The propagating species in the polymerisation of 1,3-Dioxacycloalkanes by Perchloric Acid
Abstract
The object of the work described was to discriminate between the two principal rival theories concerning the polymerisation of 1,3-dioxacycloalkanes by anhydrous perchloric acid, the “Mainz theory” and the “Keele theory”. By means of Jaacks's method for determining tertiary oxonium ions we found that in polymerisations under the driest conditions the concentration of these is negligibly small. This was done with 1,3-dioxolane (1), 4-methyl-1,3-dioxolane (4), and 1,3-dioxepane (5), and the findings are supported by determinations of the content of hydroxy groups of polymers prepared and “killed” under different conditions. It follows that when the water content of the reaction mixtures is less than ca. 10−4M the propagation is principally by secondary oxonium ions, and that it must therefore go by the ring-expansion mechanism of Plesch and Westermann. Water causes the formation of tertiary oxonium ions and this probably explains why previously other workers and ourselves had reported their presence, and sometimes their dominance, in reaction mixtures prepared under much less stringent conditions. The recent theory of Penczek, which involves co-ordinated oxy-carbenium ions, is also shown not to be applicable to the systems considered here.— The heuristic value of the ring-expansion theory is illustrated briefly by reference to a new method of synthesising crown ethers from 1,3-dioxacycloalkanes, which arose from it.
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?
Under conditions where water concentration was less than 10-4 mol L-1 and at relatively low monomer concentration, the secondary oxonium ion predominates and the ring expansion mechanism prevails in CROP of 1,3-dioxolanes.
“In a very detailed analysis Plesch et al. [42] showed that under conditions where the concentration of water was less than 10 -4 mol L -1 and at relatively low monomer concentration, the secondary oxonium ion predominates and the ring expansion mechanism prevails.”
From Ring-Opening Polymerization—An Introductory Review (2013) · cites this paper as [42]
Protons can initiate polymerization of numerous heterocyclic monomers, including oxiranes, 1,3-dioxolanes, thiiranes, aziridines, tetrahydrofurans, lactones, 1,2-oxazolines and cyclic siloxanes.
“Protons can initiate the polymerization of numerous heterocyclic monomers, e.g., oxiranes, 1,3-dioxolanes, thiiranes, aziridines, tetrahydrofurans, lactones, 1,2 oxazolines and cyclic siloxanes as shown in Figure 16 assuming an activated chain end mechanism, in analogy to Figure 12 (SN2).”
From Ring-Opening Polymerization—An Introductory Review (2013) · cites this paper as [42]
Cites
Catalysis with Cation-Exchange Resins
Astle, M. J., Zaslowsky, J. A., & Lafyatis, P. G. (1954) · Industrial & Engineering Chemistry · doi:10.1021/ie50532a049 · Cited by 68 · see citing works
Hydride ion transfer processes and cationic polymerization of cyclic acetals
Penczek, S. (1974) · Die Makromolekulare Chemie · doi:10.1002/macp.1974.021750411 · Cited by 63 · see citing works
The polymerization of 1,3‐dioxolane. I. Structure of the polymer and thermodynamics of its formation
Plesch, P. H., & Westermann, P. (1967) · Journal of Polymer Science Part C Polymer Symposia · doi:10.1002/polc.5070160724 · Cited by 59 · see citing works
Self-citationPlesch, P. H., & Westermann, P. (1969) · Polymer · doi:10.1016/0032-3861(69)90013-5 · Cited by 52 · see citing works
Self-citationJaacks, V., Boehlke, K., & Eberius, E. (1968) · Die Makromolekulare Chemie · doi:10.1002/macp.1968.021180122 · Cited by 46 · see citing works
A new method of making new crown ethers
Cooper, J. G., & Plesch, P. H. (1974) · Journal of the Chemical Society Chemical Communications · doi:10.1039/c39740001017 · Cited by 10 · see citing works
Self-citationThe polymerisation of 4‐methyl‐1,3‐dioxolane
Firat, Y., & Plesch, P. H. (1975) · Die Makromolekulare Chemie · doi:10.1002/macp.1975.021760424 · Cited by 9 · see citing works
Self-citationBoehlke, K., & Jaacks, V. (1971) · Die Makromolekulare Chemie · doi:10.1002/macp.1971.021450118 · Cited by 9 · 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
Cationic Ring-Opening Polymerization
Penczek, S., Kubisa, P., & Matyjaszewski, K. A. (1985) · Advances in polymer science · doi:10.1007/3-540-13781-5 · Cited by 73 · see citing works
Lei, C., Zhou, T., Zhang, M., Liu, T., Xu, C., Wang, R., He, X., & Liang, X. M. (2024) · Advanced Science · doi:10.1002/advs.202405482 · Cited by 42 · see citing works
Electrolyte decomposition and gas evolution in a lithium-sulfur cell upon long-term cycling
Schneider, H., Weiss, T. M., Scordilis‐Kelley, C., Maeyer, J., Leitner, K., Peng, H.-J., Schmidt, R., & Tomforde, J. (2017) · Electrochimica Acta · doi:10.1016/j.electacta.2017.05.034 · Cited by 38 · see citing works
Kubisa, P., & Penczek, S. (1979) · Die Makromolekulare Chemie · doi:10.1002/macp.1979.021800722 · Cited by 28 · see citing works
Cationic ring-opening polymerization
Penczek, S. (1979) · Die Makromolekulare Chemie · doi:10.1002/macp.1979.020031979102 · Cited by 25 · see citing works
Kubisa, P., & Penczek, S. (1978) · Die Makromolekulare Chemie · doi:10.1002/macp.1978.021790219 · Cited by 25 · see citing works
Extended‐chain crystals of POM‐copolymers: Synthesis, structure and properties
Dröscher, M., Hertwig, K., Reimann, H., & Wegner, G. (1976) · Die Makromolekulare Chemie · doi:10.1002/macp.1976.021770607 · Cited by 23 · see citing works
Random and block copolymers by ring-opening polymerization
Yamashita, Y. (2007) · Springer eBooks · doi:10.1007/3-540-08885-7_1 · Cited by 17 · see citing works
A Ring‐Fusion/Ring‐Fission Mechanism for the Metathesis Reaction of Macrocyclic Formaldehyde Acetals
Cacciapaglia, R., Stefano, S. D., & Mandolini, L. (2006) · Chemistry - A European Journal · doi:10.1002/chem.200600983 · Cited by 16 · see citing works
Some Aspects of the Polymerisation of 1,3-Dioxacycloalkanes
Plesch, P. H. (1976) · Pure and Applied Chemistry · doi:10.1351/pac197648030287 · Cited by 9 · see citing works
Self-citationYokoyama, Y., Okada, M., & Sumitomo, H. (1977) · Die Makromolekulare Chemie · doi:10.1002/macp.1977.021780223 · Cited by 8 · see citing works
On the Distinctness of Chemistry
Plesch, P. H. (1999) · Foundations of Chemistry · doi:10.1023/a:1009980225127 · Cited by 6 · see citing works
Self-citationSOME ASPECTS OF THE POLYMERISATION OF 1,3-DIOXACYCLOALKANES
Plesch, P. H. (1977) · Elsevier eBooks · doi:10.1016/b978-0-08-021367-5.50009-2 · Cited by 4 · see citing works
Self-citationKučera, M., Božek, F., Majerová, K., & Kahle, L. (1983) · Polymer · doi:10.1016/0032-3861(83)90136-2 · Cited by 3 · see citing works
Holdcroft, G. E., KABIR‐UD‐DIN, K., Khan, A. A., & Plesch, P. H. (1982) · Journal of Electroanalytical Chemistry · doi:10.1016/0022-0728(82)85111-5 · Cited by 1 · see citing works
Self-citation“The projects that never were”. A lecture given to the polymer discussion group
Plesch, P. H. (1986) · European Polymer Journal · doi:10.1016/0014-3057(86)90015-7 · Cited by 1 · see citing works
Self-citation
- Authors
- Firat, Y., Jones, F. R., Plesch, P. H., & Westermann, P. H.
- Affiliations
- Keele University (GB)
- ORCID
- Westermann, Peter H.
- Venue
- Die Makromolekulare Chemie
- Publisher
- Wiley
- Published
- 1975-06
- Volume
- 1
- Issue
- S19751
- Pages
- 203-216
- ISSN
- 0025-116X (ISSN-L)
- OpenAlex
- W2026094236
- Cited by
- 17
- References
- 8
- Citations by year
- 2024: 1 · 2017: 1 · 2013: 1
- FWCI
- 3.17
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Die Makromolekulare Chemie (publishedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Chemistry › Spectroscopy › Organic and Inorganic Chemical Reactions
- Keywords
- polymerization mechanism, 1,3-dioxolane, 1,3-dioxepane, water content effects, crown ether synthesis
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
