Rate Enhancement of Living Free-Radical Polymerizations by an Organic Acid Salt

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

“…[153][154][155][156][157] The organic acid salt 2-fluoro-1-methylpyridinium p-toluenesulfonate has been used to trap the mediating nitroxide as its oxammonium salt 47 and hydroxylamine anion salt 48 in much the same way as a Brønsted acid. 158,159 The addition of acetic anhydride has also been shown to increase TEMPO-mediated radical polymerization rates. 160 To account for this observation, it has been proposed that the N-alkoxyamine nitrogen becomes acylated.…”

Effect of initiator type and concentration on polymerization rate and molecular weight in the bimolecular nitroxide‐mediated radical polymerization of styrene

“…Another technique that has been used to increase the polymerization rate in NMRP is the use of additives, such as camphorsulfonic acid, 6−9 2-fluoro-1-methylpyridinium p-toluenesulfonate, 10 acetic anhydride, 11−14 ascorbic acid 15−17 and dodecylbenzenesulfonic acid. 18 However, the use of additives in controlled polymerization makes the process more expensive and/or complicates things further due to possible side reactions.…”

Synthesis of Model A5B1 Heteroarm Star Copolymers Using Living Radical Polymerization Mediated by 2,2,6,6-Tetramethylpiperidine-1-oxyl

“…This implies that scission occurs more easily when the linkage is between CPT and the growing radical than when it is with MPT and OPT. This may be accounted for by the fact that triphosphazene pentachloride of CPT acts as a Lewis acid for the growing chain end to advance polymerization, when it is taken into consideration that an acid 11 and organic acid salt 12 forwards TEMPO-mediated polymerization. Polymer- ization by OPT is faster than that by MPT.…”