National Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan), State Key Laboratory of Polymer Materials Engineering, College of Chemistry, Sichuan University , Chengdu 610064, China.
ACS Appl Mater Interfaces. 2017 Jun 21;9(24):20797-20807. doi: 10.1021/acsami.7b01954. Epub 2017 Jun 6.
In the present work, we demonstrated the recyclability and precisely targeted reparability of amino functionalized multiwall carbon nanotubes-epoxy resin based on dynamic covalent Diels-Alder (DA) network (NH-MWCNTs/DA-epoxy) by exploring the photothermal conversion of CNTs to trigger the reactions of dynamic chemical bonds. The covalent cross-linked networks of NH-MWCNTs/DA-epoxy resin change their topology to linear polymer by thermally activated reverse Diels-Alder (r-DA) reactions at high temperatures, which endues the resin with almost 100% recyclability. The self-healing property of the epoxy resin was confirmed by the complete elimination of cracks after the reconstruction of DA network induced by heating or near-infrared (NIR) irradiation. For heat-triggered self-healing process, heat energy may also act on those uninjured parts of the resin and cause the dissociation of the whole DA network. Therefore, redundant r-DA and DA reactions, which have no contribution to self-healing, are also triggered during thermal treatment, resulting in not only a waste of energy but also the deformation of the sample under external force. Meanwhile, for the NIR-triggered self-healing process, the samples can maintain well their original shape without observable deformation after irradiation. The NIR-triggered healing process, which uses MWCNTs as the photothermal convertor, have very good regional controllability by simply tuning the MWCNTs content, the distance from NIR laser source to sample, and the laser power. The injured samples can be locally repaired with high precision and efficiency without an obvious influence on those uninjured parts.
在本工作中,我们通过探索 CNTs 的光热转换来触发动态化学键的反应,证明了基于动态共价 Diels-Alder(DA)网络的氨基功能化多壁碳纳米管-环氧树脂(NH-MWCNTs/DA-epoxy)的可回收性和精确靶向修复性。NH-MWCNTs/DA-epoxy 树脂的共价交联网络通过在高温下热激活反 Diels-Alder(r-DA)反应改变其拓扑结构为线性聚合物,这使树脂几乎具有 100%的可回收性。通过加热或近红外(NIR)照射诱导 DA 网络的重建,环氧树脂的自修复性能得到了证实,裂纹完全消除。对于热触发的自修复过程,热能也可能作用于树脂的未受损部分,并导致整个 DA 网络的解离。因此,在热处理过程中也会触发多余的 r-DA 和 DA 反应,这些反应对自修复没有贡献,不仅浪费了能量,而且在外力作用下还会导致样品变形。同时,对于 NIR 触发的自修复过程,在照射后,样品可以保持其原始形状,没有明显的变形。NIR 触发的自修复过程,使用 MWCNTs 作为光热转化器,通过简单地调整 MWCNTs 的含量、NIR 激光源到样品的距离和激光功率,具有很好的区域可控性。可以对受损的样品进行高精度和高效率的局部修复,而对未受损的部分没有明显的影响。