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Spirocyclic bisphenoxides of Ge, Zr, and Sn as catalysts for ring-expansion polymerizations of L- and meso-lactide

  • Spirocyclic phenoxides of germanium, zirconium, and tin were prepared from 2,20-dihydroxybiphenyl and 2,20-dihydroxy-1,10-binaphthyl. Ring-expansion polymerizations of L-lactide are mainly studied at 160 or 180 °C. The reactivity of the catalysts increases in the order: Zr < Ge < Sn. Regardless of catalyst, the weight-average molecular weights (Mw) never exceed 50,000 g mol−1. The resulting poly(L-lactide)s are optically pure and have a cyclic architecture. Decreasing temperature and time favor Formation of even-numbered cycles, and at 102 ° cyclics, almost free of odd-numbered rings are obtained. Analogous polymerizations of meso-lactide give similar results >120 °C, but different results at 100 or 80 °C. Surprisingly, bell-shaped narrow molecular weight distributions are obtained <140 °C, resembling the pattern of living polymerizations found for alcohol-initiated polymerizations. An unusual transesterification mechanism yielding narrow distributions of odd-numbered cycles isSpirocyclic phenoxides of germanium, zirconium, and tin were prepared from 2,20-dihydroxybiphenyl and 2,20-dihydroxy-1,10-binaphthyl. Ring-expansion polymerizations of L-lactide are mainly studied at 160 or 180 °C. The reactivity of the catalysts increases in the order: Zr < Ge < Sn. Regardless of catalyst, the weight-average molecular weights (Mw) never exceed 50,000 g mol−1. The resulting poly(L-lactide)s are optically pure and have a cyclic architecture. Decreasing temperature and time favor Formation of even-numbered cycles, and at 102 ° cyclics, almost free of odd-numbered rings are obtained. Analogous polymerizations of meso-lactide give similar results >120 °C, but different results at 100 or 80 °C. Surprisingly, bell-shaped narrow molecular weight distributions are obtained <140 °C, resembling the pattern of living polymerizations found for alcohol-initiated polymerizations. An unusual transesterification mechanism yielding narrow distributions of odd-numbered cycles is discovered too.zeige mehrzeige weniger

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Metadaten
Autoren/innen:Steffen Weidner, H. R. Kricheldorf
Dokumenttyp:Zeitschriftenartikel
Veröffentlichungsform:Verlagsliteratur
Sprache:Englisch
Titel des übergeordneten Werkes (Englisch):Journal of Polymer Science A: Polymer Chemistry
Jahr der Erstveröffentlichung:2018
Organisationseinheit der BAM:1 Analytische Chemie; Referenzmaterialien
1 Analytische Chemie; Referenzmaterialien / 1.3 Strukturanalytik
Verlag:Wiley Periodicals
Jahrgang/Band:56
Ausgabe/Heft:24
Erste Seite:2730
Letzte Seite:2738
DDC-Klassifikation:Technik, Medizin, angewandte Wissenschaften / Ingenieurwissenschaften / Ingenieurwissenschaften und zugeordnete Tätigkeiten
Freie Schlagwörter:Cyclization; MALDI-TOF MS; Polylactides; Ring-opening polymerization; Spirocyclic
Themenfelder/Aktivitätsfelder der BAM:Material
Material / Materialien und Stoffe
DOI:https://doi.org/10.1002/pola.29259
URL:http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=Alerting&SrcApp=Alerting&DestApp=CCC&DestLinkType=FullRecord&KeyUT=CCC:000450460600004
ISSN:0887-624X
ISSN:1099-0518
Verfügbarkeit des Dokuments:Datei im Netzwerk der BAM verfügbar ("Closed Access")
Datum der Freischaltung:07.11.2018
Referierte Publikation:Ja
Datum der Eintragung als referierte Publikation:30.11.2018