Wu Guoqing, Zhang Dongjiu, Xu Wei, Zhang Hongjun, Chen Likun, Zheng Yongchao, Xin Yi, Li Hong, Cui Yan
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Key Lab of Electrical Insulation and Thermal Aging, Shanghai Jiao Tong University, No. 800 Dongchuan Road, Minhang District, Shanghai 200240, P. R. China.
State Key Laboratory of Particle Detection and Electronics, University of Science and Technology of China, Hefei 230026, P. R. China.
ACS Omega. 2022 Mar 30;7(14):12354-12364. doi: 10.1021/acsomega.2c00915. eCollection 2022 Apr 12.
Chemical warfare agents (CWAs) can be absorbed in polymeric coatings through absorption and permeation, thus presenting a lethal touch and vapor hazards to people. Developing a highly impermeable polymer coating against CWAs, especially against organophosphate CWAs (OPs), is challenging and desirable. Herein, fluorinated epoxy (F-EP) and epoxy (EP) coatings with different cross-link densities were prepared to resist OPs. The effects of the polymer coating structure, including cross-link density, chemical composition and free volume, on the chemical resistance to dimethyl methylphosphonate (DMMP, Soman simulant) were investigated in detail. Meanwhile, the chemical resistance to Soman and VX was examined. The results reveal that the cross-link density is a critical factor in determining the chemical resistance of the coatings. Highly cross-linked EP and F-EP coatings with dense and solid cross-linked networks can fully bar DMMP and OPs permeation during the test time. At low or medium cross-link densities, the EP coating with a lower retention of DMMP exhibited a higher resistance than the F-EP coating due to the lower interaction with DMMP and smaller free-volume holes and lower relative fractional free volume. These results suggest that increasing the cross-link density is a reasonable approach to control the chemical resistance of polymer networks against OPs.
化学战剂（CWAs）可通过吸收和渗透作用被聚合物涂层吸收，从而对人员构成致命的接触和蒸气危害。开发一种对化学战剂，尤其是对有机磷酸酯类化学战剂（OPs）具有高度不渗透性的聚合物涂层，既具有挑战性又十分必要。在此，制备了具有不同交联密度的氟化环氧树脂（F-EP）和环氧树脂（EP）涂层以抵抗有机磷酸酯类化学战剂。详细研究了聚合物涂层结构，包括交联密度、化学组成和自由体积，对磷酸二甲酯（DMMP，梭曼模拟物）的耐化学性的影响。同时，还检测了对梭曼和维埃克斯毒剂的耐化学性。结果表明，交联密度是决定涂层耐化学性的关键因素。具有致密且坚实交联网络的高度交联的EP和F-EP涂层在测试期间能够完全阻止DMMP和有机磷酸酯类化学战剂的渗透。在低或中等交联密度下，由于与DMMP的相互作用较低、自由体积孔较小且相对自由体积分数较低，DMMP保留率较低的EP涂层比F-EP涂层表现出更高的抗性。这些结果表明，提高交联密度是控制聚合物网络对有机磷酸酯类化学战剂耐化学性的合理方法。
