TY - JOUR
T1 - The use of spin traps for the kinetic investigation of elementary events of pseudoliving radical reversible addition-fragmentation chain-transfer polymerization
AU - Golubev, V. B.
AU - Filippov, A. N.
AU - Chernikova, E. V.
AU - Coote, M. L.
AU - Lin, C. Y.
AU - Gryn'ova, G.
PY - 2011/9/6
Y1 - 2011/9/6
N2 - The spin-trapping technique is used for the first time to study the kinetics and mechanism of addition and fragmentation elementary events in reversible addition-fragmentation chain-transfer pseudoliving radical polymerization. As shown by the example of the spin-trap-reversible addition-fragmentation chaintransfer agent model system, the constants of addition (substitution) of the model tert-butyl radical to polymeric reversible addition-fragmentation chain-transfer agents (poly(styrene dithiobenzoate), poly(n-butyl acrylate) dithiobenzoate, etc.) are one to two orders of magnitude higher than the constants of addition reactions involving low-molecular-mass reversible addition-fragmentation chain-transfer agents (tert-butyl dithiobenzoate, benzyl dithiobenzoate, di-tert-butyl trithiocarbonate, and dibenzyl trithiocarbonate). This circumstance makes it possible to significantly widen the synthetic possibilities of reversible addition-fragmentation chain-transfer polymerization. Rate constants of the fragmentation reaction for a number of intermediates are estimated, and the relationship between their structure and stability is ascertained. For the model reaction of the interaction (addition and fragmentation) of the tert-butyl radical with low-molecularmass reversible addition-fragmentation chain-transfer agents, equilibrium constants are calculated via the methods of computational chemistry.
AB - The spin-trapping technique is used for the first time to study the kinetics and mechanism of addition and fragmentation elementary events in reversible addition-fragmentation chain-transfer pseudoliving radical polymerization. As shown by the example of the spin-trap-reversible addition-fragmentation chaintransfer agent model system, the constants of addition (substitution) of the model tert-butyl radical to polymeric reversible addition-fragmentation chain-transfer agents (poly(styrene dithiobenzoate), poly(n-butyl acrylate) dithiobenzoate, etc.) are one to two orders of magnitude higher than the constants of addition reactions involving low-molecular-mass reversible addition-fragmentation chain-transfer agents (tert-butyl dithiobenzoate, benzyl dithiobenzoate, di-tert-butyl trithiocarbonate, and dibenzyl trithiocarbonate). This circumstance makes it possible to significantly widen the synthetic possibilities of reversible addition-fragmentation chain-transfer polymerization. Rate constants of the fragmentation reaction for a number of intermediates are estimated, and the relationship between their structure and stability is ascertained. For the model reaction of the interaction (addition and fragmentation) of the tert-butyl radical with low-molecularmass reversible addition-fragmentation chain-transfer agents, equilibrium constants are calculated via the methods of computational chemistry.
UR - http://www.scopus.com/inward/record.url?scp=84862911037&partnerID=8YFLogxK
U2 - 10.1134/S1811238211040023
DO - 10.1134/S1811238211040023
M3 - Article
AN - SCOPUS:84862911037
SN - 1811-2382
VL - 53
SP - 14
EP - 26
JO - Polymer Science - Series C
JF - Polymer Science - Series C
IS - 1
M1 - 14
ER -