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通过分子强制整合共价和可逆网络实现坚韧的自修复弹性体。

Tough Self-Healing Elastomers by Molecular Enforced Integration of Covalent and Reversible Networks.

机构信息

State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Chengdu, 610065, China.

School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, 02138, USA.

出版信息

Adv Mater. 2017 Oct;29(38). doi: 10.1002/adma.201702616. Epub 2017 Aug 11.

Abstract

Self-healing polymers crosslinked by solely reversible bonds are intrinsically weaker than common covalently crosslinked networks. Introducing covalent crosslinks into a reversible network would improve mechanical strength. It is challenging, however, to apply this concept to "dry" elastomers, largely because reversible crosslinks such as hydrogen bonds are often polar motifs, whereas covalent crosslinks are nonpolar motifs. These two types of bonds are intrinsically immiscible without cosolvents. Here, we design and fabricate a hybrid polymer network by crosslinking randomly branched polymers carrying motifs that can form both reversible hydrogen bonds and permanent covalent crosslinks. The randomly branched polymer links such two types of bonds and forces them to mix on the molecular level without cosolvents. This enables a hybrid "dry" elastomer that is very tough with fracture energy 13500 Jm comparable to that of natural rubber. Moreover, the elastomer can self-heal at room temperature with a recovered tensile strength 4 MPa, which is 30% of its original value, yet comparable to the pristine strength of existing self-healing polymers. The concept of forcing covalent and reversible bonds to mix at molecular scale to create a homogenous network is quite general and should enable development of tough, self-healing polymers of practical usage.

摘要

仅由可逆键交联的自修复聚合物的固有强度比常见的共价交联网络弱。在可逆网络中引入共价交联可以提高机械强度。然而,将这一概念应用于“干燥”弹性体具有挑战性,这主要是因为氢键等可逆交联通常是极性基团,而共价交联是非极性基团。这两种类型的键在没有共溶剂的情况下本质上是不混溶的。在这里,我们通过交联带有既能形成可逆氢键又能形成永久共价交联的结构单元的无规支化聚合物来设计和制造混合聚合物网络。无规支化聚合物连接这两种类型的键,并在没有共溶剂的情况下迫使它们在分子水平上混合。这使得混合的“干燥”弹性体具有非常高的韧性,断裂能为 13500 J m,与天然橡胶相当。此外,弹性体可以在室温下自修复,拉伸强度恢复到 4 MPa,为其原始值的 30%,但与现有自修复聚合物的原始强度相当。迫使共价和可逆键在分子尺度上混合以形成均匀网络的概念非常普遍,应该能够开发出具有实际用途的坚韧、自修复聚合物。

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