發(fā)布時間：2018-03-14 15:09

  本文選題：聯(lián)乙炔　切入點：PDAs　出處：《山東大學》2017年博士論文　論文類型：學位論文

【摘要】：聯(lián)乙炔基團具有共軛π-電子體系,是一種富電子基團。在UV光或γ射線輻射下,聯(lián)乙炔單體之間會發(fā)生拓撲化學聚合,形成烯-炔交替的共軛聚聯(lián)乙炔(PDAs)。PDAs是一種半導(dǎo)體聚合物,π-電子離域在整個共軛體系主鏈中,因此,PDAs具有獨特的光學和電子性質(zhì)。當PDAs接受各種環(huán)境刺激時,會發(fā)生明顯的肉眼可辨的顏色變化,這使PDAs在化學或生物傳感領(lǐng)域有廣泛的應(yīng)用。在PDAs體系中引入具有特定結(jié)構(gòu)或功能的另一組分,制備具有特異性傳感性能的PDAs傳感器,可以擴大PDAs的應(yīng)用領(lǐng)域。周期性介孔有機硅(簡稱PMOs)是一類獨特的有機-無機雜化的介孔材料,其中,橋聯(lián)有機基團共價鍵合在材料的孔壁上,呈周期性排列,不會堵塞孔道。PMOs材料具有有序的介孔孔道、較大的比表面積、孔體積以及共價嵌在孔壁上的有機官能團,使其在催化、吸附、生物醫(yī)學、光電材料以及傳感等方面均有重要的應(yīng)用價值。本論文以聯(lián)乙炔基團為基礎(chǔ),制備了聯(lián)乙炔橋聯(lián)硅氧烷和雙聯(lián)乙炔橋聯(lián)硅氧烷。以陽離子三聚表面活性劑為結(jié)構(gòu)導(dǎo)向劑,通過共縮聚和蒸發(fā)誘導(dǎo)自組裝的方法分別制備了聯(lián)乙炔雜化的PMOs納米顆粒和薄膜材料。之后,利用254 nm的紫外光輻射聯(lián)乙炔PMOs薄膜,誘導(dǎo)聯(lián)乙炔基團發(fā)生拓撲化學聚合,得到了聚聯(lián)乙炔雜化的PMOs(PDAPMOs)薄膜。通過小角X射線散射(SAXS)、高分辨率透射電子顯微鏡(HRTEM)、氮氣吸附/脫附等溫線以及固態(tài)29Si魔角旋轉(zhuǎn)核磁共振(MAS NMR)等分析技術(shù)對材料的結(jié)構(gòu)進行了表征,通過紫外-可見吸收光譜(UV-vis)、紫外-可見漫反射光譜以及傅里葉變換紅外光譜(FT-IR)等技術(shù)對材料的光學性質(zhì)進行了研究。最后,將雙聯(lián)乙炔橋聯(lián)硅氧烷與羅丹明B有機硅前驅(qū)體混合,通過蒸發(fā)誘導(dǎo)自組裝和接下來的拓撲化學聚合過程制備了羅丹明B功能化的雙聚聯(lián)乙炔(RB/bis-PDA)薄膜,成功將羅丹明B單元引入到PDAs體系中,構(gòu)建了一種對金屬鋁離子有高靈敏響應(yīng)的雙比率吸收傳感體系。主要研究內(nèi)容如下:(1)以陽離子三聚表面活性劑為結(jié)構(gòu)導(dǎo)向劑,通過聯(lián)乙炔橋聯(lián)硅氧烷(DASi)和正硅酸四乙酯(TEOS)的共縮聚作用,制備了一系列的聯(lián)乙炔雜化的周期性介孔有機硅(DAPMOs)材料。在對材料的結(jié)構(gòu)性質(zhì)進行表征的基礎(chǔ)上,進一步對材料的光學性質(zhì)進行了研究。在DASi的熒光激發(fā)光譜中,在240和285 nm處出現(xiàn)了兩個吸收帶,歸屬為共軛C≡C-C≡的π-π*電子躍遷,這與DASi的紫外-可見吸收光譜相一致。而對于雜化材料DAPMOs,除了以上信號帶之外,在330 nm處還出現(xiàn)了一個新的信號峰,這個信號的出現(xiàn)可能是因為聯(lián)乙炔分子之間形成了聚集體,因為嵌在二氧化硅框架中的聯(lián)乙炔基團排列致密、分子間相互作用很強。此外,以陽離子三聚表面活性劑和癸基紫精作為混合模板劑,構(gòu)建了孔壁和孔道間的PMOs基電荷轉(zhuǎn)移(CT)體系,其中的電子供體為孔壁中的聯(lián)乙炔基團,電子受體為孔道中的癸基紫精分子。通過紫外-可見漫反射光譜和軟X射線吸收近邊結(jié)構(gòu)光譜(XANES)證實了電荷轉(zhuǎn)移復(fù)合物的形成。在330 nm光激發(fā)下,此CT體系中還發(fā)生了從孔壁上的聯(lián)乙炔聚集體向CT復(fù)合物的能量轉(zhuǎn)移。(2)在酸性條件下,通過蒸發(fā)誘導(dǎo)自組裝和拓撲化學聚合過程制備了一系列的聚聯(lián)乙炔雜化的周期性介孔有機硅(PDAPMOs)薄膜。所得到的藍色PDAPMOs薄膜對溫度響應(yīng)靈敏,在熱刺激下,會發(fā)生一個多步的熱致變色過程,外觀顏色相繼變?yōu)樽仙�、紅色和黃色,變色溫度范圍比較寬,從室溫到150 ℃以上。這個多步的顏色轉(zhuǎn)變過程可以被分為兩大階段:可逆的藍-紫-紅轉(zhuǎn)變和不可逆的紅-黃轉(zhuǎn)變。第一階段中的紫色和紅色之間的轉(zhuǎn)變是完全可逆的,紅色相恢復(fù)為紫色相的過程非常迅速,而且此轉(zhuǎn)變過程可以多次循環(huán)。利用拉曼光譜和溫度相關(guān)的傅里葉變換紅外光譜研究了 PDAPMOs薄膜比色響應(yīng)的機理,結(jié)果表明,比色轉(zhuǎn)變與PDAs主鏈的構(gòu)象變化密切相關(guān)。此外,PDAPMOs薄膜還可以對機械力和有機溶劑比色響應(yīng),因此擴大了 PDAs在傳感器方面的應(yīng)用。(3)以六亞甲基二異氰酸酯基為連接基團,合成了雙聯(lián)乙炔橋聯(lián)硅氧烷,然后以一定的比例與羅丹明B有機硅前驅(qū)體混合,通過蒸發(fā)誘導(dǎo)協(xié)同組裝和接下來的拓撲化學聚合過程制備了羅丹明B功能化的雙聚聯(lián)乙炔(RB/bis-PDA)薄膜�？紤]到聯(lián)乙炔單元發(fā)生拓撲化學聚合的要求以及螺內(nèi)酰胺-羅丹明衍生物的開環(huán)信號的強弱,將雙聯(lián)乙炔橋聯(lián)硅氧烷和羅丹明B有機硅之間的摩爾比定為10:1。羅丹明B單元是通過相應(yīng)的有機硅氧烷的水解/縮合過程固定在PDAs基質(zhì)中的。所制備的藍色相RB/bis-PDA薄膜仍然保留了 PDAs的熱致變色特性,在高溫處理下會轉(zhuǎn)變?yōu)辄S色相。藍色和黃色RB/bis-PDA薄膜都可以選擇性識別Al3+。在結(jié)合了 Al3+的薄膜的紫外可見吸收光譜中,觀察到兩個獨立的吸收峰,分別歸屬為羅丹明單元開環(huán)的吸收峰(556 nm)和藍相(617 nm)或黃相(470 nm)PDAs的吸收峰。利用這兩個吸收信號的強度比(A556/A617或A556/A470),此RB/bis-PDA體系可以作為Al3+的比率紫外-可見吸收傳感器。最后,利用X射線吸收近邊結(jié)構(gòu)光譜(XANES)研究了 RB/bis-PDA薄膜中Al3+的配位結(jié)構(gòu),結(jié)果表明,RB/bis-PDA薄膜中的A1以6-配位的結(jié)構(gòu)存在。
[Abstract]:Diacetylene groups with conjugated electron system, is a kind of electron rich groups. In the UV light or gamma ray radiation, combined between acetylene monomer occurs topochemical polymerization, the formation of conjugated enyne alternating polydiacetylene (PDAs).PDAs is a semiconductor polymer, pi electron delocalization in the whole conjugate system of main chain, therefore, PDAs has a unique optical and electronic properties. When the PDAs to accept a variety of stimuli, color change will obviously make this recognizable, PDAs is widely used in chemical or biological sensing fields. Introduce another component has a specific structure or function in PDAs system PDAs, the sensor prepared with specific sensing performance, can expand PDAs applications. The periodic mesoporous organosilica (PMOs) is a unique class of organic-inorganic hybrid mesoporous materials, which bridged organic groups covalently bonded materials in the hole On the wall is arranged periodically, will not block pores.PMOs material with mesopore ordered, large surface area, pore volume and covalent block organic functional groups on the pore wall, the adsorption, catalysis, biomedicine, materials and application of photoelectric sensor and so on are important. This paper on the basis of diacetylene groups, diacetylene bridged siloxane and double diacetylene bridged siloxane was prepared. Using cationic Trimeric Surfactant as structure directing agent, respectively PMOs nanoparticles and thin polydiacetylene hybrid materials were prepared by CO condensation and evaporation induced self-assembly method. Then, using the UV radiation of 254 nm diacetylene PMOs films induced by diacetylene groups of topological chemical polymerization, obtained the polydiacetylene hybrid PMOs (PDAPMOs) thin film. The small angle X ray scattering (SAXS), high resolution transmission electron microscopy (HRTEM), Nitrogen adsorption / desorption isotherms and solid-state 29Si magic angle spinning nuclear magnetic resonance (MAS NMR) on the material structural analysis techniques were characterized by UV Vis absorption spectroscopy (UV-vis), UV Vis diffuse reflectance spectroscopy and Fourier transform infrared spectroscopy (FT-IR) techniques such as optical properties of materials. Study. Finally, the double acetylene bridged siloxane precursor mixed with Luo Danming B silicone, induced self-assembly and subsequent chemical polymerization process in the preparation of topological double poly Luo Danming B functionalized diacetylene was prepared by evaporation (RB/bis-PDA) film, success will be Luo Danming B element is introduced into the PDAs system, the construction of a double the ratio of high sensitive response of absorption of aluminum ion sensing system. The main contents are as follows: (1) using cationic Trimeric Surfactant as structure directing agent by diacetylene bridged siloxane (DASi) and tetraethyl Four ethyl ester (TEOS) by polycondensation, periodic mesoporous organosilica series of diacetylene hybrid was prepared (DAPMOs) materials were characterized in structure. Based on the nature of the material on the optical properties of materials were studied. The fluorescence spectra in DASi, there were two the absorption band at 240 and 285 nm, belonging to C = C-C = conjugated pi pi * electronic transition, UV - visible absorption and DASi spectra consistent. For hybrid DAPMOs, in addition to the above signal, at 330 nm also appeared a new signal peak appeared this may be because the signal between diacetylene molecules formed aggregates, because embedded in the silica framework of diacetylene groups dense, intermolecular interactions are very strong. In addition, using cationic Trimeric Surfactant and Decyl viologen as mixed templates, and constructed the hole wall PMOs based charge transfer between channel (CT) system, the electron donor for Kong Bizhong diacetylene groups as electron acceptor, decyl viologen molecules in the pores. By UV Vis diffuse reflectance spectroscopy and X ray absorption near edge spectroscopy (XANES) confirmed the formation of charge transfer complex in 330 nm under the excitation of the CT system also has shifted to the CT complex of the energy from the hole on the wall of diacetylene aggregates. (2) under acidic conditions, induced self-assembly and topochemical polymerization process in the preparation of periodic mesoporous organosilica series of polydiacetylene hybrid was prepared by evaporation (PDAPMOs) film. Blue PDAPMOs films have a temperature sensitive response in heat stimulation, photochromic process occurs as a multi-step heat, have become the appearance color of purple, red and yellow, color temperature range is wide, from room temperature to 150 degrees above this. The color change process can be divided into two stages: reversible blue - Purple - red shift and irreversible red - yellow change. In the first stage of transition between purple and red is completely reversible, red to purple phase phase recovery process is very rapid, and the transformation process can be repeated PDAPMOs thin films were investigated. The mechanism of colorimetric response by using Fourier transform infrared spectroscopy Raman spectroscopy and temperature related results show that the ratio of color change and PDAs backbone conformational changes are closely related. In addition, PDAPMOs film can also on mechanical and organic solvent colorimetric response, thus expanding the application of PDAs in sensor (. 3) with six methylene diisocyanate based connection group, double diacetylene bridged siloxane was synthesized, and then to a certain percentage of organosilicon precursor mixed with Luo Danming B, and then through the evaporation induced cooperative assembly Double poly Luo Danming B functionalized diacetylene was prepared by chemical polymerization process topology (RB/bis-PDA) thin film. Considering the diacetylene unit topochemical polymerization requirements and open loop signal strength spirolactams Luo Danming derivatives, Moore will double between acetylene bridged siloxane and Rhodamine B as the ratio of silicone 10:1. Luo Danming B unit is through hydrolysis / siloxane condensation process corresponding to the fixed in PDAs matrix. The preparation of the blue phase RB/bis-PDA film still retains the color characteristics of PDAs induced by heat treatment at high temperature, will be transformed into the yellow hue. Blue and yellow RB/bis-PDA films can selectively recognize Al3+. in combination UV visible absorption spectra of Al3+ films, observed two independent absorption peaks, absorption peak respectively belong to ring opening Luo Danming unit (556 nm) and blue (617 nm) or yellow (470 nm) The absorption peak of PDAs. Using the two absorption signal intensity ratio (A556/A617 or A556/A470), the RB/bis-PDA system can be used as a Al3+ ratio of UV Vis absorption sensor. Finally, absorption near edge spectrum by X ray (XANES) of Al3+ RB/bis-PDA films in the coordination structure, the results show that the RB/bis-PDA thin film the A1 exists in the structure of 6- coordination.

【學位授予單位】：山東大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O632.17
，

本文編號：1611745