Ring-Opening Polymerization of Cyclic Esters and Carbonates with (Thio)urea/Cyclopropenimine Organocatalytic Systems.

Organocatalyzed ring-opening polymerization is a powerful tool for the synthesis of a variety of functional, readily degradable polyesters and polycarbonates. We report the use of (thio)ureas in combination with cyclopropenimine bases as a unique catalyst for the polymerization of cyclic esters and carbonates with a large span of reactivities. Methodologies of exceptionally effective and selective cocatalyst combinations were devised to produce polyesters and polycarbonates with narrow dispersities ( Đ = 1.01-1.10). Correlations of the p K a of the various ureas and cyclopropenimine bases revealed the critical importance of matching the p K a of the two cocatalysts to achieve the most efficient polymerization conditions. It was found that promoting strong H-bonding interactions with a noncompetitive organic solvent, such as CH 2 Cl 2 , enabled greatly increased polymerization rates. The stereoselective polymerization of rac -lactide afforded stereoblock poly(lactides) that crystallize as stereocomplexes, as confirmed by wide-angle X-ray scattering.