Highly Stretchable, Recyclable, and Fast Room Temperature Self-Healable Biobased Elastomers Using Polycondensation

Abstract

The substitution of petroleum-based self-healing elastomers with biobased counterparts is crucial to the global sustainable development of the rubber industry, which highly depends on the ease of the synthesis procedure. Herein, we show that highly stretchable, recyclable, and self-healable biobased elastomers were synthesized via condensation polymerization of succinic acid, adipic acid, sebacic acid, and 1,4-butanediol in the presence of a small amount of glycerol as a curing agent and 3,3′-dithiodipropionic acid as a dynamic covalent monomer. The macroscopic properties of our elastomers, including thermal, mechanical, stress relaxation, and self-healing performance, were finely regulated via microscopic chemical and topological structure. As such, a highly stretchable (up to ∼1700%), recyclable (almost without degradation of the mechanical performance over several repeats), rapid room temperature self-healable (in 20 min) biobased vitrimeric elastomer was achieved, which is the first aliphatic disulfide metathesis assisted self-healing polymer achieved at such low temperatures. The ease of the polycondensation with which the elastomers can be readily scaled up points to exciting opportunities for sustainable polymers with minimal environmental impact.

Long-chain polyamide covalent adaptable networks based on renewable ethylene brassylate and disulfide exchange

“…We hypothesized that a simple and straightforward route to achieve such a system would be by leveraging a solvent-free, ring-opening aminolysis-condensation/crosslinking strategy of renewable ethylene brassylate, 43,44 and the fast disulfide exchange. 4,23,39 The dynamic character of the resulting long-chain PA network was verified by stress relaxation analysis and the material was thermally reprocessable over three grinding-compression molding cycles without deterioration of its properties.…”

“…Their principle is the activation of exchange reactions between dynamic bonds that overall keep the crosslink density of the network constant, but allow it to flow and rearrange its topology at high temperature. Thus, CANs meld the features of classical thermosets such as chemical resistance and dimensional stability with reprocessability, and in some cases self-healing ability and chemical recycling, [2][3][4][5][6][7] all highly attractive features for many applications. 8 Polyamide (PA) networks have rarely been reported, let alone PA networks with exchangeable bonds.…”

“…Seeking for a simpler and more sustainable alternative towards longchain PA CANs, we focused on disulfides as an intrinsically reactive bond, 31,32 that can be activated under mild conditions. 33 Disulfides have been incorporated into urea, 34 urethane, 23,35,36 ester 4,37 and epoxy-based [38][39][40] networks, and have been combined with renewable building blocks such as diacids (succinic, adipic, sebacic), 4 castor oil 24,41 and epoxidized soybean oil, 42 leading to high-performance thermosets with impressive results regarding the ease of reprocessability and retainment of the mechanical properties after several reprocessing cycles.…”

Wide temperature range damping polyurethane elastomer based on dynamic disulfide bonds

“…Reports have shown that aromatic disulfide compounds can undergo disulfide exchange reactions at room temperature 28,29 . The dynamic disulfide bonds are introduced to give polyurethane self‐healing and reprocessing properties, 30–34 but its impact on dynamic mechanical properties has been ignored. The broken of the aromatic disulfide bonds will absorb energy at and above room temperature.…”

Aspects of kerogen oxidative dissolution in subcritical water using oxygen from air

“…The main monomeric products separable from these complex organic structures are carboxylic acids and their analogs. These compounds can serve as starting materials for both the chemical and materials industries [8][9][10][11]. The commercial value of organic compounds from oil shale organic matter (kerogen) may be several times higher than that from the current use of oil shale (e.g.…”