Macromolecules, Vol.53, No.3, 946-955, 2020
Weak Lewis Pairs as Catalysts for Highly Isoselective Ring-Opening Polymerization of Epimerically Labile rac-O-Carboxyanhydride of Mandelic Acid
Ring-opening polymerization (ROP) of rac-O-carboxyanhydride of mandelic acid (rac-manOCA) is a promising method to synthesize isotactic biodegradable polyester of poly(mandelic acid), which has a high glass-transition temperature (T-g) and a high melting temperature (T-m) due to the formation of a stereocomplex. However, it is still a big challenge to synthesize isotactic poly(rac-manOCA) so far because of the easy epimerization of manOCA in the polymerization progress. In this work, a highly isoselective ROP of the rac-manOCA system as the first stereoselective example is reported using weak Lewis pairs of zinc complexes and 3-fluoropyridine (3-F-Py) as catalysts with the highest P-m value of 0.92, and no obvious epimerization happens in the polymerization progress. T-g of poly(rac-manOCA) (similar to 5.3 kg/mol) increases from 84 to 92 degrees C when the isotacticity increases from P-m = 0.60 to 0.92. Isothermally crystallized isotactic poly(rac-manOCA) (5.3 kg/mol, P-m = 0.92) demonstrates a melting point at 116 degrees C, and no obvious melting point can be found for the almost atactic poly(rac-manOCA) (5.4 kg/mol, P-m = 0.60). The T-m value of a 1:1 mixture of enantiopure poly(L-manOCA) and poly(D-manOCA) can reach 173 degrees C after isothermal crystallization.