Non-metal with metal behavior: metal-free coordination-insertion ring-opening polymerization

被引:6
作者
Wang, Xin [1 ,3 ]
Xu, Jiaxi [1 ,3 ]
Li, Zhenjiang [1 ]
Liu, Jingjing [1 ,3 ]
Sun, Jie [2 ]
Hadjichristidis, Nikos [3 ]
Guo, Kai [1 ]
机构
[1] Nanjing Tech Univ, Coll Biotechnol & Pharmaceut Engn, State Key Lab Mat Oriented Chem Engn, 30 Puzhu Rd South, Nanjing 211816, Peoples R China
[2] Nanjing Tech Univ, Coll Food Sci & Light Ind, 30 Puzhu Rd South, Nanjing 211816, Peoples R China
[3] King Abdullah Univ Sci & Technol KAUST, KAUST Catalysis Ctr, Phys Sci & Engn Div, Polymer Synth Lab, Thuwal 23955, Saudi Arabia
基金
中国国家自然科学基金;
关键词
DIIMINATE ZINC CATALYSTS; ESTER-EXCHANGE-REACTIONS; EPSILON-CAPROLACTONE; CYCLIC ESTERS; L-LACTIDE; POLYLACTONES; COMPLEXES; MECHANISM; ALUMINUM; KINETICS;
D O I
10.1039/d1sc02551a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The "coordination-insertion" ring-opening polymerization (ROP) mechanism has so far been the monopoly of metal catalysts. In this work, we present a metal-free "coordination-insertion" ROP of trimethylene carbonate (TMC) and epsilon-caprolactone (epsilon-CL), as well as their sequential block copolymerization, with N-trimethylsilyl-bis (trifluoromethanesulfonyl)imide (TMSNTf2) as the non-metallic initiator/catalyst. TMSNTf2 was proposed to work through an unprecedented metal-free "coordination-insertion" mechanism, which involves the coordination of monomer to the Si atom of TMSNTf2, the nucleophilic attack of the -NTf2 group on the coordinated monomer, and the cleavage of the acyl-oxygen bond of the monomer. The proposed metal-free "coordination-insertion" ROP was studied by NMR, SEC, and MALDI-TOF analyses. In addition, the TMSNTf2-mediated ROP of TMC and epsilon-CL led to linear and cyclic polymers following two-stage first-order polymerization processes, as evidenced by structural analyses and kinetics study, which further demonstrated the metal-free "coordination-insertion" mechanism.
引用
收藏
页码:10732 / 10741
页数:10
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