1999
DOI: 10.1002/(sici)1522-9505(19990201)264:1<73::aid-apmc73>3.3.co;2-a
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Influence of N-oxyls on the free radical autopolymerization of styrene

Abstract: SUMMARY: Through comparative studies on the controlled thermally initiated radical polymerization of styrene in the presence of N-oxyls, the effect of the type of the N-oxyls (2,2,6,6-tetramethylpiperidine-Noxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (OH-TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl (oxo-TEMPO) and 4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl (acetamido-TEMPO)), as well as the concentration of the N-oxyls (3 -20 mmol L -1 ) are discussed. The radical formation proceed… Show more

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Cited by 3 publications
(3 citation statements)
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“…Methacrylate containing random copolymer macroinitiators (MMA/S‐1,2,3, EMA/S‐1,2,3, BMA/S‐1,2,3), synthesized previously using SG1‐free nitroxide and BlocBuilder initiator, were used as macroinitiators to polymerize a fresh batch of styrene at 110 °C. This particular polymerization temperature was selected for the chain extension of styrene to avoid excessive thermal initiation of styrene commonly observed at temperatures above 120 °C 61. This set of chain extensions would demonstrate whether these macroinitiators were significantly “living” enough to polymerize a second batch of a monomer which is fairly easy to control (e.g., styrene).…”
Section: Resultsmentioning
confidence: 99%
“…Methacrylate containing random copolymer macroinitiators (MMA/S‐1,2,3, EMA/S‐1,2,3, BMA/S‐1,2,3), synthesized previously using SG1‐free nitroxide and BlocBuilder initiator, were used as macroinitiators to polymerize a fresh batch of styrene at 110 °C. This particular polymerization temperature was selected for the chain extension of styrene to avoid excessive thermal initiation of styrene commonly observed at temperatures above 120 °C 61. This set of chain extensions would demonstrate whether these macroinitiators were significantly “living” enough to polymerize a second batch of a monomer which is fairly easy to control (e.g., styrene).…”
Section: Resultsmentioning
confidence: 99%
“…This would indicate that TEMPO is playing a role as an initiator to start a propagating polymer chain. Although there are some more supporting results of this mechanism reported,27 the Mayo mechanism is still frequently applied in the styrene thermal self‐initiation in the presence of TEMPO radicals 28–32. TEMPO radicals can abstract the weakly bonded hydrogen atom from a styrene dimer and form a dimer radical and a hydroxylamine 33.…”
Section: Introductionmentioning
confidence: 89%
“…Poly(TBA) macroinitiators, synthesized previously using SG1 free nitroxide and BlocBuilder initiator, were used to polymerize a fresh batch of styrene at 115 °C. This temperature was selected for the chain extension with styrene to avoid significant thermal initiation which has been reported to become evident at temperatures which exceed 120 °C 37–39. This chain extension would demonstrate whether these macroinitiators were significantly “living” enough to polymerize a second batch of monomer and how the nature of the solvent used to make the macroinitiator affected the chain extension.…”
Section: Resultsmentioning
confidence: 99%