Mechanism of Living Free Radical Polymerizations with Narrow Polydispersity: Electron Spin Resonance and Kinetic Studies

N-tert-Butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide as counter radical in the controlled free radical polymerization of styrene: kinetic aspects

“…They also proposed approximate values of k d = 5.2 6 10 -4 N s -1 (E a = 82 kJ N mol -1 ) and k c = 1.5 6 10 7 M -1 N s -1 (E a = 4 kJ N mol -1 ) at 125 8C. This activation energy for k d was considerably less than the value of 130 kJ/mol previously observed for the release of Tempo from the styrene 1-mer, i. e. 2-benzoyloxy-1-phenylethyl adduct with Tempo (BPO-styrene-Tempo) 22) . Fukuda et al 23) have reported a value of K = 2.1 610…”

Controlled Photoradical Polymerization Mediated by 2,2,6,6-Tetramethylpiperidine-1-Oxyl

“…monomers [17][18][19][20][21]; however, the scope of the applicable monomers has been extended by improving the structure of the nitroxide [22][23][24] using alkoxyamine adducts [25,26] and utilizing additives [27,28]. The NMP still has advantages in using nonmetallic catalysts, thus creating a great variety of architectures through designing the nitroxide catalysts, and producing uncolored or less-colored polymers.…”

“…The NMP still has advantages in using nonmetallic catalysts, thus creating a great variety of architectures through designing the nitroxide catalysts, and producing uncolored or less-colored polymers. While the nitroxides with the 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxyl skeleton provide highly controlled molecular weight distributions [25], TEMPO also has been often used as the mediator for the NMP, because TEMPO is easily available with a low cost and can be converted into a variety of derivatives that have functional groups [29,30] and are supported on polymers [31][32][33][34][35]. Recent findings that the TEMPO-mediated NMP is induced by photo irradiation involve the significance of the TEMPO mediator [36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51].…”

Effects of Initiator Homolysis Rate Constant on Kinetics and Chain Length Distribution in Living Free-Radical Polymerization

“…Pv can generally be written as the ratio of the reaction rate, R", of a given reaction to the sum of all above reaction channels, (2) with M the total number of reaction channels. The time interval between two successive reactions, r, is a stochastic variable determined by,…”