| Abstract: | In this study, the catalytic behavior of dual catalysis based on isothioureas (ITUs) for ring‐opening polymerization (ROP) of macrolactone ω‐pentadecalactone (PDL) and its copolymerization with ε‐caprolactone (CL) has been investigated in detail. In the presence of benzyl alcohol (BnOH) initiator, 2,3,6,7‐tetrahydro‐5H‐thiazolo3,2‐a]pyrimidine (THTP) acted as a representative organic compound, which coupled with magnesium halides (MgX2) as cocatalysts and catalyzed the polymerization in toluene at 70 °C. Under suitable conditions, an array of polymers with controlled molecular weights and relatively narrow molecular weight distributions were synthesized. The formation of homopolymers and copolymers with different architectures was verified using GPC, DSC, NMR, and matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐ToF) mass. The MALDI‐ToF mass spectrometry (MS) analysis of poly(ω‐pentade‐calactone) (PPDL) provided direct evidence for the successful initiation of ROP of PDL using BnOH to obtain linear PPDL with a very small amount of oligomer. The NMR analysis indicated that the arrangements of PDL and CL units in the copolymer chains were completely random. The thermal stability of copolymers was composition dependent and increased with the increase in the content of PDL unit. Furthermore, the proposed polymerization mechanism is a dual catalytic mechanism. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 |
