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基于二茂铁的三元聚酰胺及其含聚二甲基硅氧烷的嵌段共聚物:合成与物理性质

Ferrocene-Based Terpolyamides and Their PDMS-Containing Block Copolymers: Synthesis and Physical Properties.

作者信息

Mushtaq Irrum, Jabeen Erum, Akhter Zareen, Javed Fatima, Hassan Azfar, Khan Muhammad Saif Ullah, Ullah Faheem, Shah Faiz Ullah

机构信息

Department of Biological Sciences, National University of Medical Sciences, The Mall Road, Rawalpindi 46000, Pakistan.

Department of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan.

出版信息

Polymers (Basel). 2022 Nov 23;14(23):5087. doi: 10.3390/polym14235087.

Abstract

Aromatic polyamides are well-known as high-performance materials due to their outstanding properties making them useful in a wide range of applications. However, their limited solubility in common organic solvents restricts their processability and becomes a hurdle in their applicability. This study is focused on the synthesis of processable ferrocene-based terpolyamides and their polydimethylsiloxane (PDMS)-containing block copolymers, using low-temperature solution polycondensation methodology. All the synthesized materials were structurally characterized using FTIR and H NMR spectroscopic techniques. The ferrocene-based terpolymers and block copolymers were soluble in common organic solvents, while the organic analogs were found only soluble in sulfuric acid. WXRD analysis showed the amorphous nature of the materials, while the SEM analysis exposed the modified surface of the ferrocene-based block copolymers. The structure-property relationship of the materials was further elucidated by their water absorption and thermal behavior. These materials showed low to no water absorption along with their high limiting oxygen index (LOI) values depicting their good flame-retardant behavior. DFT studies also supported the role of various monomers in the polycondensation reaction where the electron pair donation from HOMO of diamine monomer to the LUMO of acyl chloride was predicted, along with the calculation of various other parameters of the representative terpolymers and block copolymers.

摘要

芳族聚酰胺因其优异的性能而成为众所周知的高性能材料,使其在广泛的应用中有用。然而,它们在常见有机溶剂中的有限溶解度限制了它们的可加工性,并成为其应用中的一个障碍。本研究重点在于使用低温溶液缩聚方法合成可加工的基于二茂铁的三元聚酰胺及其含聚二甲基硅氧烷(PDMS)的嵌段共聚物。使用FTIR和1H NMR光谱技术对所有合成材料进行了结构表征。基于二茂铁的三元共聚物和嵌段共聚物可溶于常见有机溶剂,而有机类似物仅可溶于硫酸。广角X射线衍射(WXRD)分析表明材料的无定形性质,而扫描电子显微镜(SEM)分析揭示了基于二茂铁的嵌段共聚物的改性表面。通过材料的吸水性和热行为进一步阐明了材料的结构 - 性能关系。这些材料显示出低吸水性或无吸水性,同时具有高极限氧指数(LOI)值,表明它们具有良好的阻燃性能。密度泛函理论(DFT)研究也支持了各种单体在缩聚反应中的作用,其中预测了二胺单体的最高占据分子轨道(HOMO)向酰氯的最低未占分子轨道(LUMO)的电子对供体,同时计算了代表性三元共聚物和嵌段共聚物的各种其他参数。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bdb/9735706/c4b13e32d804/polymers-14-05087-g001.jpg

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