Transesterification in the solid state of cyclic and linear poly(l-lactide)s
- Poly(l-lactide)s are synthesized and annealed at 120 °C and changes of the molecular weight distribution (MWD) are monitored by matrix-assited laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. For example, benzyl alcohol+SnOct2 causes equilibration of odd- and even-numbered chains and the final goal of the transesterification is the most probable distribution. The underlying intermolecular transesterification is even observed at 100 and 80 °C in the solid state. However, cyclic tin mercaptide catalysts transform the initial most probable distribution into a MWD with maxima, which display a conspicuous fine structure due to a preferential crystallization of certain ring sizes. The optimum ring sizes for the crystallization are provided by ring-ring equilibration. The gradual formation of a special morphology shifts the melting temperature to values up to 187 °C. Annealing of commercial poly(l-lactide) with a cyclic tin catalyst also yields a distribution of massPoly(l-lactide)s are synthesized and annealed at 120 °C and changes of the molecular weight distribution (MWD) are monitored by matrix-assited laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. For example, benzyl alcohol+SnOct2 causes equilibration of odd- and even-numbered chains and the final goal of the transesterification is the most probable distribution. The underlying intermolecular transesterification is even observed at 100 and 80 °C in the solid state. However, cyclic tin mercaptide catalysts transform the initial most probable distribution into a MWD with maxima, which display a conspicuous fine structure due to a preferential crystallization of certain ring sizes. The optimum ring sizes for the crystallization are provided by ring-ring equilibration. The gradual formation of a special morphology shifts the melting temperature to values up to 187 °C. Annealing of commercial poly(l-lactide) with a cyclic tin catalyst also yields a distribution of mass peaks with a maximum showing the characteristic fine structure.…
Autor*innen: | Steffen WeidnerORCiD, Hans R. Kricheldorf |
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Dokumenttyp: | Zeitschriftenartikel |
Veröffentlichungsform: | Verlagsliteratur |
Sprache: | Englisch |
Titel des übergeordneten Werkes (Englisch): | Macromolecular Chemistry and Physics |
Jahr der Erstveröffentlichung: | 2017 |
Verlag: | Wiley-VCH |
Jahrgang/Band: | 218 |
Ausgabe/Heft: | 14 |
Erste Seite: | 1700114-1 |
Letzte Seite: | 1700114-10 |
DDC-Klassifikation: | Technik, Medizin, angewandte Wissenschaften / Ingenieurwissenschaften / Ingenieurwissenschaften und zugeordnete Tätigkeiten |
Freie Schlagwörter: | Equilibration; Mass spectrometry; Polylactides; Ring-opening polymerization; Transesterification |
DOI: | 10.1002/macp.201700114 |
ISSN: | 1521-3935 |
ISSN: | 1022-1352 |
Verfügbarkeit des Dokuments: | Datei im Netzwerk der BAM verfügbar ("Closed Access") |
Datum der Freischaltung: | 29.08.2017 |
Referierte Publikation: | Nein |