光固化氟硅低表面能涂层的制备及其表面行为研究

发布时间：2018-02-12 05:03

  本文关键词： 紫外光固化 氟硅树脂 低表面能涂层 反应型　出处：《南昌航空大学》2017年硕士论文　论文类型：学位论文

【摘要】：氟硅树脂因其具有极低的表面能而且有着较好的力学性能、与其他材料有较好的相容性和极佳的耐化学腐蚀性,在多个领域有着广泛的应用。同时紫外光固化技术由于其高效、节能、环保、经济等优点成为人们关注的重点。然而,将光固化技术与氟硅树脂相结合的研究并不多。本文合成了两类反应型光固化氟硅树脂—接枝型和接枝共聚型,并将其与市售光固化聚氨酯复配制备光固化低表面能涂层,系统研究了氟硅树脂特别是含氟侧基向涂层表面富集的机理,探究低含量氟硅树脂显著改善光固化涂层表面性能的机制,并对其耐久性和涂层物理性能、耐介质性能进行了研究。其具体研究内容如下:本文基于“巯基-烯”点击化学制备了三种不同含氟结构的羟基单体,并将其与改性后的羟基聚二甲基硅氧烷(HPDMS)以及异氟尔酮二异氰酸酯(IPDI)反应,制备出一系列以聚二甲基硅氧烷为主链,含氟基团和丙烯酸双键为侧基的新型可光固化的接枝型氟硅树脂(SG0X,X为不同含氟结构牌号,X越大含氟量越大,X分别为1、5、6B)。采用RAFT聚合反应聚合含氟单体,将其接枝于合成的环氧聚二甲基硅氧烷上,最终再和IPDI以及丙烯酸羟丙酯(HPA)反应制备出两种以聚二甲基硅氧烷为主链,含氟聚合物和丙烯酸双键为侧基的新型可光固化的接枝共聚型氟硅树脂SPG01和SP(G01-G05)。采用傅里叶变换红外光谱(FTIR)与核磁共振氢谱(1H-NMR)对两类树脂进行了表征。并采用红外光谱对二者的光固化为进行了研究,结果表明两类树脂在紫外光引发下均可以快速光固化。并将两类树脂与市售丙烯酸聚氨酯DR-U356复配制得光固化低表面能涂层。通过对各涂层样品的静态水接触角、各界面元素含量的测定,研究了接枝型氟硅树脂的添加对光固化涂层表面能影响机制。研究发现,对于同一种接枝型氟硅树脂,随着其含量从0上升到10%,静态水接触角迅速上升,接触角由59.41°上升至109.92°,表面能也从原来的66.55 mN/m降低到37.56 mN/m,特别是在较低含量时,即1wt.%时,接触角就可以上升95.31°,表面能降低到48.00 mN/m,将涂层的表面由亲水表面迅速转变为疏水表面,但在掺杂含量超过3%后,各体系的表面能几乎不再变化。其次在含量相同时随着含氟链段碳原子主链长度从3上升到6,接触角也快速上升,表面能迅速下降,如在添加量为10%时,从碳链为3时的99.4°上升到碳链长度为6时的109.92°,表面能从45.19 mN/m下降至37.56 mN/m。同时研究发现,氟硅树脂显著向固-气界面即表面迁移富集,如添加1%的SG05固化涂层,其底面氟元素含量为1.54%而其表面的氟元素含量约为2.21%,约为底面氟元素含量的1.5倍,而二者的氟元素含量均远远大于理论的体积平均值0.148%。研究还发现热处理对于该富集过程并未有促进作用。通过自行设计的“摩擦-热处理”循环实验,研究固化涂层的低表面能富集层的耐久性。研究发现,各涂层经摩擦后接触角均呈下降趋势,经120℃热处理1 h后接触角可恢复,且该回复过程可循环多次。最后研究了固化涂层的耐介质性能,结果表明,接枝型氟硅树脂的引入对涂层的耐介质性有大幅度提升的效果。通过对各涂层样品的静态水接触角,研究了接枝共聚型氟硅树脂的添加对光固化涂层表面能影响机制。研究发现,相对于接枝型氟硅树脂体系,接枝共聚型氟硅树脂的添加可以更显著的降低固化涂层的接触角和表面能,添加1~2%即可到达平衡。其次在含量相同时随着含氟链段中含氟量的增加,接触角快速上升,表面能迅速下降,如在添加量为10%时从G01共聚的99.4°上升到G01与G05共聚时的109.92°,表面能从49.09 mN/m下降至44.42 mN/m。热处理对于接枝共聚型氟硅树脂体系涂层的表面能的降低有促进作用,最大可降低15.80%。通过“摩擦-热处理”循环实验发现,接枝共聚型氟硅树脂不仅同接枝型氟硅树脂体系一样,有着极佳的耐久性能,同时其在摩擦后依旧可以保持较好的疏水性,接触角下降平均值由接枝型氟硅树脂体系的25.82°下降到1.95°,表现出极佳的耐摩擦性能。最后研究了固化涂层的耐介质性能,结果表明,接枝共聚型氟硅树脂的引入对涂层的耐介质性有大幅度提升的效果。
[Abstract]:Fluorine silicon resin because of its low surface energy and has good mechanical properties, excellent compatibility and good resistance to chemical corrosion and other materials have been widely used in many fields. At the same time, UV curing technology because of its high efficiency, energy saving, environmental protection, economic and other advantages become the focus of attention. However, the study of UV curing technology and fluorosilicone resin combination is not much. Two kinds of reaction type light cured fluorine silicone resin, graft type and graft copolymer was synthesized in this paper, and with the commercially available UV curable polyurethane compound preparation of UV curable low surface energy coatings, of silicon fluoride the resin especially fluorinated side groups to the mechanism of coating surface enrichment, explore the low content of fluorine silicon resin significantly improve the mechanism of the surface properties of the UV cured coating, and the coating durability and physical properties, dielectric properties were studied. The specific research The content is as follows: the "thiol ene" click chemistry based on the preparation of three different structures containing fluorine hydroxyl monomers, and the modified poly two methyl siloxane (HPDMS) and isophorone diisocyanate (IPDI) reaction, the preparation of a series of poly two methyl siloxane the main chain, model can be grafted silicon fluorine resin curable fluorinated groups and acrylate double bond as side group (SG0X, X for different fluorine structure grades, the greater the X fluorine content increases, X = 1,5,6B). The RAFT polymerization of fluorinated monomer, grafted to synthesis epoxy poly two methyl siloxane, and finally IPDI and hydroxypropyl acrylate (HPA) was prepared by the reaction of two kinds of poly two methyl siloxane backbone, novel photocurable graft copolymerization type fluorine silicone resin SPG01 and SP fluoropolymer and acrylic acid double side group (G01-G05) by Fourier transform. Infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (1H-NMR) of two kinds of resin were characterized by infrared spectroscopy and light cured. Two of them have been studied, the results showed that two kinds of resin can fast curing initiated by ultraviolet. And two kinds of commercially available resin and acrylic polyurethane compounded with DR-U356 light curing coating with low surface energy. Through the static water contact angle of the coating samples, the determination of the content of the interface elements, the study of graft type fluorine silicon resin addition on light curing coating surface can affect the mechanism. The study found that for the same kind of grafted silicon fluorine resin, with its content increased from 0 to 10%, the static water contact angle increases rapidly, the contact angle from 59.41 up to 109.92 degrees, the surface energy was reduced from 66.55 mN/m to 37.56 mN/m, especially in the lower content of 1wt.%, namely, the contact angle can be increased by 95.31 degrees, can reduce the surface To 48 mN/m, the coating surface from hydrophilic surface is rapidly converted to hydrophobic surfaces, but the doping content is more than 3%, the surface of each system can hardly change. In the second with the same amount of fluorinated segment carbon atom backbone length increased from 3 to 6, the contact angle of the rapid rise, surface energy decreased rapidly in addition, as of 10%, 3 from the carbon chain 99.4 degrees up to 6 when the carbon chain length of 109.92 degrees, the surface energy decreased from 45.19 mN/m to 37.56 mN/m. at the same time the study found that fluorine silicon resin significantly to the solid gas interface or surface migration enrichment, such as adding 1% SG05 curing coatings and the bottom surface of the fluorine content is 1.54% and the fluorine content of the surface is about 2.21%, about 1.5 times that of the bottom surface of the fluorine content, the fluorine content of two are far greater than the volume average theory 0.148%. studies show that heat treatment for the enrichment process did not promote In the role of the "friction and heat treatment of self-designed" cycling experiment to durability of low surface enrichment layer of cured coatings. It is found that the coating after rubbing contact angle decreased by 120 degrees of heat treatment after 1 h of contact angle can be recovered, and the recovery process can be recycled many times at the end of the cured coating. Medium resistance, the results show that the introduction of fluorine silicon resin grafted on the coating medium resistance greatly enhance the effect. Through the static water contact angle of the coated samples, studied the graft copolymerization of fluorine silicone resin addition on light curing coating surface can affect the mechanism. The study found that, compared to the grafted fluorine silicon resin, graft copolymerization type fluorine silicon resin addition could significantly decrease the cured coating contact angle and surface energy, add 1~2% to reach equilibrium. Secondly with the same amount of fluorinated chain Increase the fluoride content in the period, the contact angle increases quickly, the surface energy decreased rapidly, such as when adding amount was 10% from 99.4 degrees up to G01 copolymerization copolymerization of G01 and G05 in 109.92 degrees, the surface energy decreased from 49.09 mN/m to 44.42 mN/m. heat treatment had positive effect on reducing surface graft copolymerization type silicon fluoride resin coating can, can reduce the maximum 15.80%. found through the friction heat treatment cycle experiment, graft copolymerization type fluorine silicon resin not only with grafted silicon fluorine resin system, with excellent durability, and its friction can still maintain good hydrophobicity, the contact angle decreased the average value decreased by graft type fluorosilicone resin system 25.82 to 1.95 DEG, exhibits excellent anti friction performance. Finally the cured coating medium resistance, the results show that the introduction of graft copolymerization type silicon fluorine resin on the coating resistance of medium The effect of a large increase.

【学位授予单位】：南昌航空大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB306

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