“Living” Free Radical Ring-Opening Polymerization of 5,6-Benzo-2-methylene-1,3-dioxepane Using the Atom Transfer Radical Polymerization Method
Abstract
To clarify whether atom transfer radical polymerization can be extended to free radical ring-opening polymerization, the polymerization of 5,6-benzo-2-methylene-1,3-dioxepane (BMDO) was carried out in the presence of ethyl α-bromobutyrate/CuBr/2,2‘-bipyridine. The structure of poly(BMDO) was characterized by 1 H and 13 C NMR spectroscopy as well as gel permeation chromatography. The living polymerization of BMDO was identified by the following facts: a straight line of ln([M] 0 /[M]) versus polymerization time, linear increase of molecular weight with increasing conversion, and narrowing polydispersity. The mechanism of living free radical ring-opening polymerization was discussed.
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?
By varying the monomers or their proportions, or the mode of initiation (NMP, RAFT or ATRP), many and varied polymers can be obtained, optimized for agricultural, medicinal or pharmaceutical fields.
“It is clear that by varying the monomers or their proportions, or indeed by varying the mode of initiation, e.g., NMP (nitroxide mediated polymerization) [35], RAFT (reversible addition fragmentation transfer polymerization) [36] or ATRP (atom transfer radical polymerization) [37] many and varied polymers can be obtained, optimized for their use in agricultural, medicinal or pharmaceutical fields.”
From Ring-Opening Polymerization—An Introductory Review (2013) · cites this paper as [37]
Cites
Chiefari, J., Chong, Y. K. (., Ercole, F., Krstina, J., Jeffery, J. L., Le, T. P. T., Mayadunne, R. T. A., Meijs, G. F., Moad, C. L., Moad, G., et al. (1998) · Macromolecules · doi:10.1021/ma9804951 · Cited by 5,154 · see citing works
Kato, M., Kamigaito, M., Sawamoto, M., & Higashimura, T. (1995) · Macromolecules · doi:10.1021/ma00109a056 · Cited by 3,046 · see citing works
Narrow molecular weight resins by a free-radical polymerization process
Georges, M. K., Veregin, R. P. N., Kazmaier, P. M., & Hamer, G. K. (1993) · Macromolecules · doi:10.1021/ma00063a054 · Cited by 2,088 · see citing works
Wang, J., & Matyjaszewski, K. (1995) · Macromolecules · doi:10.1021/ma00127a042 · Cited by 1,699 · see citing works
Matyjaszewski, K. A., Patten, T. E., & Xia, J. (1997) · Journal of the American Chemical Society · doi:10.1021/ja963361g · Cited by 886 · see citing works
Polymers with Very Low Polydispersities from Atom Transfer Radical Polymerization
Patten, T. E., Xia, J., Abernathy, T., & Matyjaszewski, K. A. (1996) · Science · doi:10.1126/science.272.5263.866 · Cited by 864 · see citing works
Chong, ). Y. K., Le, T. P. T., Moad, G., Rizzardo, E., & Thang, S. H. (1999) · Macromolecules · doi:10.1021/ma981472p · Cited by 850 · see citing works
Granel, C., Dúbois, P., Jérôme, R., & Teyssié, P. (1996) · Macromolecules · doi:10.1021/ma9608380 · Cited by 554 · see citing works
Iron(II) Chloride Complex for Living Radical Polymerization of Methyl Methacrylate
Ando, T., Kamigaito, M., & Sawamoto, M. (1997) · Macromolecules · doi:10.1021/ma961478j · Cited by 452 · see citing works
Matyjaszewski, K. A., Wei, M., Xia, J., & McDermott, N. E. (1997) · Macromolecules · doi:10.1021/ma971010w · Cited by 389 · see citing works
Nickel-Mediated Living Radical Polymerization of Methyl Methacrylate
Uegaki, H., Kotani, Y., Kamigaito, M., & Sawamoto, M. (1997) · Macromolecules · doi:10.1021/ma961367k · Cited by 297 · see citing works
Bailey, W. J., Ni, Z., & Wu, S. R. (1982) · Macromolecules · doi:10.1021/ma00231a006 · Cited by 171 · see citing works
Synthesis and free radical ring‐opening polymerization of 2‐methylene‐4‐phenyl‐1,3‐dioxolane
Bailey, W. J., Wu, S., & Ni, Z. (1982) · Die Makromolekulare Chemie · doi:10.1002/macp.1982.021830811 · Cited by 139 · see citing works
Jin, S. Z., & Gonsalves, K. E. (1997) · Macromolecules · doi:10.1021/ma961590h · Cited by 114 · see citing works
Percec, V., Kim, H.-J., & Barboiu, B. (1997) · Macromolecules · doi:10.1021/ma9708508 · Cited by 112 · see citing works
Keoshkerian, B., Georges, M. K., Quinlan, M. H., Veregin, R., & Goodbrand, B. (1998) · Macromolecules · doi:10.1021/ma971686r · Cited by 99 · see citing works
Klemm, E., & Schulze, T. G. (1999) · Acta Polymerica · doi:10.1002/(sici)1521-4044(19990101)50:1 · Cited by 52 · see citing works
Volume Change in the Polymerization of Spirocyclic Monomers: Causes, Effects, and Applications
Brady, R. F. (1992) · Journal of macromolecular science. Part C, Reviews in macromolecular chemistry and physics/Journal of macromolecular science. Reviews in macromolecular chemistry and physics · doi:10.1080/15321799208021424 · Cited by 45 · see citing works
Pan, C., & Lou, X. (2000) · Macromolecular Chemistry and Physics · doi:10.1002/1521-3935(20000701)201:11 · Cited by 35 · see citing works
Self-citationAn epoxy resin copolymer with zero shrinkage
He, P., Zhiqiang, Z., Caiyuan, P., & Wu, R. (1989) · Journal of Materials Science · doi:10.1007/bf01105666 · Cited by 30 · see citing works
Sanda, F., Takata, T., & Endo, T. (1994) · Macromolecules · doi:10.1021/ma00083a006 · Cited by 29 · see citing works
Synthesis of poly(N-acylurethane)s, a new class of polyurethanes
Endo, T., Kanamaru, M., & Takata, T. (1994) · Macromolecules · doi:10.1021/ma00092a002 · Cited by 13 · see citing works
Jia, X., Li, M., Han, S., Wang, C., & Wei, Y. (1997) · Materials Letters · doi:10.1016/s0167-577x(96)00260-1 · Cited by 12 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Atom Transfer Radical Polymerization
Matyjaszewski, K. A., & Xia, J. (2001) · Chemical Reviews · doi:10.1021/cr940534g · Cited by 7,646 · see citing works
Tsarevsky, N. V., & Matyjaszewski, K. A. (2007) · Chemical Reviews · doi:10.1021/cr050947p · Cited by 1,278 · see citing works
Atrp in the design of functional materials for biomedical applications
Siegwart, D. J., Oh, J. K., & Matyjaszewski, K. (2012) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2011.08.001 · Cited by 613 · see citing works
Tardy, A., Nicolas, J., Gigmes, D., Lefay, C., & Guillaneuf, Y. (2017) · Chemical Reviews · doi:10.1021/acs.chemrev.6b00319 · Cited by 469 · see citing works
Ring-Opening Polymerization—An Introductory Review
Nuyken, O., & Pask, S. (2013) · Polymers · doi:10.3390/polym5020361 · Cited by 456 · see citing works
Pesenti, T., & Nicolas, J. (2020) · ACS Macro Letters · doi:10.1021/acsmacrolett.0c00676 · Cited by 214 · see citing works
Synthesis and Characterization of Copolymers of 5,6-Benzo-2-methylene-1,3-dioxepane and Styrene
Wickel, H., & Agarwal, S. (2003) · Macromolecules · doi:10.1021/ma034551w · Cited by 97 · see citing works
Functional Degradable Polymers by Xanthate-Mediated Polymerization
Hedir, G. G., Bell, C. A., Ieong, N. S., Chapman, E., Collins, I. R., O’Reilly, R. K., & Dove, A. P. (2014) · Macromolecules · doi:10.1021/ma500428e · Cited by 92 · see citing works
Reversible-deactivation radical polymerization of cyclic ketene acetals
Jackson, A. W. (2020) · Polymer Chemistry · doi:10.1039/d0py00446d · Cited by 89 · see citing works
Wickel, H., Agarwal, S., & Greiner, A. (2003) · Macromolecules · doi:10.1021/ma025983u · Cited by 88 · see citing works
Huang, J., Gil, R. R., & Matyjaszewski, K. A. (2005) · Polymer · doi:10.1016/j.polymer.2005.09.048 · Cited by 72 · see citing works
Controlling the synthesis of degradable vinyl polymers by xanthate-mediated polymerization
Bell, C. A., Hedir, G. G., O’Reilly, R. K., & Dove, A. P. (2015) · Polymer Chemistry · doi:10.1039/c5py01156f · Cited by 70 · see citing works
Ganda, S., Jiang, Y., Thomas, D. S., Eliezar, J., & Stenzel, M. H. (2016) · Macromolecules · doi:10.1021/acs.macromol.6b00266 · Cited by 63 · see citing works
Deng, Y., Mehner, F., & Gaitzsch, J. (2023) · Macromolecular Rapid Communications · doi:10.1002/marc.202200941 · Cited by 62 · see citing works
Ren, L., & Agarwal, S. (2007) · Macromolecular Chemistry and Physics · doi:10.1002/macp.200600484 · Cited by 60 · see citing works
Tardy, A., Delplace, V., Siri, D., Lefay, C., Harrisson, S., Pereira, B. D. F. A., Charles, L., Gigmès, D., Nicolas, J., & Guillaneuf, Y. (2013) · Polymer Chemistry · doi:10.1039/c3py00719g · Cited by 60 · see citing works
Chung, I. S., & Matyjaszewski, K. A. (2003) · Macromolecules · doi:10.1021/ma034029+ · Cited by 52 · see citing works
He, T., Zou, Y.-F., & Pan, C.-Y. (2002) · Polymer Journal · doi:10.1295/polymj.34.138 · Cited by 47 · see citing works
Self-citationDing, D., Pan, X., Zhang, Z., Li, N., Zhu, J., & Zhu, X. (2016) · Polymer Chemistry · doi:10.1039/c6py01061j · Cited by 47 · see citing works
Yuan, J., & Pan, C. (2002) · European Polymer Journal · doi:10.1016/s0014-3057(02)00085-x · Cited by 45 · see citing works
Self-citationSiebert, J. M., Baumann, D., Zeller, A., Mailänder, V., & Landfester, K. (2011) · Macromolecular Bioscience · doi:10.1002/mabi.201100236 · Cited by 44 · see citing works
Cascade Reactions in Chain-Growth Polymerization
Yuan, J., Wang, W., Zhou, Z., & Niu, J. (2020) · Macromolecules · doi:10.1021/acs.macromol.0c00417 · Cited by 44 · see citing works
Self-citationRAFT/MADIX copolymerization of vinyl acetate and 5,6‐benzo‐2‐methylene‐1,3‐dioxepane
d’Ayala, G. G., Malinconico, M., Laurienzo, P., Tardy, A., Guillaneuf, Y., Lansalot, M., D’Agosto, F., & Charleux, B. (2013) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.26976 · Cited by 41 · see citing works
Ko, J. H., Terashima, T., Sawamoto, M., & Maynard, H. D. (2017) · Macromolecules · doi:10.1021/acs.macromol.7b01973 · Cited by 40 · see citing works
Yu, X., Shi, T., Zhang, G., & An, L. (2006) · Polymer · doi:10.1016/j.polymer.2006.01.005 · Cited by 39 · see citing works
Yuan, J., & Pan, C. (2002) · European Polymer Journal · doi:10.1016/s0014-3057(02)00023-x · Cited by 36 · see citing works
Self-citationSmith, Q. A., Huang, J., Matyjaszewski, K. A., & Loo, Y. (2005) · Macromolecules · doi:10.1021/ma050393s · Cited by 35 · see citing works
Zhu, Y., Romain, C., Poirier, V., & Williams, C. K. (2015) · Macromolecules · doi:10.1021/acs.macromol.5b00225 · Cited by 32 · see citing works
Plikk, P., Tyson, T., Finne‐Wistrand, A., & Albertsson, A. (2009) · Journal of Polymer Science Part A: Polymer Chemistry · doi:10.1002/pola.23511 · Cited by 31 · see citing works
Agarwal, S. (2006) · Journal of Polymer Research · doi:10.1007/s10965-006-9058-6 · Cited by 30 · see citing works
General Mechanisms in Ring‐Opening Polymerization
Endo, T. (2009) · Wiley eBooks · doi:10.1002/9783527628407.ch2 · Cited by 29 · see citing works
Huang, Y.-S., Chen, J.-K., Kuo, S., Hsieh, Y.-A., Yamamoto, S., Nakanishi, J., & Huang, C. (2019) · Polymers · doi:10.3390/polym11061079 · Cited by 25 · see citing works
Preparation of β-cyclodextrin–polyaniline complex in supercritical CO2
Wang, B., He, J. H., Sun, D., Zhang, R., Han, B., Huang, Y., & Yang, G. (2005) · European Polymer Journal · doi:10.1016/j.eurpolymj.2005.04.036 · Cited by 22 · see citing works
Nagai, A., Ochiai, B., & Endo, T. (2003) · Chemical Communications · doi:10.1039/b310735c · Cited by 21 · see citing works
Dong, B.-T., Li, Z., Zhang, L., Du, F., & Li, Z. (2012) · Polymer Chemistry · doi:10.1039/c2py20319g · Cited by 20 · see citing works
Synthesis and characterization of AB block copolymers based on polyhedral oligomeric silsesquioxane
Fei, M., Jin, B., Wang, W., & Liu, L. (2009) · Journal of Polymer Research · doi:10.1007/s10965-009-9285-8 · Cited by 19 · see citing works
Endo, T., & Sudo, A. (2015) · ACS symposium series · doi:10.1021/bk-2015-1187.ch002 · Cited by 18 · see citing works
Han, Y.-M., Chen, H., & Huang, C. (2015) · Polymer Chemistry · doi:10.1039/c5py00388a · Cited by 18 · see citing works
Yu, X., Zhang, G., Shi, T., Han, Y., & An, L. (2007) · Polymer · doi:10.1016/j.polymer.2007.02.032 · Cited by 15 · see citing works
Atom Transfer Radical Polymerization of Methyl Bicyclobutane-1-carboxylate
Chen, X., Padías, A. B., & Hall (2001) · Macromolecules · doi:10.1021/ma010219d · Cited by 15 · see citing works
Yu, X., Shi, T., An, L., Guo, Z. X., & Dutta, P. K. (2006) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.21814 · Cited by 13 · see citing works
Huang, C., Kuo, S., Moravčíková, D., Liao, J.-C., Han, Y.-M., Lee, T., Wang, P.-H., Lee, R., Tsiang, R. C., & Mosnáček, J. (2016) · RSC Advances · doi:10.1039/c6ra06186a · Cited by 13 · see citing works
Mehner, F., Hopkins, B., Reynolds‐Green, M., Keddie, D. J., Howdle, S. M., & Gaitzsch, J. (2024) · Polymer · doi:10.1016/j.polymer.2024.127373 · Cited by 10 · see citing works
Chatterjee, U., Wang, X., Jewrajka, S. K., & Soucek, M. D. (2011) · Macromolecular Chemistry and Physics · doi:10.1002/macp.201100083 · Cited by 10 · see citing works
Wang, Z., & Debuigne, A. (2023) · Journal of macromolecular science. Part C, Reviews in macromolecular chemistry and physics/Journal of macromolecular science. Reviews in macromolecular chemistry and physics · doi:10.1080/15583724.2023.2181819 · Cited by 9 · see citing works
Progress in the Preparation of Functional and (Bio)Degradable Polymers via Living Polymerizations
Lin, S.-T., Wang, C., Chang, C., Nakamura, Y., Lin, K. A., & Huang, C. (2020) · International Journal of Molecular Sciences · doi:10.3390/ijms21249581 · Cited by 8 · see citing works
PREPARATION OF WELL-DEFINED AND DEGRADABLE ALDEHYDE-FUNCTIONALIZED GLYCOPOLYMERIC NANOSPHERES
Xiao, N., Zhong, L., Zhai, W.-J., & Bai, W.-D. (2012) · Acta Polymerica Sinica · doi:10.3724/sp.j.1105.2012.11362 · Cited by 8 · see citing works
Atom transfer radical homo‐ and block copolymerization of methyl 1‐bicyclobutanecarboxylate
Chen, X., Padías, A. B., & Hall, H. K. (2002) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.10274 · Cited by 6 · see citing works
Nishimura, S., Uryu, M., & Koga, T. (2025) · Macromolecules · doi:10.1021/acs.macromol.5c01438 · Cited by 4 · see citing works
Radical Ring-Opening Polymerization
Endo, T. (2012) · Elsevier eBooks · doi:10.1016/b978-0-444-53349-4.00120-5 · Cited by 4 · see citing works
Tsarevsky, N. V. (2011) · Wiley eBooks · doi:10.1002/9783527636167.ch11 · Cited by 4 · see citing works
Kitayama, Y., Sakamoto, R., & Harada, A. (2026) · Angewandte Chemie International Edition · doi:10.1002/anie.202524666 · Cited by 3 · see citing works
Nishimura, S., Hasegawa, M. L., Ueda, K., & Koga, T. (2024) · New Journal of Chemistry · doi:10.1039/d4nj04328f · Cited by 3 · see citing works
Kinetic Features of Radical Ring-Opening Polymerization of Ketene Acetals
Zaremski, M. Y., & Aliev, E. E. (2024) · Polymer Science Series B · doi:10.1134/s156009042460147x · Cited by 3 · see citing works
SYNTHESIS AND CHARACTERIZATION OF BIODEGRADABLE COPOLYMERS AS NON-PHOSPHOROUS DETERGENT BUILDERS
Guo, J., Ma, Q., Cui, Y., Liu, S., & Peng, J. (2012) · Acta Polymerica Sinica · doi:10.3724/sp.j.1105.2012.12007 · Cited by 3 · see citing works
Gao, J., Ding, Y. J., Chen, H., Song, Q., & Zhang, Q. (2008) · Chinese Journal of Chemical Physics · doi:10.1088/1674-0068/21/04/387-392 · Cited by 3 · see citing works
Fundamentals of Atom Transfer Radical Polymerization
Golas, P. L., Mueller, L., & Matyjaszewski, K. A. (2007) · Wiley eBooks · doi:10.1002/0471440264.pst555 · Cited by 3 · see citing works
Mehner, F., Bukane, A. R., Keddie, D. J., Geisler, M., Lederer, A., Voit, B. I., & Gaitzsch, J. (2026) · Communications Chemistry · doi:10.1038/s42004-026-01997-6 · Cited by 2 · see citing works
Mothe, S. R., Ang, P., Lau, H. H., Oh, A. B. Y., & Thoniyot, P. (2023) · Next Materials · doi:10.1016/j.nxmate.2023.100055 · Cited by 2 · see citing works
Zhao, Y. (2002) · Science China Chemistry · doi:10.1360/02yb9019 · Cited by 2 · see citing works
Kitayama, Y., Sakamoto, R., & Harada, A. (2026) · Angewandte Chemie · doi:10.1002/ange.202524666 · Cited by 1 · see citing works
Atom Transfer Radical Polymerization of Styrene Using a Bifunctional Initiator
Yuan, J., Zheng, Q., Tao, L., & Pan, C. (2001) · Chinese Journal of Chemistry · doi:10.1002/cjoc.20010190914
Self-citationSynthesis of (Bio)degradable Polymers by Controlled/“Living” Radical Polymerization
Woodruff, S. R., & Tsarevsky, N. V. (2017) · Wiley eBooks · doi:10.1002/9781118967904.ch11
Кинетические особенности радикальной полимеризации кетенацеталей с раскрытием цикла
Заремский, М. Ю., & Aliev, E. E. (2024) · Высокомолекулярные соединения С · doi:10.31857/s2308114724020019
Deng, Y., Mehner, F., & Gaitzsch, J. (2026) · Elsevier eBooks · doi:10.1016/b978-0-323-95486-0.00202-7
Radical ring-opening polymerization
Sanda, F., & Endo, T. (2001) · Journal of Polymer Science Part A: Polymer Chemistry · doi:10.1002/1099-0518(20010115)39:2
- Authors
- Yuan, J.-Y., Pan, C.-Y., & Tang, B. Z.
- Affiliations
- Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, People's Republic of China, and Department of Chemistry, Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, People's Republic of China
- University of Science and Technology of China (CN)
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2000-12-14
- Volume
- 34
- Issue
- 2
- Pages
- 211-214
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2039537363
- Cited by
- 68
- References
- 23
- Citations by year
- 2026: 4 · 2025: 1 · 2024: 4 · 2023: 3 · 2022: 1 · 2020: 4 · 2019: 1 · 2018: 1 · 2017: 3 · 2016: 3 · 2015: 4 · 2014: 1 · 2013: 3 · 2012: 4
- FWCI
- 3.76
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Rare & Special e-Zone (The Hong Kong University of Science and Technology) (submittedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Photopolymerization techniques and applications
- Keywords
- atom transfer radical polymerization, copper bromide, 2,2'-bipyridine, polydispersity, molecular weight growth
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