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Titolo:
Modeling termination kinetics of non-stationary free-radical polymerizations
Autore:
Buback, M; Barner-Kowollik, C; Egorov, M; Kaminsky, V;
Indirizzi:
LY Karpov Phys Chem Res Inst, Moscow 103064, Russia LY Karpov Phys Chem Res Inst Moscow Russia 103064 Moscow 103064, Russia Univ Gottingen, Inst Chem Phys, D-37077 Gottingen, Germany Univ GottingenGottingen Germany D-37077 hys, D-37077 Gottingen, Germany
Titolo Testata:
MACROMOLECULAR THEORY AND SIMULATIONS
fascicolo: 4, volume: 10, anno: 2001,
pagine: 209 - 218
SICI:
1022-1344(20010516)10:4<209:MTKONF>2.0.ZU;2-4
Fonte:
ISI
Lingua:
ENG
Soggetto:
LENGTH DEPENDENT TERMINATION; CONTROLLED VINYL POLYMERIZATION; DIFFUSION-CONTROLLED PROCESSES; PULSED-LASER POLYMERIZATION; RATE COEFFICIENT; METHYL-METHACRYLATE; MOLECULAR-WEIGHT; RATE-CONSTANT; PROPAGATION; SYSTEMS;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
30
Recensione:
Indirizzi per estratti:
Indirizzo: Buback, M LY Karpov Phys Chem Res Inst, Ul Vorontsovo Pole 10, Moscow 103064, Russia LY Karpov Phys Chem Res Inst Ul Vorontsovo Pole 10 Moscow Russia 103064
Citazione:
M. Buback et al., "Modeling termination kinetics of non-stationary free-radical polymerizations", MACROMOL TH, 10(4), 2001, pp. 209-218

Abstract

Pulsed-laser induced polymerization is modeled via an approach presented in a previous paper.([1]) An equation for the time dependence of free-radical concentration is derived. It is shown that the termination rate coefficient may vary significantly as a function of time after applying the laser pulse despite of the fact that the change in monomer concentration during oneexperiment is negligible. For the limiting case of t >> c(-1) (k(p)M)(-1),where c is it dimensionless chain-transfer constant, k(p) the propagation rate coefficient and M the monomer concentration an analytical an analytical expression for k(t) is derived. It is also shown that time-resolved single pulse-laser polymerization (SP-PLP) experiments can yield the parameters that allow the modeling of k(t) in quasi-stationary polymerization. The influence of inhibitors is also considered. The conditions are analyzed under which M(t) curves recorded at different extents of laser-induced photo-initiator decomposition intersect. It is shown that such type of behavior is associated with a chain-length dependence of k(t).

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Documento generato il 05/04/20 alle ore 12:13:26