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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 | |
| Hui, Jiwen1; Wang, Xiaowu1; Yao, Xiaoqian3; Li, Zhibo1,2 | |
| 2022-12-06 | |
| Source Publication | POLYMER CHEMISTRY
 |
| ISSN | 1759-9954 |
| Volume | 13Issue:47Pages:6551-6563 |
| Abstract | 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. |
| DOI | 10.1039/d2py01001a |
| Language | 英语 |
| WOS Keyword | CYCLIC ANHYDRIDES ; METAL-FREE ; PROPYLENE-OXIDE ; BLOCK POLYMERS ; ACCESS ; POLYESTERS ; POLYMERIZATION ; ROUTE ; ORGANOCATALYSTS ; COMPLEXES |
| Funding Project | National Key R&D Program of China ; National Natural Science Foundation of China ; [2021YFA1501600] ; [22175105] ; [22031005] |
| WOS Research Area | Polymer Science |
| WOS Subject | Polymer Science |
| Funding Organization | National Key R&D Program of China ; National Natural Science Foundation of China |
| WOS ID | WOS:000886043200001 |
| Publisher | ROYAL SOC CHEMISTRY |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.ipe.ac.cn/handle/122111/55836 |
| Collection | 中国科学院过程工程研究所 |
| Corresponding Author | Wang, Xiaowu; Yao, Xiaoqian; Li, Zhibo |
| Affiliation | 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 |
| Recommended Citation 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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