Zur Aufklärung des Initiierungsschrittes der kationischen Polymerisation von Tetrahydrofuran mit PF5
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.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
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]
Cites
METHODEN DER ORGANISCHEN CHEMIE
(1966) · Elsevier eBooks · doi:10.1016/b978-0-08-012210-6.50116-2 · Cited by 496 · see citing works
Organic chemistry of synthetic high polymers
Perkins, M. J. (1968) · Journal of the Franklin Institute · doi:10.1016/0016-0032(68)90099-9 · Cited by 355 · see citing works
Die Polymerisation des Tetrahydrofurans
Meerwein, H. F., Delfs, D., & Morschel, H. (1960) · Angewandte Chemie · doi:10.1002/ange.19600722402 · Cited by 210 · see citing works
Phosphorus-31 Nuclear Magnetic Resonance Spectra of Phosphorus Compounds.
Moedritzer, K., Maier, L., & Groenweghe, L. C. D. (1962) · Journal of Chemical & Engineering Data · doi:10.1021/je60013a043 · Cited by 132 · see citing works
Dreyfuss, P., & Dreyfuss, M. P. (1967) · Advances in polymer science · doi:10.1007/bfb0051094 · Cited by 131 · see citing works
The Infrared Spectra of PF3, POF3, and PF5
Gutowsky, H. S., & Liehr, A. D. (1952) · The Journal of Chemical Physics · doi:10.1063/1.1700242 · Cited by 79 · see citing works
Geilmann, W., & Voigt, A. (1930) · Zeitschrift für anorganische und allgemeine Chemie · doi:10.1002/zaac.19301930126 · Cited by 73 · see citing works
31P and 19F Nuclear Magnetic Resonance Studies of Phosphorus-Fluorine Compounds
Reddy, G. S., & Schmutzler, R. (1970) · Zeitschrift für Naturforschung B · doi:10.1515/znb-1970-1101 · Cited by 68 · see citing works
Chemistry of phosphorus fluorides
MUETTERTIES, E. L., Bither, T. A., Farlow, M. W., & Coffman, D. D. (1960) · Journal of Inorganic and Nuclear Chemistry · doi:10.1016/0022-1902(60)80086-3 · Cited by 66 · see citing works
Brown, H. C., & Adams, R. M. (1942) · Journal of the American Chemical Society · doi:10.1021/ja01263a009 · Cited by 62 · see citing works
Phosphorus-31 nuclear magnetic resonance studies of phosphorus—fluorine compounds
Nixon, J. F., & Schmutzler, R. (1964) · Spectrochimica Acta · doi:10.1016/0371-1951(64)80187-9 · Cited by 59 · see citing works
Jaacks, V., & Mathes, N. (1970) · Die Makromolekulare Chemie · doi:10.1002/macp.1970.021310123 · Cited by 50 · see citing works
Polymerization of tetrahydrofuran
Burrows, R. C., & Crowe, B. F. (1962) · Journal of Applied Polymer Science · doi:10.1002/app.1962.070062212 · Cited by 38 · see citing works
Mathes, N., & Jaacks, V. (1971) · Die Makromolekulare Chemie · doi:10.1002/macp.1971.021420118 · Cited by 34 · see citing works
Reed, D., Critchfield, F. E., & Elder, D. K. (1963) · Analytical Chemistry · doi:10.1021/ac60197a009 · Cited by 34 · see citing works
Nuclear Magnetic Resonance Studies on the Polymerization of Cyclic Ethers
Pruckmayr, G., & Wu, T. K. (1973) · Macromolecules · doi:10.1021/ma60031a005 · Cited by 32 · see citing works
Yamashita, Y., Kozawa, S., Hirota, M., Chiba, K., Matsui, H., Hirao, A., Kodama, M., & Ito, K. (1971) · Die Makromolekulare Chemie · doi:10.1002/macp.1971.021420115 · Cited by 29 · see citing works
Polymerisation of tetrahydrofuran (part II)
Sims, D. (1966) · Die Makromolekulare Chemie · doi:10.1002/macp.1966.020980123 · Cited by 26 · see citing works
Jaacks, V., Eisenbach, C. D., & Kern, W. (1972) · Die Makromolekulare Chemie · doi:10.1002/macp.1972.021610109 · Cited by 25 · see citing works
Über ein Salz der Phosphor‐hexafluorwasserstoffsäure, HPF
Lange, W. (1928) · Berichte der deutschen chemischen Gesellschaft (A and B Series) · doi:10.1002/cber.19280610429 · Cited by 23 · see citing works
Jaacks, V., & Franzmann, G. (1971) · Die Makromolekulare Chemie · doi:10.1002/macp.1971.021430127 · Cited by 22 · see citing works
The Thermal Rearrangement of Phosphorus Pentafluoride Adducts of Dimethyl Ether and Dimethyl Sulfide
Goodrich, R. A., & Treichel, P. M. (1966) · Journal of the American Chemical Society · doi:10.1021/ja00967a008 · Cited by 22 · see citing works
Mathes, N., & Jaacks, V. (1970) · Die Makromolekulare Chemie · doi:10.1002/macp.1970.021350106 · Cited by 20 · see citing works
Über ein neues Verfahren zur Bestimmung der Perchlorsäure
Loebich, O. (1926) · Analytical and Bioanalytical Chemistry · doi:10.1007/bf02423283 · Cited by 18 · see citing works
Über Zwitterionen, die nur aus Kohlenstoff, Wasserstoff und Stickstoff aufgebaut sind
Kuhn, R. J., & Kainer, H. (1953) · Angewandte Chemie · doi:10.1002/ange.19530651703 · Cited by 17 · see citing works
Block Copolymerization. II. Polymerization of Tetrahydrofuran by Bifunctional Cationic Initiator
Yamashita, Y., Hirota, M., Matsui, H., Hirao, A., & Nobutoki, K. (1971) · Polymer Journal · doi:10.1295/polymj.2.43 · Cited by 17 · see citing works
Harris, J. J., & Rudner, B. (1968) · The Journal of Organic Chemistry · doi:10.1021/jo01268a020 · Cited by 16 · see citing works
Luydvig, Y. B., Rozenberg, B. A., Zvereva, T. M., Gantmakher, A. R., & Medvedev, S. S. (1965) · Polymer Science U.S.S.R. · doi:10.1016/0032-3950(65)90053-5 · Cited by 16 · see citing works
Andruzzi, F., Pescia, A., & Ceccarelli, G. (1975) · Die Makromolekulare Chemie · doi:10.1002/macp.1975.021760412 · Cited by 15 · see citing works
Über Verbindungen des Typs “P(OR)2F3”
Kolditz, L., Lehmann, K., Wieker, W., & GRIMMER, A. ‐. (1968) · Zeitschrift für anorganische und allgemeine Chemie · doi:10.1002/zaac.19683600505 · Cited by 15 · see citing works
Block copolymerization I, ion coupling of polytetrahydrofuran dication and polystyrene dianion
Yamashita, Y., Hirota, M., Nobutoki, K., Nakamura, Y., Hirao, A., Kozawa, S., Chiba, K., Matsui, H., Hattori, G., & Okada, M. (1970) · Journal of Polymer Science Part B Polymer Letters · doi:10.1002/pol.1970.110080703 · Cited by 13 · see citing works
Perfluoroalkoxy-substituted fluorophosphoranes
Young, D., & Fox, W. B. (1971) · Inorganic and Nuclear Chemistry Letters · doi:10.1016/0020-1650(71)80024-7 · Cited by 11 · see citing works
CYCLIC OXYGEN COMPOUNDS OTHER THAN EPOXIDES
Rose, J. B. (1963) · Elsevier eBooks · doi:10.1016/b978-1-4832-0096-5.50016-9 · Cited by 6 · see citing works
Hoene, R., & Reichert, K. W. (1973) · Die Makromolekulare Chemie · doi:10.1002/macp.1973.021680114 · Cited by 3 · see citing works
Self-citationÖchsner, W., & Reichert, K. (1971) · Die Makromolekulare Chemie · doi:10.1002/macp.1971.021500101 · Cited by 3 · see citing works
Self-citationNotes- Reaction of Phenols with Phosphorus Pentachloride
Pinkus, A. G., & Waldrep, P. G. (1959) · The Journal of Organic Chemistry · doi:10.1021/jo01089a618 · Cited by 2 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Ring-Opening Polymerization—An Introductory Review
Nuyken, O., & Pask, S. (2013) · Polymers · doi:10.3390/polym5020361 · Cited by 456 · see citing works
Laruelle, S., Pilard, S., Guénot, P., Grugeon, S., & Tarascon, J. ‐. (2004) · Journal of The Electrochemical Society · doi:10.1149/1.1760992 · Cited by 111 · see citing works
Olah, G. A., Farooq, O., Li, C. X., Farnia, M. F., & Aklonis, J. J. (1992) · Journal of Applied Polymer Science · doi:10.1002/app.1992.070450805 · Cited by 31 · see citing works
The Polymerization of Tetrahydrofuran Initiated by Niobium(V) and Tantalum(V) Halides
Marchetti, F., Pampaloni, G., & Repo, T. (2008) · European Journal of Inorganic Chemistry · doi:10.1002/ejic.200701348 · Cited by 29 · see citing works
Cationic Ring-opening Polymerization: Ethers
Penczek, S., & Kubisa, P. (1989) · Comprehensive Polymer Science and Supplements · doi:10.1016/b978-0-08-096701-1.00110-5 · Cited by 28 · see citing works
Electron-beam-induced polymerization of epoxides
Davidson, R. S., & Wilkinson, S. A. (1991) · Journal of Photochemistry and Photobiology A Chemistry · doi:10.1016/1010-6030(91)87103-3 · Cited by 22 · see citing works
Uryu, T., Ito, K., Kobayashi, K., & Matsuzaki, K. (1979) · Die Makromolekulare Chemie · doi:10.1002/macp.1979.021800610 · Cited by 21 · see citing works
Cationic Ring-Opening Polymerization of Cyclic Ethers
Kubisa, P. (2012) · Elsevier eBooks · doi:10.1016/b978-0-444-53349-4.00102-3 · Cited by 18 · see citing works
Cationic polymerization of alkenes and heterocyclics. More similarities than differences
Matyjaszewski, K. A. (1992) · Makromolekulare Chemie Macromolecular Symposia · doi:10.1002/masy.19920540108 · Cited by 15 · see citing works
Ring-Opening Polymerization of Cyclic Acetals
Kubisa, P., & Vairon, J. (2012) · Elsevier eBooks · doi:10.1016/b978-0-444-53349-4.00103-5 · Cited by 14 · see citing works
Kučera, M., Božek, F., & Majerová, K. (1979) · Polymer · doi:10.1016/0032-3861(79)90201-5 · Cited by 13 · see citing works
Jeong, B.-Y., Lee, S., Shin, H., Kwon, S., Kim, S. H., Ryu, J. H., & Yoon, S. M. (2022) · ACS Materials Letters · doi:10.1021/acsmaterialslett.2c00606 · Cited by 11 · see citing works
Sikkema, D. J., & Hoogland, P. (1986) · Polymer · doi:10.1016/0032-3861(86)90050-9 · Cited by 9 · see citing works
Electron Beam Curing of Composites
Wolff‐Fabris, F., Altstädt, V., Arnold, U., & Döring, M. (2010) · Carl Hanser Verlag GmbH & Co. KG eBooks · doi:10.3139/9783446433465 · Cited by 5 · see citing works
Kučera, M., Salajka, Z., Majerová, K., & Navrátil, M. (1983) · Die Makromolekulare Chemie · doi:10.1002/macp.1983.021840307 · Cited by 5 · see citing works
Dreyfuss, M. P., & Dreyfuss, P. (2011) · Encyclopedia of Polymer Science and Technology · doi:10.1002/0471440264.pst520 · Cited by 3 · see citing works
Burlakov, V. V., BOGDANOV, V. S., Sokolova, O. O., Arndt, P., Spannenberg, A., Minacheva, M. K., Lyssenko, K. A., Anan'ev, I. A., Rosenthal, U., & Shur, V. B. (2017) · ChemistrySelect · doi:10.1002/slct.201601732 · Cited by 2 · see citing works
Rare earth–transition metal cooperativity in the ring-opening polymerisation of tetrahydrofuran
Panda, R., Rang, F., Flecken, F., Weis, P., Schneider, S., Théato, P., & Hanf, S. (2025) · Polymer Chemistry · doi:10.1039/d5py00853k · Cited by 1 · see citing works
(1992) · Elsevier eBooks · doi:10.1016/s0069-8040(08)70220-6 · Cited by 1 · see citing works
Taganov, N. G., Komratov, G. N., Barzykina, R. A., Korovina, G. V., & Éntelis, S. G. (1981) · Polymer Science U.S.S.R. · doi:10.1016/0032-3950(81)90474-3 · Cited by 1 · see citing works
Wolff‐Fabris, F., Altstädt, V., Arnold, U., & Döring, M. (2010) · doi:10.3139/9783446433465.bm
- 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
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review