Cited by 21Advanced Polymer Synthesis and CharacterizationOrganic and Inorganic Chemical ReactionsOrganometallic Complex Synthesis and Catalysis

Zur Aufklärung des Initiierungsschrittes der kationischen Polymerisation von Tetrahydrofuran mit PF5

Hoene, Richard, Reichert, Karl‐Heinz W.·1976·Die Makromolekulare Chemie

Abstract

Abstract Es wurde der Ablauf der kationischen Initiierung der ringöffnenden Polymerisation von Tetrahydrofuran (THF) mit Phosphorpentafluorid (2) im Bereich oberhalb der Ceiling‐Temperatur untersucht. Bei der Reaktion von 2 mit THF bzw. mit 2‐Methyltetrahydrofuran (MTHF) wurde qualitativ und quantitativ die Bildung von Hexafluorophosphat aus dem zunächst spontan entstehenden Donor‐Acceptor‐Komplex zwischen Ringäther und 2 nachgewiesen, die dem Induktionsschritt der THF‐Polymerisation entspricht. Als Reaktionsprodukt von 2 mit THF wurde ein Dikation, 1,1′‐Tetramethylen‐bis(tetrahydrofuranylium)‐bis(hexafluorophosphat), (6), isoliert, dessen Struktur durch Gruppenanalyse, chemische Reaktionen, 1H‐NMR und 31P‐NMR sichergestellt wurde. Dabei entstehendes POF3 wurde qualitativ nachgewiesen. Postulierte Reaktionszwischenstufen blieben unter der analytischen Nachweisschwelle. Aufgrund der Ergebnisse werden bifunktionelle Oxoniumionen als aktive Spezies der Polymerisation von THF mit 2 diskutiert, die ein bifunktionelles Kettenwachstum auslösen.

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Crossref · 10.1002/macp.1976.021771208

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  • Detailed studies using PF5 for polymerization of THF have proposed a mechanism supported by 19F and 31P NMR spectroscopy.

    “Detailed studies have also been made using PF5, e.g., for the polymerization of THF for which a mechanism supported by 19 F and 31 P NMR spectroscopy has been proposed (see Figure 21) [61].”

    From Ring-Opening Polymerization—An Introductory Review (2013) · cites this paper as [61]

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Authors
Hoene, R., & Reichert, K. W.
Affiliations
University of Stuttgart (DE)
Venue
Die Makromolekulare Chemie
Publisher
Wiley
Published
1976-12
Volume
177
Issue
12
Pages
3545-3570
ISSN
0025-116X (ISSN-L)
OpenAlex
W2030466555
Cited by
21
References
36
Citations by year
2025: 1 · 2022: 1 · 2017: 1 · 2013: 1 · 2012: 2
FWCI
1.16
Type
journal article
Language
en
Open access
closed
Locations
Die Makromolekulare Chemie (publishedVersion)
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
  • Physical Sciences › Chemistry › Spectroscopy › Organic and Inorganic Chemical Reactions
  • Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
Keywords
tetrahydrofuran, cationic polymerization, phosphorus pentafluoride, initiation mechanism, ring-opening polymerization, hexafluorophosphate, charge-transfer complexes, 2-methyltetrahydrofuran, oxonium ions, ceiling temperature

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