本文關鍵詞： 紫外光固化 氟硅樹脂 低表面能涂層 反應型　出處：《南昌航空大學》2017年碩士論文　論文類型：學位論文

【摘要】：氟硅樹脂因其具有極低的表面能而且有著較好的力學性能、與其他材料有較好的相容性和極佳的耐化學腐蝕性,在多個領域有著廣泛的應用。同時紫外光固化技術由于其高效、節(jié)能、環(huán)保、經(jīng)濟等優(yōu)點成為人們關注的重點。然而,將光固化技術與氟硅樹脂相結合的研究并不多。本文合成了兩類反應型光固化氟硅樹脂—接枝型和接枝共聚型,并將其與市售光固化聚氨酯復配制備光固化低表面能涂層,系統(tǒng)研究了氟硅樹脂特別是含氟側基向涂層表面富集的機理,探究低含量氟硅樹脂顯著改善光固化涂層表面性能的機制,并對其耐久性和涂層物理性能、耐介質性能進行了研究。其具體研究內容如下:本文基于“巰基-烯”點擊化學制備了三種不同含氟結構的羥基單體,并將其與改性后的羥基聚二甲基硅氧烷(HPDMS)以及異氟爾酮二異氰酸酯(IPDI)反應,制備出一系列以聚二甲基硅氧烷為主鏈,含氟基團和丙烯酸雙鍵為側基的新型可光固化的接枝型氟硅樹脂(SG0X,X為不同含氟結構牌號,X越大含氟量越大,X分別為1、5、6B)。采用RAFT聚合反應聚合含氟單體,將其接枝于合成的環(huán)氧聚二甲基硅氧烷上,最終再和IPDI以及丙烯酸羥丙酯(HPA)反應制備出兩種以聚二甲基硅氧烷為主鏈,含氟聚合物和丙烯酸雙鍵為側基的新型可光固化的接枝共聚型氟硅樹脂SPG01和SP(G01-G05)。采用傅里葉變換紅外光譜(FTIR)與核磁共振氫譜(1H-NMR)對兩類樹脂進行了表征。并采用紅外光譜對二者的光固化為進行了研究,結果表明兩類樹脂在紫外光引發(fā)下均可以快速光固化。并將兩類樹脂與市售丙烯酸聚氨酯DR-U356復配制得光固化低表面能涂層。通過對各涂層樣品的靜態(tài)水接觸角、各界面元素含量的測定,研究了接枝型氟硅樹脂的添加對光固化涂層表面能影響機制。研究發(fā)現(xiàn),對于同一種接枝型氟硅樹脂,隨著其含量從0上升到10%,靜態(tài)水接觸角迅速上升,接觸角由59.41°上升至109.92°,表面能也從原來的66.55 mN/m降低到37.56 mN/m,特別是在較低含量時,即1wt.%時,接觸角就可以上升95.31°,表面能降低到48.00 mN/m,將涂層的表面由親水表面迅速轉變?yōu)槭杷砻?但在摻雜含量超過3%后,各體系的表面能幾乎不再變化。其次在含量相同時隨著含氟鏈段碳原子主鏈長度從3上升到6,接觸角也快速上升,表面能迅速下降,如在添加量為10%時,從碳鏈為3時的99.4°上升到碳鏈長度為6時的109.92°,表面能從45.19 mN/m下降至37.56 mN/m。同時研究發(fā)現(xiàn),氟硅樹脂顯著向固-氣界面即表面遷移富集,如添加1%的SG05固化涂層,其底面氟元素含量為1.54%而其表面的氟元素含量約為2.21%,約為底面氟元素含量的1.5倍,而二者的氟元素含量均遠遠大于理論的體積平均值0.148%。研究還發(fā)現(xiàn)熱處理對于該富集過程并未有促進作用。通過自行設計的“摩擦-熱處理”循環(huán)實驗,研究固化涂層的低表面能富集層的耐久性。研究發(fā)現(xiàn),各涂層經(jīng)摩擦后接觸角均呈下降趨勢,經(jīng)120℃熱處理1 h后接觸角可恢復,且該回復過程可循環(huán)多次。最后研究了固化涂層的耐介質性能,結果表明,接枝型氟硅樹脂的引入對涂層的耐介質性有大幅度提升的效果。通過對各涂層樣品的靜態(tài)水接觸角,研究了接枝共聚型氟硅樹脂的添加對光固化涂層表面能影響機制。研究發(fā)現(xiàn),相對于接枝型氟硅樹脂體系,接枝共聚型氟硅樹脂的添加可以更顯著的降低固化涂層的接觸角和表面能,添加1~2%即可到達平衡。其次在含量相同時隨著含氟鏈段中含氟量的增加,接觸角快速上升,表面能迅速下降,如在添加量為10%時從G01共聚的99.4°上升到G01與G05共聚時的109.92°,表面能從49.09 mN/m下降至44.42 mN/m。熱處理對于接枝共聚型氟硅樹脂體系涂層的表面能的降低有促進作用,最大可降低15.80%。通過“摩擦-熱處理”循環(huán)實驗發(fā)現(xiàn),接枝共聚型氟硅樹脂不僅同接枝型氟硅樹脂體系一樣,有著極佳的耐久性能,同時其在摩擦后依舊可以保持較好的疏水性,接觸角下降平均值由接枝型氟硅樹脂體系的25.82°下降到1.95°,表現(xiàn)出極佳的耐摩擦性能。最后研究了固化涂層的耐介質性能,結果表明,接枝共聚型氟硅樹脂的引入對涂層的耐介質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.

【學位授予單位】：南昌航空大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TB306

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