An ESR approach to the estimation of the rate constants of the addition and fragmentation processes involved in the RAFT polymerization of styrene (Articolo in rivista)

Type

• Prodotto della ricerca (Classe)
• Articolo in rivista (Classe)

Label

• An ESR approach to the estimation of the rate constants of the addition and fragmentation processes involved in the RAFT polymerization of styrene (Articolo in rivista) (literal)

Anno

• 2006-01-01T00:00:00+01:00 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi

• 10.1002/hlca.200690200 (literal)

Alternative label

• A. Alberti, M. Benaglia, H. Fischer, M Guerra, M. Laus, D, Macciantelli, A. Postma, K. Sparnacci (2006)
  An ESR approach to the estimation of the rate constants of the addition and fragmentation processes involved in the RAFT polymerization of styrene
  in Helvetica chimica acta
  (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori

• A. Alberti, M. Benaglia, H. Fischer, M Guerra, M. Laus, D, Macciantelli, A. Postma, K. Sparnacci (literal)

Pagina inizio

• 2103 (literal)

Pagina fine

• 2118 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume

• 89 (literal)

Rivista

• Helvetica chimica acta (Rivista)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo

• 10 (literal)

Note

• ISI Web of Science (WOS) (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni

• CNR, ISOF, Area Ric Bologna, I-40129 Bologna, Italy; Univ Zurich, Inst Chem Phys, CH-8057 Zurich, Switzerland; INSTM, Dipartimento Sci & Tecnol Avanzate, UdR Alessqandria, I-15100 Alessandria, Italy; CSIRO, Mol Sci, CRC Polymer, Clayton, Vic 3169, Australia (literal)

Titolo

• An ESR approach to the estimation of the rate constants of the addition and fragmentation processes involved in the RAFT polymerization of styrene (literal)

Abstract

• The reversible-addition-fragmentation chain transfer (RAFT) controlled radical polymerization of such vinylic monomers as styrene (=ethenylbenzene) has gained increasing popularity in current years. While there is a general agreement on the mechanism of RAFT polymerization, there is an ongoing debate about the values of the rate constants of its key steps, i.e., the addition of the propagating radicals to the mediator and the fragmentation of the resulting spin adducts. By carrying out an ESR spectroscopic investigation of the AIBN-initiated polymerization of styrene (AIBN=2,2'-azobis[2-methylpropanenitrile]), mediated by benzyl (diethoxyphosphoryl)dithioformate (5) as RAFT agent, we were able to detect and characterize four different radical species involved in the process. By reproducing their concentration-time profiles through a kinetic model, the addition and fragmentation rate constants at 90 of the propagating radicals to and from the mediator were estimated to be ca. 10(7) M(-1)s(-1) and ca. 10(3) s(-1), respectively. The validity of the kinetic model was supported by hybrid meta DFT calculations with the BB1K functional that predicted addition- and fragmentation-rate-constant values in good agreement with those estimated from the ESR experiments. (literal)

Prodotto di

• Institute for organic syntheses and photoreactivity (ISOF) (Istituto)
• Processi di polimerizzazione radicalica: polimerizzazione RAFT, applicazioni delle radiazioni ad alta energia e della spettroscopia ESR (PM.P02.015.001) (Modulo)

Autore CNR

• ANGELO ALBERTI (Persona)
• MAURIZIO GUERRA (Persona)
• DANTE MACCIANTELLI (Unità di personale interno)
• MASSIMO BENAGLIA (Persona)

Incoming links:

Prodotto

• Institute for organic syntheses and photoreactivity (ISOF) (Istituto)
• Processi di polimerizzazione radicalica: polimerizzazione RAFT, applicazioni delle radiazioni ad alta energia e della spettroscopia ESR (PM.P02.015.001) (Modulo)

Autore CNR di

• MAURIZIO GUERRA (Persona)
• ANGELO ALBERTI (Persona)
• DANTE MACCIANTELLI (Unità di personale interno)
• MASSIMO BENAGLIA (Persona)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#rivistaDi

• Helvetica chimica acta (Rivista)