Copolymerization of Carbonyl Sulfide and Propylene Oxide via a Heterogeneous Prussian Blue Analogue Catalyst with High Productivity and Selectivity |
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| Authors: | Munir Ullah Khan Safir Ullah Khan Xiaohan Cao Muhammad Usman Xinchen Yue Abdul Ghaffar Muhammad Hassan Prof Chengjian Zhang Prof Xinghong Zhang |
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| Institution: | 1. State Key Laboratory of Motor Vehicle Biofuel Technology, International Research Center for X Polymers, Department of Polymer Science and Engineering, Zhejiang University, 310027 Hangzhou, P. R. China;2. Hefei National Laboratory for Physical Science at the Microscale, School of Life Sciences, University of Science and Technology of China, 230027 Hefei, P. R. China;3. Key Laboratory of Macromolecular Synthesis and Functionalization (Ministry of Education), International Research Center for X Polymers, Department of Polymer Science and Engineering, Zhejiang University, 310027 Hangzhou, P. R. China;4. Advanced Materials Research Center, Zhejiang University-University of Illinois at Urbana-Champaign Institute (ZJU–UIUC), 718 East Haizhou Road, Haining, 314400 Zhejiang, P. R. China |
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| Abstract: | This study demonstrates the superiority of a stable and well-defined heterogeneous cobalt hexacyanocobaltate (Co3Co(CN)6]2), a typical cobalt Prussian Blue Analogue (CoCo-PBA) that catalyzes the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO) to produce poly(propylene monothiocarbonate)s (PPMTC). The number-average molecular weights of the PPMTC were 66.4 to 139.4 kg/mol, with a polydispersity of 2.0–3.9. The catalyst productivity reached 1040 g polymer/g catalyst (12.0 h). The oxygen-sulfur exchange reaction (O/S ER), which would generate random thiocarbonate and carbonate units, was effectively suppressed, and thus the selectivity of the monothiocarbonate over carbonate linkages was up to >99%. It was shown that no cyclic thiocarbonate byproduct was produced during the heterogeneous catalysis of COS/PO copolymerization using CoCo-PBA as the catalyst. The content of monothiocarbonate and ether units in the copolymer chain could be regulated by tuning the feeding amount of COS. |
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| Keywords: | Carbonyl sulfide Copolymerization Heterogeneous catalysis Poly(propylene monothiocarbonate)s Co3[Co(CN)6]2 |
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