Postpolymerization Modification and Topological Structure Design of Poly(vinyl ether)s Based on the Selective Addition Reaction of Electrophilic Selenium Reagent and Divinyl Monomers

Abstract

Poly(vinyl ether)s (PVEs) are typical products from living cationic polymerization. However, postpolymerization modification (PPM) and topological structure design of poly(vinyl ether)s under relatively mild conditions are rare, which limits their practical applications. Herein, we report a facile method to overcome this limitation by exploiting the selective addition reaction of electrophilic selenium reagent and divinyl monomers, which can produce PVEs with pendent vinyl groups in each repeat unit or end-functionalized PVEs. PPM of PVEs was realized by a thiol−ene click reaction. Furthermore, brush polymers and core cross-linked star polymers were successfully prepared by using endfunctionalized PVEs as macromonomers, providing a general method for the preparation of topological polymers and laying a foundation for the development and application of PVEs.

Zinc-Mediated Living Cationic Polymerization

“…The 1 H NMR analysis of the obtained PIBVE showed the characteristic peak belonging to the phenyl group, appearing at 7.2 and 7.5 ppm (Figure E), indicating the presence of a phenyl selenium group at the α-end of the polymer chain. This achievement demonstrates a facile way to introduce functionality into the polymer. ,, Two series of peaks in matrix-assisted laser desorption time-of-flight mass spectrometry were found. The main series could be assigned to the structure featuring a phenyl selenium group at the α-end and a methoxy group at the ω-end, which is consistent with the 1 H NMR result (Figure S8).…”

“…This achievement demonstrates a facile way to introduce functionality into the polymer. 32,52,53 Two series of peaks in matrixassisted laser desorption time-of-flight mass spectrometry were found. The main series could be assigned to the structure featuring a phenyl selenium group at the α-end and a methoxy group at the ω-end, which is consistent with the 1 H NMR result (Figure S8).…”

Recent advances in green cationic polymerization

“…Sadahito Aoshima used a variety of metal oxides as heterogeneous initiators for living cationic polymerization of isobutyl vinyl 76,77 . Jian Zhu, V. Kostjuk, et al have also made many outstanding progress in the field of heterogeneous catalytic cationic polymerization 78–80 …”

“…In 1999, Sawamoto successfully conducted aqueous suspension polymerization of p ‐methoxystyrene using Yb(OTf) 3 as a co‐initiator, which marked a significant breakthrough in cationic polymerization 83 . Subsequently, Sawamoto, 84,85 Ganachaud, 86 and Wu 87 conducted extensive studies on water‐resistant co‐initiators, challenging the conventional notion that “cationic polymerization must be carried out under anhydrous and anaerobic conditions.” This polymerization technique not only holds great potential in the synthesis of well‐defined structure polymers but also revitalizes traditional suspension and emulsion polymerization methods 76–86,88 . Kostjuk 71 has conducted a detailed review on cationic polymerization of vinyl monomers in aqueous media in 2009.…”