表面引發(fā)自由基聚合法制備潤濕性可控的聚離子液體刷
發(fā)布時間：2019-04-01 06:30
【摘要】： 表面潤濕性是固體表面的重要特征之一，對自然界中動、植物的種種生命活動，人類的日常生活及工、農(nóng)業(yè)生產(chǎn)具有重要的影響。眾所周知，表面潤濕性由固體表面自由能和表面粗糙度的大小來決定。目前，關(guān)于超疏水性材料的構(gòu)筑已經(jīng)有很多研究，方法已漸成熟，但具有動態(tài)可控性質(zhì)的表面設計研究才剛剛起步，而表面潤濕性動態(tài)可控的可逆超疏水/超親水性材料由于可以對外部刺激做出精確和可預測的改變和調(diào)控，在刺激響應器件、自清潔表面、液體微球操縱器、變焦鏡頭等方面具有巨大的應用潛能，所以，尋求操作簡便，易于工業(yè)推廣，膜穩(wěn)定性高，結(jié)構(gòu)和粗糙度可控，可逆性好的超疏水/超親水性可逆轉(zhuǎn)換材料仍然是表面材料科學中最有挑戰(zhàn)性的課題。 控制表面潤濕性的方法有很多，如機械表面形貌變化法，它通過控制表面粗糙度來實現(xiàn)潤濕性的調(diào)控，而通過改變表面自由能來調(diào)控材料的潤濕性能則主要是通過在材料表面涂覆或接枝有機聚合物層，通過控制有機聚合物層的構(gòu)成來實現(xiàn)潤濕性的調(diào)控。表面接枝法通過在基底表面形成以牢固的化學鍵相結(jié)合的端接枝聚合物層而備受關(guān)注。其中表面引發(fā)自由基聚合反應能夠在固體基底表面形成高度取向、結(jié)合牢固、高密度的聚合物層，薄膜層分布均勻、便于納微圖形化和加工成型，并且薄膜厚度可在分子水平上方便地調(diào)控，從而大大拓寬了聚合物的應用領域。 聚離子液體由于其結(jié)構(gòu)特點，成為實現(xiàn)表面潤濕性可逆調(diào)節(jié)的首選結(jié)構(gòu)單元之一，利用表面引發(fā)聚合反應將功能離子液體單元引入到材料表面，然后通過選擇適當?shù)膶﹄x子來調(diào)節(jié)材料表面的潤濕性變化。 本文利用表面引發(fā)自由基聚合反應，在不同的材料基底表面引入不同的聚離子液體刷，再通過對離子轉(zhuǎn)換實現(xiàn)固體表面的親疏水轉(zhuǎn)換。這些新型的潤濕性可控的功能材料鮮有報道，具有廣闊的應用前景。 首先合成了一種新的離子液單體烯丙基三苯基六氟磷酸擕，根據(jù)文獻合成出離子液單體1-（4-乙烯基芐基-）-3-丁基咪唑六氟磷酸鹽，并用核磁共振波譜等技術(shù)手段進行了表征。 以1-(4-乙烯基芐基)）-3-丁基咪唑六氟磷酸鹽為單體，2-溴-2-甲基-N-（3-（三甲氧基硅基）丙基）丙酰胺為表面引發(fā)劑，以SmCl3為催化劑，乳酸為配體，AIBN為自由基引發(fā)劑，DMF為溶劑，利用RATRP法在銅基底表面接枝了聚離子液體刷；以烯丙基三苯基六氟磷酸擕為單體，2-溴-2-甲基-N-（3-（三乙氧基硅基）丙基）丙酰胺(BTPAm)為表面引發(fā)劑，TEMPO為氮氧自由基引發(fā)劑，環(huán)己酮為溶劑，，利用表面引發(fā)NMP法在硅基底表面接枝了聚離子液體刷；以1-(4-乙烯基芐基)）-3-丁基咪唑六氟磷酸鹽為單體，2-溴-2-甲基-N-（3-（三乙氧基硅基）丙基）丙酰胺為表面引發(fā)劑，TEMPO為氮氧自由基引發(fā)劑，二甲苯為溶劑，利用NMP法在硅基底表面接枝了聚離子液體刷。利用X-射線光電子能譜（XPS）、接觸角儀、橢圓偏光儀、原子力顯微鏡（AFM）、核磁共振波譜（1H和13C NMR）和凝膠滲透色譜（GPC）分別對它們進行了表征。動力學研究表明，無論利用哪種方法，聚合物刷的厚度均隨聚合時間的增長呈線性關(guān)系，由此證明了聚離子液體刷在材料表面的增長是可控的活性聚合。此外，通過簡單的對陰離子交換，成功實現(xiàn)了材料表面親疏水性的可逆轉(zhuǎn)換。
[Abstract]:The surface wettability is one of the important characteristics of the solid surface, which has an important influence on the life activities of the moving and the plants in nature, the daily life of the human beings and the work and the agricultural production. It is well known that the surface wettability is determined by the free energy of the solid surface and the size of the surface roughness. At present, there are many researches on the construction of super-hydrophobic materials, and the method has become mature, but the surface design study with dynamic and controllable properties has just started. The reversible super-hydrophobic/ super-hydrophilic material with controllable surface wettability can make accurate and predictable changes and control to external stimuli, and has great application potential in the aspects of stimulation response device, self-cleaning surface, liquid microsphere manipulator, zoom lens and the like, so, The super-hydrophobic/ super-hydrophilic reversible conversion material has the advantages of simple and convenient operation, easy industrial popularization, high film stability, controllable structure and roughness, and good reversibility, and the super-hydrophobic/ super-hydrophilic reversible conversion material is still the most challenging topic in the surface material science. The method for controlling the wettability of the surface has many methods, such as the mechanical surface morphology change method, which realizes the control of the wettability by controlling the surface roughness, and the wettability of the material can be controlled by changing the surface free energy, mainly by coating or grafting the organic poly on the surface of the material. a composition layer for realizing the wettability by controlling the structure of the organic polymer layer The surface grafting process is prepared by forming an end-grafted polymer layer in combination with a strong chemical bond on the surface of the substrate The surface-initiated free-radical polymerization reaction can form a high-orientation on the surface of the solid substrate, and the high-density and high-density polymer layer is combined, the distribution of the thin-film layer is uniform, the micro-patterning and the processing and forming are facilitated, and the film thickness can be conveniently carried out at the molecular level. The regulation and control of the polymer greatly broadens the content of the polymer, in that field, the polyionic liquid is one of the preferred structural unit for realizing the reversible regulation of the surface wettability due to the structure characteristic of the polyionic liquid, The surface wettability changes. In this paper, the surface-induced free radical polymerization is used to introduce different polyionic liquid brushes on the surface of different materials. These new types of wettability-controllable functional materials have little to do with the water-to-water conversion of the solid surface. The invention provides a new ionic liquid monomer allyl triphenyl hexafluorophosphate, and the ionic liquid monomer 1-(4-vinyl-base-) -3-butyl detomorhexis phosphate is synthesized according to the literature, and the new ionic liquid monomer allyl triphenyl hexafluorophosphate is synthesized according to the literature, A 1-(4-vinyl-based) -3-Budetomycin hexafluorophosphate as a monomer,2-bromo-2-methyl-N-(3-(trimethoxysilyl) propyl) propylamine as a surface initiator is used as a catalyst, and lactic acid is a ligand. AIBN is a free radical initiator, DMF is a solvent, a polyionic liquid brush is grafted on the surface of the copper substrate by a RATRP method, the allyl triphenyl hexafluorophosphate is a monomer, and 2-bromo-2-methyl-N-(3-(triethoxysilyl) propyl) propylamine (BTPAm) is a surface initiator, and the TE The MPO is a nitrogen-oxygen free-radical initiator, cyclohexanone is a solvent, and a polyionic liquid brush is grafted on the surface of the silicon substrate by using a surface-induced NMP method, and 1-(4-vinyl-base)) -3-butyl detomycin hexafluorophosphate is a monomer, and 2-bromo-2-methyl-N-(3-(3-( triethoxysilyl) propyl) propylamine is a surface initiator, TEMPO is a nitrogen-oxygen free-radical initiator, xylene is a solvent, The ionic liquid brush was grafted on the surface of the silicon substrate by NMP. The X-ray photoelectron spectroscopy (XPS), the contact angle instrument, the ellipsometry, the atomic force microscope (AFM), the nuclear magnetic resonance spectrum (1H and 13C NMR) and the gel were used. The dynamic studies show that the thickness of the polymer brush has a linear relationship with the growth of the polymerization time, and thus the polyion is proved. the growth of the liquid brush on the surface of the material is a controlled, active polymerization. in addition, the anion exchange is achieved by a simple pair of anion exchange,
【學位授予單位】：西北師范大學
【學位級別】：碩士
【學位授予年份】：2010
【分類號】：O631.5
本文編號：2451282
[Abstract]:The surface wettability is one of the important characteristics of the solid surface, which has an important influence on the life activities of the moving and the plants in nature, the daily life of the human beings and the work and the agricultural production. It is well known that the surface wettability is determined by the free energy of the solid surface and the size of the surface roughness. At present, there are many researches on the construction of super-hydrophobic materials, and the method has become mature, but the surface design study with dynamic and controllable properties has just started. The reversible super-hydrophobic/ super-hydrophilic material with controllable surface wettability can make accurate and predictable changes and control to external stimuli, and has great application potential in the aspects of stimulation response device, self-cleaning surface, liquid microsphere manipulator, zoom lens and the like, so, The super-hydrophobic/ super-hydrophilic reversible conversion material has the advantages of simple and convenient operation, easy industrial popularization, high film stability, controllable structure and roughness, and good reversibility, and the super-hydrophobic/ super-hydrophilic reversible conversion material is still the most challenging topic in the surface material science. The method for controlling the wettability of the surface has many methods, such as the mechanical surface morphology change method, which realizes the control of the wettability by controlling the surface roughness, and the wettability of the material can be controlled by changing the surface free energy, mainly by coating or grafting the organic poly on the surface of the material. a composition layer for realizing the wettability by controlling the structure of the organic polymer layer The surface grafting process is prepared by forming an end-grafted polymer layer in combination with a strong chemical bond on the surface of the substrate The surface-initiated free-radical polymerization reaction can form a high-orientation on the surface of the solid substrate, and the high-density and high-density polymer layer is combined, the distribution of the thin-film layer is uniform, the micro-patterning and the processing and forming are facilitated, and the film thickness can be conveniently carried out at the molecular level. The regulation and control of the polymer greatly broadens the content of the polymer, in that field, the polyionic liquid is one of the preferred structural unit for realizing the reversible regulation of the surface wettability due to the structure characteristic of the polyionic liquid, The surface wettability changes. In this paper, the surface-induced free radical polymerization is used to introduce different polyionic liquid brushes on the surface of different materials. These new types of wettability-controllable functional materials have little to do with the water-to-water conversion of the solid surface. The invention provides a new ionic liquid monomer allyl triphenyl hexafluorophosphate, and the ionic liquid monomer 1-(4-vinyl-base-) -3-butyl detomorhexis phosphate is synthesized according to the literature, and the new ionic liquid monomer allyl triphenyl hexafluorophosphate is synthesized according to the literature, A 1-(4-vinyl-based) -3-Budetomycin hexafluorophosphate as a monomer,2-bromo-2-methyl-N-(3-(trimethoxysilyl) propyl) propylamine as a surface initiator is used as a catalyst, and lactic acid is a ligand. AIBN is a free radical initiator, DMF is a solvent, a polyionic liquid brush is grafted on the surface of the copper substrate by a RATRP method, the allyl triphenyl hexafluorophosphate is a monomer, and 2-bromo-2-methyl-N-(3-(triethoxysilyl) propyl) propylamine (BTPAm) is a surface initiator, and the TE The MPO is a nitrogen-oxygen free-radical initiator, cyclohexanone is a solvent, and a polyionic liquid brush is grafted on the surface of the silicon substrate by using a surface-induced NMP method, and 1-(4-vinyl-base)) -3-butyl detomycin hexafluorophosphate is a monomer, and 2-bromo-2-methyl-N-(3-(3-( triethoxysilyl) propyl) propylamine is a surface initiator, TEMPO is a nitrogen-oxygen free-radical initiator, xylene is a solvent, The ionic liquid brush was grafted on the surface of the silicon substrate by NMP. The X-ray photoelectron spectroscopy (XPS), the contact angle instrument, the ellipsometry, the atomic force microscope (AFM), the nuclear magnetic resonance spectrum (1H and 13C NMR) and the gel were used. The dynamic studies show that the thickness of the polymer brush has a linear relationship with the growth of the polymerization time, and thus the polyion is proved. the growth of the liquid brush on the surface of the material is a controlled, active polymerization. in addition, the anion exchange is achieved by a simple pair of anion exchange,
【學位授予單位】：西北師范大學
【學位級別】：碩士
【學位授予年份】：2010
【分類號】：O631.5
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