Superacids and Their Derivatives. IV. Kinetic Studies on the Ring-Opening Polymerization of Tetrahydrofuran Initiated with Ethyl Trifluoromethanesulfonate by Means of 19F and 1H Nuclear Magnetic Resonance Spectroscopy. Evidence for the Oxonium-Ester Equilibrium of the Propagating Species

Kobayashi, Shiro; Danda, Hidenori; Saegusa, Takeo

doi:10.1021/ma60040a004

Cited by 48Organic and Inorganic Chemical ReactionsAdvanced Polymer Synthesis and CharacterizationPhysical Organic Chemistry and Reaction Kinetics

The DOI matches its Crossref record.

Superacids and Their Derivatives. IV. Kinetic Studies on the Ring-Opening Polymerization of Tetrahydrofuran Initiated with Ethyl Trifluoromethanesulfonate by Means of 19F and 1H Nuclear Magnetic Resonance Spectroscopy. Evidence for the Oxonium-Ester Equilibrium of the Propagating Species

Kobayashi, Shiro, Danda, Hidenori, Saegusa, Takeo·1974·Macromolecules

DOI 10.1021/ma60040a004

Open this paper in CoChat — free account

Abstract

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSuperacids and Their Derivatives. IV. Kinetic Studies on the Ring-Opening Polymerization of Tetrahydrofuran Initiated with Ethyl Trifluoromethanesulfonate by Means of 19F and 1H Nuclear Magnetic Resonance Spectroscopy. Evidence for the Oxonium-Ester Equilibrium of the Propagating SpeciesShiro Kobayashi, Hidenori Danda, and Takeo SaegusaCite this: Macromolecules 1974, 7, 4, 415–420Publication Date (Print):July 1, 1974Publication History Published online1 May 2002Published inissue 1 July 1974https://pubs.acs.org/doi/10.1021/ma60040a004https://doi.org/10.1021/ma60040a004research-articleACS PublicationsRequest reuse permissionsArticle Views202Altmetric-Citations45LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Integrity signals

Registry

Crossref · 10.1021/ma60040a004

Cites

Statistics

Recomputing p-values needs the paper’s full text.

Claims the paper makes

This paper’s full text isn’t openly available, so its claims and self-check weren’t run. The registry and citation checks still apply.

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?

Esters of Brönsted acids (e.g., ROSO2CF3 and ROSO2F) can be used as initiators, acting as precursors for carbenium ion initiation.
“Esters of Brönsted acids (e.g., ROSO2CF3 and ROSO2F) can also be used as initiators [57 -59], whereby the covalent initiators act as precursors for a carbenium ion initiation ( vide supra ).”
From Ring-Opening Polymerization—An Introductory Review (2013) · cites this paper as [58]

Sorted by citations

Ring-Opening Polymerization—An Introductory Review
Nuyken, O., & Pask, S. (2013) · Polymers · doi:10.3390/polym5020361 · Cited by 456
“, ROSO2CF3 and ROSO2F) can also be used as initiators [57–59], whereby the covalent initiators act as precursors for a carbenium ion initiation (vide supra).”
Background
Cationic Ring-Opening Polymerization of Heterocyclic Monomers
Penczek, S., Kubisa, P., & Matyjaszewski, K. A. (1980) · Advances in polymer science · doi:10.1007/bfb0023043 · Cited by 145
Ring‐Opening Polymerization and ring‐closing depolymerization
Höcker, H., & Keul, H. (1994) · Advanced Materials · doi:10.1002/adma.19940060104 · Cited by 61
Kinetics and mechanism of the cationic polymerization of tetrahydrofuran in solution: THF‐CH3NO2 system
Matyjaszewski, K. A., Słomkowski, S., & Penczek, S. (1979) · Journal of Polymer Science Polymer Chemistry Edition · doi:10.1002/pol.1979.170170108 · Cited by 37
Kinetics and mechanism of the cationic polymerization of tetrahydrofuran in solution. I. THF–CCI4 system
Matyjaszewski, K. A., Kubisa, P., & Penczek, S. (1975) · Journal of Polymer Science Polymer Chemistry Edition · doi:10.1002/pol.1975.170130401 · Cited by 37
The Polymerization of Azetidines and Azetidine Derivatives
Goethals, E. J., Schacht, E. H., Bogaert, Y., Ali, S. I., & Tezuka, Y. (1980) · Polymer Journal · doi:10.1295/polymj.12.571 · Cited by 31
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
Superacids and Their Derivatives. X. Mechanistic Studies of Selective Cyclodimerization of Ethylene Oxide by Superacid Ester Catalysts
Kobayashi, S., Morikawa, K., & Sàegusa, T. (1979) · Polymer Journal · doi:10.1295/polymj.11.405 · Cited by 24
Self-citation
Ring-Opening Polymerizations
Ravve, A. (2012) · Springer eBooks · doi:10.1007/978-1-4614-2212-9_5 · Cited by 23
Cationic polymerization of styrenes by protonic acids and their derivatives, 3. Propagating species in the polymerization of styrene by trifluoroacetic acid
Sawamoto, M., Masuda, T., Higashimura, T., Kobayashi, S., & Sàegusa, T. (1977) · Die Makromolekulare Chemie · doi:10.1002/macp.1977.021780211 · Cited by 21
Self-citation
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
Graft copolymers by oxonium polymerization. V. Grafting polytetrahydrofuran from polymeric triflate esters
Dreyfuss, P., & Kennedy, J. P. (1976) · Journal of Polymer Science Polymer Letters Edition · doi:10.1002/pol.1976.130140303 · Cited by 18
SYNTHESIS AND SOME REACTIONS OF 1-ADAMANTYL TRIFLUOROMETHANESULFONATE
Takeuchi, K., Moriyama, T., Kinoshita, T., et al. (1980) · Chemistry Letters · doi:10.1246/cl.1980.1395 · Cited by 17
Theoretical basis and kinetic sense of covalent propagation in cationic polymerization
Matyjaszewski, K. A. (1987) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.1987.080250303 · Cited by 16
Neighboring group participation in the macroester ⇌ macroion equilibrium in the cationic polymerization of tetrahydrofuran
Matyjaszewski, K. A., Buyle, A., & Penczek, S. (1976) · Journal of Polymer Science Polymer Letters Edition · doi:10.1002/pol.1976.130140301 · Cited by 16
Pseudoperiodic “Living” and/or Controlled Cationic Ring-Opening Copolymerization of Oxetane with Tetrahydropyran: Microstructure of Polymers vs Kinetics of Chain Growth
Bouchékif, H., Philbin, M. I., Colclough, E., & Amass, A. J. (2009) · Macromolecules · doi:10.1021/ma902119p · Cited by 16
Antibacterial and pH-responsive Quaternized Hydroxypropyl Cellulose-g-Poly(THF-co-epichlorohydrin) Graft Copolymer: Synthesis, Characterization and Properties
Deng, J., Zhao, C.-L., & Wu, Y. (2020) · Chinese Journal of Polymer Science · doi:10.1007/s10118-020-2372-3 · Cited by 14
Synthesis of Narrow Distribution Poly(tetrahydrofuran) Initiated by Alkylboron Triflates
McCarthy, B. J., & Hogen‐Esch, T. E. (1996) · Macromolecules · doi:10.1021/ma951314n · Cited by 13
Cationic ring‐opening polymerization of oxetane derivatives initiated by superacids: Studies on their propagating mechanism and species by means of 19F‐NMR
Liu, Y., Hsiue, G., & Chiu, Y. (1994) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.1994.080321317 · Cited by 14
Superacids and Their Derivatives. V. Kinetics and Mechanism of the Cationic Polymerization of 3,3-Bis(chloromethyl)oxacyclobutane Initiated by Ethyl Trifluoromethanesulfonate. Evidence for Ester Type Propagating Species
Kobayashi, S., Danda, H., & Sàegusa, T. (1974) · Bulletin of the Chemical Society of Japan · doi:10.1246/bcsj.47.2699 · Cited by 14
Self-citation
Cationic Homo- and Co-polymerizations of Ethyl Glycidate
Sàegusa, T., Kobayashi, T., Kobayashi, S., et al. (1979) · Polymer Journal · doi:10.1295/polymj.11.463 · Cited by 14
Self-citation
Generation of “Living” Species Using Perfluoroalkylsulfonic Acids in Concurrent Cationic Vinyl-Addition and Ring-Opening Copolymerization via Crossover Reactions
Hotta, D., Kanazawa, A., & Aoshima, S. (2018) · Macromolecules · doi:10.1021/acs.macromol.8b01686 · Cited by 12
Mechanistic studies on cationic ring-opening polymerisation of cyclodextrin derivatives using various Lewis acids
Bösch, A., Nimtz, M., & Mischnick, P. (2006) · Cellulose · doi:10.1007/s10570-005-9029-9 · Cited by 12
“In case of MeOTf, further stabilisation of the carboxonium ion is possible by the recombination of an ion pair resulting in a covalent ester as has been described for THF and ethyl triflate ( Kobayashi et al. 1974; Matyjaszewski et al. 1974).”
Poly(THF-co-cyano ethylene oxide): Cyano Ethylene Oxide (CEO) Copolymerization with THF Leading to Multifunctional and Water-Soluble PolyTHF Polyelectrolytes
Christ, E.-M., Herzberger, J., Montigny, M., Tremel, W., & Frey, H. (2016) · Macromolecules · doi:10.1021/acs.macromol.6b00113 · Cited by 10
Studies on the polymerization mechanism of 3‐nitratomethyl‐3′‐methyloxetane and 3‐azidomethyl‐3′‐methyloxetane and the synthesis of their respective triblock copolymers with tetrahydrofuran
Liu, Y., Hsiue, G., & Chiu, Y. (1995) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.1995.080331007 · Cited by 10
Reactivity of Cyclic Imino Ether Salts Having Vinyl Group V. Spontaneous and Base-Catalyzed Polymerization of N-Protio Salts of 2-Alkenyl-2-oxazolines and 2-Alkenyl-5,6-dihydro-4H-1,3-oxazines
Miyamoto, M., Sano, Y., & Sàegusa, T. (1987) · Polymer Journal · doi:10.1295/polymj.19.557 · Cited by 9
Self-citation
Ring-Opening Polymerizations
Ravve, A. (2000) · Springer eBooks · doi:10.1007/978-1-4615-4227-8_4 · Cited by 8
Coordinate polymerization of heterocycles: 2. Oligomerization of tetrahydrofuran by TiCl4 in the presence of acetyl chloride or epichlorohydrin
Kučera, M., Zahradníčková, A., & Majerová, K. (1976) · Polymer · doi:10.1016/0032-3861(76)90135-x · Cited by 7
Ionic and covalent species in the cationic polymerization – equilibria and reactivities
Matyjaszewski, K. A., Szymański, R., Kubisa, P., & Penczek, S. (1984) · Acta Polymerica · doi:10.1002/actp.1984.010350104 · Cited by 7
Time and Temperature Dependence of Macro-ion-Macro-ester Equilibrium in the Cationic Polymerization of Tetrahydrofuran by HOSO2F
Mahmud, M. U., Wegner, G., Kern, W., Lando, J. B., & Osada, Y. (1977) · Journal of Macromolecular Science Part A - Chemistry · doi:10.1080/00222337708061361 · Cited by 7
Cationic Oligomerization of Ethylene Oxide
Kobayashi, S., Kobayashi, T., & Sàegusa, T. (1983) · Polymer Journal · doi:10.1295/polymj.15.883 · Cited by 6
Self-citation
Oxonium Ion Ring-Opening Polymerization
Dreyfuss, M. P. (1975) · Journal of Macromolecular Science Part A - Chemistry · doi:10.1080/00222337508065891 · Cited by 6
Chapter 4 Polymerization of Cyclic Ethers and Sulphides
Dreyfuss, P., & Dreyfuss, M. P. (1976) · Elsevier eBooks · doi:10.1016/s0069-8040(08)70050-5 · Cited by 6
Ring-Opening Polymerizations
Ravve, A. (1995) · Springer eBooks · doi:10.1007/978-1-4899-1283-1_4 · Cited by 5
Dithiadiazolium salts as initiators for the cationic ring‐opening polymerization of tetrahydrofuran
Banister, A. J., & Luke, A. W. (1992) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.1992.080301219 · Cited by 5
The cationic ring-opening polymerization of 7-tetradecene oxide with methyl trifluoromethansulfonate. An investigation of the mechanism and the kinetics by means of 1H, 13C and 19F NMR
Clericuzio, M., Cobianco, S., Fabbi, M., et al. (1999) · Polymer · doi:10.1016/s0032-3861(97)10005-2 · Cited by 4
Kinetic Studies on the Cationic Polymerization of 1,3-Dioxolane Initiated with Methyl Fluorosulfonate
Yokoyama, Y., Okada, M., & Sumitomo, H. (1979) · Polymer Journal · doi:10.1295/polymj.11.365 · Cited by 4
Superacids and Their Derivatives. VI. Kinetics of the Cationic Ring-Opening Polymerization of Tetrahydrofuran Initiated by Ethyl 2,4,6-Trinitrobenzenesulfonate
Kobayashi, S., Nakagawa, T., Danda, H., et al. (1974) · Bulletin of the Chemical Society of Japan · doi:10.1246/bcsj.47.2706 · Cited by 3
Self-citation
Living Ring‐Opening Polymerization of Heterocyclic Monomers
Penczek, S., Cypryk, M., Duda, A., Kubisa, P., & Słomkowski, S. (2009) · Wiley eBooks · doi:10.1002/9783527629091.ch5 · Cited by 5
New Developments in Ring-Opening Polymerization
Sàegusa, T. (1982) · Elsevier eBooks · doi:10.1016/b978-0-08-026226-0.50008-7 · Cited by 2
Self-citation
Electrospray ionization mass spectrometry: a powerful tool to investigate the oligomerization mechanism of tetrahydrofuran by phosphoryl chloride
Zhou, G., Xu, P., Ye, Y., et al. (2005) · Journal of Mass Spectrometry · doi:10.1002/jms.822 · Cited by 2
Ring-opening Polymerization of Tetrahydrofuran Initiated by the 2-Norbornyl Cation Generated from exo-2-Norbornyl Tosylate in the Presence of Lithium Perchlorate
Takeuchi, K., Kato, Y., & Okamoto, K. (1981) · Bulletin of the Chemical Society of Japan · doi:10.1246/bcsj.54.3881 · Cited by 1
Living Polymers: Their Significance and Applications
Szwarc, M. (1977) · Survey of progress in chemistry · doi:10.1016/b978-0-12-610508-7.50008-6 · Cited by 1
Initiation and Propagation of Ionic Polymerization
Szwarc, M., & Beylen, M. V. (1993) · Springer eBooks · doi:10.1007/978-94-011-1478-3_3
Perfluorohalogenoorgano Compounds of Main Group 6 Elements (Continuation)
Haas, A., Gerstenberger, M. R. C., & Koschel, D. (1987) · Springer eBooks · doi:10.1007/978-3-662-06321-7_1
Chapter 4 Active centres of polymerizations
(1992) · Elsevier eBooks · doi:10.1016/s0069-8040(08)70221-8
Disproportionation and ring-opening polymerization of silmethylene-siloxane derivatives
Pasquet, C. (2013) · doi:10.70675/ca0b819fzcdbez4e03z8214z78ccd2a9d7da

Synthesis of Di‐block Copolymers Containing Regioregular Poly(3‐hexylthiophene) and Poly(tetrahydrofuran) by a Combination of Grignard Metathesis and Cationic Polymerizations
Alemseghed, M. G., Gowrisanker, S., Servello, J., et al. (2009) · Macromolecular Chemistry and Physics · doi:10.1002/macp.200900262 · Cited by 56
Ring-opening polymerization by N-heterocyclic carbenes as catalysts: Characteristics and kinetics
Wang, Y., Li, N., Zhang, L., Guo, J., & Liu, Q. (2014) · Kinetics and Catalysis · doi:10.1134/s0023158414040168 · Cited by 1
Zinc acetate as a catalyst for the bulk ring opening polymerization of cyclic esters and lactide
Gowda, R. R., & Chakraborty, D. (2010) · Journal of Molecular Catalysis A Chemical · doi:10.1016/j.molcata.2010.10.013 · Cited by 54
Co2O3 and MnO2 as inexpensive catalysts for the ring-opening polymerization of cyclic esters
Mandal, M., & Chakraborty, D. (2021) · Journal of Polymer Research · doi:10.1007/s10965-020-02381-1 · Cited by 7
Characteristics and mechanism of L-lactide polymerization using N-heterocyclic carbene organocatalyst
Wang, Y., Zhang, L., Guo, X.-N., Zhang, R., & Li, J. (2013) · Journal of Polymer Research · doi:10.1007/s10965-013-0087-7 · Cited by 18

Authors: Kobayashi, S., Danda, H., & Saegusa, T.
Venue: Macromolecules
Publisher: American Chemical Society (ACS)
Published: 1974-07
Volume: 7
Issue: 4
Pages: 415-420
ISSN: 0024-9297 (ISSN-L)
1520-5835
DOI: 10.1021/ma60040a004
OpenAlex: W2040758182
Cited by: 48
References: 0
Citations by year: 2025: 1 · 2020: 1 · 2018: 1 · 2016: 1 · 2013: 2 · 2012: 2
FWCI: 4.15
Type: journal article
Language: en
Open access: closed
Locations: Macromolecules (publishedVersion)
Topics: Physical Sciences › Chemistry › Organic Chemistry › Organic and Inorganic Chemical Reactions
Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
Physical Sciences › Chemistry › Organic Chemistry › Physical Organic Chemistry and Reaction Kinetics
Keywords: superacids, trifluoromethanesulfonic acid, tetrahydrofuran, ring-opening polymerization, polymerization kinetics, 19F NMR, 1H NMR

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

Superacids and Their Derivatives. IV. Kinetic Studies on the Ring-Opening Polymerization of Tetrahydrofuran Initiated with Ethyl Trifluoromethanesulfonate by Means of 19F and 1H Nuclear Magnetic Resonance Spectroscopy. Evidence for the Oxonium-Ester Equilibrium of the Propagating Species

Abstract

Overview

Integrity signals

Verification

Claims the paper makes

Claims other papers make about this one

Citations

Cited by

Related

Metadata

Record

About these checks