Free-Radical Polymerization of Dimethyl Vinylbenzylphosphonate Controlled by Tempo

Abstract

The free radical polymerization of a phosphonated styrene, dimethyl vinylbenzylphosphonate (VBP), in the presence of stable nitroxide 2,2,6,6-tetramethyl-1-piperidinyloxyl radical (TEMPO), initiated by dicumyl peroxide (DCP) at 125 °C, has been studied. The apparent rate of polymerization K p[M•] is eight times higher than that of styrene, but the “living” character of the polymerization could not be verified by SEC. So, a macromolecular initiator PS−TEMPO was used in order to follow the evolution of average number molecular weights by 1H NMR. Under these conditions, the “living” character of the polymerization could be checked and various block copolymers (11000/7500; 11000/11000) were prepared. As for vinylbenzyl chloride and other monomers bearing electroattractive groups, the polymerization was shown to be much faster than that of styrene.

Recent advances in “living”/controlled radical polymerization of phosphorus-containing monomers and their potential applications

“…It was recently shown that radical polymerization controlled by 2,2,6,6-tetramethyl-1-piperidinyloxyl radical (TEMPO) can be applied to produce polystyrene-b-poly (dimethyl vinylbenzylphosphonate) (PS-b-PVBP) block copolymers [26]. Polymerization of a phosphonated styrene VBP initiated by dicumyl peroxide (DCP) at 125 °C in the presence of stable TEMPO has been studied (Scheme 4): the material was further hydrolyzed in order to obtain the amphiphilic property.…”

“…Scheme 4 Homopolymerization of styrene or dimethyl vinylbenzylphosphonate (DVBP) [26]. polymerization of phosphorus-containing monomers.…”

Hybrid polyion complex micelles from poly(vinylphosphonic acid)-based double hydrophilic block copolymers and divalent transition metal ions

“…Reversible deactivation radical polymerization (RDRP) technologies such as nitroxide mediated polymerization [48] and atom transfer radical polymerization [49] allow precisely controlled phosphonic esterfunctional polymers to be synthesized. More recently, reversible addition fragmentation chain transfer polymerization (RAFT) [50] and macromolecular design by interchange of xanthates (MADIX) [50] have become the most versatile strategies for the preparation of phosphonated polymers of controlled molar mass and low dispersity [51e55].…”

Well-defined phosphonate-functional copolymers through RAFT copolymerization of dimethyl-p-vinylbenzylphosphonate

“…Indeed, diisopropyl and diethyl p‐ vinylbenzylphosphonate were polymerized by atom transfer radical polymerization. Aminoxyl‐mediated polymerization of diethyl and dimethyl p ‐vinylbenzylphosphonate were also carried out in a controlled manner in the presence of nitroxyl stable radicals.…”