Iterative Convergent Synthesis of Large Cyclic Polymers and Block Copolymers with Discrete Molecular Weights

We report here the synthesis of cyclic polymers and block copolymers consisting of discrete numbers of repeating units without linear contaminants. The synthesis utilizes the intramolecular cyclization of end-functionalized poly­(rac-lactide) (PLA) and its block copolymers with as many as 512 lactic acid units (37 kDa), synthesized by the iterative linear convergence of orthogonally protected building blocks. By exploiting the change in hydrodynamic volume upon cyclization of the linear polymers, macrocyclic polymers were isolated without linear precursors by preparative size-exclusion chromatography as a purification method. Our procedure also allowed the synthesis of a monodisperse cyclic block copolymer in a desired block ratio as a single compound (14 kDa).