Polymerization of free secondary amine bearing monomers by RAFT polymerization and other controlled radical techniques

Abstract

This work describes the polymerization of the free secondary amine bearing monomer 2,2,6,6‐tetramethylpiperidin‐4‐yl methacrylate (TMPMA) by means of different controlled radical polymerization techniques (ATRP, RAFT, NMP). In particular, reversible addition‐fragmentation chain transfer (RAFT) polymerization enabled a good control at high conversions and a polydispersity index below 1.3, thereby enabling the preparation of well‐defined polymers. Remarkably, the polymerization of the secondary amine bearing methacrylate monomer was not hindered by the presence of the free amine that commonly induces degradation of the RAFT reagent. Subsequent oxidation of the polymer yielded the polyradical poly(2,2,6,6‐tetramethylpiperidinyloxy‐4‐yl methacrylate), which represents a valuable material used in catalysis as well as for modern batteries. The obtained polymers having a molar mass (Mn) of 10,000–20,000 g/mol were used to fabricate well‐defined, radical‐bearing polymer films by inkjet‐ printing. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Living Radical Polymerization by the RAFT Process – A Third Update

“…It has been reported that the extent of branching is higher 289 [186,187,229,577] 290 [175,203,305] 291 [211] 295 [308] 301 [165] 306 CSSQMA [389] 302 [164] 303 [209] 304 [305] 307 [578,579] 308 [579] 305 [212] 297 [188] 298 [201] 299 [201] 300 [387] 292 [189] 293 [173] 294 [210] Glycerol monomethacrylate Solketal methacrylate 296 [197,390] for conventional radical polymerization than for RDRP (ATRP, RAFT, and NMP). [443] A qualitative explanation was proposed in terms of the differences in the concentrations of short-chain radicals between RDRP and conventional radical polymerization.…”

“…[162] RAFT polymerization is not usually compatible with unprotected primary or secondary amines. Janoschka et al [209] have reported that RAFT polymerization can be successfully carried out in the presence of an unprotected hindered amine (2,2,6,6-tertramethylpiperidene) functionality in the methacrylate 194. However, the polymerization had to be conducted in aqueous ethanol as solvent (polymerization was not successful in toluene) and with a higher than usual concentration of initiator.…”

Polymers with n-type nitroxide side groups: Synthesis and electrochemical characterization

“…Typically, nitroxides are often embedded in rings, like the six-membered ring of the TEMPO-radical [8][9][10][11][12] or the five-membered ring in the PROXYL-radical [14]. These radicals are often used in organic radical batteries [2,3,5,6,[8][9][10][11][12]15,16] and organic memory devices [17] because of their reversible redox-chemistry.…”

“…These radicals are often used in organic radical batteries [2,3,5,6,[8][9][10][11][12]15,16] and organic memory devices [17] because of their reversible redox-chemistry.…”

“…Today there are hundreds of stable nitroxide-radicals known and one of the most commonly used nitroxide is the 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) radical [1][2][3][8][9][10][11][12]. Nitroxide-radicals are usually stable against water and air.…”