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- W2089020346 abstract "Abstract Styrene radical polymerizations mediated by the imidazolidinone nitroxides 2,5‐bis(spirocyclohexyl)‐3‐methylimidazolidin‐4‐one‐1‐oxyl (NO88Me) and 2,5‐bis(spirocyclohexyl)‐3‐benzylimidazolidin‐4‐one‐1‐oxyl (NO88Bn) were investigated. Polymeric alkoxyamine (PS‐NO88Bn)‐initiated systems exhibited controlled/living characteristics at 100–120 °C but not at 80 °C. All systems exhibited rates of polymerization similar to those of thermal polymerization, with the exception of the PS‐NO88Bn system at 80 °C, which polymerized twice as quickly. The dissociation rate constants ( k d ) for the PS‐NO88Me and PS‐NO88Bn coupling products were determined by electron spin resonance at 50–100 °C. The equilibrium constants were estimated to be 9.01 × 10 −11 and 6.47 × 10 −11 mol L −1 at 120 °C for NO88Me and NO88Bn, respectively, resulting in the combination rate constants ( k c ) 2.77 × 10 6 (NO88Me) and 2.07 × 10 6 L mol −1 s −1 (NO88Bn). The similar polymerization results and kinetic parameters for NO88Me and NO88Bn indicated the absence of any 3‐N‐transannular effect by the benzyl substituent relative to the methyl substituent. The values of k d and k c were 4–8 and 25–33 times lower, respectively, than the reported values for PS‐TEMPO at 120 °C, indicating that the 2,5‐spirodicyclohexyl rings have a more profound effect on the combination reaction rather than the dissociation reaction. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 327–334, 2003" @default.
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- W2089020346 date "2002-12-09" @default.
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- W2089020346 title "Mechanism and kinetics of the imidazolidinone nitroxide-mediated free-radical polymerization of styrene" @default.
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- W2089020346 doi "https://doi.org/10.1002/pola.10582" @default.
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