A Solvent‐Resistant and Biocompatible Self‐Healing Supramolecular Elastomer with Tunable Mechanical Properties

Abstract

to achieve self-healing ability under specific environment or external stimulus such as heat or solvent. [10][11][12][13][14] To obtain self-healing ability at room temperature, supramolecular elastomers based on small-molecule system were obtained recently. Leibler and coworkers [15,16] first synthesized a selfhealing elastomer by utilizing vegetable oil fatty acid derivatives with diethylenetriamine (DETA) and urea through a two-step reaction. The obtained material, whose glass transition temperature (T g ) was 28 °C, exhibited rubber-like behavior only if heating over 90 °C or adding 11% w/w dodecane as plasticizer, and showed a spontaneous self-healing ability at room temperature. Montarnal et. al. [17] obtained four different classes of materials by using oligocondensation of 2-aminoethylimidazolidone endcapped mixture of fatty acid with DETA and urea. Bao and co-workers [18] described an elastic nanocomposite material with the ability to rapidly self-heal at room temperature by combining a fatty tri-acid, DETA, and graphene oxide as a macrocrosslinker. Zhang and co-workers [19] obtained supramolecular elastomers through reacting linear carboxyl-terminated polydimethylsiloxane oligomers (PDMS-COOH 2 ) with DETA and urea. Our previous work [20] synthesized a self-healing supramolecular elastomer with small-molecular biological acids. The synthesized materials behaved as rubber at room temperature without additional plasticizers or crosslinkers.However, the small-molecule systems by hydrogen-bond interactions are easier to suffer from low mechanical properties and poor solvent-resistance than macromolecular systems due to the lack of molecular chain entanglement. In order to overcome this problem, hybrid networks containing covalent and hydrogen bonds were developed. These researches used epoxide (diepoxide and tetraepoxide) as manageable crosslinker to enhance mechanical properties and insolubility by controlling stoichiometries and side reactions, [21][22][23] which in turn decreased self-healing behavior. Hence, a supramolecular elastomer with self-healing behavior and solvent-resistance and tunable mechanical properties is desirable.Herein, we design a new reaction system and use sebacic acid and lignin as main raw materials to synthesize a ligninbased supramolecular elastomer (LSE). The synthesis route of Self-Healing ElastomersThe purpose of this work is to demonstrate a new design strategy to produce a self-healing supramolecular elastomer with solvent resistance and biocompatibility and tunable mechanical properties. This aim is successfully achieved by synthesizing a lignin-based supramolecular elastomer (LSE) through branching amide molecular chains on the lignin. The use of lignin effectively reduces the glass transition temperature and the degree of crystallinity of LSEs and generates urea-modified hydrogen bond groups to obtain self-healing capability. The synthesized LSEs behave as rubber and exhibit spontaneous self-healing behavior at room temperature without external stimuli. The mechanical an...

Combing experimental methods and molecular simulations to study self-healing behaviors of polyurethane elastomers containing multiple hydrogen bond networks and flexible blocks

“…Thus, in order to achieve environmental protection and effectively deal with the problem of resource shortages, the developments and promotions of self-healing polymeric materials are imminent. 2–9…”

“…Thus, in order to achieve environmental protection and effectively deal with the problem of resource shortages, the developments and promotions of self-healing polymeric materials are imminent. [2][3][4][5][6][7][8][9] Since rubbers or elastomers belong to one kind of important and irreplaceable polymer materials, a lot of efforts have been invested in the design and preparation of self-healing polymers, including rubbers or elastomers. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] Generally, the main idea of the design of self-healing polymers is to introduce reversible bonds or interactions into polymer materials, such as reversible covalent bonds, hydrogen bonds, ionic interactions and metal-ligand coordinations.…”

Materials Based on Technical Bulk Lignin

“…Zhang and co-workers developed lignin-based self-healing polyamide supramolecular elastomers (LSEs) that had good solvent resistance, biocompatibility and tunable mechanical properties . Since alkaline lignin has multiple OH groups, it was used as the branching agent for amide molecular chains.…”

“…Zhang and co-workers developed lignin-based self-healing polyamide supramolecular elastomers (LSEs) that had good solvent resistance, biocompatibility and tunable mechanical properties. 86 Since alkaline lignin has multiple OH groups, it was used as the branching agent for amide molecular chains. The addition of lignin brought properties including reducing the glass transition temperature, decreasing the degree of crystallinity, and generating urea-modified hydrogen bonds to obtain self-healing capability.…”

Self-healing polyurethane elastomers based on charge-transfer interactions for biomedical applications

“…[11][12][13] Although elastomers are available as structural components of artificial tissues and organs and also coatings on them, in which hydrogels cannot be substitutes, to date, self-healable and biocompatible elastomers have rarely reported. [15][16][17][18][19][20][21][22][23][24] Here we report self-healable and cell-compatible polyurethane elastomers based on the charge-transfer (CT) interaction between electron-rich pyrene (Py) and electron-deficient naphthalene diimide (NDI) as a reversible interaction (Figure 1). 25 Unlike hydrogen bonding, one of the most common reversible bonds/interactions in self-healing polymers, 26,27 CT interactions are hardly affected by water molecules and promise to work in physiological conditions.…”