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Single-Site Bifunctional Catalysts for COX (X = O or S)/Epoxides Copolymerization: Combining High Activity, Selectivity, and Durability

发表时间:2019-03-09
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论文类型:
期刊论文
第一作者:
Ren, Wei-Min
通讯作者:
Ren, WM (reprint author), Dalian Univ Technol, State Key Lab Fine Chem, 2 Linggong Rd, Dalian 116024, Peoples R China.
合写作者:
Liu, Ye,Xin, An-Xiang,Fu, Song,Lu, Xiao-Bing
发表时间:
2015-12-08
发表刊物:
MACROMOLECULES
收录刊物:
SCIE、EI、Scopus
文献类型:
J
卷号:
48
期号:
23
页面范围:
8445-8450
ISSN号:
0024-9297
摘要:
Unprecedented activity (TOP > 270 000 h(-1)), high polymer selectivity (>99%), and excellent durability (TON > 600 000) were observed in the copolymerization of carbonyl sulfide (COS) and epoxides mediated by the single-site bifunctional chromium catalyst containing a Lewis acidic metal center and a sterically hindered organic base in a molecule, selectively producing the corresponding poly(thiocarbonate)s with completely alternating structure, high molecular weight, and narrow monodispersity. No oxygen sulfur exchange reaction occurred even at an elevated temperature of 80 degrees C. Nevertheless, this catalyst was not efficient for CO2/epoxides copolymerization. The presence of CO2 completely inhibits the reactivity of COS. Contrarily, the corresponding Co(III) complex with the same ligand showed very low activity for COS/epoxides copolymerization but excellent activity (TOP > 13 000 h(-1)) for CO2/epoxides copolymerization at both ambient and high temperatures, affording the polycarbonates with >99% carbonate linkages and high molecular weight up to 467.0 kg/mol.
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