Characteristics and Mechanism of Vinyl Ether Cationic Polymerization in Aqueous Media Initiated by Alcohol/B(C(6)F(5))(3)/Et(2)O

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(C(6)F(5))(3)/Et(2)O 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(C(6)F(5))(3)/Et(2)O 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 H(2)O and alcohol combined with B(C(6)F(5))(3) for providing a theoretical basis. The effectiveness of the proposed mechanism for the aqueous cationic polymerization of vinyl ethers using CumOH/B(C(6)F(5))(3)/Et(2)O was confirmed.