Synthesis of ultra‐small branched star poly(ε‐caprolactone)s and their high end group concentration effects on crystallization

We successfully synthesize the three‐ and six‐branched star poly(ε‐caprolactone)s with extremely small branched segments (USB‐SPCLs) using a facile pseudo‐one‐pot process in a pilot scale and investigate the effect of ultra‐small branches on their crystallization behaviors. The number of branched segments and the individual branched segment lengths for USB‐SPCLs are precisely controlled via manipulating monomer‐to‐core ratio, adjusting monomer‐to‐polymer conversion, end‐capping the terminal hydroxyl groups, and vacuum purification, which results in USB‐SPCLs having the branched segments below five degree of polymerization with a high yield exceeding 93%. The molecular weights obtained from ¹H NMR spectroscopy are consistent with that obtained from MALDI‐TOF‐MS and the molecular weight distributions are narrow with M_w/M_n ≤ 1.2, indicating that USB‐SPCLs have mono‐dispersed branches. USB‐SPCLs have low melting temperatures and broad double‐melting peaks attributed to their extremely small branches, and the crystallization behaviors for USB‐SPCLs depend on the end group concentration. On the other hand, the glass transitions for USB‐SPCLs depend on the total molecular weights, regardless of the number and length of branched segments. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1134–1142