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A one-component phosphonium borane Lewis pair serves as a dual initiator and catalyst in the ring-opening alternating copolymerization of anhydrides and epoxides

文献类型：期刊论文

作者Hui, Jiwen1; Wang, Xiaowu1; Yao, Xiaoqian3; Li, Zhibo1,2
刊名POLYMER CHEMISTRY
出版日期2022-12-06
卷号13期号:47页码:6551-6563
ISSN号1759-9954
DOI10.1039/d2py01001a
英文摘要Lewis pairs as synergistic catalysts have demonstrated versatile adaptabilities towards different monomers. Herein, we converted a bi-component Lewis pair into a one-component Lewis pair by integrating a Lewis acid and ionic Lewis base within one molecule to enhance the synergistic effect on the polymerization reaction. To exemplify the design strategy, one-component phosphonium borane Lewis pairs 1-6 were rationally designed, readily synthesized, and employed as metal-free catalysts for the ring-opening alternating copolymerization (ROAC) of anhydrides and epoxides. Detailed MALDI-ToF MS analysis illustrated the microstructure of the obtained copolymers and verified the presence of two types of initiating species derived from Br- and cyclohexane-1,2-diol (CHD) in the polymerization set-up. Kinetic studies and in situ B-11{H-1} NMR experiments further clarified the mechanism of polymerization. Strikingly, Lewis pair 3 featuring pentamethyl-ene -(CH2)(5)- linked triphenylphosphonium bromide (Lewis base) and a borabicyclo[3.3.1]nonane moiety (Lewis acid) showed high activity (TOF = 1920 h(-1)), thermal robustness (120 degrees C) and good alternating selectivity (>92%) in the ROAC of phthalic anhydride (PA) and cyclohexene oxide (CHO). Lewis pair 3 achieved a feed ratio of CHO/PA/catalyst = 15 000 :10 000 :1 in 96% conversion within 5 h at 150 degrees C. The higher molecular weight fraction of the produced P(PA-alt-CHO) had an M-n value of 51.8 kg mol(-1) with a polydispersity D = 1.10. The lower molecular weight fraction was ascribed to Br- initiation. In particular, P(PA-alt-CHO) with unimodal distribution can be generated by deliberate addition of water. The relatively larger radius parameter of the phosphonium countercation led to a weak electrostatic interaction, thus yielding a loose Lewis pair to allow for much easier dissociation of carboxylate active species, accounting for the high catalytic and synergistic behavior of the designed phosphonium borane Lewis pair in the ROAC of PA and CHO. One-component Lewis pairs will not only diversify organocatalyst structures, but also deepen our understanding of the polymerization mechanism and provide a possibility to realize controlled copolymerization of anhydrides and epoxides.
WOS关键词CYCLIC ANHYDRIDES ; METAL-FREE ; PROPYLENE-OXIDE ; BLOCK POLYMERS ; ACCESS ; POLYESTERS ; POLYMERIZATION ; ROUTE ; ORGANOCATALYSTS ; COMPLEXES
资助项目National Key R&D Program of China ; National Natural Science Foundation of China ; [2021YFA1501600] ; [22175105] ; [22031005]
WOS研究方向Polymer Science
语种英语
出版者ROYAL SOC CHEMISTRY
WOS记录号WOS:000886043200001
资助机构National Key R&D Program of China ; National Natural Science Foundation of China
源URL[http://ir.ipe.ac.cn/handle/122111/55835]  
专题中国科学院过程工程研究所
通讯作者Wang, Xiaowu; Yao, Xiaoqian; Li, Zhibo
作者单位1.Qingdao Univ Sci & Technol, Coll Chem Engn, 53 Zhengzhou Rd, Qingdao 266042, Peoples R China
2.Qingdao Univ Sci & Technol, Coll Polymer Sci & Engn, 53 Zhengzhou Rd, Qingdao 266042, Peoples R China
3.Chinese Acad Sci, Inst Proc Engn, CAS Key Lab Green Proc & Engn, Beijing Key Lab Ion Liquids Clean Proc,State Key L, Beijing 100190, Peoples R China
推荐引用方式
GB/T 7714		 Hui, Jiwen,Wang, Xiaowu,Yao, Xiaoqian,et al. A one-component phosphonium borane Lewis pair serves as a dual initiator and catalyst in the ring-opening alternating copolymerization of anhydrides and epoxides[J]. POLYMER CHEMISTRY,2022,13(47):6551-6563.
APA Hui, Jiwen,Wang, Xiaowu,Yao, Xiaoqian,&Li, Zhibo.(2022).A one-component phosphonium borane Lewis pair serves as a dual initiator and catalyst in the ring-opening alternating copolymerization of anhydrides and epoxides.POLYMER CHEMISTRY,13(47),6551-6563.
MLA Hui, Jiwen,et al."A one-component phosphonium borane Lewis pair serves as a dual initiator and catalyst in the ring-opening alternating copolymerization of anhydrides and epoxides".POLYMER CHEMISTRY 13.47(2022):6551-6563.

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来源：过程工程研究所

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