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http://hdl.handle.net/1942/18129
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DC Field | Value | Language |
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dc.contributor.author | RANIERI, Kayte | - |
dc.contributor.author | Delaittre, Guillaume | - |
dc.contributor.author | Barner-Kowollik, Christopher | - |
dc.contributor.author | JUNKERS, Tanja | - |
dc.date.accessioned | 2015-01-19T12:34:49Z | - |
dc.date.available | 2015-01-19T12:34:49Z | - |
dc.date.issued | 2014 | - |
dc.identifier.citation | MACROMOLECULAR RAPID COMMUNICATIONS, 35 (23), p. 2023-2028 | - |
dc.identifier.issn | 1022-1336 | - |
dc.identifier.uri | http://hdl.handle.net/1942/18129 | - |
dc.description.abstract | The beta-scission rate coefficient of tert-butyl radicals fragmenting off the intermediate resulting from their addition to tert-butyl dithiobenzoate-a reversible addition-fragmentation chain transfer (RAFT) agent-is estimated via the recently introduced electron spin resonance (ESR)-trapping methodology as a function of temperature. The newly introduced ESR-trapping methodology is critically evaluated and found to be reliable. At 20 degrees C, a fragmentation rate coefficient of close to 0.042 s(-1) is observed, whereas the activation parameters for the fragmentation reaction-determined for the first time-read E-A = 82 +/- 13.3 kJ mol(-1) and A = (1.4 +/- 0.25) x 10(13) s(-1). The ESR spin-trapping methodology thus efficiently probes the stability of the RAFT adduct radical under conditions relevant for the pre-equilibrium of the RAFT process. It particularly indicates that stable RAFT adduct radicals are indeed formed in early stages of the RAFT polymerization, at least when dithiobenzoates are employed as controlling agents as stipulated by the so-called slow fragmentation theory. By design of the methodology, the obtained fragmentation rate coefficients represent an upper limit. The ESR spin-trapping methodology is thus seen as a suitable tool for evaluating the fragmentation rate coefficients of a wide range of RAFT adduct radicals. | - |
dc.description.sponsorship | T.J. and K.R. thank the FWO (Fonds Wetenschappelijk Onderzoek) in the framework of the new initiative "Utilization of Nitrones in Polymerizations and Polymer Conjugation." C.B.-K. acknowledges continued funding from the Karlsruhe Institute of Technology (KIT) in the context of the STN Helmholtz program. G.D. thanks the German Federal Ministry of Education and Research (BMBF) for financial support. | - |
dc.language.iso | en | - |
dc.publisher | WILEY-V C H VERLAG GMBH | - |
dc.rights | © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. | - |
dc.subject.other | electron spin resonance; fragmentation rate; kinetics; polymer reactions; reversible addition-fragmentation chain transfer; spin-trapping | - |
dc.subject.other | electron spin resonance; fragmentation rate; kinetics; polymer reactions; reversible addition–fragmentation chain transfer; spin-trapping | - |
dc.title | Direct Access to Dithiobenzoate RAFT Agent Fragmentation Rate Coefficients by ESR Spin-Trapping | - |
dc.type | Journal Contribution | - |
dc.identifier.epage | 2028 | - |
dc.identifier.issue | 23 | - |
dc.identifier.spage | 2023 | - |
dc.identifier.volume | 35 | - |
local.format.pages | 6 | - |
local.bibliographicCitation.jcat | A1 | - |
dc.description.notes | [Ranieri, Kayte; Junkers, Thomas] Hasselt Univ, Inst Mat Res IMO, Polymer React Design Grp, B-3590 Diepenbeek, Belgium. [Delaittre, Guillaume; Barner-Kowollik, Christopher] Karlsruhe Inst Technol, Inst Tech Chem & Polymerchem, D-76128 Karlsruhe, Germany. [Delaittre, Guillaume] Karlsruhe Inst Technol, Inst Toxicol & Genet, D-76344 Karlsruhe, Germany. [Barner-Kowollik, Christopher] Karlsruhe Inst Technol, Inst Biol Grenzflachen, D-76344 Eggenstein Leopoldshafen, Germany. [Junkers, Thomas] IMEC, Div IMOMEC, B-3590 Diepenbeek, Belgium. | - |
local.publisher.place | WEINHEIM | - |
local.type.refereed | Refereed | - |
local.type.specified | Article | - |
dc.identifier.doi | 10.1002/marc.201400518 | - |
dc.identifier.isi | 000345977300007 | - |
item.fullcitation | RANIERI, Kayte; Delaittre, Guillaume; Barner-Kowollik, Christopher & JUNKERS, Tanja (2014) Direct Access to Dithiobenzoate RAFT Agent Fragmentation Rate Coefficients by ESR Spin-Trapping. In: MACROMOLECULAR RAPID COMMUNICATIONS, 35 (23), p. 2023-2028. | - |
item.fulltext | With Fulltext | - |
item.validation | ecoom 2016 | - |
item.contributor | RANIERI, Kayte | - |
item.contributor | Delaittre, Guillaume | - |
item.contributor | Barner-Kowollik, Christopher | - |
item.contributor | JUNKERS, Tanja | - |
item.accessRights | Restricted Access | - |
crisitem.journal.issn | 1022-1336 | - |
crisitem.journal.eissn | 1521-3927 | - |
Appears in Collections: | Research publications |
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ranieri 1.pdf Restricted Access | Published version | 469.57 kB | Adobe PDF | View/Open Request a copy |
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