Abstract
This contribution reports an efficient approach for preparing polycarbonate block terpolymers by immortal stepwise copolymerization of CO2 with different epoxides in the presence of enol chain transfer, mediated by robust cobalt catalyst systems consisting of the fluorine substituted salenCo(III)NO3 or biphenol-linker bimetallic Co(III) complex in conjunction with an ionic cocatalyst, PPNX (PPN = bis(triphenylphosphine)iminium, X = NO3− or 2,4-dinitrophenoxide). Various polycarbonate block terpolymers were obtained in perfectly unimodal distribution of their molecular weights with narrow polydispersity. They all possessed only one broad glass transition temperature, which could be adjusted by altering the length of different polycarbonate segments.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Darensbourg, D. J. Making plastics from carbon dioxide. Salen metal complexes as catalysts for the production of polycarbonates from epoxides and CO2. Chem. Rev.2007, 107, 2388–2410.
Qin, Y.; Wang X. Carbon dioxide-based copolymers: Environmental benefits of PPC, an industrially viable catalyst. Biotechnol. J.2010, 5, 1164–1180.
Qin, Y.; Gu, L.; Wang, X. Progress in functional carbon dioxide based aliphatic polycarbonates. Acta Polymerica Sinica (in Chinese) 2013, 600–608.
Li, Y.; Zhang, Y. Y.; Hu, L. F.; Zhang, X. H.; Du, B. Y.; Xu, J. T. Carbon dioxide-based copolymers with various architectures. Prog. Polym. Sci.2018, 82, 120–157.
Xu, Y.; Lin, L.; Xiao, M.; Wang, S.; Smith, A. T.; Sun, L.; Meng, Y. Synthesis and properties of CO2-based plastics: Environmentally-friendly, energy-saving and biomedical polymeric materials. Prog. Polym. Sci.2018, 82, 163–182.
Inoue, S.; Koinuma, H.; Tsuruta, T. Copolymerization of carbon dioxide and epoxide. J. Polym. Sci., Polym. Lett.1969, 7, 287–292.
Klaus, S.; Lehenmeier, M. W.; Anderson, C. E.; Rieger, B. Recent advances in CO2/epoxide copolymerization-new strategies and cooperative mechanisms. Coord. Chem. Rev.2011, 255, 1460–1479.
Kember, M. R.; Buchard, A.; Williams, C. K. Catalysts for CO2/epoxide copolymerisation. Chem. Commun.2011, 47, 141–163.
Lu, X. B.; Darensbourg, D. J. Cobalt catalysts for the coupling of CO2 and epoxides to provide polycarbonates and cyclic carbonates. Chem. Soc. Rev.2012, 41, 1462–1484.
Luo, M.; Li, Y.; Zhang, Y. Y.; Zhang, X. H. Using carbon dioxide and its sulfur analogues as monomers in polymer synthesis. Polymer2016, 82, 406–431.
Moore, D. R.; Cheng, M.; Lobkovsky, E. B.; Coates, G. W. Electronic and steric effects on catalysts for CO2/epoxide polymerization: Subtle modifications resulting in superior activities. Angew. Chem. Int. Ed.2002, 41, 2599–2602.
Kissling, S.; Lehenmeier, M. W.; Altenbuchner, P. T.; Kronast, A.; Reiter, M.; Deglmann, P.; Seemann, U. B.; Rieger, B. Dinuclear zinc catalysts with unprecedented activities for the co-polymerization of cyclohexene oxide and CO2. Chem. Commun.2015, 51, 4579–4582.
Nakano, K.; Kamada, T.; Nozaki, K. Selective formation of polycarbonate over cyclic carbonate: Copolymerization of epoxides with carbon dioxide catalyzed by a cobalt(III) complex with a piperidinium end-capping arm. Angew. Chem. Int. Ed2006, 45, 7274–7277.
Sujith, S.; Min, K. K.; Seong, J. E.; Na, S. J.; Lee, B. Y. A highly active and recyclable catalytic system for CO2/propylene oxide copolymerization. Angew. Chem. Int. Ed.2008, 47, 7306–7309.
Ren, W. M.; Liu, Z. W.; Wen, Y. Q.; Zhang, R.; Lu, X. B. Mechanistic aspects of the copolymerization of CO2 with epoxides using a thermally stable single-site cobalt(III) catalyst. J. Am. Chem. Soc.2009, 131, 11509–11518.
Xie, D.; Quan, Z.; Wang, X.; Zhao, X.; Wang, F. Terpolymerization of carbon dioxide, propylene oxide and cyclohexene oxide catalyzed by rare-earth ternary catalyst. Chem. J. Chin. Univ.2005, 26, 2360–2362.
Shi, L.; Lu, X. B.; Zhang, R.; Peng, X. J.; Zhang, C. Q.; Li, J. F.; Peng, X. M. Asymmetric alternating copolymerization and terpolymerization of epoxides with carbon dioxide at mild conditions. Macromolecules2006, 39, 5679–5685.
Coates, G. W. Precise control of polyolefin stereochemistry using single-site metal catalysts. Chem. Rev.2000, 100, 1223–1252.
Lu, X. B.; Ren, W. M.; Wu, G. P. CO2 copolymers from epoxides: Catalyst activity, product selectivity, and stereochemistry control. Acc. Chem. Res.2012, 45, 1721–1735.
Liu, Y.; Ren, W. M.; Liu, J.; Lu, X. B. Asymmetric copolymerization of CO2 with meso-epoxides mediatedby dinuclear co-balt(III) complexes: Unprecedented enantioselectivity and activity. Angew. Chem. Int. Ed.2013, 52, 11594–11598.
Lu, X. B.; Shi, L.; Wang, Y. M.; Zhang, R.; Zhang, Y. J.; Peng, X. J.; Zhang, Z. C.; Li, B. Design of highly active binary catalyst systems for CO2/epoxide copolymerization: Polymer selectivity, enantioselectivity, and stereochemistry control. J. Am. Chem. Soc.2006, 128, 1664–1674.
DiCiccio, A. M.; Longo, J. M.; Rodriguez-Calero, G. G.; Coates, G. W. development of highly active and regioselective catalysts for the copolymerization of epoxides with cyclic anhydrides: An unanticipated effect of electronic variation. J. Am. Chem. Soc.2016, 138, 7107–7113.
Aida, T.; Inoue, S. Metalloporphyrins as initiators for living and immortal polymerizations. Acc. Chem. Res.1996, 29, 39–48.
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (No. 21690073) and the Program for Changjiang Scholars and Innovative Research Team in University (No. IRT-17R14).
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Jiang, YJ., Ren, WM., Liu, Y. et al. Synthesis of Polycarbonate Block Terpolymers Using Robust Cobalt Catalyst Systems. Chin J Polym Sci 37, 1200–1204 (2019). https://doi.org/10.1007/s10118-019-2270-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10118-019-2270-8