Yu Xuecheng, Xiong Ying, Li Zhen, Tang Hongding
Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, Sauvage Center for Molecular Sciences, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
Polymers (Basel). 2020 Jul 22;12(8):1629. doi: 10.3390/polym12081629.
Three series of silicone modified polyurethane acrylate (SPUA) prepolymers were prepared from dicyclohexylmethane-4, 4'-diisocyanate (HMDI), PPG1000, triethylene glycol (TEG), 2-hydroxyethyl acrylate (HEA), and multi-hydroxyalkyl silicone (MI-III) with tris(trimethylsiloxy)silyl propyl side groups. Their structures were confirmed by H NMR, C NMR, and Fourier transformed infrared (FTIR) analysis, and SPUA films were obtained by UV curing. The properties of films were investigated by attenuated total reflection (ATR)-FTIR, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), water contact angle (WCA), thermogravimetric analysis (TGA), differential scanning calorimeter (DSC), water and hexane resistance, and tensile testing. The results showed that the structures and dosages of MI-III could influence the polymerization properties, surface properties, water and n-hexane resistance, and thermal and tensile properties of SPUA. For instance, the surface aggregation of tris(trimethylsiloxy)silyl propyl groups (even ~2.5 wt%) could endow SPUA films with less microphase separation, good hydrophobicity, lipophilicity, thermal stability, and mechanical properties. Interestingly, obvious regular winkles appeared on the surfaces of SPUAIII films, which are characterized by relatively high WCA values. However, relatively smooth were observed on the surfaces of SPUAIII films, which also exhibit lower water absorption ratio values. Furthermore, the ordinary cotton textiles would be transformed into hydrophobic and oleophilic textiles after treating with SPUA simply, and they were used in the oil/water separation study. Among them, consistent with water and hexane resistance analysis of SPUA films, SPUAII treated cotton textiles are characterized by relatively small liquid absorption capacity (LAC) values. Thus, phenyl groups and side-chain tris(trimethylsiloxy)silyl propyl groups are helpful to improve the hydrophobicity and lipophilicity of SPUA films. SPUAII-5 (even with 5 wt% MII) treated cotton textiles could efficiently separate the oil/water mixture, such as n-hexane, cyclohexane, or methylbenzene with water. Thus, this material has great potential in the application of hydrophobic treatment, oil/water separation, and industrial sewage emissions, among others.
以二环己基甲烷 - 4,4'-二异氰酸酯（HMDI）、聚丙二醇1000（PPG1000）、三甘醇（TEG）、丙烯酸 - 2 - 羟乙酯（HEA）和带有三（三甲基硅氧基）甲硅烷基丙基侧基的多羟基烷基硅氧烷（MI - III）制备了三个系列的有机硅改性聚氨酯丙烯酸酯（SPUA）预聚物。通过¹H NMR、¹³C NMR和傅里叶变换红外光谱（FTIR）分析确认了它们的结构，并通过紫外光固化获得了SPUA薄膜。通过衰减全反射（ATR）-FTIR、扫描电子显微镜（SEM）、能量色散X射线光谱（EDS）、水接触角（WCA）、热重分析（TGA）、差示扫描量热仪（DSC）、耐水和耐正己烷性能以及拉伸测试对薄膜的性能进行了研究。结果表明，MI - III的结构和用量会影响SPUA的聚合性能、表面性能、耐水和耐正己烷性能以及热性能和拉伸性能。例如，三（三甲基硅氧基）甲硅烷基丙基基团的表面聚集（甚至~2.5 wt%）可使SPUA薄膜具有较少的微相分离、良好的疏水性、亲脂性、热稳定性和机械性能。有趣的是，SPUAIII薄膜表面出现了明显规则的褶皱，其特征是具有相对较高的WCA值。然而，在SPUAIII薄膜表面观察到相对光滑，其吸水率值也较低。此外，普通棉织物经SPUA简单处理后可转变为疏水亲油织物，并用于油/水分离研究。其中，与SPUA薄膜的耐水和耐正己烷性能分析一致，经SPUAII处理的棉织物的液体吸收容量（LAC）值相对较小。因此，苯基和侧链三（三甲基硅氧基）甲硅烷基丙基基团有助于提高SPUA薄膜的疏水性和亲脂性。经SPUAII - 5（甚至含5 wt% MII）处理的棉织物能够有效地分离油/水混合物，如正己烷、环己烷或甲苯与水的混合物。因此，这种材料在疏水处理、油/水分离和工业污水排放等应用中具有巨大潜力。
