- 學位論文
奈米二氧化矽粒子／高分子之核殼複合材料之合成及其性質研究
Preparation and properties of core-shell nanohybrids of silica nanoparticles and polymers
摘要
本研究主要進行奈米二氧化矽粒子之表面，並根據改質後批覆在二氧化矽表面之高分子之性質，進行其應用方面的研究。利用奈米二氧化矽粒子上的矽烷醇基，與N-(p-carboxyphenyl)maleimide( p-CPM)上之羧基所具有的高反應性(酯化反應)，成功的將二氧化矽粒子表面官能基化，命名為Si-p-CPM，利用FT-IR、TGA以及ESCA證明二氧化矽的表面官能基結構。接著以Si-p-CPM為起始物，利用臭氧致使高分子官能化，將非反應性高分子官能基化，透過自由基加成反應，將高分子批覆在改質過後的二氧化矽粒子上，成為以二氧化矽粒子為核心，高分子為殼層的核(二氧化矽)-殼(高分子)結構粒子。在本研究中所使用臭氧改質官能基化之非反應性高分子，包括Poly(vinylidene fluoride)(PVDF)、Polybenzimidazole( PBI)以及Poly Lactic Acid(PLA)；另外利用自由基加成反應，亦將帶有呋喃官能基的benzoxazine化合物FDP-FBz，利用Diels-Alder反應接枝於在改質過後的二氧化矽粒子表面。 將所形成之核(二氧化矽)-殼(高分子)結構粒子，利用氫氟酸蝕掉核心的二氧化矽，即可形成高分子奈米中空球，經由FT-IR、熱重分析以及元素分析，鑑定其反應前後之結構；此外，利用SEM、TEM可觀察到明顯的核-殼結構，以及經由氫氟酸處理過後，所形成之奈米中空球。隨後將氮氣注入奈米中空球後，利用超音波顯影設備，觀察其顯影效果。 另一方面，所形成之核-殼結構之一Si-p-CPM-FDP-FBz，由於FDP-FBz本身所具備之螢光性質，經由接枝在二氧化矽粒子表面，而有螢光增強的現象產生，可以經由紫外光/可見光光譜儀、螢光放射光譜儀觀察所產生之螢光現象。將Si-p-CPM-FDP-FBz與PMMA摻混形成膜材，製備出具有螢光性質之複合膜材，其螢光現象可以藉由紫外光/可見光光譜儀、螢光放射光譜儀鑑定，實際以波長為365 nm的紫外光照射膜材，觀察其螢光特性。
並列摘要
In this research, the surface modification of silica nanoparticles was processed. The modification of silica particles was performed through the reaction between the silanol group on silica and the carboxyl group of N-(p-carboxyphenyl)maleimide( p-CPM). The chemical structures of the prepared materials were characterized with FT-IR and ESCA. We synthesized the particles with core-shell structures by ozone-mediated functionalization and free radical addition reaction. The inner silica of core-shell nanoparticles was etched by hydrofluoric acid, and the nano-scaled hollow spheres were formed. The structure of the hollow spheres was characterized with FT-IR, thermal analysis and elemental analysis. In addition, the core-shell structure can be clearly observed by SEM and TEM. Then the hollow spheres were injected into N2 gas, and the gas-filled hollow spheres show ultrasound-induced imaging behavior. The fluorescent properties and fluorescence enhancement were observed about Si-p-CPM-FDP-FBz. The phenomenon of fluorescent generated can be observed by UV / Vis spectroscope and photoluminescence spectroscopy. The Si-p-CPM-FDP-FBz was added into PMMA polymer matrix to prepare composite membranes which show fluorescent properties, and also the fluorescence phenomenon was characterized by UV / Vis spectroscope and photoluminescence spectroscopy. The composite membranes show the fluorescent emission under UV irradiation with 365 nm.