Synthesis of High Molecular Weight Cyclic Poly(ε‐caprolactone)s of Variable Ring Size Based on a Light‐Induced Ring‐Closure Approach

High molecular weight cyclic poly(ε-caprolactone)s (cPCLs) with variable ring size are synthesized via light-induced ring closure of α,ω-anthracene-terminated PCL (An-PCL-An). The ring size of cPCL is tunable simply by adjusting the polymer concentration from 10 to 100 mg mL(-1) in THF. The cyclo-addition via the bimolecular cyclization of An-PC-An is well characterized by a variety of analyses such as (1) H NMR and UV-vis spectroscopies, gel-permeation chromatography, and differential scanning calorimetry. The reversible dimerization of An induced by heating enables the cyclic PCL to have a switchable "on-off" capability. This novel light-induced ring-closure technique can be one of the most powerful candidates for producing various well-defined cyclic polymers in highly concentrated polymer solution.