Synthesis of Hyperbranched Poly(ε-caprolactone) Containing Terminal Azobenzene Structure via Combined Ring-Opening Polymerization and “Click” Chemistry

A novel well-defined linear poly(ε-caprolactone) (P1) containing terminal azobenzene and ethyne groups was successfully synthesized through tin-catalyzed ring-opening polymerization of ε-caprolactone in the presence of N,N′-bis(2-hydroxyethyl)-4-(3ethynylphenylazo)aniline (BHA) in bulk. Subsequent reactions allowed the synthesis of the corresponding bromoester end-functionalized polymer (P2), which was converted into AB2 type polymer (P3) containing terminal azide groups with NaN3. Consequently, hyperbranched poly(ε-caprolactone) (HPCL) was prepared with AB2 macromonomer (P3) by “click” chemistry under the catalysis of CuSO4·5H2O/sodium ascorbate/H2O. The structure of the resultant HPCL was characterized by gel permeation chromatography (GPC), proton nuclear magnetic resonance (1H-NMR), ultraviolet-visible (UV-Vis) spectroscopy and fourier transform infrared spectroscopy (FT-IR). Thermal and crystallization properties of P1 and HPCL were further studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and polarised optical microscopy (POM). These results indicated that the crystallinity of HPCL was slightly lower than that of P1 due to the hyperbranched structure of HPCL. Additionally, the photo-induced trans-cis isomerization behaviors of BHA, P1 and HPCL containing terminal azobenzene were investigated in chloroform solution, and the photoisomerization rate constant (kexp) of small molecule (BHA) was nearly three times faster than that of polymers P1 and HPCL, which was due to the sterically hindering effect of the polymer-chain configuration. OPEN ACCESS Polymers 2015, 7 1249