A novel reactive phosphonium-containing polyelectrolyte with multiple reactivities: monomer synthesis, RAFT polymerization and post-polymerization modifications

Abstract

A reactive polyelectrolyte can be defined as a kind of functional polymer which possesses not only the basic properties of a polyelectrolyte but also wide post-polymerization modification possibilities, which can be achieved via various reactions.

Phosphine Oxide-Containing Multifunctional Polymer via RAFT Polymerization and Its High-Density Post-Polymerization Modification in Water

“…Three signals appearing at 6.68–6.75, 5.78–5.82, and 2.21–5.24 ppm belonged to the vinyl group, while the signals at 5.37–5.41 ppm were contributed to hydroxyl groups. The 31 P NMR signal of VBzBHPO was quite different from VBzTHPC (26.70 ppm in D 2 O), and only one peak of the signal was located at 42.96 ppm. The 13 C NMR spectrum of the monomer is shown in Figure b, and the signals of the carbon atoms in benzene ring appeared at 126.51–126.54, 130.50–130.55, 132.75–132.67, and 135.65–135.68 ppm.…”

“…An excellent linear agreement between the molecular weight and monomer conversion was found (Figure d). The difference between the calculated ( M n,cal ) and theoretical ( M n,th ) molecular weight was due to the larger hydrodynamic volume of polyVBzPO-2OBn compared with the polystyrene standards . This was mainly caused by the polar PO bond and steric hindrance of benzyl groups.…”

“…The first task of this research was the synthesis of a brand-new phosphine oxide-containing monomer VBzBHPO according to the route described in Scheme . The phosphonium starting feedstock VBzTHPC was rapidly converted to 4-vinylbenzyl-bis-hydroxymethyl phosphine (VBzBHP, a strong reductive intermediate because of the presence of P III ) in NaOH solution, which was in situ oxidized by water to form stable VBzBHPO (P III → P IV ) by releasing an equal amount of H 2 gas. The oxidization reaction mechanism has been well studied by Moiseev and James during the synthesis of tris­(hydroxymethyl)­phosphine oxide from THPC .…”

“…The chain transfer agent (CTA), namely, 2-(butylsulfanylthicarbonothioylsulfanyl)­propanoic acid, was synthesized according to the reported procedure . 4-Vinylbenzyl-trihydroxymethyl phosphonium chloride (VBzTHPC) was synthesized in a laboratory . Styrene was purified by washing successively with 5% NaOH solution, deionized water, and then distilled out under reduced pressure.…”

“…Recently, a PH 3 -derived phosphonium-containing reactive polymer with multiple hydroxymethyl functionalities was designed and synthesized via RAFT polymerization in our group . Owing to its high reactivity, the polyelectrolyte polymer was used as a reactive precursor to prepare diversely functional materials by post-polymerization modification.…”