Ionic (Co)Organocatalyst with (Thio)Urea Anion and Tetra‑n‑butyl Ammonium Cation for the Polymerization of γ‐Butyrolactone

AbstractAn effective ionic organocatalyst system is developed for the challenging ring‐opening polymerization (ROP) of γ‐butyrolactone (GBL) at low temperature. The catalysts are prepared by dehydration reaction between tetra‐n‐butyl ammonium hydroxide (TBAOH) and (thio)ureas at ambient temperature, and utilized with or without extra benzyl alcohol (BnOH) initiator. The solid‐state structure of TUA‐3 comprising thiourea anion is characterized by X‐ray diffraction analysis. Typically, a mixture of cyclic and linear poly(GBL) with low molecular weights (5000–1600 g mol−1) and slightly narrow molecular distribution Ð (1.2–1.4) is obtained by single base with/without combination with (thio)ureas. Interestingly, solely linear high‐molecular‐weight poly(GBL) (10 400 g mol−1) can be achieved by a synergistic effect of TBAOH/N,N′‐isopropylthiourea in the presence of BnOH. The obtained poly(GBL) is characterized with NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy (MALDI‐TOF MS). Mechanistic studies reveal different polymerization initiation steps in this reported catalyst system, which leads to poly(GBL) with divergent end groups.