Hydrogen Bond Donor Catalyzed Cationic Polymerization of Vinyl Ethers

Abstract

The synthesis of high‐molecular‐weight poly(vinyl ethers) under mild conditions is a significant challenge, since cationic polymerization reactions are highly sensitive to chain‐transfer and termination events. We identified a novel and highly effective hydrogen bond donor (HBD)–organic acid pair that can facilitate controlled cationic polymerization of vinyl ethers under ambient conditions with excellent monomer compatibility. Poly(vinyl ethers) of molar masses exceeding 50 kg mol−1 can be produced within 1 h without elaborate reagent purification. Modification of the HBD structure allowed tuning of the polymerization rate, while DFT calculations helped elucidate crucial intermolecular interactions between the HBD, organic acid, and polymer chain end.

Fluorinated Polymeric Surfactant with a Pluronic-like Structure and Its Application as a Drug Carrier

“…BF 3 ·THF (15 mL) was added under argon and the mixture was stirred for approximately 30 min at 0 °C. This mixture was then cooled to about −10 °C, followed by addition of EPTF dissolved in dichloromethane over about 12 h to maintain the active monomer mechanism of cationic polymerization. − The reaction was maintained under argon overnight and brought to room temperature. The reaction was quenched by water for 30 min and diluted with water and a 2 wt % sodium chloride solution (50 mL) to break the emulsion.…”