Dynamic Bottlebrush Polymer Networks: Self-Healing in Super-Soft Materials
Abstract
Here, we introduce a design strategy to expand the range of accessible mechanical properties in covalent adaptable networks (CANs) using bottlebrush polymer building blocks. Well-defined bottlebrush polymers with rubbery poly(4-methylcaprolactone) side-chains were crosslinked in formulations that include a bislactone and strong Lewis acid (tin ethylhexanoate). The resulting materials exhibit tunable stress relaxation rates at elevated temperatures (160–180 °C) due to dynamic ester crosslinks that undergo transesterification with residual hydroxy groups. Varying the crosslinker loading or bottlebrush backbone degree of polymerization yields predictable low-frequency shear moduli ca. 10–100 kPa, well below values typical of linear polymer CANs (1 MPa). These extensible networks can be stretched to strains as large as 350% before failure and undergo efficient self-healing to recover >85% of their original toughness upon repeated fracture and melt processing. In summary, molecular architecture creates new opportunities to tailor the mechanical properties of CANs in ways that are otherwise difficult to achieve.
- Publication Date:
- Research Org.:
- Univ. of California, Santa Barbara, CA (United States)
- Sponsoring Org.:
- US DOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
- OSTI Identifier:
- 1615621
- Grant/Contract Number:
- SC0019001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 142; Journal Issue: 16; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysts; self healing materials; nucleic acid structure; materials; polymers
Citation Formats
Self, Jeffrey L., Sample, Caitlin S., Levi, Adam E., Li, Kexin, Xie, Renxuan, de Alaniz, Javier Read, and Bates, Christopher M. Dynamic Bottlebrush Polymer Networks: Self-Healing in Super-Soft Materials. United States: N. p., 2020.
Web. doi:10.1021/jacs.0c01467.
Self, Jeffrey L., Sample, Caitlin S., Levi, Adam E., Li, Kexin, Xie, Renxuan, de Alaniz, Javier Read, & Bates, Christopher M. Dynamic Bottlebrush Polymer Networks: Self-Healing in Super-Soft Materials. United States. https://doi.org/10.1021/jacs.0c01467
Self, Jeffrey L., Sample, Caitlin S., Levi, Adam E., Li, Kexin, Xie, Renxuan, de Alaniz, Javier Read, and Bates, Christopher M. Tue .
"Dynamic Bottlebrush Polymer Networks: Self-Healing in Super-Soft Materials". United States. https://doi.org/10.1021/jacs.0c01467. https://www.osti.gov/servlets/purl/1615621.
@article{osti_1615621,
title = {Dynamic Bottlebrush Polymer Networks: Self-Healing in Super-Soft Materials},
author = {Self, Jeffrey L. and Sample, Caitlin S. and Levi, Adam E. and Li, Kexin and Xie, Renxuan and de Alaniz, Javier Read and Bates, Christopher M.},
abstractNote = {Here, we introduce a design strategy to expand the range of accessible mechanical properties in covalent adaptable networks (CANs) using bottlebrush polymer building blocks. Well-defined bottlebrush polymers with rubbery poly(4-methylcaprolactone) side-chains were crosslinked in formulations that include a bislactone and strong Lewis acid (tin ethylhexanoate). The resulting materials exhibit tunable stress relaxation rates at elevated temperatures (160–180 °C) due to dynamic ester crosslinks that undergo transesterification with residual hydroxy groups. Varying the crosslinker loading or bottlebrush backbone degree of polymerization yields predictable low-frequency shear moduli ca. 10–100 kPa, well below values typical of linear polymer CANs (1 MPa). These extensible networks can be stretched to strains as large as 350% before failure and undergo efficient self-healing to recover >85% of their original toughness upon repeated fracture and melt processing. In summary, molecular architecture creates new opportunities to tailor the mechanical properties of CANs in ways that are otherwise difficult to achieve.},
doi = {10.1021/jacs.0c01467},
journal = {Journal of the American Chemical Society},
number = 16,
volume = 142,
place = {United States},
year = {Tue Mar 31 00:00:00 EDT 2020},
month = {Tue Mar 31 00:00:00 EDT 2020}
}
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Works referenced in this record:
Direct Silyl Ether Metathesis for Vitrimers with Exceptional Thermal Stability
journal, September 2019
- Tretbar, Chase A.; Neal, James A.; Guan, Zhibin
- Journal of the American Chemical Society, Vol. 141, Issue 42
Making Insoluble Polymer Networks Malleable via Olefin Metathesis
journal, May 2012
- Lu, Yi-Xuan; Tournilhac, François; Leibler, Ludwik
- Journal of the American Chemical Society, Vol. 134, Issue 20
Room-Temperature Self-Healing Polymers Based on Dynamic-Covalent Boronic Esters
journal, March 2015
- Cash, Jessica J.; Kubo, Tomohiro; Bapat, Abhijeet P.
- Macromolecules, Vol. 48, Issue 7
High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis
journal, April 2017
- Röttger, Max; Domenech, Trystan; van der Weegen, Rob
- Science, Vol. 356, Issue 6333
Silica-Like Malleable Materials from Permanent Organic Networks
journal, November 2011
- Montarnal, D.; Capelot, M.; Tournilhac, F.
- Science, Vol. 334, Issue 6058
A fully bio-based polyimine vitrimer derived from fructose
journal, January 2019
- Dhers, Sébastien; Vantomme, Ghislaine; Avérous, Luc
- Green Chemistry, Vol. 21, Issue 7
Varying PEG density to control stress relaxation in alginate-PEG hydrogels for 3D cell culture studies
journal, April 2019
- Nam, Sungmin; Stowers, Ryan; Lou, Junzhe
- Biomaterials, Vol. 200
Self-Healing Boronic Acid-Based Hydrogels for 3D Co-cultures
journal, August 2018
- Smithmyer, Megan E.; Deng, Christopher C.; Cassel, Samantha E.
- ACS Macro Letters, Vol. 7, Issue 9
Stress relaxing hyaluronic acid-collagen hydrogels promote cell spreading, fiber remodeling, and focal adhesion formation in 3D cell culture
journal, February 2018
- Lou, Junzhe; Stowers, Ryan; Nam, Sungmin
- Biomaterials, Vol. 154
Adaptable Crosslinks in Polymeric Materials: Resolving the Intersection of Thermoplastics and Thermosets
journal, September 2019
- Scheutz, Georg M.; Lessard, Jacob J.; Sims, Michael B.
- Journal of the American Chemical Society, Vol. 141, Issue 41
Recyclable and Malleable Epoxy Thermoset Bearing Aromatic Imine Bonds
journal, November 2018
- Zhao, Shou; Abu-Omar, Mahdi M.
- Macromolecules, Vol. 51, Issue 23
Catechol-Mediated Glycidylation toward Epoxy Vitrimers/Polymers with Tunable Properties
journal, May 2019
- Zhao, Shou; Abu-Omar, Mahdi M.
- Macromolecules, Vol. 52, Issue 10
Malleable and Self-Healing Covalent Polymer Networks through Tunable Dynamic Boronic Ester Bonds
journal, May 2015
- Cromwell, Olivia R.; Chung, Jaeyoon; Guan, Zhibin
- Journal of the American Chemical Society, Vol. 137, Issue 20
Dynamic Covalent Polymer Networks Based on Degenerative Imine Bond Exchange: Tuning the Malleability and Self-Healing Properties by Solvent
journal, August 2016
- Chao, Albert; Negulescu, Ioan; Zhang, Donghui
- Macromolecules, Vol. 49, Issue 17
Poly(thioether) Vitrimers via Transalkylation of Trialkylsulfonium Salts
journal, August 2017
- Hendriks, Benjamin; Waelkens, Jelle; Winne, Johan M.
- ACS Macro Letters, Vol. 6, Issue 9
Olefin Metathesis for Effective Polymer Healing via Dynamic Exchange of Strong Carbon–Carbon Double Bonds
journal, August 2012
- Lu, Yi-Xuan; Guan, Zhibin
- Journal of the American Chemical Society, Vol. 134, Issue 34
Vitrimeric Silicone Elastomers Enabled by Dynamic Meldrum’s Acid-Derived Cross-Links
journal, March 2018
- Ishibashi, Jacob S. A.; Kalow, Julia A.
- ACS Macro Letters, Vol. 7, Issue 4
Catalytic Control of the Vitrimer Glass Transition
journal, June 2012
- Capelot, Mathieu; Unterlass, Miriam M.; Tournilhac, François
- ACS Macro Letters, Vol. 1, Issue 7
Brønsted-Acid-Catalyzed Exchange in Polyester Dynamic Covalent Networks
journal, June 2018
- Self, Jeffrey L.; Dolinski, Neil D.; Zayas, Manuel S.
- ACS Macro Letters, Vol. 7, Issue 7
Mechanically Activated, Catalyst-Free Polyhydroxyurethane Vitrimers
journal, November 2015
- Fortman, David J.; Brutman, Jacob P.; Cramer, Christopher J.
- Journal of the American Chemical Society, Vol. 137, Issue 44
Catalyst-Free Vitrimers from Vinyl Polymers
journal, February 2019
- Lessard, Jacob J.; Garcia, Luis F.; Easterling, Charles P.
- Macromolecules, Vol. 52, Issue 5
Chemical control of the viscoelastic properties of vinylogous urethane vitrimers
journal, March 2017
- Denissen, Wim; Droesbeke, Martijn; Nicolaÿ, Renaud
- Nature Communications, Vol. 8, Issue 1
Reprocessing Cross-Linked Polyurethanes by Catalyzing Carbamate Exchange
journal, August 2019
- Fortman, David J.; Sheppard, Daylan T.; Dichtel, William R.
- Macromolecules, Vol. 52, Issue 16
Reversibly tuning hydrogel stiffness through photocontrolled dynamic covalent crosslinks
journal, January 2018
- Accardo, Joseph V.; Kalow, Julia A.
- Chemical Science, Vol. 9, Issue 27
Photoinduced Plasticity in Cross-Linked Polymers
journal, June 2005
- Scott, T. F.
- Science, Vol. 308, Issue 5728
CO 2 -Cross-Linked Frustrated Lewis Networks as Gas-Regulated Dynamic Covalent Materials
journal, December 2018
- Chen, Liang; Liu, Renjie; Hao, Xiang
- Angewandte Chemie, Vol. 131, Issue 1
Block Copolymer Vitrimers
journal, December 2019
- Lessard, Jacob J.; Scheutz, Georg M.; Sung, Seung Hyun
- Journal of the American Chemical Society, Vol. 142, Issue 1
Inherently Photohealable and Thermal Shape-Memory Polydisulfide Networks
journal, July 2013
- Michal, Brian T.; Jaye, Colin A.; Spencer, Emily J.
- ACS Macro Letters, Vol. 2, Issue 8
Shape memory polymer network with thermally distinct elasticity and plasticity
journal, January 2016
- Zhao, Qian; Zou, Weike; Luo, Yingwu
- Science Advances, Vol. 2, Issue 1
Multiblock Polymers: Panacea or Pandora's Box?
journal, April 2012
- Bates, F. S.; Hillmyer, M. A.; Lodge, T. P.
- Science, Vol. 336, Issue 6080
Star Polymers
journal, June 2016
- Ren, Jing M.; McKenzie, Thomas G.; Fu, Qiang
- Chemical Reviews, Vol. 116, Issue 12
Miktoarm Stars via Grafting-Through Copolymerization: Self-Assembly and the Star-to-Bottlebrush Transition
journal, February 2019
- Levi, Adam E.; Lequieu, Joshua; Horne, Jacob D.
- Macromolecules, Vol. 52, Issue 4
Efficient Synthesis of Asymmetric Miktoarm Star Polymers
journal, January 2020
- Levi, Adam E.; Fu, Liangbing; Lequieu, Joshua
- Macromolecules, Vol. 53, Issue 2
Control of Grafting Density and Distribution in Graft Polymers by Living Ring-Opening Metathesis Copolymerization
journal, March 2017
- Lin, Tzu-Pin; Chang, Alice B.; Chen, Hsiang-Yun
- Journal of the American Chemical Society, Vol. 139, Issue 10
Synthetic approaches for the preparation of cyclic polymers
journal, January 2009
- Laurent, Boyd A.; Grayson, Scott M.
- Chemical Society Reviews, Vol. 38, Issue 8
Solvent-free, supersoft and superelastic bottlebrush melts and networks
journal, November 2015
- Daniel, William F. M.; Burdyńska, Joanna; Vatankhah-Varnoosfaderani, Mohammad
- Nature Materials, Vol. 15, Issue 2
Molecular brushes as super-soft elastomers
journal, September 2006
- Pakula, Tadeusz; Zhang, Ying; Matyjaszewski, Krzysztof
- Polymer, Vol. 47, Issue 20
Cylindrical polymer brushes
journal, January 2005
- Zhang, Mingfu; Müller, Axel H. E.
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 43, Issue 16, p. 3461-3481
Comb and Bottlebrush Polymers with Superior Rheological and Mechanical Properties
journal, February 2019
- Abbasi, Mahdi; Faust, Lorenz; Wilhelm, Manfred
- Advanced Materials, Vol. 31, Issue 26
Grubbs’ and Schrock’s Catalysts, Ring Opening Metathesis Polymerization and Molecular Brushes—Synthesis, Characterization, Properties and Applications
journal, February 2019
- Choinopoulos, Ioannis
- Polymers, Vol. 11, Issue 2
Universal Approach to Photo-Crosslink Bottlebrush Polymers
journal, January 2020
- Mukherjee, Sanjoy; Xie, Renxuan; Reynolds, Veronica G.
- Macromolecules, Vol. 53, Issue 3
Mimicking biological stress–strain behaviour with synthetic elastomers
journal, September 2017
- Vatankhah-Varnosfaderani, Mohammad; Daniel, William F. M.; Everhart, Matthew H.
- Nature, Vol. 549, Issue 7673
Reversibly Cross-linkable Bottlebrush Polymers as Pressure-Sensitive Adhesives
journal, July 2018
- Arrington, Kyle J.; Radzinski, Scott C.; Drummey, Kevin J.
- ACS Applied Materials & Interfaces, Vol. 10, Issue 31
Compressing and Swelling To Study the Structure of Extremely Soft Bottlebrush Networks Prepared by ROMP
journal, March 2018
- Sarapas, Joel M.; Chan, Edwin P.; Rettner, Emma M.
- Macromolecules, Vol. 51, Issue 6
ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties
journal, July 2015
- Bates, Christopher M.; Chang, Alice B.; Momčilović, Nebojša
- Macromolecules, Vol. 48, Issue 14
Brush polymer ion gels
journal, October 2015
- Bates, Christopher M.; Chang, Alice B.; Schulze, Morgan W.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 54, Issue 2
Supersoft and Hyperelastic Polymer Networks with Brushlike Strands
journal, January 2018
- Liang, Heyi; Sheiko, Sergei S.; Dobrynin, Andrey V.
- Macromolecules, Vol. 51, Issue 2
Characteristic Ratio and Plateau Modulus of 1,2-Polybutadiene. A Comparison with Other Rubbers
journal, November 1990
- Roovers, Jacques; Toporowski, Paul M.
- Rubber Chemistry and Technology, Vol. 63, Issue 5
Rubber Elasticity of Well-Characterized Polybutadiene Networks
journal, January 1979
- Dossin, Luc M.; Graessley, William W.
- Macromolecules, Vol. 12, Issue 1
Super-soft solvent-free bottlebrush elastomers for touch sensing
journal, January 2020
- Reynolds, Veronica G.; Mukherjee, Sanjoy; Xie, Renxuan
- Materials Horizons, Vol. 7, Issue 1
Bottlebrush Elastomers: A New Platform for Freestanding Electroactuation
journal, November 2016
- Vatankhah-Varnoosfaderani, Mohammad; Daniel, William F. M.; Zhushma, Alexandr P.
- Advanced Materials, Vol. 29, Issue 2
Chameleon-like elastomers with molecularly encoded strain-adaptive stiffening and coloration
journal, March 2018
- Vatankhah-Varnosfaderani, Mohammad; Keith, Andrew N.; Cong, Yidan
- Science, Vol. 359, Issue 6383
Soft biological materials and their impact on cell function
journal, January 2007
- Levental, Ilya; Georges, Penelope C.; Janmey, Paul A.
- Soft Matter, Vol. 3, Issue 3
Inherently pre-strained elastomers with self-healing property: new generation of freestanding electroactuators (Conference Presentation)
conference, May 2017
- Vatankhah-Varnosfaderani, Mohammad; Sheyko, Sergei S.; Matyjaszewski, Krzysztof
- Electroactive Polymer Actuators and Devices (EAPAD) XIX, Electroactive Polymer Actuators and Devices (EAPAD) 2017
Vitrimers: permanent organic networks with glass-like fluidity
journal, January 2016
- Denissen, Wim; Winne, Johan M.; Du Prez, Filip E.
- Chemical Science, Vol. 7, Issue 1
Synthesis of amorphous low T g polyesters with multiple COOH side groups and their utilization for elastomeric vitrimers based on post-polymerization cross-linking
journal, January 2019
- Hayashi, Mikihiro; Yano, Ryoto; Takasu, Akinori
- Polymer Chemistry, Vol. 10, Issue 16
Polylactide Vitrimers
journal, June 2014
- Brutman, Jacob P.; Delgado, Paula A.; Hillmyer, Marc A.
- ACS Macro Letters, Vol. 3, Issue 7
Strong, Resilient, and Sustainable Aliphatic Polyester Thermoplastic Elastomers
journal, May 2017
- Watts, Annabelle; Kurokawa, Naruki; Hillmyer, Marc A.
- Biomacromolecules, Vol. 18, Issue 6
Covalent Adaptable Networks: Reversible Bond Structures Incorporated in Polymer Networks
journal, March 2012
- Bowman, Christopher N.; Kloxin, Christopher J.
- Angewandte Chemie International Edition, Vol. 51, Issue 18
Dynamics and reaction kinetics of coarse-grained bulk vitrimers: a molecular dynamics study
journal, January 2019
- Wu, Jian-Bo; Li, Shu-Jia; Liu, Hong
- Physical Chemistry Chemical Physics, Vol. 21, Issue 24
Vitrimers Designed Both To Strongly Suppress Creep and To Recover Original Cross-Link Density after Reprocessing: Quantitative Theory and Experiments
journal, July 2018
- Li, Lingqiao; Chen, Xi; Jin, Kailong
- Macromolecules, Vol. 51, Issue 15
50th Anniversary Perspective: Networks and Gels: Soft but Dynamic and Tough
journal, October 2017
- Creton, Costantino
- Macromolecules, Vol. 50, Issue 21