以糠胺和双马莱酰亚胺为Diels-Alder(DA)反应单体,通过两步合成法合成热可逆DA反应自修复聚氨酯(DA-PU);以商用单层氧化石墨烯(GO)为原料,先将GO溶解在二甲基甲酰胺中,然后通过溶液共混和流延成膜工艺将氧化石墨烯引入到DA-PU体系中制备GO-DA-PU复合膜,研究了复合膜的微观结构、热学、力学和红外热修复性能等。结果表明:GO在复合膜中可实现均匀分布,GO改善了复合膜的导热性能,含有3% GO的复合膜具有最高的导热系数,约为0.364W/(m·K),是纯TPU膜的导热系数的2.26倍,而且在红外光照1min下复合膜的温度可升至139.9℃,约为纯DA-PU膜温度的1.93倍;GO改善了复合膜的拉伸强度,但降低了柔韧性;随着复合膜中GO含量增加,修复效率先增加而后下降,含有1%和3% GO的复合膜经红外光照修复5min的修复效率分别为94%和96%,红外光照10min可实现完全修复,且拉伸强度高于未有划痕的样品;随着自修复次数的增加,纯DA-PU膜和复合膜的修复效率均下降,但是复合膜的修复效率仍然较纯DA-PU膜的修复效率高;纯DA-PU膜和含有1%和2% GO的复合膜的红外热修复的第一次修复效率分别为95%、103%和105%,第五次修复效率分别为78%、82%和86%,说明GO改善了DA-PU多次自修复能力。
Thermo-reversible reaction polyurethane (PU) was synthesized by two-step synthesis using furfurylamine and bismaleimide as Diels-Alder (DA) reaction monomers.Subsequently,commercial monolayer graphene oxide (GO) was dissolved into dimethylformamide,and then GO was introduced into the DA-PU system to prepare GO-DA-PU self-healing composite film by mixing and tape casting process.Further,the microstructures,thermal,mechanical and infrared thermal self-healing properties of the composite films were studied.The experimental results showed that GO sheets could be uniformly distributed in the composite film,GO improved the thermal conductivity of the composite film,and the composite film containing 3wt% GO had the highest thermal conductivity of about 0.364W/(m·K),which was 2.26 times that of pure TPU film.The temperature of the composite film could be increased to 139.9℃ under infrared irradiation for 1 minute,which was about 1.93 times that of the pure DA-PU film.GO improved the tensile strength of the composite film,but reduced the flexibility.With the increase of GO content in the composite film,the self-healing efficiency first increased and then decreased.The self-healing efficiencies of the composite films containing 1 wt% and 3 wt% GO were 94% and 96% after 5 minutes of infrared irradiation,respectively.Infrared illumination for 10 min could realize complete repair,and the tensile strength was higher than that of the samples without scratches.With the increase of self-healing times,the self-healing efficiencies of both pure DA-PU film and composite films decreased,but the self-healing efficiency of composite film was still higher than that of pure DA-PU film.The first self-healing efficiencies of the pure DA-PU film and the composite films containing 1 wt% and 2 wt% GO under infrared irradiation were 95%,103% and 105%,respectively,and the fifth repair efficiencies were 78%,82% and 86%,respectively,indicating that GO improved the multiple self-healing ability of the DA-PU.
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基金资助
广东省教育厅创新团队项目(2020KCXTD030)
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