H-bonding binary organocatalysis promoted amine-initiated ring-opening polymerizations of lactide from polysarcosine to diblock copolymers

Abstract Alcohol-initiated ring-opening polymerization (ROP) of cyclic esters for synthesizing polyesters was well established, but amine-initiated ROP of cyclic esters was rare. A challenge is slow initiation and fast propagation in the amine-initiated ROPs. To address the difficulties, an ionic H-bond donor (iHBD) and H-bond acceptor (HBA) binary organocatalysis in amine-initiated ROP of lactide (LA) was developed. Guanidinium hexahydro-2 H -pyrimido[1,2- a ] pyrimidin-1-ium [(HppH 2 ) + ] and tertiary amine sparteine (SP), cooperatively played the role of iHBD/HBA binary catalysts, efficiently promoted ROP of LA from amine initiators toward polylactide (PLA) and polysarcosine- block -polylactide diblock copolymer (PSar- b -PLA). Benzyl amine and N -methylbenzylamine initiated ROPs of LA under mild conditions produced PLAs with predictable molecular weights ( M n,NMR  = 2.9–17.1 kg mol −1 ) and narrow dispersities ( Ð M,SEC  = 1.13–1.23). Macroinitiator PSar copolymerized with LA under the iHBD/HBA catalysis, producing PSar- b -PLAs with controlled molecular weights ( M n,NMR  = 5.7–14.8 kg mol −1 ) and low dispersities ( Ð M,SEC  = 1.16–1.21). Kinetics and chain extension experiments confirmed that the amine-initiated ROP of LA in presence of (HppH 2 ) + BF 4 − /SP was in controlled/living manner. 1 H NMR, 13 C NMR, SEC, and MALDI-ToF MS analyses indicated that the obtained PLA was exclusively initiated from the corresponding amine with amide linkage. An iHBD/HBA binary activation mechanism was proposed.