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    基于聚二甲基硅氧烷改性超支化聚硫氨酯制备紫外光固化易清洁涂层

    Preparation of UV-Curable Easy-to-Clean Coatings Based on Polydimethylsiloxane-Modified Hyperbranched Polythiourethane

    • 摘要: 以单羟基封端聚二甲基硅氧烷(PDMS-OH)、异佛尔酮二异氰酸酯(IPDI)和三羟甲基丙烷三(3-巯基丙酸酯)(TMPMP)为原料,合成含聚二甲基硅氧烷链段超支化聚硫氨酯(PDMS-HBPTU),并将其添加至聚己内酯型聚氨酯丙烯酸酯(LPUA)涂料中,经紫外光固化得到了含有不同质量分数PDMS-HBPTU的易清洁涂层。系统研究了PDMS-HBPTU质量分数对易清洁涂层润湿性、透光率、防污性及耐磨性的影响。结果表明,当PDMS-HBPTU质量分数为2.0%时,涂层的水接触角与十六烷接触角显著提高,水滑动角与涂层表面能显著降低,同时保持较高的透光率和较低的表面粗糙度。PDMS链段在涂层表面富集,形成了低表面能界面。所制备的易清洁涂层对油性记号笔笔迹和多种常见液体表现出优异的防污与易清洁效果。经5000次棉布摩擦后,涂层水接触角仅下降6.02%,仍保持良好的防涂鸦性,显示出优异的耐磨性。超支化结构有效改善了PDMS与基体树脂的相容性。当PDMS-HBPTU质量分数为2.0%时,涂层在保持高透光性的同时,兼具优异的表面疏水/油、易清洁及耐摩擦性能,表现出良好的实际应用前景。

       

      Abstract: Polydimethylsiloxane (PDMS)-containing hyperbranched polythiourea (PDMS-HBPTU) is synthesized using monohydroxyl-terminated polydimethylsiloxane (PDMS-OH), isophorone diisocyanate (IPDI), and trimethylolpropane tris(3-mercaptopropionate) (TMPMP) as raw materials. The PDMS-HBPTU is then added to polycaprolactone-based polyurethane acrylate (LPUA) coatings to prepare a series of easy-cleaning coatings with different mass fractions of PDMS-HBPTU. The effects of mass fractions PDMS-HBPTU on the wettability, light transmittance, anti-pollution properties, and wear resistance of the easy-to-clean coatings were systematically investigated using an optical contact angle meter, a UV-Vis spectrophotometer, oil-based markers/ink, and a tribometer. The results indicate that when the mass fraction of PDMS-HBPTU is 2.0%, the contact angles of water and hexadecane on the coating surface are significantly increased, while the sliding angle of water and the surface energy of the coating are reduced. Additionally, the coating maintains a high light transmittance and exhibits decreased surface roughness. XPS data indicates that the PDMS segments are enriched on the coating surface, forming a low-surface-energy interface. The coating demonstrates excellent anti-staining and easy-cleaning properties against oil-based marker ink as well as common liquids including milk, cooking oil, and beverages. After 5000 cycles of rubbing with cotton cloth, the water contact angle of the coating decreases by only 6.02%, maintaining good anti-graffiti properties, which highlights its excellent wear resistance. The hyperbranched structure effectively improves the compatibility between PDMS and the matrix resin. When the PDMS-HBPTU content is 2.0%, the coating not only maintains high transmittance but also possesses excellent surface hydrophobicity/lipophobicity, easy-cleaning properties, and wear resistance, showing good prospects for practical applications.

       

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