以光聚合法與化學縮合法製備有機/無機奈米複合材料及其性質研究

Synthesis and Properties of Organic-Inorganic Nanocomposite Materials Prepared by Photopolymerization and Chemical Imidization

洪偉毅(Wei-I Hung)

指導教授 ： 葉瑞銘

中原大學/理學院/化學研究所/碩士(2007年)

https://doi.org/10.6840/cycu200700220

摘要

本論文是以不同的合成技術與材料，以製備有機/無機混成複材(高分子奈米複合材料)，進而探討其結構、性質的分析與應用。在本論文研究中主要分為二個部分:

第一部分，首先以化學還原法合成不同大小的金奈米粒子，經修飾後利用2-Hydroxyethyl methacrylate (HEMA)與Methy methacrylate (MMA)為共聚高分子當作兩性介面活性劑，使其形成W/O的微乳液結構，並利用BPO為光起始劑，在無溶劑的狀態下照光進行總體聚合，形成壓克力共聚物/金粒子奈米複合材料。而此材料則利用紫外光-可見光光譜儀及穿透式電子顯微鏡偵測金奈米粒子的變化。在研究中並將此材料進行物理發泡，使其成為具孔洞性的發泡材，針對此發泡材探討金奈米粒子的晶核效果，並以掃描式電子顯微鏡為佐證。在性質研究上，皆測試材料發泡前與發泡後的熱性質(熱重分析儀、微差掃描式熱分析儀、熱傳導分析儀)，最後以機械性質證實材料發泡後具有優異的耐衝擊性。

第二部分，利用化學醯亞胺化法將二胺(BDAF)與二酸酐(OPDA)合成含氟的可溶性聚醯亞胺(SPI)，並加入四乙氧基矽烷(TEOS)為無機材進行溶膠-凝膠反應，製備可溶性聚醯亞胺/二氧化矽奈米複合材料。此研究中，以變溫防腐蝕為性質研究的重點，探討在30、45、60℃下的防蝕效果。其結果顯示，在高溫(60℃)的條件下，只需添加少量的二氧化矽於含氟的可溶性聚醯亞胺中，其防蝕效果比未塗佈高分子的鐵片在室溫(30℃)下有著優異的表現，且跟只塗佈含氟的可溶性聚醯亞胺的鐵片在室溫(30℃)下防腐蝕效果是差不多的。此試驗中加入一組不含氟但結構相似的可溶性聚醯亞胺為對照組，並利用表面接觸角分析儀說明高分子中具有氟官能基即可達到疏水的效果，此因素亦可有效提升塗層材料的抗腐蝕性能。另外，也藉由氣體透過率分析儀、熱分析儀和機械分析儀說明二氧化矽在高分子基材中達奈米分散時，可有效提升阻氣性質、熱性質及機械性質。

關鍵字

光聚合 ； 溶膠凝膠法 ； 奈米複合材料 ； 金奈米粒子 ； 發泡材

並列摘要

In this thesis, we prepared two kinds of organic-inorganic hybrid materials (polymer nanocomposites) by different nano-technologies and materials. This essay is divided into two parts.
In the first part, we outline a method for fabricating W/O microemulsion architectures containing different sizes of gold nanoparticles core in which surface-modified with carboxyl groups and poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) (PHM) copolymer shell materials (BGN) via chemisorption followed by photopolymerization. Unlike in curing of composite components by ultraviolet radiation for most studies, we have demonstrated the amphiphilic copolymer can be used as surfactants which encapsulated gold nanoparticles without solvent and enable the formation of thicker (bulk) structures than traditionally achieved. The morphology of gold colloidal nanoparticles were invertigated by transmission electron microscopy (TEM) technique and ultraviolet-visible (UV-Vis) absorption spectroscopy. In this study, the bulk nanocomposites were then foamed by using N2 as blowing agent in a batch foaning process in order to discuss the nucleation effect of gold nanoparticles on the polyacrylate foams. The relational of compositions of bulk and foam observed by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and Hot disk. Moreover, it has been observed that the BGN materials have possess of higher compression modulus than PHM materials.
The second part, a series of organic-inorganic hybrid materials have been successfully prepared by using acid-catalyzed sol-gel process that comprise organic soluble polyimide (SPI) and inorganic silica (SiO2). The as-synthesized hybrid materials were subsequently characterized by Fourier-transformation infrared (FTIR) spectroscopy, transmission electron microscopy (TEM) and scanning electron microscopy (SEM) mapping technique. In this study, we are found that the hybrid materials containing 5 wt-% loading of silica exhibit an observable enhanced corrosion protection on cold-rolled steel (CRS) electrode at higher operational temperature at 60℃, which is much better than that of uncoated and similar to electrode-coated with SPI alone at room temperature at 30℃ based on the electrochemical parameter evaluations (e.g., Ecorr, Rp, Icorr, and Rcorr). Furthermore, we demonstrated that 6F-containing soluble polyimide display a good hydrophobic owing to the presence of hexafluoroisopropylidene unit by contact angle. In addition, the effects of the material composition on the gas barrier, thermal stability and mechanical properties were also evaluated by gas permeability analyzer (GPA) (e.g., O2 and N2), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA), respectively.

並列關鍵字

Foam ； Sol-Gel ； Gold nanoparticles ； Photopolymerization ； Nanocomposite

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