Department of Organic and Polymeric Materials, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo, 152-8550, Japan.
Department of Chemical Science and Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo, 152-8550, Japan.
Angew Chem Int Ed Engl. 2017 Feb 13;56(8):2016-2021. doi: 10.1002/anie.201611049. Epub 2017 Jan 20.
Intrinsically exchangeable dynamic covalent bonds that can be triggered by readily usable stimuli offer easy incorporation of their dynamic properties in various molecular systems, but the library of such bonds is still being developed. Herein, we report the dynamic covalent chemistry of 2,2,6,6-tetramethylpiperidine-1-sulfanyl (TEMPS) dimers derived from thermally reversible homolytic dissociation of disulfide linkages. High air stability of TEMPS was observed even at 100 °C, affording facile employment of thermal dissociation-association equilibria and adjustable bond exchange properties under atmospheric conditions. We also established an efficient synthetic route for a modifiable derivative of the dimer that enabled incorporation of dynamic properties into linear and network polymer structures. The obtained polymers showed controllable molecular weights, temperature-dependent swelling properties, healing ability, and recyclability, reflecting the thermally tunable dynamics of the dimer.
可由易得刺激触发的本征可交换动态共价键为各种分子系统轻松纳入其动态特性提供了可能，但这种键的库仍在不断发展中。在此，我们报告了源自二硫键热可逆均裂的 2,2,6,6-四甲基哌啶-1-硫基（TEMPS）二聚体的动态共价化学。即使在 100°C 时，TEMPS 也表现出高空气稳定性，从而在大气条件下轻松实现热解离-缔合平衡和可调的键交换性能。我们还建立了一种可修饰的二聚体衍生物的有效合成路线，该路线能够将动态特性纳入线性和网络聚合物结构中。所得聚合物具有可控的分子量、温度依赖性溶胀性能、愈合能力和可回收性，反映了二聚体的热可调动力学。
