Involvement of supramolecular complexes in the capture and release of protonic acids during the cationic ring-opening polymerization of epoxides
Abstract
The kinetics of the cationic ring-opening polymerizations of epoxide monomers were controlled through the use of supramolecular proton complexes. α,ω-Diglycidyl oligoethylene oxides bearing multiple ethyleneoxy spacer groups form metastable supramolecular proton complexes with strong Brønsted acids generated either by the photolysis of onium salts or by their redox reactions with reducing agents. Trapping of the Brønsted acids by in situ complex formation results in a delay of the onset of cationic ring-opening. However, once polymerization begins, the epoxide groups of the monomer are very rapidly consumed resulting in characteristically highly exothermic autoaccelerated polymerization reactions. Crown ethers can also form supramolecular complexes with hydronium ions derived from the reaction of protonic acids with water and these complexes can be used to modify the kinetic behavior of the cationic ring-opening thermal and photopolymerizations of a variety of epoxide monomers. The ring size of a crown ether has a strong influence on the stability of the supramolecular complex formed, and this was shown to have a major impact on the kinetics of the cationic ring-opening polymerizations.
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CROP of epoxides and oxetanes via Brönsted acids are often characterized by an induction period.
“The CROP of epoxides and oxetanes via Brönsted acids are often characterized by an induction period and, although not completely explained, the more recent studies of Crivello's group [48] modifying the kinetics of the photo initiated CROP by the addition of crown ethers (which are similar in structure to the oligomers formed in the early stages of polymerization) or 2,6 di-tert-butyl pyridine do”
From Ring-Opening Polymerization—An Introductory Review (2013) · cites this paper as [48]
Cites
Gokel, G. W. (1991) · Royal Society of Chemistry eBooks · doi:10.1039/9781788010917 · Cited by 754 · see citing works
Upper and lower critical solution temperatures in poly (ethylene glycol) solutions
Saeki, S., Kuwahara, N., Nakata, M., & Kaneko, M. (1976) · Polymer · doi:10.1016/0032-3861(76)90208-1 · Cited by 657 · see citing works
Role of Competitive PEO−Water and Water−Water Hydrogen Bonding in Aqueous Solution PEO Behavior
Dormidontova, E. E. (2001) · Macromolecules · doi:10.1021/ma010804e · Cited by 432 · see citing works
Cloud-point curves of polymer solutions from thermooptical measurements
Bae, Y. C., Lambert, S. M., Soane, D. S., & Prausnitz, J. M. (1991) · Macromolecules · doi:10.1021/ma00015a024 · Cited by 249 · see citing works
Alkoxy‐substituted diaryliodonium salt cationic photoinitiators
Crivello, J. V., & Lee, J. L. (1989) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.1989.080271207 · Cited by 239 · see citing works
Self-citationCrown Ethers and Analogs (1989)
Weber, E., Toner, J. L., Goldberg, I., Vögtle, F., Laidler, D. A., Stoddart, J. F., Bartsch, R. A., & Liotta, C. L. (1989) · Patai's chemistry of functional groups · doi:10.1002/9780470772232 · Cited by 221 · see citing works
Tuemmler, B., Maass, G., Weber, E., Wehner, W., & Vögtle, F. (1977) · Journal of the American Chemical Society · doi:10.1021/ja00456a026 · Cited by 178 · see citing works
Curcumin: A naturally occurring long‐wavelength photosensitizer for diaryliodonium salts
Crivello, J. V., & Bulut, U. (2005) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.21017 · Cited by 175 · see citing works
Self-citationInvestigation of the Reactivity of Epoxide Monomers in Photoinitiated Cationic Polymerization
Bulut, U., & Crivello, J. V. (2005) · Macromolecules · doi:10.1021/ma050106k · Cited by 130 · see citing works
Self-citationPhotoinduced cationic ring‐opening frontal polymerizations of oxetanes and oxiranes
Crivello, J. V., Falk, B., & Zonca, M. R. (2004) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.20012 · Cited by 109 · see citing works
Self-citationMonitoring photopolymerization reactions with optical pyrometry
Falk, B., Vallinas, S. M., & Crivello, J. V. (2003) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.10602 · Cited by 107 · see citing works
Self-citationCationic photopolymerization of alkyl glycidyl ethers
Crivello, J. V. (2006) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.21419 · Cited by 69 · see citing works
Self-citationReactivity of oxetane monomers in photoinitiated cationic polymerization
Bulut, U., & Crivello, J. V. (2005) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.20723 · Cited by 66 · see citing works
Self-citationHydration of the hydronium ion
Fornili, S. L., Migliore, M., & Palazzo, M. A. (1986) · Chemical Physics Letters · doi:10.1016/0009-2614(86)85183-1 · Cited by 55 · see citing works
Crivello, J. V., & Varlemann, U. (1995) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.1995.080331420 · Cited by 53 · see citing works
Self-citation(1992) · Studies in organic chemistry · doi:10.1016/b978-0-444-88191-5.50003-0 · Cited by 45 · see citing works
Akhtar, S. R., Crivello, J. V., Lee, J. L., & Schmitt, M. (1990) · Chemistry of Materials · doi:10.1021/cm00012a027 · Cited by 43 · see citing works
Self-citationBühl, M., & Wipff, G. (2002) · Journal of the American Chemical Society · doi:10.1021/ja012428j · Cited by 41 · see citing works
Chênevert, R., Chamberland, D., Simard, M. G., & BRISSE, F. (1989) · Canadian Journal of Chemistry · doi:10.1139/v89-006 · Cited by 40 · see citing works
Dual photo‐ and thermally initiated cationic polymerization of epoxy monomers
Crivello, J. V., & Bulut, U. (2006) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.21791 · Cited by 39 · see citing works
Self-citationSharma, R. B., & Kebarle, P. (1984) · Journal of the American Chemical Society · doi:10.1021/ja00326a005 · Cited by 38 · see citing works
A stable OH 3 + –cyclic polyether complex characterised by infrared spectroscopy
Izatt, R. M., Haymore, B. L., & Christensen, J. (1972) · Journal of the Chemical Society Chemical Communications · doi:10.1039/c39720001308 · Cited by 35 · see citing works
Redox initiated cationic polymerization
Crivello, J. V. (2009) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.23284 · Cited by 30 · see citing works
Self-citationInitiatorsysteme für kationische Photopolymerisationen
Baumann, H., Timpe, H., & Böttcher, H. (1983) · Zeitschrift für Chemie · doi:10.1002/zfch.19830231103 · Cited by 23 · see citing works
Redox Initiated Cationic Polymerization: Reduction of Triarylsulfonium Salts by Silanes
Crivello, J. V. (2009) · Silicon · doi:10.1007/s12633-009-9007-1 · Cited by 18 · see citing works
Self-citationSynthesis and crystal structures of oxonium ion complexes of 21-crown-7 and dibenzo-30-crown-10
Junk, . C., & Atwood, J. L. (1997) · Journal of the Chemical Society Dalton Transactions · doi:10.1039/a705351g · Cited by 17 · see citing works
Redox-Initiated Cationic Polymerization: Reduction of Dialkylphenacylsulfonium Salts by Silanes
Molleo, M., & Crivello, J. V. (2009) · Macromolecules · doi:10.1021/ma900482d · Cited by 11 · see citing works
Self-citationKolthoff, I. M., & Chantooni, M. K. (1992) · Canadian Journal of Chemistry · doi:10.1139/v92-029 · Cited by 10 · see citing works
Aqua complexes of 18—crown-6 with H3PO4, H2TiF6, and HNO3: synthesis and vibrational spectra
Chênevert, R., Rodrigue, A., Chamberland, D., Ouellet, J., & Savoie, R. (1985) · Journal of Molecular Structure · doi:10.1016/0022-2860(85)87020-4 · Cited by 10 · see citing works
Dimonie, M., & Teodorescu, M. (1993) · Die Angewandte Makromolekulare Chemie · doi:10.1002/apmc.1993.052090106 · Cited by 9 · see citing works
Redox initiated cationic polymerization: The unique behavior of alkyl glycidyl ethers
Crivello, J. V. (2011) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.24644 · Cited by 8 · see citing works
Self-citationFar-IR Studies of Carbon Acid Complexes of 18-Crown-6
McKenna, W. P., & Eyring, E. M. (1986) · Applied Spectroscopy · doi:10.1366/0003702864815600 · Cited by 6 · see citing works
Agra, C., Amado, S., Leis, J. R., & Ríos, A. (1997) · The Journal of Physical Chemistry B · doi:10.1021/jp971242x · Cited by 3 · see citing works
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Cationically UV-Cured Epoxy Composites
Atif, M., Bongiovanni, R. M., & Yang, J. (2015) · Journal of macromolecular science. Part C, Reviews in macromolecular chemistry and physics/Journal of macromolecular science. Reviews in macromolecular chemistry and physics · doi:10.1080/15583724.2014.963236 · Cited by 60 · see citing works
Chiolerio, A., Roppolo, I., Bejtka, K., Asvarov, A., & Pirri, C. F. (2016) · RSC Advances · doi:10.1039/c6ra10503c · Cited by 57 · see citing works
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Crivello, J. V., & Aldersley, M. F. (2012) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.26452 · Cited by 25 · see citing works
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- Authors
- Ryu, C. Y., Spencer, M. J., & Crivello, J. V.
- Affiliations
- Rensselaer Polytechnic Institute (US)
- Corresponding author
- Crivello, J. V.
- ORCID
- Ryu, C. Y.
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-02-22
- Volume
- 45
- Issue
- 5
- Pages
- 2233-2241
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2330015625
- Cited by
- 25
- References
- 33
- Citations by year
- 2024: 3 · 2023: 2 · 2022: 1 · 2021: 1 · 2020: 4 · 2019: 2 · 2018: 1 · 2016: 3 · 2015: 2 · 2013: 4 · 2012: 2
- FWCI
- 1.18
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Chemistry › Organic Chemistry › Supramolecular Chemistry and Complexes
- Physical Sciences › Chemistry › Organic Chemistry › Photopolymerization techniques and applications
- Keywords
- cationic ring-opening polymerization, epoxides, Brønsted acid, onium salts, photolysis, redox reactions, exothermic polymerization, crown ethers, hydronium ion, polymerization kinetics, photopolymerization, thermal polymerization, ring size effects
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