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Bioinspired Design Of Elastomeric Vitrimers With Sacrificial Metal-ligand Interactions Leading To Supramechanical Robustness And Retentive Malleability

Siwu Wu, S. Fang, Zheng-hai Tang, F. Liu, Baochun Guo
Published 2020 · Materials Science

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Abstract Most elastomeric vitrimers suffer from mechanical weakness in practical applications. Inspired by the development of strong and tough biomaterials relying on sacrificial bond-detachment mechanisms, herein we describe the biomimetic design of elastomeric vitrimers with mechanical robustness, preservable malleability, and recyclability by engineering sacrificial metal-ligand coordination bonds into exchangeable networks. In particular, we use a commercially available metal complex, aluminum acetylacetonate (Al(acac)3), to catalyze cross-linking based on the silylation reaction between hydroxylated natural rubber and hydrosilanes, thus introducing dynamic silyl ether-based architectures into the rubber matrix. At the same time, the Al3+ ions can interact with the free oxygen-containing moieties on the rubber skeleton, enabling labile Al3+ O coordination bonds in the covalent framework to substantially dissipate mechanical energy through reversible bond detachment/reattachment upon deformation. As the organic acetylacetonate ligands of Al(acac)3 can facilitate the dispersion of Al3+ ions in the matrix, incorporating a small amount of organometallic complex (0.68 wt% of elastomer matrix) achieves an unparalleled improvement of the strength, modulus, and toughness of the resulting vitrimers. Moreover, due to their temperature-dependent nature, the Al3+ O coordination bonds will partially dissociate at elevated temperatures, which only slightly compromises the topological rearrangements of the silyl ether-based network, but barely affects the reprocessability.
This paper references
10.1016/S0032-3861(96)00710-0
Partial conversion of epoxide groups to diols in epoxidized natural rubber
S. N. Gan (1997)
10.1039/C1SC00260K
A mechanistic study of Lewis acid-catalyzed covalent organic framework formation
Eric L. Spitler (2011)
10.1021/ACS.MACROMOL.7B01261
Malleable, Mechanically Strong, and Adaptive Elastomers Enabled by Interfacial Exchangeable Bonds
Z. Tang (2017)
10.1039/c9py01260e
Dynamic covalent chemistry in polymer networks: a mechanistic perspective
J. Winne (2019)
10.1039/C5GC00754B
Crack healing and reclaiming of vulcanized rubber by triggering the rearrangement of inherent sulfur crosslinked networks
H. Xiang (2015)
10.1016/J.POLYMER.2010.10.023
Epoxidized natural rubber/dicarboxylic acid self-vulcanized blends
M. Pire (2010)
10.1002/adma.201901561
Multiscale Toughening Mechanisms in Biological Materials and Bioinspired Designs.
W. Huang (2019)
10.1016/S1386-1425(02)00013-6
Vibrational assignment of aluminum(III) tris-acetylacetone.
S. F. Tayyari (2002)
10.1007/s10118-018-2131-x
Effects of Binding Energy of Bioinspired Sacrificial Bond on Mechanical Performance of cis-1,4-Polyisoprene with Dual-crosslink
S. Wang (2018)
10.5254/RCT.12.87973
Rubber Recycling: Chemistry, Processing, and Applications
M. Myhre (2012)
10.1055/S-1996-4350
Selective Deprotection of Silyl Ethers
T. Nelson (1996)
10.1021/ACS.MACROMOL.9B00503
Using Dynamic Bonds to Enhance the Mechanical Performance: From Microscopic Molecular Interactions to Macroscopic Properties
Chi Zhang (2019)
10.1039/c7cs00276a
Progress in bio-inspired sacrificial bonds in artificial polymeric materials.
Xinxin Zhou (2017)
10.1021/jacs.9b07922
Adaptable Crosslinks in Polymeric Materials: Resolving the Intersection of Thermoplastics and Thermosets.
Georg M. Scheutz (2019)
10.1002/POLA.28577
Recyclable polybutadiene elastomer based on dynamic imine bond
H. Zhang (2017)
10.1039/c9ta10909a
Biomimetic design of elastomeric vitrimers with unparalleled mechanical properties, improved creep resistance and retained malleability by metal–ligand coordination
Yingjun Liu (2019)
10.1016/J.PMATSCI.2012.03.001
Biological materials: Functional adaptations and bioinspired designs
Po-Yu Chen (2012)
10.1021/JA01466A014
Infrared Spectra of Metal Chelate Compounds. II. Infrared Spectra of Acetylacetonates of Trivalent Metals1
K. Nakamoto (1961)
10.1016/J.PMATSCI.2009.05.001
Merger of structure and material in nacre and bone - Perspectives on de novo biomimetic materials
H. Espinosa (2009)
10.1021/ACSMACROLETT.9B00012
Integrating Sacrificial Bonds into Dynamic Covalent Networks toward Mechanically Robust and Malleable Elastomers
Y. Liu (2019)
10.1021/ja303356z
Making insoluble polymer networks malleable via olefin metathesis.
Y. Lu (2012)
10.1016/j.cej.2019.123820
Vitrimers: Associative dynamic covalent adaptive networks in thermoset polymers
B. Krishnakumar (2020)
10.1039/c3cs60046g
Covalent adaptable networks: smart, reconfigurable and responsive network systems.
Christopher J Kloxin (2013)
10.1021/ACS.IECR.8B05309
Multifunctional Vitrimer-Like Polydimethylsiloxane (PDMS): Recyclable, Self-Healable, and Water-Driven Malleable Covalent Networks Based on Dynamic Imine Bond
Zhanbin Feng (2019)
10.1016/J.POLYMER.2018.06.042
Tailoring vinylogous urethane chemistry for the cross-linked polybutadiene: Wide freedom design, multiple recycling methods, good shape memory behavior
Z. Liu (2018)
10.1021/ACS.MACROMOL.6B00826
Silica–Epoxy Vitrimer Nanocomposites
A. Legrand (2016)
10.1016/J.EURPOLYMJ.2016.03.016
From landfilling to vitrimer chemistry in rubber life cycle
L. Imbernon (2016)
10.1021/acsami.8b09863
Covalently Cross-Linked Elastomers with Self-Healing and Malleable Abilities Enabled by Boronic Ester Bonds.
Y. Chen (2018)
10.1021/ACS.MACROMOL.9B00419
Mechanically Robust, Self-Healable, and Reprocessable Elastomers Enabled by Dynamic Dual Cross-Links
Y. Chen (2019)
10.1021/jacs.7b08826
Silyl Ether as a Robust and Thermally Stable Dynamic Covalent Motif for Malleable Polymer Design.
Y. Nishimura (2017)
10.1021/MA500240V
Evidence for an in Situ Developed Polymer Phase in Ionic Elastomers
D. Basu (2014)
10.1039/C4SC00543K
Carbon nanotube–vitrimer composite for facile and efficient photo-welding of epoxy
Y. Yang (2014)
10.1016/S0079-6700(00)00020-4
Reclamation and recycling of waste rubber
B. Adhikari (2000)
10.1039/C8TA09866B
Malleable organic/inorganic thermosetting hybrids enabled by exchangeable silyl ether interfaces
Siwu Wu (2019)
10.1038/s41467-019-11144-6
Detecting topology freezing transition temperature of vitrimers by AIE luminogens
Yang Yang (2019)
10.1021/jacs.5b01601
Enhancing mechanical performance of a covalent self-healing material by sacrificial noncovalent bonds.
J. A. Neal (2015)
10.1021/MA2001614
Structure and Dynamics of Zinc-Neutralized Sulfonated Polystyrene Ionomers
A. Castagna (2011)
10.1126/science.1212648
Silica-Like Malleable Materials from Permanent Organic Networks
Damien Montarnal (2011)
10.1002/anie.201504127
Catalytic Silylations of Alcohols: Turning Simple Protecting-Group Strategies into Powerful Enantioselective Synthetic Methods.
L. Xu (2015)
10.1063/1.1747424
Statistical Mechanics of Swelling of Network Structures
P. J. Flory (1950)
10.1002/MAME.200400034
The Reinforcement of Elastomeric Networks by Fillers
L. Bokobza (2004)
10.1016/J.COMPSCITECH.2018.10.017
Reprocessable and robust crosslinked elastomers via interfacial CN transalkylation of pyridinium
Jing Huang (2018)
10.1039/C5PY00459D
Chemically crosslinked yet reprocessable epoxidized natural rubber via thermo-activated disulfide rearrangements
L. Imbernon (2015)
10.1039/C8GC02932F
A real recycling loop of sulfur-cured rubber through transalkylation exchange of C–S bonds
Z. Tang (2018)
10.1038/s41598-017-11485-6
Recyclable Polydimethylsiloxane Network Crosslinked by Dynamic Transesterification Reaction
Huan Zhang (2017)
10.1002/anie.201813525
Dynamic Covalent Bonds in Polymeric Materials.
Progyateg Chakma (2019)
10.1021/ACSSUSCHEMENG.9B01875
Mechanically Robust and Recyclable EPDM Rubber Composites by a Green Cross-Linking Strategy
Ganggang Zhang (2019)
10.1016/J.COMPOSITESB.2008.01.002
Effects of particle size, particle/matrix interface adhesion and particle loading on mechanical properties of particulate–polymer composites
S. Fu (2008)
10.1021/ACSMACROLETT.8B00166
Vitrimeric Silicone Elastomers Enabled by Dynamic Meldrum’s Acid-Derived Cross-Links
Jacob S A Ishibashi (2018)



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