State Key Laboratory of Electroanalytical Chemistry , Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , Changchun 130022 , PR China.
Jilin Province Key Laboratory of Green Chemistry and Process , Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , Changchun 130022 , PR China.
ACS Appl Mater Interfaces. 2019 Dec 18;11(50):47413-47421. doi: 10.1021/acsami.9b17677. Epub 2019 Dec 9.
The transformation of CO into polymeric materials is an important and hot research topic from the viewpoint of renewable resources and environmental effects. Herein, a series of polyureas have been synthesized by polycondensation from CO with diamines of 1,12-diaminododecane (DAD) and/or 4,7,10-trioxa-1,13-tridecanediamine (TTD). The properties of polyureas synthesized were characterized by FTIR, H NMR, C NMR, XRD, DSC, TGA, and DMA. The polyureas synthesized from CO with a mixture of diamines presented high performances compared to those of polyureas synthesized from CO with a single diamine. The thermal and mechanical properties were improved largely by the variation in the crystallization and the chain flexibility depending on the changes in the density and/or intensity of hydrogen bonds. With increasing amounts of TTD from 0 to 100% in weight, the melting (), crystallization (), and glass transition () temperatures decreased from 207 to 116 °C, from 181 to 54 °C, and from 66 to -34 °C, respectively. When the TTD content was increased from 0 to 50 wt %, the Young's modulus decreased from 1170 to 406 MPa, and the tensile strength decreased from 53.3 to 42.9 MPa. However, the elongation at break increased from 13 to 330%. Furthermore, the chain length of aliphatic diamines and polyetheramines had a significant effect on the mechanical properties. The initial decomposition temperature () is >295 °C, about 110 °C higher than the (116-207 °C), which is advantageous for the postprocessing. The mechanical properties of the polyureas synthesized herein are superior to those of polycarbonate and polyamide 6. Thus, polyureas synthesized from the renewable and cheap resources, CO and diamines, will find wide potential applications in the field of polymeric materials.
将 CO 转化为聚合材料是一个从可再生资源和环境影响的角度来看非常重要且热门的研究课题。在此，通过 CO 与 1,12-二氨基十二烷（DAD）和/或 4,7,10-三氧杂-1,13-十三烷二胺（TTD）的缩聚反应合成了一系列聚脲。通过 FTIR、H NMR、C NMR、XRD、DSC、TGA 和 DMA 对合成的聚脲的性能进行了表征。与由 CO 与单一二胺合成的聚脲相比，由 CO 与混合二胺合成的聚脲表现出更高的性能。通过改变结晶度和链柔性，可以改变氢键的密度和/或强度，从而大大提高热性能和机械性能。随着 TTD 含量从 0 重量%增加到 100 重量%，熔融（）、结晶（）和玻璃化转变（）温度分别从 207°C 降低到 116°C、从 181°C 降低到 54°C、从 66°C 降低到-34°C。当 TTD 含量从 0 增加到 50 重量%时，杨氏模量从 1170 MPa 降低到 406 MPa，拉伸强度从 53.3 MPa 降低到 42.9 MPa。然而，断裂伸长率从 13%增加到 330%。此外，脂肪族二胺和聚醚胺的链长对机械性能有显著影响。起始分解温度（）大于 295°C，比（116-207°C）高约 110°C，有利于后处理。本文合成的聚脲的机械性能优于聚碳酸酯和聚酰胺 6。因此，由可再生且廉价的资源 CO 和二胺合成的聚脲将在聚合物材料领域有广泛的应用潜力。
