Covalently cross-linked rubbers are renowned for their high elasticity that play an indispensable role in various applications including tires, seals, and medical implants. Development of self-healing and malleable rubbers is highly desirable as it allows for damage repair and reprocessability to extend the lifetime and alleviate environmental pollution. Herein, we propose a facile approach to prepare permanently cross-linked yet self-healing and recyclable diene-rubber by programming dynamic boronic ester linkages into the network. The network is synthesized through one-pot thermally initiated thiol-ene "click" reaction between a novel dithiol-containing boronic ester cross-linker and commonly used styrene-butadiene rubber without modifying the macromolecular structure. The resulted samples are covalently cross-linked and possess relatively high mechanical strength which can be readily tailored by varying boronic ester content. Owing to the transesterification of boronic ester bonds, the samples can alter network topologies, endowing the materials with self-healing ability and malleability.
Covalent
cross-linking of rubbers is essential for obtaining high
resilience and environmental resistance but prevents healing and recycling.
Integrating dynamic covalent bonds into cross-linked rubbers can resolve
the trade-off between permanent cross-linking and plasticity. The
state-of-the-art elastomer-based dynamic covalent networks require
either intricate molecular makeup or present poor mechanical properties.
In this work, we demonstrate a simple way to prepare mechanically
robust yet healable and recyclable elastomeric vitrimers by engineering
dynamic dual cross-links of boronic esters and coordination bonds
into a commercial rubber. Specifically, epoxidized natural rubber
is covalently cross-linked with a boronic ester cross-linker carrying
dithiol through chemical reaction between epoxy and thiol groups.
The covalently cross-linked networks are able to alter the topologies
through boronic ester transesterifications, thereby conferring them
with healing ability and reprocessability. In particular, the mechanical
properties can be remarkably enhanced by introducing sacrificial metal–ligand
coordination bonds into the networks without compromising the healing
ability or reprocessability.
Vitrimers are a class of covalently cross-linked polymers that have drawn great attention due to their fascinating properties such as malleability and reprocessability. The state of art approach to improve their mechanical properties is the addition of fillers, which, however, greatly restricts the chain mobility and impedes network topology rearrangement, thereby deteriorating the dynamic properties of vitrimer composites. Here, we demonstrate that the integration of sacrificial bonds into a vitrimeric network can remarkably enhance the overall mechanical properties while facilitating network rearrangement. Specifically, commercially available epoxidized natural rubber is covalently cross-linked with sebacic acid and simultaneously grafted with N-acetylglycine (NAg) through the chemical reaction between epoxy and carboxyl groups, generating exchangeable β-hydroxyl esters and introducing amide functionalities into the networks. The hydrogen bonds arising from amide functionalities act in a sacrificial and reversible manner, that is, preferentially break prior to the covalent framework and undergo reversible breaking and reforming to dissipate mechanical energy under external load, which leads to a rarely achieved combination of high strength, modulus, and toughness. The topology rearrangement of the cross-linked networks can be accomplished through transesterification reactions at high temperatures, which is accelerated with the increase of grafting NAg amount due to the dissociation of transient hydrogen bonds and increase of the ester concentration in the system.
Imine bond crosslinked networks with tunable mechanical and dynamic properties are prepared by varying the precursor molecular weight and network crosslinking degree.
An advanced elastomer was developed by incorporating a dual-dynamic network into cis-polyisoprene, which combines excellent mechanical properties with high self-healing capability.
Elastomeric vitrimers with an integration of unparalleled mechanical properties, improved creep resistance and retained malleability by engineering dynamic and sacrificial Zn2+−imidazole complex into the network.
Interfacial silyl ether networks can reshuffle the topological structure upon trans-oxyalkylation reactions, enabling malleability and recyclability to organic/inorganic hybrid vitrimers.
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