本文關(guān)鍵詞： APTS 親核加成/開環(huán)縮合反應(yīng) 納米顆粒 溫度響應(yīng)性 pH響應(yīng)性　出處：《鄭州大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：當受到外部刺激如溫度、p H、光等,響應(yīng)性納米顆粒的性能、尺寸、結(jié)構(gòu)或相互作用會發(fā)生變化,從而使得顆粒發(fā)生重排或聚集相發(fā)生變化,這使得響應(yīng)性納米顆粒具有獨特的物理和化學(xué)性能,因此其在油回收、傳感器和藥物傳輸方面具有潛在應(yīng)用。聚醚中聚乙二醇(PEO)結(jié)構(gòu)中的醚鍵與水之間具有氫鍵作用,使其具有溫度響應(yīng)性;此外,PEO具有毒性小、生物相容性好等優(yōu)點,因此選用PEO來制備響應(yīng)性納米顆粒。然而,單獨的PEO結(jié)構(gòu)機械穩(wěn)定性較差,而含有硅氧烷的無機組分的加入能夠改善此種狀況。本課題利用氨基和環(huán)氧基團之間的親核加成/開環(huán)縮合反應(yīng)制備有機硅雜化納米顆粒,此合成方法與原子轉(zhuǎn)移自由基聚合(ATRP)和可逆加成-斷裂鏈轉(zhuǎn)移聚合(RAFT)方法相比,具有簡便、綠色、無污染等特點。本課題利用該合成方法成功制備出了有機硅雜化納米顆粒,通過透射電鏡(TEM)、動態(tài)光散射(DLS)和濁點(CP)等研究表明,該納米顆粒為具有核殼結(jié)構(gòu)的球狀結(jié)構(gòu),且具有溫度和p H刺激響應(yīng)性能。具體研究內(nèi)容及結(jié)果如下:1、以聚乙二醇二縮水甘油醚(PEO-DE)和氨丙基三乙氧基硅烷(APTS)為原料成功制備出了中間產(chǎn)物,并采用核磁共振氫譜(1H NMR)、傅里葉紅外光譜(FT-IR)等對其進行了表征。通過直接溶解法制備了膠束,加入三乙胺促進APTS上的乙氧基水解縮合,得到有機硅雜化納米顆粒,通過動態(tài)光散射(DLS)研究表明,其z均半徑為76.26nm,且單分散性好。利用透射電鏡(TEM)觀察發(fā)現(xiàn),其為帶有支臂的球狀結(jié)構(gòu)。通過DLS研究發(fā)現(xiàn)有機硅雜化納米顆粒具有p H響應(yīng)性。2、以PEO-DE、聚丙二醇二縮水甘油醚(PPO-DE)和APTS為原料成功合成出了中間產(chǎn)物,采用了1H NMR、FT-IR、凝膠滲透色譜(GPC)等對其進行了表征。采用直接溶解法制備膠束,然后通過加入三乙胺促進APTS上的乙氧基水解縮合,制備出有機硅雜化納米顆粒。以芘為探針通過熒光光譜儀測定了其在水中的臨界膠束濃度(CMC),為4.3×10-6mol/L。用掃描電鏡(SEM)和TEM觀察發(fā)現(xiàn),其為具有核殼結(jié)構(gòu)的規(guī)整球狀結(jié)構(gòu)。通過DLS和濁點(CP)研究發(fā)現(xiàn),其具有明顯的溫度和p H響應(yīng)性能。利用可見分光光度計研究發(fā)現(xiàn),有機硅雜化納米顆粒對石墨具有一定的分散性。通過紫外-可見光譜研究發(fā)現(xiàn),有機硅雜化納米顆粒對水溶性染料甲基橙、酸性紅18和羅丹明B具有選擇性吸附性能。
[Abstract]:When exposed to external stimuli such as temperature, light, and so on, the properties, size, structure or interaction of responsive nanoparticles will change, resulting in the change of particle rearrangement or aggregation phase. This enables responsive nanoparticles to have unique physical and chemical properties, so that they are recovered in oil. It has potential applications in sensor and drug transport. The ether bond in PEO structure of polyether has hydrogen bond with water, which makes it temperature-responsive. In addition, PEO has the advantages of low toxicity, good biocompatibility and so on. Therefore, PEO is used to prepare responsive nanoparticles. However, the mechanical stability of the single PEO structure is poor. The addition of inorganic components containing siloxane can improve this situation. In this study, organosilicon hybrid nanoparticles were prepared by nucleophilic addition / ring opening condensation reaction between amino and epoxy groups. Compared with atom transfer radical polymerization (ATRP) and reversible addition-break chain transfer polymerization (RAFT), this method is simple and green. In this paper, organosilicon hybrid nanoparticles were successfully prepared by using this synthetic method. The results of transmission electron microscopy (TEM), dynamic light scattering (DLS) and cloud point (CPP) show that the organic silicon hybrid nanoparticles have been successfully prepared. The nanoparticles are spherical structure with core-shell structure, and have the properties of temperature and pH stimulation response. The specific research contents and results are as follows: 1. The intermediate product was prepared by using PEO-DEG and APTSs as raw materials, and 1H NMR was used. The micelles were prepared by direct dissolution method and triethylamine was added to promote the hydrolysis and condensation of ethoxy on APTS to obtain organosilicon hybrid nanoparticles. The results of dynamic light scattering (DLS) show that the z mean radius is 76.26 nm, and its monodispersity is good. The organosilicon hybrid nanoparticles were found to be p-H responsive to PEO-DE by DLS. Polypropanediol diglycidyl ether (PPO-DE) and APTS were used as raw materials to synthesize the intermediate product, and 1H-NMR-FT-IR was used. Gel permeation chromatography (GPC) was used to characterize the micelles. The micelles were prepared by direct dissolution method. Triethylamine was added to promote the hydrolysis and condensation of ethoxy on APTS. Organosilicon hybrid nanoparticles were prepared and the critical micelle concentration (CMC) in water was determined by fluorescence spectrometer using pyrene as a probe. It was found to be a regular spherical structure with core-shell structure by scanning electron microscopy (SEM) and TEM. It was found by DLS and cloud point analysis. The organosilicon hybrid nanoparticles were found to be dispersed to graphite by visible spectrophotometer. Organosilicon hybrid nanoparticles have selective adsorption properties for water-soluble dyes methyl orange, acid red 18 and rhodamine B.
【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TB383.1

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本文編號：1465776