Polycaprolactone-based novel degradable ionomers by radical ring-opening polymerization of 2-methylene-1,3-dioxepane
Abstract
This work reports the first successful synthesis of polycaprolactone (PCL)-based degradable ionomers using free-radical chemistry. Degradable cationic ionomers were synthesized by random radical terpolymerization of 2-methylene-1,3-dioxepane (MDO), methyl methacrylate (MMA), and N,N -dimethylaminoethyl methacrylate (DMAEMA) and followed by quaternization of amine with alkyl bromide. The terpolymerization of MDO, MMA, and DMAEMA led to a polymer with ester group randomly distributed in the polymer chains. The small-angle X-ray scattering (SAXS) analysis, the transmission electron microscope (TEM), and dynamic mechanical analysis (DMA) showed ionic aggregates existing in ionomers. Ionomers quaternized by ethyl bromide showed relative strong ionic interaction and showed aggregates with a diameter around 30 nm, which had a separate glass transition temperature ( T g ) and performed rather as filler material. Ionomers containing 40 mol % of ester group and 20 mol % of ionic group showed biodegradability after being buried in compost.
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?
Increasing interest in biodegradable polyesters and the versatility of RROP with respect to structures accessible via different monomers and their copolymerization with conventional vinyl monomers has changed the situation significantly.
“However, with the increasing interest in biodegradable polyesters and the versatility of RROP with respect to the structures accessible via very different monomers [25] and their copolymerization with conventional vinyl monomers [26 -34] has changed the situation significantly.”
From Ring-Opening Polymerization—An Introductory Review (2013) · cites this paper as [28]
Cites
Theory of Filler Reinforcement
Guth, E. (1945) · Journal of Applied Physics · doi:10.1063/1.1707495 · Cited by 1,235 · see citing works
A new multiplet-cluster model for the morphology of random ionomers
Eisenberg, A., Hird, B., & Moore, R. B. (1990) · Macromolecules · doi:10.1021/ma00220a012 · Cited by 958 · see citing works
Lutz, J., Andrieu, J., Üzgün, S., Rudolph, C., & Agarwal, S. (2007) · Macromolecules · doi:10.1021/ma7021474 · Cited by 294 · see citing works
Bailey, W. J., Ni, Z., & Wu, S. (1982) · Journal of Polymer Science Polymer Chemistry Edition · doi:10.1002/pol.1982.170201101 · Cited by 259 · 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
Wickel, H., Agarwal, S., & Greiner, A. (2003) · Macromolecules · doi:10.1021/ma025983u · Cited by 88 · see citing works
Ishida, K., Wang, Y., & Inoue, Y. (2001) · Biomacromolecules · doi:10.1021/bm010115a · Cited by 67 · see citing works
Dynamic mechanical and melt rheological properties of sulfonated poly(butylene succinate) ionomers
Han, S., Im, S. S., & Kim, D. K. (2003) · Polymer · doi:10.1016/s0032-3861(03)00673-6 · Cited by 67 · see citing works
Dielectric and Mechanical Relaxations in a Nafion Precursor
Hodge, I. M., & Eisenberg, A. (1978) · Macromolecules · doi:10.1021/ma60062a002 · Cited by 60 · see citing works
Ren, L., & Agarwal, S. (2007) · Macromolecular Chemistry and Physics · doi:10.1002/macp.200600484 · Cited by 60 · see citing works
Microstructural Characterisation and Properties Evaluation of Poly (methyl methacrylate-co-ester)s
Agarwal, S. (2006) · Polymer Journal · doi:10.1295/polymj.pj2006137 · Cited by 57 · see citing works
Biodegradable Aliphatic Polyester Ionomers
Han, S., Yoo, Y., Kim, D. K., & Im, S. S. (2004) · Macromolecular Bioscience · doi:10.1002/mabi.200300095 · Cited by 46 · see citing works
Ren, L., Speyerer, C., & Agarwal, S. (2007) · Macromolecules · doi:10.1021/ma0711588 · Cited by 39 · see citing works
Agarwal, S. (2006) · Journal of Polymer Research · doi:10.1007/s10965-006-9058-6 · Cited by 30 · see citing works
Physical properties and biodegradation of poly(butylene adipate) ionomers
Yoo, Y. T., Lee, B. J., Han, S., Im, S. S., & Kim, D. K. (2002) · Polymer Degradation and Stability · doi:10.1016/s0141-3910(02)00289-6 · Cited by 26 · see citing works
Infrared Studies of Ionic Aggregation of Ethylene- and Butadiene-Based Ionomers
Andreeva, E. D., Никитин, В. Н., & Boyartchuk, Y. M. (1976) · Macromolecules · doi:10.1021/ma60050a012 · Cited by 18 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
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
Degradable vinyl polymers for biomedical applications
Delplace, V., & Nicolas, J. (2015) · Nature Chemistry · doi:10.1038/nchem.2343 · Cited by 400 · see citing works
PDMAEMA based gene delivery materials
Agarwal, S., Zhang, Y., Maji, S., & Greiner, A. (2012) · Materials Today · doi:10.1016/s1369-7021(12)70165-7 · Cited by 343 · see citing works
Plastic Pollution: A Material Problem?
Millican, J. M., & Agarwal, S. (2021) · Macromolecules · doi:10.1021/acs.macromol.0c02814 · Cited by 267 · see citing works
Agarwal, S. (2010) · Polymer Chemistry · doi:10.1039/c0py00040j · Cited by 263 · see citing works
Self-assembled polymer nanostructures for delivery of anticancer therapeutics
Wiradharma, N., Zhang, Y., Venkataraman, S., Hedrick, J. L., & Yang, Y. Y. (2009) · Nano Today · doi:10.1016/j.nantod.2009.06.001 · Cited by 191 · see citing works
Polymer Colloids: Current Challenges, Emerging Applications, and New Developments
Aguirre, M., Ballard, N., González, E., Hamzehlou, S., Sardón, H., Calderón, M., Paulis, M., Tomovská, R., Dupin, D., Bean, R. H., et al. (2023) · Macromolecules · doi:10.1021/acs.macromol.3c00108 · Cited by 131 · see citing works
Delplace, V., Tardy, A., Harrisson, S., Mura, S., Gigmès, D., Guillaneuf, Y., & Nicolas, J. (2013) · Biomacromolecules · doi:10.1021/bm401157g · Cited by 109 · see citing works
Lefay, C., & Guillaneuf, Y. (2023) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2023.101764 · Cited by 101 · 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
Zhang, Y., Chu, D., Zheng, M., Kissel, T., & Agarwal, S. (2012) · Polymer Chemistry · doi:10.1039/c2py20403g · Cited by 86 · see citing works
Li, Y., Hu, X., Tian, S., Li, Y., Zhang, G., Zhang, G., & Liu, S. (2013) · Biomaterials · doi:10.1016/j.biomaterials.2013.10.077 · Cited by 77 · see citing works
Zeng, T., You, W., Chen, G., Nie, X., Zhang, Z., Xia, L., Hong, C., Chen, C., & You, Y. (2020) · iScience · doi:10.1016/j.isci.2020.100904 · Cited by 75 · see citing works
Guégain, E., Michel, J., Boissenot, T., & Nicolas, J. (2018) · Macromolecules · doi:10.1021/acs.macromol.7b02655 · Cited by 72 · see citing works
Design and fabrication of functional polycaprolactone
Chen, T., Cai, T., Jin, Q., & Ji, J. (2015) · e-Polymers · doi:10.1515/epoly-2014-0158 · Cited by 71 · see citing works
Tran, J., Guégain, E., Ibrahim, N., Harrisson, S., & Nicolas, J. (2016) · Polymer Chemistry · doi:10.1039/c6py00778c · Cited by 69 · see citing works
Jin, Q., Maji, S., & Agarwal, S. (2012) · Polymer Chemistry · doi:10.1039/c2py20364b · Cited by 58 · see citing works
Guégain, E., Tran, J., Deguettes, Q., & Nicolas, J. (2018) · Chemical Science · doi:10.1039/c8sc02256a · Cited by 55 · see citing works
Tran, J., Pesenti, T., Cressonnier, J., Lefay, C., Gigmès, D., Guillaneuf, Y., & Nicolas, J. (2018) · Biomacromolecules · doi:10.1021/acs.biomac.8b01500 · Cited by 52 · see citing works
Ko, K., Lundberg, D. J., Johnson, A. M., & Johnson, J. A. (2024) · Journal of the American Chemical Society · doi:10.1021/jacs.3c14554 · Cited by 45 · 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
Main-chain degradable single-chain cyclized polymers as gene delivery vectors
Gao, Y., Böhmer, V. I., Zhou, D., Zhao, T., Wang, W., & Paulusse, J. M. J. (2016) · Journal of Controlled Release · doi:10.1016/j.jconrel.2016.07.046 · Cited by 41 · see citing works
Biodegradable phosphorylcholine copolymer for cardiovascular stent coating
Liu, J., Wang, J., Xue, Y., Chen, T., Huang, D., Wang, Y., Ren, K., Wang, Y., Fu, G., & Ji, J. (2020) · Journal of Materials Chemistry B · doi:10.1039/d0tb00813c · Cited by 40 · see citing works
Functional Degradable Polymers via Radical Ring‐Opening Polymerization and Click Chemistry
Maji, S., Zheng, M., & Agarwal, S. (2011) · Macromolecular Chemistry and Physics · doi:10.1002/macp.201100375 · Cited by 39 · see citing works
Enzymatically Degradable Polyester-Based Adhesives
Shi, Y., Zhou, P., Jérôme, V., Freitag, R., & Agarwal, S. (2015) · ACS Biomaterials Science & Engineering · doi:10.1021/acsbiomaterials.5b00217 · Cited by 37 · see citing works
Hyperbranched Polycaprolactone through RAFT Polymerization of 2-Methylene-1,3-dioxepane
Xu, P., Huang, X., Pan, X., Li, N., Zhu, J., & Zhu, X. (2019) · Polymers · doi:10.3390/polym11020318 · Cited by 31 · see citing works
Shi, Y., & Agarwal, S. (2015) · e-Polymers · doi:10.1515/epoly-2015-0096 · Cited by 29 · see citing works
Pesenti, T., Zhu, C., Gonzalez-Martinez, N., Tomás, R. M. F., Gibson, M. I., & Nicolas, J. (2022) · ACS Macro Letters · doi:10.1021/acsmacrolett.2c00298 · Cited by 25 · see citing works
Zeng, T., Xia, L., Zhang, Z., Hong, C., & You, Y. (2020) · Polymer Chemistry · doi:10.1039/d0py00200c · Cited by 23 · see citing works
Ai, X., Pan, J., Xie, Q., Ma, C., & Zhang, G. (2021) · Polymer Chemistry · doi:10.1039/d1py00810b · Cited by 22 · see citing works
Degradable elastomeric block copolymers based on polycaprolactone by free-radical chemistry
Grabe, N., Zhang, Y., & Agarwal, S. (2011) · Macromolecular Chemistry and Physics · doi:10.1002/macp.201100031 · Cited by 20 · see citing works
Tungchaiwattana, S., Groves, R., Lovell, P. A., Pinprayoon, O., & Saunders, B. R. (2012) · Journal of Materials Chemistry · doi:10.1039/c2jm16223g · Cited by 18 · see citing works
Synthesis and properties evaluation of quaternized polyurethanes as antibacterial adhesives
Pin, H., Greiner, A., & Agarwal, S. (2019) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.29321 · Cited by 18 · see citing works
Synthesis, properties and applications of degradable ionomers
Johnston, P., & Adhikari, R. (2017) · European Polymer Journal · doi:10.1016/j.eurpolymj.2017.08.009 · Cited by 17 · see citing works
Asoh, T., Nakajima, T., Matsuyama, T., & Kikuchi, A. (2015) · Langmuir · doi:10.1021/acs.langmuir.5b01149 · Cited by 17 · see citing works
Agarwal, S. (2012) · Elsevier eBooks · doi:10.1016/b978-0-444-53349-4.00145-x · Cited by 15 · see citing works
Joubert, F., & Pasparakis, G. (2020) · Journal of Polymer Science · doi:10.1002/pol.20200303 · Cited by 13 · see citing works
Biodegradable polyacrylate copolymer coating for bio-functional magnesium alloy
Shi, H., Hong, L., Pan, K., Wei, W., Liu, X., & Li, X. (2021) · Progress in Organic Coatings · doi:10.1016/j.porgcoat.2021.106422 · Cited by 12 · see citing works
Degradable Vinyl-Based Polymers by Radical Ring-Opening Polymerization: A User Guide
Luzel, B., Kouider, S., D’Agosto, F., Gigmès, D., Lansalot, M., Bates, C. M., Ackerman, E., Labalme, S., Johnson, J. A., Niu, J., et al. (2026) · ACS Polymers Au · doi:10.1021/acspolymersau.5c00191 · Cited by 11 · see citing works
Truong, T. T., Thai, S. H., Nguyên, H. T., Vuong, V., & Nguyen, L.-T. T. (2017) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.28454 · Cited by 10 · see citing works
Zhao, K., Pi, B., Zhao, L., Tian, S., Ge, J., Yang, H., Sha, W., & Wang, L. (2019) · RSC Advances · doi:10.1039/c9ra01638d · Cited by 10 · see citing works
Tungchaiwattana, S., Musa, M. S., Yan, J., Lovell, P. A., Shaw, P. L., & Saunders, B. R. (2014) · Soft Matter · doi:10.1039/c4sm00695j · Cited by 7 · see citing works
Hiraguri, Y., & Aiba, S. (2014) · Journal of Macromolecular Science Part A · doi:10.1080/10601325.2014.916180 · Cited by 7 · 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
Shi, Y., Zheng, Z., & Agarwal, S. (2014) · Chemistry - A European Journal · doi:10.1002/chem.201400238 · Cited by 4 · see citing works
Nakayama, Y., MATSUBARA, N., Tanaka, R., Cai, Z., Shiono, T., Shirahama, H., & Tsutsumi, C. (2014) · Journal of the Japan Institute of Energy · doi:10.3775/jie.93.916 · Cited by 4 · see citing works
Hyat, M. K., Hassan, A., Sajid, I., Das, R., Zhou, S., Irfan, A., Shahid, M., Begum, R., & Farooqi, Z. H. (2026) · Reactive and Functional Polymers · doi:10.1016/j.reactfunctpolym.2026.106777 · Cited by 3 · see citing works
Design of Soft Materials from Liquid Triblock Co-Oligomers and Metal Nanoparticles
Pletsch, H., Schnepf, M. J., & Agarwal, S. (2014) · Chemistry of Materials · doi:10.1021/cm502322g · Cited by 3 · see citing works
Functional (Bio)degradable Polyesters by Radical Ring‐Opening Polymerization
Agarwal, S. (2015) · Wiley eBooks · doi:10.1002/9783527656950.ch2 · Cited by 2 · see citing works
Antibacterial piperazine‐derived quaternized copolyesters with controlled degradability
Goel, S., Kaur, M., Singh, N., & Jacob, J. (2023) · Journal of Applied Polymer Science · doi:10.1002/app.53677
Deng, Y., Mehner, F., & Gaitzsch, J. (2026) · Elsevier eBooks · doi:10.1016/b978-0-323-95486-0.00202-7
Ying, Y., Wu, Y., 郭锦棠, & Hu, M. (2026) · Chemical Engineering Journal · doi:10.1016/j.cej.2026.182753
- Authors
- Seema, A., & Liqun, R.
- Affiliations
- Philipps University of Marburg (DE)
- Philipps-Universität Marburg, Fachbereich Chemie, Hans Meerwein Strasse, D-35032 Marburg, Germany
- Corresponding author
- Seema, Agarwal
- ORCID
- Seema, Agarwal
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2009-02-05
- Volume
- 42
- Issue
- 5
- Pages
- 1574-1579
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2010358903
- Cited by
- 58
- References
- 17
- Citations by year
- 2026: 5 · 2024: 1 · 2023: 3 · 2022: 2 · 2021: 3 · 2020: 6 · 2019: 4 · 2018: 4 · 2017: 3 · 2016: 2 · 2015: 6 · 2014: 6 · 2013: 3 · 2012: 6
- FWCI
- 1.46
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Keywords
- polycaprolactone, 2-methylene-1,3-dioxepane, radical ring-opening polymerization, terpolymerization, methyl methacrylate, N,N-dimethylaminoethyl methacrylate, quaternization, ionic aggregates, biodegradability, composting, glass transition temperature, fillers
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