A genuine H-bond donor and Lewis base amine cocatalyst in ring-opening polymerizations.

• A bidentate H-bond donor and base successfully catalyzed ROPs without proton abstraction. • Produced PLAs possess broad molecular weight ranges and extremely narrow dispersities. • A strict HBD/base cocatalysis mechanism was validated by NMR titrations. Hydrogen bond donor (HBD) and organic base binary cocatalyst established a gold standard in organocatalytic ring-opening polymerizations (ROPs). In depth probe of the mechanisms revealed that proton abstraction of the acidic H on the HBDs by the bases do occur frequently. A truly simple HBD and Lewis base (LB) cocatalysis, however, was elusive. We proposed genuine HBD/LB cocatalyst for ROPs by introducing 3-amino-1,2,4-benzothiadiazine-1,1-dioxide (ABTD) as a bidentate H-bond donor and triethylamine (TEA) as a mild Lewis base. ROPs of lactide (LA) and trimethylene carbonate (TMC) in solutions at room temperature were success. The mild ROPs produced polylactide (PLA) of predictable molecular weights (from 1.6 to 26.7 kg mol−1) and extremely narrow dispersities (Đ 1.01 to 1.06). Furthermore, well-defined diblock copolymers PTMC-b-PLA were synthesized. NMR titration experiments verified exclusive H-bond donor activation of the monomer and TEA activation of the hydroxyl chain end without trace of proton abstraction. [ABSTRACT FROM AUTHOR]