電活性環氧樹脂/中孔洞二氧化矽球奈米複合材料的合成與物性鑑定

Preparation, Characterization and Properties of Electroactive Epoxy resin-silica sphere Mesocomposite Material

徐偉倫(Wei-Lun Hsu)

指導教授 ： 葉瑞銘

中原大學/理學院/化學研究所/碩士(2011年)

https://doi.org/10.6840/cycu201101072

摘要

本論文之研究主軸在製備並鑑定一系列之具低介電常數及低熱傳常數之電活性環氧樹脂/二氧化矽介孔複合材料。 內容部分將分為下列兩個部份並逐一介紹︰
首先，利用果糖做為模板再以“非界面活性劑模板法” 來製備 “胺基” 改質型具約3.4奈米之不規則中孔洞之二氧化矽微球(平均粒徑約500奈米)，並利用氮氣吸/脫附儀(BET)量測材料之表面積，約可達到600 m2/g。 以掃描式電子顯微鏡(SEM)鑑定中孔洞二氧化矽微球表面形態為單分散圓形微球，其平均粒徑約為500奈米。 其次，以穿透式電子顯微鏡(TEM)鑑定其內部結構為具有不規則孔穴之中孔洞二氧化矽微球。 進一步以反射式紅外線光譜儀(ATR)鑑定二氧化矽微球表面已鍵結胺基且果糖已從微球中移除。 最後，利用29Si、13C固態核磁共振分析儀鑑定其胺基確實已鍵結在微球表面。
其次，運用 “熱開環聚合法” 合成電活性環氧樹脂介孔複合材料。首先利用本實驗室開發”熱偶合法”製備出具胺基封端之苯胺三聚體作為電活性環氧樹脂之硬化劑；並導入第一部分之胺基官能化介孔微球以製備出一系列電活性環氧樹脂介孔複合材料。 並利用反射式紅外線光譜儀(ATR)鑑定電活性環氧樹脂介孔複合材料已確實開環熟化；以穿透式電子顯微鏡(TEM)鑑定微球確實分散於電活性環氧樹脂中；利用熱重分析儀(TGA)鑑定複合材料之熱裂解溫度可上升約40℃；微差掃描式熱分析儀(DSC)鑑定複合材料之熱安定性可上升約53℃；利用熱傳等分析儀(TPS)鑑定複合材料之熱傳係數可降低至0.1093 w/mk；利用動態機械分析儀(DMA)、萬能試驗機(UTM)鑑定複合材料之抗拉強度約可上升近約1倍；利用介電雙磁分析儀(DAS)鑑定複合材料之介電常數約可下降約20%；最後，利用循環伏特安培儀(CV)鑑定複合材料之電活性，發現複合材料仍可保有電活性。

關鍵字

非界面活性劑 ； 中孔洞 ； 電活性 ； 苯胺三聚體

並列摘要

In this thesis, we present the first preparation of electroactive epoxy resin/silica meso-composite materials with ultra-low dielectric constant and thermal conductivity.
Preparation, characterization and property studies of as-synthesized meso- composite materials were divided into two parts as follows: First, the amino-modified silica mesoporous silica spheres was prepared by base-catalyzed sol-gel process of TEOS and APTES in the presence of non-surfactant template (i.e., D-(-) Fructose). The pore size and surface volume can be determined by nitrogen sorption measurements (BET). Morphological image of mesoporous silica spheres can be observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Pore size and average diameter of as-synthesized mesoporous silica sphere was ca. ~ 3.4 nm ~ 500 nm, respectively. FTIR spectroscopy was used to confirm the attachment of amino- group onto the surface and into the channel of mesoporous silica spheres, respectively. Besides, the removal of non-surfactant template can also be identified by FTIR spectroscopy. 13C and 29Si-NMR spectroscopy was used to demonstrate the chemical structure of amino-modified mesoporous silica spheres, indicating that the amino- group have been attached onto the surface of mesoporous spheres.
Subsequently, electroactive epoxy resin/silica meso-composite materials can be prepared by thermal ring-opening polymerization reactions. First of all, amine-capped aniline trimer (ACAT) was synthesized by oxidative coupling reactions of aniline and 4,4'-Iminodianiline Sulfate. After that, the as-synthesized ACAT was reacted with DGEBA with DMAC as solvent by programmed heating process up to operational temperature of 180℃. Characterization of as-prepared mesoporous materials was performed by FTIR, TEM. Epoxy ring opening of DGEBA/ACAT mixture was confirmed by the FTIR spectroscopy. For example, disappearance of epoxy-ring characteristic peak of 915 cm-1 was found after the completeness of thermal curing process. The dispersion capability of silica spheres without/with porous structure in epoxy matrix can be observed by transmission electron microscopy (TEM).
For the property studies, it should be noted that the thermal conductivity and dielectric constant of as-synthesized meso-composite materials containing amino-modified mesoporous silica was significantly lower than corresponding counterpart. The more loading the mesoporous silica incorporated, the more lowering of thermal conductivity and dielectric constant obtained, as identified by Transient Plane Source (TPS) and Dielectric Analysis System (DAS). Thermal stability, mechanical strength and electroactivity of as-prepared composites was further investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), Universal Testing Machine (UTM) and electrochemical cyclic voltammetry (CV), respectively.

並列關鍵字

aniline trimer ； electroactivity ； mesoporous ； non-surfactant

參考文獻

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