The DOI matches its Crossref record.
A Surprise from 1954: Siloxane Equilibration Is a Simple, Robust, and Obvious Polymer Self-Healing Mechanism
Abstract
Tetramethylammonium silanolate-initiated ring-opening copolymerization of octamethylcyclotetrasiloxane (D(4)) and bis(heptamethylcyclotetrasiloxanyl)ethane (bis-D(4)) renders cross-linked network polymers that contain ethylene bridges and active silanolate end groups. These "living" reactive anionic species are not neutralized by ambient atmosphere exposure (are stable to water, oxygen, CO(2)) and promote thermally activated equilibration among different network isomers and cyclic oligomers. The cross-link density of these living networks can be controlled by the ratio of D(4):bis-D(4), and the density of active chain ends is determined from the initiator:monomer ratio. We report that samples prepared with particular ratios of initiator:D(4):bis-D(4) can be cut with a sharp knife, even into two pieces, and can heal by siloxane equilibration to restore the original strength of the silicone sample. Fracture toughness measurements were carried out and revealed complete (mechanical) healing. Broken and healed samples generally failed in locations other than the initially cracked region. We call attention to publications and patents from the 1950s that suggest that this self-healing behavior was likely obvious 60 years ago.
Overview
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Integrity signals
Registry
Cites
Statistics
Verification
Claims the paper makes
The claims and statistics of this paper haven’t been checked yet.
Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.
Self-check
Percentages, sums and reported differences re-computed from the paper’s own numbers.
The self-check needs the paper’s full text.
Citations
Cited by
Self-healing polymeric materials
Yang, Y., & Urban, M. W. (2013) · Chemical Society Reviews · doi:10.1039/c3cs60109a · Cited by 1,444
Wang, S., & Urban, M. W. (2020) · Nature Reviews Materials · doi:10.1038/s41578-020-0202-4 · Cited by 1,374
Covalent adaptable networks: smart, reconfigurable and responsive network systems
Kloxin, C. J., & Bowman, C. N. (2013) · Chem. Soc. Rev. · doi:10.1039/c3cs60046g · Cited by 1,370
Catalytic Control of the Vitrimer Glass Transition
Capelot, M., Unterlass, M. M., Tournilhac, F., & Leibler, L. (2012) · ACS Macro Letters · doi:10.1021/mz300239f · Cited by 1,206
Metal-Catalyzed Transesterification for Healing and Assembling of Thermosets
Capelot, M., Montarnal, D., Tournilhac, F., & Leibler, L. (2012) · Journal of the American Chemical Society · doi:10.1021/ja302894k · Cited by 1,198
Dynamic Covalent Polymer Networks: from Old Chemistry to Modern Day Innovations
Zou, W., Dong, J., Luo, Y., Zhao, Q., & Xie, T. (2017) · Advanced Materials · doi:10.1002/adma.201606100 · Cited by 1,014
Dynamic Covalent Bonds in Polymeric Materials
Chakma, P., & Konkolewicz, D. (2019) · Angewandte Chemie International Edition · doi:10.1002/anie.201813525 · Cited by 1,014
Dynamic urea bond for the design of reversible and self-healing polymers
Ying, H., Zhang, Y., & Cheng, J. (2014) · Nature Communications · doi:10.1038/ncomms4218 · Cited by 988
Scheutz, G. M., Lessard, J. J., Sims, M. B., & Sumerlin, B. S. (2019) · Journal of the American Chemical Society · doi:10.1021/jacs.9b07922 · Cited by 934
Heat‐ or Water‐Driven Malleability in a Highly Recyclable Covalent Network Polymer
Taynton, P., Yu, K., Shoemaker, R. K., Jin, Y., Qi, H. J., & Zhang, W. (2014) · Advanced Materials · doi:10.1002/adma.201400317 · Cited by 890
PDMS with designer functionalities—Properties, modifications strategies, and applications
Wolf, M. P., Salieb-Beugelaar, G. B., & Hunziker, P. (2018) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2018.06.001 · Cited by 853
Mechanically Activated, Catalyst-Free Polyhydroxyurethane Vitrimers
Fortman, D. J., Brutman, J. P., Cramer, C. J., Hillmyer, M. A., & Dichtel, W. R. (2015) · Journal of the American Chemical Society · doi:10.1021/jacs.5b08084 · Cited by 811
Dynamic covalent chemistry in polymer networks: a mechanistic perspective
Winne, J. M., Leibler, L., & Du Prez, F. E. (2019) · Polymer Chemistry · doi:10.1039/c9py01260e · Cited by 736
Vitrimers: Permanently crosslinked polymers with dynamic network topology
Van Zee, N. J., & Nicolaÿ, R. (2020) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2020.101233 · Cited by 734
Stretchable and self-healing polymers and devices for electronic skin
Benight, S. J., Wang, C., Tok, J. B. H., & Bao, Z. (2013) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2013.08.001 · Cited by 617
Thermoset Shape‐Memory Polyurethane with Intrinsic Plasticity Enabled by Transcarbamoylation
Zheng, N., Fang, Z., Zou, W., Zhao, Q., & Xie, T. (2016) · Angewandte Chemie International Edition · doi:10.1002/anie.201602847 · Cited by 607
Silyl Ether as a Robust and Thermally Stable Dynamic Covalent Motif for Malleable Polymer Design
Nishimura, Y., Chung, J., Muradyan, H., & Guan, Z. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.7b08826 · Cited by 586
Zhang, Z. P., Rong, M. Z., & Zhang, M. Q. (2018) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2018.03.002 · Cited by 586
Lei, Z. Q., Xiang, H. P., Yuan, Y. J., Rong, M. Z., & Zhang, M. Q. (2014) · Chemistry of Materials · doi:10.1021/cm4040616 · Cited by 578
Making Insoluble Polymer Networks Malleable via Olefin Metathesis
Lu, Y.-X., Tournilhac, F., Leibler, L., & Guan, Z. (2012) · Journal of the American Chemical Society · doi:10.1021/ja303356z · Cited by 568
Approaches to Sustainable and Continually Recyclable Cross-Linked Polymers
Fortman, D. J., Brutman, J. P., De Hoe, G. X., Snyder, R. L., Dichtel, W. R., & Hillmyer, M. A. (2018) · ACS Sustainable Chemistry & Engineering · doi:10.1021/acssuschemeng.8b02355 · Cited by 559
Chemical and physical aspects of self-healing materials
Yang, Y., Ding, X., & Urban, M. W. (2015) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2015.06.001 · Cited by 536
Shape memory polymer network with thermally distinct elasticity and plasticity
Zhao, Q., Zou, W., Luo, Y., & Xie, T. (2016) · Science Advances · doi:10.1126/sciadv.1501297 · Cited by 514
Poly(vinyl alcohol) Hydrogel Can Autonomously Self-Heal
Zhang, H., Xia, H., & Zhao, Y. (2012) · ACS Macro Letters · doi:10.1021/mz300451r · Cited by 509
Neal, J. A., Mozhdehi, D., & Guan, Z. (2015) · Journal of the American Chemical Society · doi:10.1021/jacs.5b01601 · Cited by 465
Diesendruck, C. E., Sottos, N. R., Moore, J. S., & White, S. R. (2015) · Angewandte Chemie International Edition · doi:10.1002/anie.201500484 · Cited by 455
Li, L., Chen, X., Jin, K., & Torkelson, J. M. (2018) · Macromolecules · doi:10.1021/acs.macromol.8b00922 · Cited by 424
Oxime-Based and Catalyst-Free Dynamic Covalent Polyurethanes
Liu, W.-X., Zhang, C., Zhang, H., Zhao, N., Yu, Z.-X., & Xu, J. (2017) · Journal of the American Chemical Society · doi:10.1021/jacs.7b03967 · Cited by 426
Boronic Ester Based Vitrimers with Enhanced Stability via Internal Boron–Nitrogen Coordination
Zhang, X., Wang, S., Jiang, Z., Li, Y., & Jing, X. (2020) · Journal of the American Chemical Society · doi:10.1021/jacs.0c10244 · Cited by 363
Malleable and Recyclable Thermosets: The Next Generation of Plastics
Jin, Y., Lei, Z., Taynton, P., Huang, S., & Zhang, W. (2019) · Matter · doi:10.1016/j.matt.2019.09.004 · Cited by 359
Li, X., Yu, R., He, Y., Zhang, Y., Yang, X., Zhao, X., & Huang, W. (2019) · ACS Macro Letters · doi:10.1021/acsmacrolett.9b00766 · Cited by 355
Azcune, I., & Odriozola, I. (2016) · European Polymer Journal · doi:10.1016/j.eurpolymj.2016.09.023 · Cited by 339
Carbon nanotube–vitrimer composite for facile and efficient photo-welding of epoxy
Yang, Y., Pei, Z., Zhang, X., Tao, L., Wei, Y., & Ji, Y. (2014) · Chem. Sci. · doi:10.1039/c4sc00543k · Cited by 320
Self‐Healing Supramolecular Block Copolymers
Hentschel, J., Kushner, A. M., Ziller, J., & Guan, Z. (2012) · Angewandte Chemie International Edition · doi:10.1002/anie.201204840 · Cited by 309
Bao, C., Jiang, Y., Zhang, H., Lu, X., & Sun, J. (2018) · Advanced Functional Materials · doi:10.1002/adfm.201800560 · Cited by 266
Cao, L., Fan, J., Huang, J., & Chen, Y. (2019) · Journal of Materials Chemistry A · doi:10.1039/c8ta11587g · Cited by 266
Poly(oxime–ester) Vitrimers with Catalyst-Free Bond Exchange
He, C., Shi, S., Wang, D., Helms, B. A., & Russell, T. P. (2019) · Journal of the American Chemical Society · doi:10.1021/jacs.9b06668 · Cited by 229
Li, L., Chen, X., & Torkelson, J. M. (2019) · Macromolecules · doi:10.1021/acs.macromol.9b01359 · Cited by 224
Light-triggered topological programmability in a dynamic covalent polymer network
Zou, W., Jin, B., Wu, Y., Song, H., Luo, Y., Huang, F., Qian, J., Zhao, Q., & Xie, T. (2020) · Science Advances · doi:10.1126/sciadv.aaz2362 · Cited by 143
Visible Light-Induced Plasticity of Shape Memory Polymers
Ji, S., Fan, F., Sun, C., Yu, Y., & Xu, H. (2017) · ACS Applied Materials & Interfaces · doi:10.1021/acsami.7b11188 · Cited by 134
Zhang, G., Zhao, Q., Zou, W., Luo, Y., & Xie, T. (2016) · Advanced Functional Materials · doi:10.1002/adfm.201504028 · Cited by 73
Metadata
- Authors
- Zheng, P., & McCarthy, T. J.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-01-20
- Volume
- 134
- Issue
- 4
- Pages
- 2024-2027
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W1966698178
- Cited by
- 625
- References
- 0
- FWCI
- 22.13
- Type
- journal article
- Language
- en
- Open access
- closed
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
Data sources
Bibliographic data: Semantic Scholar, OpenAlex, Crossref.
Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).
Semantic Scholar’s data is described in: Kinney, R., et al. (2023). The Semantic Scholar Open Data Platform. arXiv:2301.10140.