Synthesis of Chiral Sulfur-Containing Polymers: Asymmetric Copolymerization of meso-Epoxides and Carbonyl Sulfide
Tian-Jun Yue
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian, 116024 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Wei-Min Ren
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian, 116024 China
Search for more papers by this authorLi Chen
Faculty of Machenical Engineering Materials and Energy, Dalian University of Technology, 2 Linggong Road, Dalian, 116024 China
Search for more papers by this authorGe-Ge Gu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian, 116024 China
Search for more papers by this authorDr. Ye Liu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian, 116024 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Xiao-Bing Lu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian, 116024 China
Search for more papers by this authorTian-Jun Yue
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian, 116024 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Wei-Min Ren
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian, 116024 China
Search for more papers by this authorLi Chen
Faculty of Machenical Engineering Materials and Energy, Dalian University of Technology, 2 Linggong Road, Dalian, 116024 China
Search for more papers by this authorGe-Ge Gu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian, 116024 China
Search for more papers by this authorDr. Ye Liu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian, 116024 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Xiao-Bing Lu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, 2 Linggong Road, Dalian, 116024 China
Search for more papers by this authorGraphical Abstract
A worthy COS: Chiral sulfur-containing polymers with good thermal and optical properties were synthesized for the first time by stereoselective desymmetrization copolymerization of achiral meso-epoxides and COS. The reaction is catalyzed by an enantiopure binaphthol-linked bimetallic catalyst and provides the polymers with >99 % isotacticity.
Abstract
Synthesis of chiral sulfur-containing polymers was realized for the first time by the asymmetric alternating copolymerization of achiral meso-epoxides with carbonyl sulfide (COS) using catalyst systems based on enantiopure binaphthol-linked dinuclear CoIII complexes under mild reaction conditions. The resultant poly(monothiocarbonate)s have main-chain chirality and more than 99 % isotacticity. Notably, the stereoregular copolymers are typical semicrystalline thermoplastics with high melting temperatures up to 232 °C. Additionally, these sulfur-containing polymers have good optical properties with refractive indices of up to 1.56 and Abbe's numbers of up to 43.
Supporting Information
As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.
| Filename | Description |
|---|---|
| anie201805200-sup-0001-misc_information.pdf1.7 MB | Supplementary |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1A. Kultys, Sulfur-Containing Polymers in Encyclopedia of Polymer Science and Technology, 4th ed., Wiley, Hoboken, 2010.
- 2K. Nakabayashi, T. Imai, M.-C. Fu, S. Ando, T. Higashihara, M. Ueda, Macromolecules 2016, 49, 5849–5856.
- 3A. Kausar, S. Zulfiqar, M. I. Sarwar, Polym. Rev. 2014, 54, 185–267.
- 4
- 4aT. Lütke-Eversloh, A. Fischer, U. Remminghorst, J. Kawada, R. H. Marchessault, A. Bogershausen, M. Kalwei, H. Eckert, R. Reichelt, S. J. Liu, A. Steinbuchel, Nat. Mater. 2002, 1, 236–240;
- 4bH. R. Kricheldorf, G. Schwarz, J. Macromol. Sci. Part A 2007, 44, 625–649;
- 4cP. P. Datta, M. K. Kiesewetter, Macromolecules 2016, 49, 774–780.
- 5
- 5aY. Y. Zhang, K. M. Konopka, R. S. Glass, K. Char, J. Pyun, Polym. Chem. 2017, 8, 5167–5173;
- 5bY. Y. Zhang, T. S. Kleine, K. J. Carothers, D. D. Phan, R. S. Glass, M. E. Mackay, K. Chard, J. Pyun, Polym. Chem. 2018, 9, 2290–2294.
- 6
- 6aK. Soga, H. Imamura, S. Ikeda, Makromol. Chem. 1975, 176, 807–811;
- 6bH. R. Kricheldorf, D. O. Damrau, Macromol. Chem. Phys. 1998, 199, 2589–2596;
10.1002/(SICI)1521-3935(19981101)199:11<2589::AID-MACP2589>3.0.CO;2-P CAS Web of Science® Google Scholar
- 6cF. Sanda, J. Kamatani, T. Endo, Macromolecules 1999, 32, 5715–5717.
- 7Y. Z. You, C. Y. Hong, C. Y. Pan, Macromol. Rapid Commun. 2002, 23, 776–780.
- 8N. Nemoto, F. Sanda, T. Endo, Macromolecules 2000, 33, 7229–7231.
- 9K. Nakano, G. Tatsumi, K. Nozaki, J. Am. Chem. Soc. 2007, 129, 15116–15117.
- 10
- 10aX.-H. Zhang, F. Liu, X.-K. Sun, S. Chen, B.-Y. Du, G.-R. Qi, K.-M. Wan, Macromolecules 2008, 41, 1587–1590;
- 10bD. J. Darensbourg, J. R. Andreatta, M. J. Jungman, J. H. Reibenspies, Dalton Trans. 2009, 8891–8899;
- 10cD. J. Darensbourg, S. J. Wilson, A. D. Yeung, Macromolecules 2013, 46, 8102–8110;
- 10dM. Luo, X.-H. Zhang, D. J. Darensbourg, Macromolecules 2015, 48, 5526–5532;
- 10eJ. Diebler, H. Komber, L. Hausler, A. Lederer, T. Werner, Macromolecules 2016, 49, 4723–4731.
- 11M. Luo, X.-H. Zhang, D. J. Darensbourg, Acc. Chem. Res. 2016, 49, 2209–2219.
- 12
- 12aM. Luo, X.-H. Zhang, B.-Y. Du, Q. Wang, Z.-Q. Fan, Macromolecules 2013, 46, 5899–5904;
- 12bW.-M. Ren, Y. Liu, A.-X. Xin, S. Fu, X.-B. Lu, Macromolecules 2015, 48, 8445–8450;
- 12cH.-L. Wu, J.-L. Yang, M. Luo, R.-Y. Wang, J.-T. Xu, B.-Y. Du, X.-H. Zhang, D. J. Darensbourg, Macromolecules 2016, 49, 8863–8868;
- 12dW.-M. Ren, T.-J. Yue, M.-R. Li, Z.-Q. Wan, X.-B. Lu, Macromolecules 2017, 50, 63–68;
- 12eJ.-L. Yang, H.-L. Wu, Y. Li, X.-H. Zhang, D. J. Darensbourg, Angew. Chem. Int. Ed. 2017, 56, 5774–5779; Angew. Chem. 2017, 129, 5868–5873.
- 13
- 13aG. W. Coates, Chem. Rev. 2000, 100, 1223–1252;
- 13bL. S. Baugh, J. A. M. Canich, Stereoselective Polymerization with Single-site Catalysts, Taylor & Francis Group, New York, 2008;
- 13cM. Ian Childers, J. M. Longo, N. J. Van Zee, A. M. LaPointe, Chem. Rev. 2014, 114, 8129–8152.
- 14T.-J. Yue, W.-M. Ren, Y. Liu, Z.-Q. Wan, X.-B. Lu, Macromolecules 2016, 49, 2971–2976.
- 15
- 15aK. Nozaki, K. Nakano, T. Hiyama, J. Am. Chem. Soc. 1999, 121, 11008–11009;
- 15bM. Cheng, N. A. Darling, E. B. Lobkovsky, G. W. Coates, Chem. Commun. 2000, 2007–2008;
- 15cK. Nakano, K. Nozaki, T. Hiyama, J. Am. Chem. Soc. 2003, 125, 5501–5510;
- 15dG.-P. Wu, W.-M. Ren, Y. Luo, B. Li, W.-Z. Zhang, X.-B. Lu, J. Am. Chem. Soc. 2012, 134, 5682–5688;
- 15eK. Nishioka, H. Goto, H. Sugimoto, Macromolecules 2012, 45, 8172–8192;
- 15fW. C. Ellis, Y. Jung, M. Mulzer, R. Di Girolamo, E. B. Lobkovsky, G. W. Coates, Chem. Sci. 2014, 5, 4004–4011;
- 15gY. Z. Hua, L. J. Lu, P. J. Huang, D. H. Wei, M. S. Tang, M. C. Wang, J. B. Chang, Chem. Eur. J. 2014, 20, 12394–12398.
- 16
- 16aY. Liu, W.-M. Ren, J. Liu, X.-B. Lu, Angew. Chem. Int. Ed. 2013, 52, 11594–11598; Angew. Chem. 2013, 125, 11808–11812;
- 16bY. Liu, W.-M. Ren, K.-K. He, X.-B. Lu, Nat. Commun. 2014, 5, 5687;
- 16cX.-B. Lv, Acta Polym. Sin. 2016, 9, 1166–1178.
- 17J. Li, Y. Liu, W.-M. Ren, X.-B. Lu, J. Am. Chem. Soc. 2016, 138, 11493–11496.
- 18
- 18aM. Luo, X.-H. Zhang, D. J. Darensbourg, Macromolecules 2015, 48, 6057–6062;
- 18bM. Luo, X.-H. Zhang, D. J. Darensbourg, Polym. Chem. 2015, 6, 6955–6958;
- 18cM. Luo, X.-H. Zhang, B.-Y. Du, Q. Wang, Z.-Q. Fan, Polym. Chem. 2015, 6, 4978–4983.
- 19M. Luo, X. H. Zhang, B. Y. Du, Q. Wang, Z. Q. Fan, Polymer 2014, 55, 3688–3695.
- 20Sulfur molecules are chemisorbed onto and react with active cobalt sites, preventing the access of reactants. V. Ramana, R. Pendyala, B. H. Davis, Catal. Today 2018, 299, 14–19.
- 21Using Abbe's refractometer, refractive indices of the CHO/COS copolymer and CPO/COS copolymer were measured to be 1.74 and 1.76 (cast film, 20 °C), respectively.
- 22T. Higashihara, M. Ueda, Macromolecules 2015, 48, 1915–1929.
