Living Polymerization of Conjugated Polar Alkenes Catalyzed by N‑Heterocyclic Olefin-Based Frustrated Lewis Pairs

Living Polymerization of Conjugated Polar Alkenes Catalyzed by N‑Heterocyclic Olefin-Based Frustrated Lewis Pairs

The living polymerization of conjugated polar alkenes such as methacrylates by a noninteracting, authentic frustrated Lewis pair (FLP) has remained elusive ever since the report on FLP-promoted polymerization in 2010. Here we report that the polymerization of alkyl methacrylates by a FLP system base...

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Veröffentlicht in:ACS catalysis 2018-04, Vol.8 (4), p.3571-3578
Hauptverfasser: Wang, Qianyi, Zhao, Wuchao, Zhang, Sutao, He, Jianghua, Zhang, Yuetao, Chen, Eugene Y.-X
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container_end_page 3578
container_issue 4
container_start_page 3571
container_title ACS catalysis
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creator Wang, Qianyi
Zhao, Wuchao
Zhang, Sutao
He, Jianghua
Zhang, Yuetao
Chen, Eugene Y.-X
description The living polymerization of conjugated polar alkenes such as methacrylates by a noninteracting, authentic frustrated Lewis pair (FLP) has remained elusive ever since the report on FLP-promoted polymerization in 2010. Here we report that the polymerization of alkyl methacrylates by a FLP system based on a strongly nucleophilic N-heterocyclic olefin (NHO) Lewis base and sterically encumbered but modestly strong Lewis acid MeAl­(4-Me-2,6- t Bu2-C6H2O)2 is not only rapid but also living. This living polymerization was indicated by the formation of a linear, living chain, capped with NHO/H chain ends, without backbiting-derived cyclic chain ends. The true livingness of this FLP-promoted polymerization has been unequivocally verified by five lines of evidence, including the predicted polymer number-average molecular weight (M n, up to 351 kg·mol–1) coupled with low dispersity (Đ = 1.05) values; obtained high to quantitative initiation efficiencies; an observed linear increase of polymer M n vs monomer conversion and the monomer-to-initiator ratio; found precision in multiple chain extensions; and formed well-defined diblock and ABA triblock copolymers with narrow molecular weight distributions (Đ = 1.09–1.13), regardless of the comonomer addition order.
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