Analysis of poly(bisphenol A carbonate) by size exclusion chromatography/matrix-assisted laser desorption/ionization. 2. Self-association due to phenol end groups (Articolo in rivista)

Type
Label
  • Analysis of poly(bisphenol A carbonate) by size exclusion chromatography/matrix-assisted laser desorption/ionization. 2. Self-association due to phenol end groups (Articolo in rivista) (literal)
Anno
  • 1999-01-01T00:00:00+01:00 (literal)
Alternative label
  • Concetto Puglisi, Filippo Samperi, Sabrina Carroccio and Giorgio Montaudo (1999)
    Analysis of poly(bisphenol A carbonate) by size exclusion chromatography/matrix-assisted laser desorption/ionization. 2. Self-association due to phenol end groups
    in RCM. Rapid communications in mass spectrometry
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Concetto Puglisi, Filippo Samperi, Sabrina Carroccio and Giorgio Montaudo (literal)
Pagina inizio
  • 2268 (literal)
Pagina fine
  • 2277 (literal)
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  • 13 (literal)
Rivista
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  • 10 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo
  • 22 (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • CNR, Università Catania (literal)
Titolo
  • Analysis of poly(bisphenol A carbonate) by size exclusion chromatography/matrix-assisted laser desorption/ionization. 2. Self-association due to phenol end groups (literal)
Abstract
  • We report here a case of apparent failure of the size exclusion chromatography/matrix-assisted laser desorption/ionization (SEC/MALDI) method to provide polymer fractions with narrow molar mass distribution, showing that intermolecular chain association is responsible for this phenomenon. Poly(bisphenol A carbonate) (PC) chains terminated with hydroxyl groups undergo self-association by hydrogen bonding, providing macromolecular aggregates with higher hydrodynamic volume. These aggregates are eluted through SEC columns at the same volume as higher molar mass chains, which remain non-associated. Thus, self-association affects negatively the SEC fractionation experiments, and even the sharpest SEC fractions contain a heterogeneous mixture of PC chains of different size. When the off-line SEC/MALDI procedure is applied, the SEC fraction is diluted in the matrix which, being a dissociating medium (carboxylic acid) for hydrogen-bonded aggregates, suppresses the chains' self-association. Therefore, the MALDI spectra of these PC fractions indicate a polydisperse character, with irregular bimodal distributions of peaks. As a consequence, in the presence of chain association, the SEC/MALDI method for the calculation of molar masses of polymers cannot be directly applied. In the present case we have found that, under opportune experimental conditions, self-association in polycarbonates can be avoided, so that nearly monodisperse SEC fractions can be obtained and the SEC/MALDI method can be applied. Our results also show that MALDI is a very sensitive technique for the detection of association of polymers in dilute solutions. (literal)
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