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新型具有丙烯酸钴与4'-苯基-2,2':6',2″-三联吡啶配合物的自修复金属超分子共聚物

New Self-Healing Metallosupramolecular Copolymers with a Complex of Cobalt Acrylate and 4'-Phenyl-2,2':6',2″-terpyridine.

作者信息

Sorin Evgeny S, Baimuratova Rose K, Uflyand Igor E, Perepelitsina Evgeniya O, Anokhin Denis V, Ivanov Dmitry A, Dzhardimalieva Gulzhian I

机构信息

Federal Research Centre of Problems of Chemical Physics and Medicinal Chemistry RAS, 142432 Chernogolovka, Russia.

Department of Fundamental Physical and Chemical Engineering, Lomonosov Moscow State University, 119234 Moscow, Russia.

出版信息

Polymers (Basel). 2023 Mar 16;15(6):1472. doi: 10.3390/polym15061472.

Abstract

Currently, the chemistry of self-healing polymers is aimed not only at obtaining materials with high self-healing efficiency, but also at improving their mechanical performance. This paper reports on a successful attempt to obtain self-healing copolymers films of acrylic acid, acrylamide and a new metal-containing complex of cobalt acrylate with a 4'-phenyl-2,2':6',2″-terpyridine ligand. Samples of the formed copolymer films were characterized by ATR/FT-IR and UV-vis spectroscopy, elemental analysis, DSC and TGA, SAXS, WAXS and XRD studies. The incorporation of the metal-containing complex directly into the polymer chain results in an excellent tensile strength (122 MPa) and modulus of elasticity (4.3 GPa) of the obtained films. The resulting copolymers demonstrated self-healing properties both at acidic pH (assisted by HCl healing) with effective preservation of mechanical properties, and autonomously in a humid atmosphere at room temperature without the use of initiators. At the same time, with a decrease in the content of acrylamide, a decrease in the reducing properties was observed, possibly due to an insufficient amount of amide groups to form hydrogen bonds through the interface with terminal carboxyl groups, as well as a decrease in the stability of complexes in samples with a high content of acrylic acid.

摘要

目前,自修复聚合物的化学研究不仅旨在获得具有高自修复效率的材料,还致力于改善其机械性能。本文报道了一种成功的尝试,即制备丙烯酸、丙烯酰胺与一种含钴丙烯酸酯与4'-苯基-2,2':6',2″-三联吡啶配体的新型含金属配合物的自修复共聚物薄膜。通过ATR/FT-IR和UV-vis光谱、元素分析、DSC和TGA、SAXS、WAXS和XRD研究对所形成的共聚物薄膜样品进行了表征。将含金属配合物直接引入聚合物链中,使得所得薄膜具有优异的拉伸强度(122 MPa)和弹性模量(4.3 GPa)。所得共聚物在酸性pH值下(借助HCl修复)表现出自我修复性能,且机械性能得到有效保留,在室温潮湿气氛中无需使用引发剂即可自主修复。同时,随着丙烯酰胺含量的降低,还原性能下降,这可能是由于酰胺基团数量不足,无法通过与末端羧基的界面形成氢键,以及高丙烯酸含量样品中配合物稳定性降低所致。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9dbf/10053782/b4403eb5b1ca/polymers-15-01472-sch001.jpg

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