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Characteristics and Mechanism of Vinyl Ether Cationic Polymerization in Aqueous Media Initiated by Alcohol/B(C6F5)3/Et2O

1
College of Material Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
2
Department of Materials Science and Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China
3
Beijing Key Lab of Special Elastomeric Composite Materials, Beijing 102617, China
*
Authors to whom correspondence should be addressed.
Polymers 2019, 11(3), 500; https://doi.org/10.3390/polym11030500
Received: 28 February 2019 / Revised: 11 March 2019 / Accepted: 11 March 2019 / Published: 14 March 2019
(This article belongs to the Collection Design and Synthesis of Polymers)
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Abstract

Aqueous cationic polymerizations of vinyl ethers (isobutyl vinyl ether (IBVE), 2-chloroethyl vinyl ether (CEVE), and n-butyl vinyl ether (n-BVE)) were performed for the first time by a CumOH/B(C6F5)3/Et2O initiating system in an air atmosphere. The polymerization proceeded in a reproducible manner through the careful design of experimental conditions (adding initiator, co-solvents, and surfactant or decreasing the reaction temperature), and the polymerization characteristics were systematically tested and compared in the suspension and emulsion. The significant difference with traditional cationic polymerization is that the polymerization rate in aqueous media using B(C6F5)3/Et2O as a co-initiator decreases when the temperature is lowered. The polymerization sites are located on the monomer/water surface. Density functional theory (DFT) was applied to investigate the competition between H2O and alcohol combined with B(C6F5)3 for providing a theoretical basis. The effectiveness of the proposed mechanism for the aqueous cationic polymerization of vinyl ethers using CumOH/B(C6F5)3/Et2O was confirmed. View Full-Text
Keywords: aqueous cationic polymerization; suspension polymerization; emulsion polymerization; poly(vinyl ether); tris(pentafluorophenyl)borane; density functional theory aqueous cationic polymerization; suspension polymerization; emulsion polymerization; poly(vinyl ether); tris(pentafluorophenyl)borane; density functional theory
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Zhang, J.; Wu, Y.; Chen, K.; Zhang, M.; Gong, L.; Yang, D.; Li, S.; Guo, W. Characteristics and Mechanism of Vinyl Ether Cationic Polymerization in Aqueous Media Initiated by Alcohol/B(C6F5)3/Et2O. Polymers 2019, 11, 500.

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