本文選題：硅片 + RATRP��； 參考：《西北師范大學》2011年碩士論文

【摘要】：潤濕特性是固體表面的重要性質之一,其中超疏水表面是近年來表面潤濕性研究領域的一個熱點。尤其是對外界環(huán)境(如光照、電場、熱和化學等)有刺激響應的表面親疏水可逆轉化材料更是引起了研究人員極大的關注。由于這類表面在智能裝置領域有著潛在的應用前景,因此,合理設計并制備潤濕性可控的表面,是實現(xiàn)固體潤濕性多元化應用的關鍵環(huán)節(jié)。表面潤濕性的調控可以通過兩種途徑實現(xiàn):一種是表面微結構的調控,另一種是表面自由能調控。第二種途徑是在保持材料表面形貌的條件下,利用外界環(huán)境的刺激作用定向改變材料表面化學組成從而改變表面自由能,使液滴在表面的接觸角相應地發(fā)生變化。目前有多種調控固體表面自由能的方法,其中將聚合物刷,通過“Grafting from”技術接枝到各種基體表面,利用表面化學成分的不同對潤濕性進行調控就是方法之一。多種聚合反應技術都可應用于“Grafting from”方法中,其中反向原子轉移自由基聚合反應作為對傳統(tǒng)的原子轉移自由基聚合反應的改進和拓展,在制備預定結構、預定分子量以及窄分子量分布聚合物方面具有其它方法所無法替代的優(yōu)點,成為今后高分子合成化學領域的研究熱點。而室溫離子液體是近年來綠色化學新興研究領域之一,研究者充分利用離子液體的獨特性質,在合成高分子量縮聚產(chǎn)物等方面取得了很大的研究進展,且對于不同的陰離子所對應的離子液體,其親疏水性不同。 因此,本文的研究內(nèi)容主要包括: (1)離子液體單體的合成。通過兩步法合成了三種雙鍵功能化的吡啶類離子液體單體烯丙基吡啶六氟磷酸鹽(ALPY-PF_6)、1-(4-乙烯基芐基-)-吡啶六氟磷酸鹽(VBPy-PF_6)和1-芐基-1′-[4-(乙烯基)芐基]-4,4′-聯(lián)吡啶六氟磷酸鹽(BVBBP-PF_6),利用核磁共振等技術手段對它們進行了表征。 (2)硅片表面引發(fā)劑單分子層的固載。將表面引發(fā)劑2-溴-2-甲基-N-(3-(三乙氧基硅基)丙基)丙酰胺(BTPAm)以自組裝的方式沉積在預處理過的硅片上,實驗結果表明,表面固載的引發(fā)劑具有良好的的引發(fā)反向原子轉移自由基聚合反應(RATRP)的能力。 (3)硅片表面接枝聚合物刷的制備以及潤濕性的可逆調控。首先以烯丙基吡啶六氟磷酸鹽、1-(4-乙烯基芐基-)-吡啶六氟磷酸鹽和1-芐基-1′-[4-(乙烯基)芐基]-4,4′-聯(lián)吡啶六氟磷酸鹽為單體,CuC_(l2)/2,2′-聯(lián)吡啶的絡合物為催化體系,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,AIBN為自由基引發(fā)劑,環(huán)己酮為溶劑,在不同溫度條件下,利用反向原子轉移自由基聚合反應(RATRP)在硅片上接枝了聚離子液體刷,最后通過對陰離子交換,成功實現(xiàn)了材料表面親疏水性的可逆轉換。動力學研究結果表明利用RATRP在含有溴硅烷的硅表面接枝聚離子液體刷的過程是活性/可控的。
[Abstract]:Wettability is one of the important properties of solid surface, and superhydrophobic surface is a hot spot in the field of surface wettability research in recent years. In particular, surface hydrophobic reversible conversion materials with stimulative responses to external environments (such as light, electric field, heat and chemistry) have attracted much attention. Because this kind of surface has a potential application prospect in the field of intelligent device, it is the key link to realize the multiplex application of solid wettability to design and fabricate the wettable controllable surface reasonably. The regulation of surface wettability can be achieved by two ways: one is the regulation of surface microstructure and the other is the regulation of surface free energy. The second way is to change the surface chemical composition of the material and change the free energy of the surface by using the stimuli of the external environment under the condition of maintaining the surface morphology of the material, so that the contact angle of the droplets on the surface changes correspondingly. At present, there are many methods to control the free energy of solid surface, among which the polymer brushes are grafted onto various matrix surfaces by "lifting from" technique, and the wettability is regulated by the different chemical composition of the surface. A variety of polymerization techniques can be used in the "lifting from" method, in which the reverse atomic transfer radical polymerization is used as an improvement and extension of the conventional atomic transfer radical polymerization, in the preparation of a predetermined structure. The polymer with predetermined molecular weight and narrow molecular weight distribution has many advantages which can not be replaced by other methods, and has become a hotspot in the field of polymer synthesis chemistry in the future. Room temperature ionic liquid is one of the new research fields of green chemistry in recent years. Researchers have made great progress in the synthesis of high molecular weight Polycondensation products by making full use of the unique properties of ionic liquids. The hydrophobicity of ionic liquids corresponding to different anions is different. Therefore, the main contents of this study include: 1) synthesis of ionic liquid monomers. Three double bonded pyridine ionic liquid monomers, allyl pyridine hexafluorophosphate (ALPY-PF6) were synthesized by two step method. Fluorophosphate (BVBBP-PF6) was characterized by nuclear magnetic resonance (NMR). The surface initiator 2-bromo-2-methyl-N-n- (triethoxysilyl) propionamide BTPAmwas deposited on the pre-treated silicon wafer in a self-assembled manner. The experimental results showed that, The surface immobilized initiators have a good ability to initiate reverse atom transfer radical polymerization (RATRP). 3) preparation of graft polymer brushes on the surface of silicon wafers and reversible control of wettability. First of all, the complexes of allyl pyridine hexafluorophosphate, 1-butadiene-4-vinyl-benzyl-keto-pyridine-hexafluorophosphate and 1-benzyl-1- [4-( vinyl) benzyl] -4-dipyridyl hexafluorophosphate were used as the monomers of CuCC2N / 2O2-bipyridine as catalytic systems. Bromo-2-methyl-N-butadiene (triethoxysilyl) propamide (BTPAmA) was used as surface initiator and AIBN as free radical initiator. Cyclohexanone was used as solvent and the reverse atom transfer radical polymerization (RATRP) was used to graft polyionic liquid brush onto silicon wafer at different temperatures. Finally, the reversible conversion of hydrophobicity on the surface of the material was successfully realized by exchange of anions. The kinetic results show that the process of grafting polyionic liquid brush with RATRP on the surface of silane containing bromosilane is active / controllable.
【學位授予單位】：西北師范大學
【學位級別】：碩士
【學位授予年份】：2011
【分類號】：O631.5

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