved Protonic Impurities Tolerance

Abstract

Synthesis of unsaturated polyesters (UPES) via ring-opening copolymerization (ROCOP) of maleic anhydride (MAH) and epoxides still remains a great challenge, because the reported catalytic systems generally showed low catalytic activity or complete deactivation at low catalyst concentration and exhibit poor tolerance to protonic impurities. In this work, we synthesized a series of bipyridine bisphenolate aluminum (BpyBph-Al) complexes and used these complexes to catalyze the MAH/epoxide copolymerization for synthesis of UPES. UPES with perfectly alternating structure could be synthesized using BpyBph-Al complexes without onium salt as cocatalyst, and the catalytic activities seem to be dependent on the steric and electronic effects of the ligands as well as the leaving ability of the axial group. The catalytic activities were further increased in the binary catalysts consisting of a BpyBph-Al as Lewis acid and an onium salt as a Lewis base. Compared with salen-Al/onium salt and typical Lewis pairs, the BpyBph-Al/onium salt binary system exhibited a completely maintained catalytic activity even when the [epoxide]/[MAH]/[catalyst pair] feed ratio was high up to 25 000:5000:1 ([catalyst pair] = 0.004 mol %). In addition, BpyBph-Al/onium salt exhibited better tolerance to protonic impurity than salen-Al/onium salt and Lewis pairs. The catalytic activity was slightly decreased (about 15%) in the presence of 100 equiv (relative to catalyst) of external-added maleic acid, while a substantial decrease in activity or complete deactivation was observed in the ROCOPs catalyzed by salen-Al/onium salt and Lewis pairs. These features of BpyBph-Al/onium salt further allowed UPES synthesis by using commercial MAH without any purification as a comonomer. The maleic acid residuals in the commercial MAH could serve as a chain transfer agent (CTA), and UPES polyols with uniform −OH chain ends were obtained via reversible-deactivation chain transfer reaction. Chain extension could be initiated by the active alkoxide end when adding the second cyclic anhydride after the full conversion of MAH, finally producing ABA-type triblock copolymers.