Ponomareva Polina, Lokiaeva Zalina, Zakharova Daria, Tretyakov Ilya, Platonova Elena, Shapagin Aleksey, Alexeeva Olga, Antoshkina Evgenia, Solodilov Vitaliy, Yurkov Gleb, Berlin Alexandr
Semenov Institute of Chemical Physics, Russian Academy of Sciences, 119991 Moscow, Russia.
NTI Center "Digital Materials Science: New Materials and Substances", Bauman Moscow State Technical University, 2nd Baumanskaya Street 5, 105005 Moscow, Russia.
Polymers (Basel). 2025 Jul 16;17(14):1951. doi: 10.3390/polym17141951.
The repair efficiency of various self-healing materials often depends on the ability of the prepolymer and curing agent to form mixtures. This paper presents a synthesis and study of the properties of modified self-healing polyurethanes using the Diels-Alder reaction (DA reaction), obtained from a maleimide-terminated preform and a series of furan-urethane curing agents. The most commonly used isocyanates (4,4'-methylene diphenyl diisocyanate (MDI), 2,4-tolylene diisocyanate (TDI), and hexamethylene diisocyanate (HDI)) and furan derivatives (furfurylamine, difurfurylamine, and furfuryl alcohol) were used as initial reagents for the synthesis of curing agents. For comparative analysis, polyurethanes were also obtained using the well-known "traditional" approach-from furan-terminated prepolymers based on mono- and difurfurylamine, as well as furfuryl alcohol and the often-used bismaleimide curing agent 1,10-(methylenedi-1,4-phenylene)bismaleimide (BMI). The structure and composition of all polymers were studied using spectroscopic methods. Molecular mass was determined using gel permeation chromatography (GPC). Thermal properties were studied using TGA, DSC, and TMA methods. The mechanical and self-healing properties of the materials were investigated via a uniaxial tensile test. Visual assessment of the completeness of damage restoration after the self-healing cycle was carried out using a scanning electron microscope. It was shown that the proposed modified approach helps obtain more durable polyurethanes with a high degree of self-healing of mechanical properties after damage.
各种自愈材料的修复效率通常取决于预聚物和固化剂形成混合物的能力。本文介绍了一种利用狄尔斯-阿尔德反应(DA反应)合成和研究改性自愈聚氨酯性能的方法,该聚氨酯由马来酰亚胺封端的预聚物和一系列呋喃-聚氨酯固化剂制得。最常用的异氰酸酯(4,4'-亚甲基二苯基二异氰酸酯(MDI)、2,4-甲苯二异氰酸酯(TDI)和六亚甲基二异氰酸酯(HDI))以及呋喃衍生物(糠胺、二糠胺和糠醇)被用作合成固化剂的起始试剂。为了进行对比分析,还采用了众所周知的“传统”方法制备聚氨酯,即由基于单糠胺、二糠胺以及糠醇的呋喃封端预聚物和常用的双马来酰亚胺固化剂1,10-(亚甲基二-1,4-亚苯基)双马来酰亚胺(BMI)制备。使用光谱方法研究了所有聚合物的结构和组成。通过凝胶渗透色谱法(GPC)测定分子量。使用热重分析法(TGA)、差示扫描量热法(DSC)和热机械分析法(TMA)研究热性能。通过单轴拉伸试验研究材料的力学性能和自愈性能。使用扫描电子显微镜对自愈循环后损伤修复的完整性进行目视评估。结果表明,所提出的改性方法有助于获得更耐用的聚氨酯,其在损伤后具有高度的力学性能自愈能力。