Accessing New Materials through Polymerization and Modification of a Polycarbonate with a Pendant Activated Ester

Functionalized polycarbonates were synthesized by organocatalytic ring-opening polymerization (ROP) of a cyclic monomer with a pendant activated ester (MTC-OC<sub>6</sub>F<sub>5</sub>) followed by a postpolymerization modification with both small molecules and macromolecules. Controlled ROP to form homopolymers and diblock copolymers was realized using catalytic quantities of triflic acid. For the homopolymers, a linear relationship between [M]<sub>0</sub>/[I]<sub>0</sub> and molecular weight (by GPC) demonstrated the living nature of the polymerization. Poly­(MTC-OC<sub>6</sub>F<sub>5</sub>) was functionalized under mild reaction conditions with a variety of amines to obtain polymers with pendant primary, secondary, and tertiary amides. Graft polymers with a high grafting density of over 87% were synthesized using amine-terminated poly­(ethylene glycol) of two different molecular weights (2 and 5 kDa). The preparation of poly­(MTC-OC<sub>6</sub>F<sub>5</sub>) provides a means of accessing a wide range of functional polycarbonates with minimal synthetic steps. This new methodology for the formation of functionalized polycarbonates provides a simple and versatile platform for the synthesis of new and innovative materials.