Ring-Opening Polymerization of ε-Caprolactone with Anhydrous Iron (III) Chloride as Catalyst

Abstract:

A green and nontoxic ring-opening polymerization (ROP) of ε-caprolactone (CL) with appreciably high molecular weight (M_n), low dispersity (PDI), and high conversion was achieved using FeCl₃ as a catalyst and Benzyl alcohol as an initiator in solvents at ambient temperature. Effects of Fe compounds, solvents, reaction temperature, catalyst concentration, and monomer concentration were investigated. The kinetic experiments reveal the controlled nature of using FeCl₃ as a catalyst.

• Periodical: Solid State Phenomena (Volume 367)
• Pages: 9-14
• DOI: https://doi.org/10.4028/p-Za6SSE
• Online since: December 2024
• Authors: Jin Bo Zhang*
• Keywords: Aliphatic Polyesters, Anhydrous Iron (III) Chloride, Biological Materials, PCL, Ring-Opening Polymerization

References

[1] Fagnani, D.E.; Tami, J. L.; Copley, G.; Clemons, M. N.; Getzler, Y.D.Y.L.; McNeil, A.J., 100th Anniversary of Macromolecular Science Viewpoint: Redefining Sustainable Polymers. ACS Macro Lett., 10 (2021) 41-53.

DOI: 10.1021/acsmacrolett.0c00789

[2] Santos, C.C.O.; V. Ferreira, F.; Pinheiro, I.F.; Lona, L.M.F., Lignin Valorization through Polymer Grafting by Ring-opening Polymerization and its Application in Health, Packaging, and Coating. J. Environ. Chem. Eng., 11 (2023) 109691.

DOI: 10.1016/j.jece.2023.109691

[3] Zhang, X.; Fevre, M.; Jones, G.O.; Waymouth, R.M., Catalysis as an Enabling Science for Sustainable Polymers. Chem. Rev., 118 (2018) 839-885.

DOI: 10.1021/acs.chemrev.7b00329

[4] Song, Q.; Pascouau, C.; Zhao, J.; Zhang, G.; Peruch, F.; Carlotti, S., Ring-opening polymerization of γ-Lactones and Copolymerization with Other Cyclic Monomers. Prog. Polym. Sci., 110 (2020) 101309.

DOI: 10.1016/j.progpolymsci.2020.101309

[5] Wei, B.; Wang, C.; Miao, H.; Qin, Z.; Huang, M.; Xu, Y.; Xue, W.; Yang, S.; Liu, C.; Bai, C.; Chen, Z., Novel Bidentate N-coordinated Alkylaluminum Complexes: Synthesis, Characterization, and Efficient Catalysis for Hydrophosphonylation. Dalton Trans., 53 (2024) 4185-4193.

DOI: 10.1039/d3dt04087a

[6] Zaitsev, K.V.; Trubachev, A. D.; Oprunenko, Y. F.; Piskun, Y.A.; Vasilenko, I.V.; Churakov, A. V.; Kostjuk, S.., Aluminum Salen Complexes Modified with Unsaturated Alcohol: Synthesis, Characterization, and Their Activity towards Ring-Opening Polymerization of ε-Caprolactone and D, L-Lactide. Molecules, 28 (2023) 1262.

DOI: 10.3390/molecules28031262

[7] Hu, S.; Zhao, J.; Zhang, G.; Schlaad, H., Macromolecular Architectures through Organocatalysis. Prog. Polym. Sci., 74 (2017) 34-77.

DOI: 10.1016/j.progpolymsci.2017.07.002

[8] Morodo, R.; Dumas, D.M.; Zhang, J.; Lui, K. H.; Hurst, P. J.; Bosio, R.; Campos, L. M.; Park, N. H.; Waymouth, R. M.; Hedrick, J. L., Ring-Opening Polymerization of Cyclic Esters and Carbonates with (Thio)urea/Cyclopropenimine Organocatalytic Systems. ACS Macro Lett., 13 (2024) 181-188.

DOI: 10.1021/acsmacrolett.3c00716

[9] Hao, T. Z.; Chen, Y. H.; Li, L. L.; Xuan, P., Research Progress on Ring-opening Polymerization Catalysts and the Synthesis of Aliphatic Polyesters. Acta Polym. Sin., 53 (2022) 1057-1071.

[10] Gowda, R. R.; Chakraborty, D., Environmentally Benign Process for Bulk Ring Opening Polymerization of Lactones using Iron and Ruthenium Chloride Catalysts. J. Mol. Catal. A: Chem., 301 (2009) 84-92.

DOI: 10.1016/j.molcata.2008.11.010

[11] Yu, B.; Xu, X.; Huang, Z.-N.; Tao, K.; Sun, H.-L.; Yang, Q.-Z.; Wang, W., Iron-Aryloxide Complex Bearing Bis(dipyrromethene) Ligands for the Ring-Opening Polymerization of ε-Caprolactone. Organometallics, 42 (2023) 565-570.

DOI: 10.1021/acs.organomet.2c00618