Coexistence of Activated Monomer and Active Chain End Mechanisms in Cationic Copolymerization of Tetrahydrofuran with Ethylene Oxide

Bednarek, Melania; Kubisa, Przemysław; Penczek, Stanisław

doi:10.1021/ma9900939

Cited by 44Advanced Polymer Synthesis and CharacterizationPolymer Synthesis and Characterizationbiodegradable polymer synthesis and properties

The DOI matches its Crossref record; 6 of the 6 references it cites were found in a registry or an index.

Coexistence of Activated Monomer and Active Chain End Mechanisms in Cationic Copolymerization of Tetrahydrofuran with Ethylene Oxide

Bednarek, Melania, Kubisa, Przemysław, Penczek, Stanisław·1999·Macromolecules

DOI 10.1021/ma9900939

Open this paper in CoChat — free account

Abstract

Cationic copolymerization of tetrahydrofuran (THF) with ethylene oxide (EO) in the presence of diols proceeds with simultaneous participation of secondary and tertiary oxonium ions. This process comprises therefore some features of the activated monomer (AM) and the active chain end (ACE) mechanisms. The mechanism of copolymer formation was evaluated, and the kinetics of competing reactions involving both secondary and tertiary oxonium ions with nucleophiles present in the system was studied. The apparent rate constants were derived, allowing the estimation of the influence of copolymerization conditions on the composition and microstructure of copolymers.

Integrity signals

Registry

Crossref · 10.1021/ma9900939

Cites

6 of 6 references verified0 citation errors · 0 not checkable

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?

For some systems it has been shown that both activated chain end and activated monomer mechanisms operate simultaneously.
“For some systems it has been shown that both mechanisms operate simultaneously [46].”
From Ring-Opening Polymerization—An Introductory Review (2013) · cites this paper as [46]

Macromolecular Design of Polymeric Materials
Hatada, K., Kitayama, T., & Vogl, O. (1997) · M. Dekker eBooks · Cited by 222
Activated monomer mechanism in cationic polymerization, 1. Ethylene oxide, formulation of mechanism
Brzezinska, K. R., Szymański, R., Kubisa, P., & Penczek, S. (1986) · Die Makromolekulare Chemie Rapid Communications · doi:10.1002/marc.1986.030070101 · Cited by 109
Self-citation
Polyepichlorohydrin diols free of cyclics: Synthesis and characterization
Biedroń, T., Kubisa, P., & Penczek, S. (1991) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.1991.080290502 · Cited by 82
Self-citation
Ion‐trapping in cationic polymerization
Brzezinska, K. R., Chwiałkowska, W., Kubisa, P., Matyjaszewski, K. A., & Penczek, S. (1977) · Die Makromolekulare Chemie · doi:10.1002/macp.1977.021780836 · Cited by 74
Self-citation
Ion‐trapping in cationic polymerization, 2. Relative rates of trapping and relative chemical shifts for structurally differing phosphines as trapping agents
Matyjaszewski, K. A., & Penczek, S. (1981) · Die Makromolekulare Chemie · doi:10.1002/macp.1981.021820614 · Cited by 28
Self-citation
Monomer Syntheses, Polymerization, and Copolymerization of Vinylthiazoles
Schilling, C. L., & Mulvaney, J. E. (1968) · Macromolecules · doi:10.1021/ma60005a015 · Cited by 20

Flagged first, then by citations

Research works printed but not linked: 14

Kubisa P., 1989, Comprehensive Polymer Science, 3, 786
Pruckmayr G., 1979, Macromolecules, 11, 270
Penczek S., 1986, Macromol. Symp.
Penczek S., 1993, Polym. Mater. Sci. Eng., 69, 431
Bednarek M., 1998, Macromol. Symp.
Bednarek M., 1991, Macromol. Symp.
Bednarek M., J. Polym. Sci., in press.
Geller N. M., 1966, Vysokomol. Soed., 450, 453
Arnett E. M., 1963, Prog. Phys. Org. Chem., 1, 403
Searles S., 1967, The Chemistry of Functional Groups. The Chemistry of Ether Linkage, 308
Matyjaszewski K., 1979, J. Polym. Sci., Polym. Chem. Ed., 17, 2422
Gritter R., 1967, The Chemistry of Functional Groups. The Chemistry of Ether Linkage, 444
Szymañski R., 1976, J. Chem. Soc., Chem. Commun., 33, 35
Meerwein, H.Methoden der Organishen Chemie, 4th ed.; Georg Thieme Verlag: Stuttgart, Germany, 1965; Volume VI/3, p 325.

Sorted by citations

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation
Herzberger, J., Niederer, K., Pohlit, H., Seiwert, J., Worm, M., Wurm, F. R., & Frey, H. (2015) · Chemical Reviews · doi:10.1021/acs.chemrev.5b00441 · Cited by 888
Ring-Opening Polymerization—An Introductory Review
Nuyken, O., & Pask, S. (2013) · Polymers · doi:10.3390/polym5020361 · Cited by 456
“For some systems it has been shown that both mechanisms operate simultaneously [46].”
Control of reactions and network structures of epoxy thermosets
Vidil, T., Tournilhac, F., Musso, S., Robisson, A., & Ludwik Leibler, B. (2016) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2016.06.003 · Cited by 437
Cationic activated monomer polymerization of heterocyclic monomers
Kubisa, P., & Penczek, S. (1999) · Progress in Polymer Science · doi:10.1016/s0079-6700(99)00028-3 · Cited by 298
Self-citation
Hyperbranched polyethers by ring‐opening polymerization: Contribution of activated monomer mechanism
Kubisa, P. (2002) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.10605 · Cited by 93
Self-citation
Activated Monomer Mechanism (AMM) in Cationic Ring-Opening Polymerization. The Origin of the AMM and Further Development in Polymerization of Cyclic Esters
Penczek, S., & Pretula, J. (2021) · ACS Macro Letters · doi:10.1021/acsmacrolett.1c00509 · Cited by 65
Self-citation
Macromolecular architectures based on organocatalytic ring-opening (co)polymerization of epoxides
Xia, Y., & Zhao, J. (2018) · Polymer · doi:10.1016/j.polymer.2018.03.047 · Cited by 60
Sequence-Controlled Polymers via Simultaneous Living Anionic Copolymerization of Competing Monomers
Rieger, E., Alkan, A., Manhart, A., Wagner, M., & Wurm, F. R. (2016) · Macromolecular Rapid Communications · doi:10.1002/marc.201600092 · Cited by 53
Polymerization of epoxidized vegetable oil derivatives: Ionic‐coordinative polymerization of methylepoxyoleate
del Río, E., Galià, M., Cádiz, V., Lligadas, G., & Ronda, J. C. (2010) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.24297 · Cited by 52
Efficient Polymerization of Methyl-ε-Caprolactone Mixtures To Access Sustainable Aliphatic Polyesters
Batiste, D. C., Meyersohn, M. S., Watts, A., & Hillmyer, M. A. (2020) · Macromolecules · doi:10.1021/acs.macromol.0c00050 · Cited by 49
Characterization of a Poly(fluorooxetane) and Poly(fluorooxetane-co-THF) by MALDI Mass Spectrometry, Size Exclusion Chromatography, and NMR Spectroscopy
Wesdemiotis, C., Pingitore, F., Polce, M. J., Russell, V. M., Kim, Y., Kausch, C. M., Connors, T. H., Medsker, R. E., & Thomas, R. R. (2006) · Macromolecules · doi:10.1021/ma0610414 · Cited by 47
The living anionic polymerization of activated aziridines: a systematic study of reaction conditions and kinetics
Rieger, E., Gleede, T., Weber, K., Manhart, A., Wagner, M., & Wurm, F. R. (2017) · Polymer Chemistry · doi:10.1039/c7py00436b · Cited by 46
Brønsted acid-free controlled polymerization of tetrahydrofuran catalyzed by recyclable rare earth triflates in the presence of epoxides
You, L., Hogen‐Esch, T. E., Zhu, Y., Ling, J., & Shen, Z. (2012) · Polymer · doi:10.1016/j.polymer.2012.07.047 · Cited by 46
Photoinduced ring-opening polymerizations
Guy, N., Giani, O., Blanquer, S., Pinaud, J., & Robin, J. (2021) · Progress in Organic Coatings · doi:10.1016/j.porgcoat.2021.106159 · Cited by 45
Nanothermite composites with a novel cast curable fluoropolymer
Nie, H., Tan, L. P., Pisharath, S., & Hng, H. H. (2021) · Chemical Engineering Journal · doi:10.1016/j.cej.2021.128786 · Cited by 37
Combining cationic ring‐opening polymerization and click chemistry for the design of functionalized polyurethanes
Baśko, M., Bednarek, M., Billiet, L., Kubisa, P., Goethals, E. J., & Prez, F. D. (2011) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.24583 · Cited by 35
Self-citation
Zwitterionic Ring-Opening Copolymerization of Tetrahydrofuran and Glycidyl Phenyl Ether with B(C6F5)3
Asenjo‐Sanz, I., Veloso, A., Miranda, J. I., Alegría, Á., Pomposo, J. A., & Barroso‐Bujans, F. (2015) · Macromolecules · doi:10.1021/acs.macromol.5b00096 · Cited by 33
Synthesis and Characterization of Poly(3‐azidomethyl‐3‐methyl oxetane) by the Azidation of Poly(3‐mesyloxymethyl‐3‐methyl oxetane)
Wang, G., Ge, Z., & Luo, Y. (2015) · Propellants Explosives Pyrotechnics · doi:10.1002/prep.201500064 · Cited by 25
Supramolecular Control of Propagation in Cationic Polymerization of Room Temperature Curable Epoxy Compositions
Vidil, T., & Tournilhac, F. (2013) · Macromolecules · doi:10.1021/ma401720j · Cited by 24
Synthesis of periodic copolymers via ring‐opening copolymerizations of cyclic anhydrides with tetrahydrofuran using nonafluorobutanesulfonimide as an organic catalyst and subsequent transformation to aliphatic polyesters
Tang, T., Oshimura, M., Yamada, S., Takasu, A., Yang, X., & Cai, Q. (2012) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.26103 · Cited by 22
Model for the effects of water on the cationic UV-curing of cyclohexyl epoxides
Soucek, M. D., & Chen, J. (2003) · Journal of Coatings Technology · doi:10.1007/bf02697913 · Cited by 20
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
Self-citation
Real‐time monitoring of ring‐opening polymerization of tetrahydrofuran via in situ Fourier Transform Infrared Spectroscopy
Deng, H., Shen, Z., Li, L., Yin, H., & Chen, J. (2014) · Journal of Applied Polymer Science · doi:10.1002/app.40503 · Cited by 16
Ionic and Coordination Ring‐Opening Polymerization
Penczek, S., Duda, A., Kubisa, P., & Słomkowski, S. (2007) · Wiley eBooks · doi:10.1002/9783527631421.ch4 · Cited by 16
Self-citation
Polyols from epoxidized soybean oil and alpha hydroxyl acids and their adhesion properties from UV polymerization
Li, Y., & Sun, X. S. (2015) · International Journal of Adhesion and Adhesives · doi:10.1016/j.ijadhadh.2015.07.013 · Cited by 15
Preparation of a P(THF-co-PO)-b-PB-b-P(THF-co-PO) triblock copolymer via cationic ring-opening polymerization and its use as a thermoset polymer
Zhang, W., Fan, X., Tian, W. J., Chen, H., Zhu, X., & Zhang, H. (2015) · RSC Advances · doi:10.1039/c5ra10407f · Cited by 15
Janus Polymerization: A One‐Shot Approach towards Amphiphilic Multiblock Poly(ester‐acetal)s Directly from 1, 3‐Dioxolane with ε‐Caprolactone
Qiu, H., Shen, T., Yang, Z., Wu, F., Li, X., Tu, Y., & Ling, J. (2021) · Chinese Journal of Chemistry · doi:10.1002/cjoc.202100782 · Cited by 14
Enhancing epoxide kinetics and tuning polymer properties using hydroxyl-containing (meth)acrylates in hybrid photopolymerizations
Schissel, S. M., & Jessop, J. L. P. (2018) · Polymer · doi:10.1016/j.polymer.2018.12.010 · Cited by 14
Network regulation and properties optimization of glycidyl azide polymer‐based materials as a candidate of solid propellant binder via alternating the functionality of propargyl‐terminated polyether
Qi, C., Tang, G., Guo, X., Liu, C., Pang, A., Gan, L., & Huang, J. (2019) · Journal of Applied Polymer Science · doi:10.1002/app.48016 · Cited by 13
Copolymerization with the feeding of one of the comonomers: Cationic activated monomer copolymerization of ε‐caprolactone with ethylene oxide
Bednarek, M., & Kubisa, P. (2005) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.20881 · Cited by 10
Self-citation
Online monitoring of reaction temperature during cationic ring opening polymerization of epichlorohydrin in presence of BF3 and 1,4‐butanediol
Kim, J.-S., Kweon, J.-O., & Noh, S. (2013) · Journal of Applied Polymer Science · doi:10.1002/app.39912 · Cited by 10
The linear relations and living feature in cationic ring-opening copolymerization of epoxy/THF system
Wu, Q., Liang, L., Yu, Y., & Tang, X. (2008) · Colloid & Polymer Science · doi:10.1007/s00396-007-1832-4 · Cited by 9
Chain‐growth limiting reactions in the cationic polymerization of 3‐ethyl‐3‐hydroxymethyloxetane
Bednarek, M., & Kubisa, P. (2003) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.11002 · Cited by 9
Self-citation
Synthesis of poly(1,2-butylene oxide-stat-tetrahydrofuran) by controllable polymerization over Sc(OTf)3 for use in high-performance lubricating oil
Zeng, X., Wang, L., Cao, Y., Liu, C., Han, Z., He, P., & Li, H. (2022) · European Polymer Journal · doi:10.1016/j.eurpolymj.2022.111483 · Cited by 7
Polypropylene Glycol-Polyoxytetramethylene Glycol Multiblock Copolymers with High Molecular Weight: Synthesis, Characterization, and Silanization
Hu, W., Wang, L., Wang, Q., Luan, A., Mai, Y., Huang, L., Chen, Y., Yan, S., & Xiong, W. (2019) · Molecules · doi:10.3390/molecules24234317 · Cited by 6
Ionic and Coordination Ring‐Opening Polymerization
Penczek, S., Biela, T., Cypryk, M., Duda, A., Łapienis, G., Kubisa, P., Pretula, J., Słomkowski, S., & Szymański, R. (2022) · Wiley eBooks · doi:10.1002/9783527815562.mme0026 · Cited by 6
Self-citation
Synthesis and characterization of a novel azido fluoroalkyl oligoether energetic plasticizer
Ong, Y. J., Pisharath, S., See, Y. F. A., Tay, C. Y., & Hng, H. H. (2022) · Journal of materials research/Pratt's guide to venture capital sources · doi:10.1557/s43578-022-00525-1 · Cited by 5
Ring‐Opening Polymerization of Epoxides Through Organocatalysis
Liu, L., Zhou, Y., Tang, X., & Zhao, J. (2025) · Wiley eBooks · doi:10.1002/9783527843077.ch8 · Cited by 5
Structure‐Property Relationships of Multi‐Armed Glycidyl Azide Polymer Binders
Keerthi, V., Ong, Y. J., Rao, A. D., Deng, S., Pisharath, S., & Hng, H. H. (2025) · Propellants Explosives Pyrotechnics · doi:10.1002/prep.12079 · Cited by 4
Lewis Acid-Initiated Ring-Opening Reactions of Five- and Six-Membered Cyclic Ethers Based on the Oxonium Ylide Intermediates
Jiang, D., Xiao, J., Zhang, Y., Liu, K., Li, J., & Liu, J. (2024) · Organics · doi:10.3390/org5030011 · Cited by 4
Industrially relevant epoxy-acrylate hybrid resin photopolymerizations
Ajiboye, G. I. (2012) · doi:10.17077/etd.0xa1exp7 · Cited by 3
Real‐Time IR Study of Ultra‐Thin Film Photopolymerization of Liquid Porphyrin Monomer
Lintinen, K., Granqvist, N., Efimov, A., & Lemmetyinen, H. J. (2010) · Macromolecular Rapid Communications · doi:10.1002/marc.201000315 · Cited by 2
Metal-free Polyether Synthesis by Organocatalyzed Ring-opening Polymerization
Taton, D. (2018) · Royal Society of Chemistry eBooks · doi:10.1039/9781788015738-00328 · Cited by 2
Photothermal synergistic curing of one-component epoxy resin adhesive based on active monomer mechanism
Liang, S., Bai, J., Peng, X., Ji, Y., Han, X., Wang, Z., & Liu, F. (2024) · The Journal of Adhesion · doi:10.1080/00218464.2024.2413016 · Cited by 1

Lithium chloride as catalyst for the ring-opening polymerization of lactide in the presence of hydroxyl-containing compounds
Xie, W., Chen, D., Fan, X., Li, J., Wang, P. G., CHENG, H. N., & Nickol, R. G. (1999) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/(sici)1099-0518(19990901)37:17 · Cited by 53
Self-citation
Fractionated crystallisation of polyethylene and ethylene/-olefin copolymers dispersed in immiscible polystyrene matrices
Arnal, M. L., & Müller, A. J. (1999) · Macromolecular Chemistry and Physics · doi:10.1002/(sici)1521-3935(19991101)200:11 · Cited by 80
Self-citation
Kinetic and thermodynamic control in the cationic copolymerization of cyclic ethers
Bednarek, M., Kubisa, P., & Penczek, S. (1996) · Macromolecular Symposia · doi:10.1002/masy.19961070114 · Cited by 4
Self-citation
The mechanism of polymerization of tetrahydrofuran
Rosenberg, B. A., Ludvig, E. B., Gantmakher, A. R., & Medvedev, S. S. (1967) · Journal of Polymer Science Part C Polymer Symposia · doi:10.1002/polc.5070160407 · Cited by 16
Activated monomer mechanism in the cationic polymerization of cyclic ethers
Kubisa, P. (1988) · Makromolekulare Chemie Macromolecular Symposia · doi:10.1002/masy.19880130116 · Cited by 53
Self-citation

Authors: Bednarek, M., Kubisa, P., & Penczek, S.
Affiliations: Centrum Badań Molekularnych i Makromolekularnych Polskiej Akademii Nauk (PL)
ORCID: Bednarek, Melania
Kubisa, Przemysław
Penczek, Stanisław
Venue: Macromolecules
Publisher: American Chemical Society (ACS)
Published: 1999-07-23
Volume: 32
Issue: 16
Pages: 5257-5263
ISSN: 0024-9297 (ISSN-L)
1520-5835
DOI: 10.1021/ma9900939
OpenAlex: W2012170425
Cited by: 44
References: 6
Citations by year: 2025: 2 · 2024: 2 · 2022: 3 · 2021: 4 · 2020: 1 · 2019: 2 · 2018: 3 · 2017: 1 · 2016: 2 · 2015: 5 · 2014: 1 · 2013: 3 · 2012: 4
FWCI: 0.61
Type: journal article
Language: en
Open access: closed
Locations: Macromolecules (publishedVersion)
Topics: Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
Physical Sciences › Materials Science › Polymers and Plastics › Polymer Synthesis and Characterization
Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
Keywords: cationic copolymerization, tetrahydrofuran, ethylene oxide, activated monomer mechanism, oxonium ions, diols, copolymerization kinetics, copolymer composition, copolymer microstructure, nucleophilic attack

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

Coexistence of Activated Monomer and Active Chain End Mechanisms in Cationic Copolymerization of Tetrahydrofuran with Ethylene Oxide

Abstract

Overview

Integrity signals

Verification

Claims the paper makes

Claims other papers make about this one

Citations

Cites

Cited by

Related

Metadata

Record

About these checks