Investigation of the Locked-Unlocked Mechanism in Living Anionic Polymerization Realized with 1-(Tri-isopropoxymethylsilylphenyl)-1-phenylethylene
Pibo Liu
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorCorresponding Author
Hongwei Ma
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorLi Han
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorHeyu Shen
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorLincan Yang
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorChao Li
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorXinyu Hao
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorYang Li
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorPibo Liu
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorCorresponding Author
Hongwei Ma
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorLi Han
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorHeyu Shen
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorLincan Yang
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorChao Li
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorXinyu Hao
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorYang Li
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorGraphical Abstract
Locked in: An intriguing advance in living anionic polymerization (LAP) by a “locked-unlocked” mechanism was investigated. The living anionic species can be quantitatively locked by end-capping with 1-(tri-isopropoxymethylsilylphenyl)-1-phenylethylene (DPE-Si(O-iPr)3) and can be unlocked by adding the key, sodium 2,3-dimethylpentan-3-olate (NaODP).
Abstract
Reported is an intriguing advance in living anionic polymerization (LAP) by a “locked-unlocked” mechanism in which the living anionic species can be quantitatively locked by end-capping with 1-(tri-isopropoxymethylsilylphenyl)-1-phenylethylene (DPE-Si(O-iPr)3) and can be unlocked by adding the key, sodium 2,3-dimethylpentan-3-olate (NaODP). These new insights into this mechanism were carefully confirmed by designing reactions involving sequential feeding of quantitative DPE-Si(O-iPr)3 and traditional monomers mixed with NaODP, and subsequently characterizing the corresponding samples, taken during the feeding process, by GPC, NMR, and MALDI-TOF-MS techniques. The switch from the locked to unlocked state was clearly confirmed by these characterization techniques. The putative locked-unlocked mechanism in the LAP was simulated by the Gaussian method. This intriguing mechanistic finding of LAP reactions is expected to supplement the existing knowledge and facilitate the tailoring of specific structures for these polymerizations.
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