Hao, Jing, Patricia C. Granowski, and Mihaela C. Stefan. Macromolecular rapid communications 33.15 (2012): 1294-1299.
Zinc undecylenate (ZU) has been demonstrated as an effective catalyst for the ring-opening polymerization (ROP) of ε-caprolactone and γ-octyloxy-ε-caprolactone monomers, facilitating the synthesis of well-defined polyesters with controlled molecular weights. The polymerizations were conducted in bulk at 90 and 110 °C, using benzyl alcohol as an initiator under an inert nitrogen atmosphere to ensure an oxygen-free environment.
Kinetic studies revealed that γ-octyloxy-ε-caprolactone polymerized at a slower rate compared to ε-caprolactone, consistent with steric and electronic influences of the side substituent. Sequential monomer addition enabled the successful synthesis of diblock copolymers, underscoring the living/controlled nature of the ZU-catalyzed ROP system. Conversion rates and polymer molecular weights were monitored by ^1H NMR spectroscopy and size exclusion chromatography (SEC), confirming precise control over polymer chain growth.
The use of zinc undecylenate offers advantages including mild reaction conditions, high catalytic efficiency, and tunable polymer architectures, which are critical for tailoring polyester properties in biomedical and packaging applications. This catalyst system's ability to mediate controlled/living polymerization enhances reproducibility and molecular design flexibility, thereby expanding its potential for sustainable polymer synthesis.
In conclusion, zinc undecylenate is a robust catalyst for the synthesis of functional poly(ε-caprolactone)-based copolymers through ROP, enabling advanced material design with precise molecular weight control and block sequence fidelity.
Washington, K. E., Kularatne, R. N., Du, J., Gillings, M. J., Webb, J. C., Doan, N. C., ... & Stefan, M. C. (2016). Journal of Polymer Science Part A: Polymer Chemistry, 54(22), 3601-3608.
Zinc undecylenate has been effectively employed as a catalyst in the ring-opening polymerization (ROP) of ε-caprolactone and γ-2-[2-(2-methoxyethoxy)ethoxy]ethoxy-ε-caprolactone monomers, facilitating the synthesis of amphiphilic diblock copolymers with tailored architectures, including linear and 4-arm star-like structures. These copolymers exhibit significant potential as micellar drug delivery vehicles due to their ability to form stable nanoscale assemblies.
The polymerization was conducted under inert nitrogen atmosphere at 110 °C using benzyl alcohol as an initiator, ensuring controlled sequential monomer addition and polymer growth. The star-like copolymers demonstrated enhanced thermodynamic stability and lower critical micelle concentration (CMC) of 5.62 × 10^-4 g L^-1, approximately half that of their linear counterparts, indicating more efficient micelle formation at lower polymer concentrations. Moreover, the star-like micelles exhibited reduced hydrodynamic size and superior drug loading capacity for doxorubicin, underscoring their suitability for targeted drug delivery.
The catalytic activity of zinc undecylenate allowed precise control over molecular weight and polymer architecture, enabling reproducible synthesis of block copolymers with desirable physicochemical properties such as viscosity, size, and degradability. This versatility enhances the development of advanced polymeric micelles with optimized pharmacokinetics and therapeutic efficacy.
In summary, zinc undecylenate serves as a robust catalyst for the preparation of amphiphilic diblock copolymers with distinct architectures, advancing the design of efficient, stable, and high-capacity drug delivery nanocarriers.