摘要
透明光学材料的雾化与结露是生产、生活中的常见问题。解决这类问题的主要方法有物理加热除雾、涂覆亲水或疏水涂层防雾。目前传统的热固化成膜方法存在能耗高、效率低、容易使基材变形等缺陷,且涂膜容易沾污、不易清洁。本文利用紫外光固化涂料的高效、节能、室温固化优势,结合含氟表面活性低聚物的低表面张力特性,制备一种以光敏性亲水丙烯酸树脂为主体的光固化防雾涂料,以克服传统热固化防雾涂料的不足。本论文首先以聚氧乙烯单全氟烷基醚、2,4-甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、丙烯酸-β-羟乙酯(HEA)、季戊四醇三丙烯酸酯(PETA)为主要原料,合成了一系列含氟聚氨酯丙烯酸酯表面活性低聚物。研究发现,这类低聚物可显著降低水的表面张力。同时,本论文以丙烯酸、丙烯酸羟乙酯、聚乙二醇单甲醚丙烯酸酯为亲水单体,丙烯酸乙酯为疏水单体,通过可见光活化室温RAFT聚合、光引发低聚物双硫酯端基脱除及低聚物与甲基丙烯酸缩水甘油酯的开环反应,制备了分子量可控、分子分布较窄的光固化亲水性丙烯酸酯树脂,并用1HNMR、GPC对其进行表征。以上述光固化亲水性丙烯酸酯树脂、含氟聚氨酯丙烯酸酯表面活性低聚物为主体材料,辅以其它亲水性单体、多官能交联单体、低聚物、光引发剂等,配制了光固化涂料。固化成膜后检测其防雾、耐水等性能。结果表明,合成亲水丙烯酸树脂的亲水单体中,丙烯酸的亲水性最好,其防雾性能也最好,当亲水单体含量超过60%时,涂料的耐水性变差,加入少量表面活性含氟低聚物(<0.05%)的涂膜在防雾的同时,也能改善涂膜与油的接触角。但是,加入过量的表面活性含氟低聚物(>2%),虽然涂膜与油的接触角增大到47°,但使涂膜丧失防雾的功能。另外,活性稀释与交联剂、光引发剂的含量对涂膜防雾性能和机械性能也起着至关重要的作用。
Fogging and dewing condensation on the surface of transparent optical materials is a common problem. There are many methods to solve such problem, such as physical heating, painting an hydrophilic or hydrophobic film. The traditional methods to prepare film by thermo-curing bring the follow flaws:high energy consumption, low-efficiency, easy to make deformation of base materials. What's more, it is easy to contamination and difficult to clean. In this thesis, by means of combining the advantage of UV coatings (efficient, energy conservation, curable at room temperature, etc.) and the low surface tension of fluoro-containing surfactant, we prepared a new type of photo-curable coatings using an photo-sensitive hydrophilic acrylate as a basic resin, to overcome the defect of traditional anti-fogging thermo-curing coatings. Firstly, a series of oligomeric fluoro-containing urethane acrylates with surface activity were synthesized, using poly(ethylene oxide) fluoro-alkyl ether,2,4-toluene diisocyanate (TDI) or isopropyl ketone diisocyanate (IPDI),2-hydroxyethyl acrylate (HEA), pentaerythritol triacrylate (PETA) as raw materials. The results demonstrated that such oligomers can significantly reduce the surface tension of water. A series of well-defined hydrophilic acrylate resins were synthesized subsequently via the visible light activating room-temperature RAFT polymerization, light-triggered removal of chain transfer agent residues and ring-opening reaction of glycidyl methacrylate, using acrylic acid, 2-hydroxyethyl acrylate (HEA), poly(ethylene glycol) monomethyl ether acrylate as hydrophilic monomers, and ethyl acrylate as a hydrophobic monomer. The anti-fogging UV-curable paint was prepared using film-forming substance such as acrylic acid,2-hydroxyethyl acrylate, methyl acrylate, poly(ethylene glycol) acrylate, cross-linkers, photo-initiators and other additives, etc. The anti-fogging and water resistant performance of this film was tested. The film prepared by these 3 hydrophilic acrylates exhibited excellent hydrophilic anti-fogging performance. However, the water resistance becomes poor as hydrophilic monomer over 60%. A little fluoro-oligomer (<0.05%) was sufficient to prevent fogging. However, adding excess of fluoro-oligomer (>2%) may deteriorate the anti-fogging property of their films. In addition, the content of active dilutes, cross-linkers and photo-initiator play important roles in the anti-fogging and mechanical performance of their coatings.
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