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Salvacion P. Cresidio, Fawaz Aldabbagh, W. Ken Busfield, Ian D. Jenkins, San H. Thang, Clovia Zayas-Holdsworth and Per B. Zetterlund Alkoxyamine-mediated “living” radical polymerization: MS investigation of the early stages of styrene polymerization initiated by cumyl-TEISO Journal of Polymer Science Part A: Polymer Chemistry 39

Article first published online: 28 FEB 2001 | DOI: 10.1002/pola.1100

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This typical ion-current spectrum (SIR mode) from the high-performance liquid chromatographic/mass spectrometric analyses of the attempted nitroxide-mediated living polymerization of styrene at 60 °C shows the presence of oligomers 18 after 6 h reaction time. Although the concentration of oligomers steadily increases with reaction time, their distribution stays constant. This conclusively shows that up to eight styrene units can add to the initiating cumyl radicals before nitroxide trapping. Once trapped, the styryl radicals undergo no further addition at this temperature. Normal living polymerization is observed in this system at 110 °C.

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