溶膠-凝膠法製備環氧樹脂/二氧化矽有機無機混成體

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蔡松伯(Sung-Po Tsai) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

溶膠-凝膠法製備環氧樹脂/二氧化矽有機無機混成體

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摘要(中)

本研究利用溶膠-凝膠法(sol-gel process)藉由無機中的二氧化矽來製備環氧樹脂( Epoxy)與二氧化矽( SiO2)混成材料，並將製成的混成材料以TGA測試其耐熱性質。
首先無機二氧化矽相是先將系統中的四乙氧基矽烷、水、乙醇在不同酸鹼性環境下進行水解縮合反應，所生成產物稱為「前置物(precursor)」，並將此前置物與有機系統環氧樹脂進行混合再經後製硬化反應即可得環氧樹脂/二氧化矽有機無機混成體，同時稱此種方法為溶膠-凝膠聚合反應。
另外有機系統環氧樹脂部分主要探討含無機二氧化矽的環氧樹脂含浸液對促進劑2-MI的影響，同時利用恆溫DSC分析環氧樹脂含浸液在無機二氧化矽的存下在對反應溫度的影響。
最後在有機無機混成體的製備中，主要探討以下三部分：
(1) 利用矽偶合劑能提供有機無機兩相間良好共價性質並同時改變矽偶合劑的添加量從1%增加到100%，探討是否有助於有機無機混成體的耐熱性質提升。
(2) 提高無機二氧化矽在混成體中的含量從1%增加到10%，探討是否有助於有機無機混成體的耐熱性質提升。
(3) 使用不同矽偶合劑，分別為本身帶有兩個可進行水解縮合的矽乙氧烷官能基KBE-402與帶有三個可進行水解縮合的矽甲氧烷官能基KBM-403，探討有機無機混成體的耐熱性質差異。
研究結果顯示，利用前置物法在酸性觸媒下製得之環氧樹脂/二氧化矽混成體比在鹼性觸媒下所製得之混成體有較好的耐熱性質。同時利用前置物法所製備之混成體也比直接摻混的有機無機產物有較佳的耐熱性。
而在有機環氧樹脂含浸液中因無機二氧化矽的添加使得最大放熱峰從原本的166℃提高至197℃，同時在經改變促進劑的添加量後發現最大放熱峰的位置並沒明顯變化，顯示混成體並不會因促進劑的添加而改變其最大放熱峰的位置。不過在經添加1.17%的促進劑於含有無機二氧化矽的環氧樹脂含浸液後，經恆溫硬化反應可得當反應溫度在170℃反應一個小時後可得最佳耐熱性質之混成體。
另外在無機系統中添加矽偶合劑製成之環氧樹脂/二氧化矽混成體，經由熱重損失分析(TGA)發現高溫熱重損失率降低釵h，顯示矽偶合劑在有機無機相間提供部分的共價鍵能因此更佳提升混成體的耐熱性質，同時發現矽偶合劑在添加2.5%之後即可使混成體耐熱性質提升。
除此之外經由DSC與TGA的測試顯示，隨著無機二氧化矽在混成體中添加量的增加是有助於混成體玻璃轉移溫度與耐熱性質的提升；另外由FTIR也顯示有機無機混成體中同時存在著二氧化矽與環氧樹脂兩種成分。
最後在使用不同矽偶合劑製成之混成體經由TGA顯示其圖形往較高溫處移動，顯示添加此兩種矽偶合劑皆能達到耐熱性質的幼纂C

摘要(英)

This project is base on sol-gel process, which is using inorganic SiO2 to produce hybrid is blended from Epoxy and SiO2 together. Also test the hybrid’s heat-resistant property by using the TGA process.
To beginning with the inorganic system (SiO2) that is use Tetraethoxysilane, water, and Ethanol under different acidity and alkalinity catalysts and proceeded with hydrolysis-condensation reaction and the product which is called precursor. Also blended precursor and organic system (epoxy) then proceeded with curing reaction. According to the reaction then will produce the epoxy resin and SiO2 organic/inorganic mixtures. This method is called sol-gel polymerization.
Additional in the organic system, which is focus on effect of the inorganic SiO2’s epoxy varnish to the accelerating agent (2-MI). In the meantime, to proceed analyzed the epoxy varnish under the inorganic SiO2 the effect of reaction temperature by using isothermal DSC method.
In conclusion, there have three main conditions in organic-inorganic hybrids process.
1. Using silane coupling agent can provide good covalence between organic and inorganic also it has change amount of the silane coupling agent from 1% to 100%. This is discussing is it help to rise up the heat-resistant property of the organic/inorganic hybrid.
2. Increasing amount of inorganic SiO2 in hybrid from 1% to 10%. This is to discussing is it help to rise up the heat-resistant property of the organic/inorganic hybrid.
3. By using different silane coupling agents, individually, itself carry two KBE-402 (γ-glycidoxypropyl-methyldiethoxysilane) and three KBM-403 (γ-glycidoxypropyl-trimethoxysilane) to proceeded hydrolysis reaction, this is to discussing difference of the heat-resistant property between organic/inorganic hybrids.
The conclusion has shown, the method of precursor under acid catalyst can produce better heat-resistant property of the epoxy / SiO2 hybrid to compare with base catalyst. In the meantime, use the method of precursor to produce hybrid has better heat-resistant property than direct blend method products.
However, the epoxy varnish caused add inorganic SiO2 has resulted the maximum of exothermic peak has been increase from 166℃ to 197℃. At the same time it has been change the accelerating agent quantities the resulted has exhibited the position of maximum of exothermic peak didn’t obviously change, also exhibited hybrid doesn’t change the position of maximum of exothermic peak caused to increase accelerating agent. But after inorganic SiO2’s epoxy varnish has been add 1.17% accelerating agent and through the isothermal test and curing reaction, it can resulted when reaction temperatures in 170℃ has been processed one hour latter can produce great hybrid with heat-resistant property.
Additional, by add silane coupling agent’s hybrid into inorganic system which is made from epoxy / SiO2, it has been to heat weight less analysis (TGA) and found the heat weight less rate has decrease. It is show that silane-coupling agent between organic and inorganic has provided part of covalent bond. Therefore it also can promote hybrid’s heat-resistant property. In the meantime, also it can found out after add 2.5% silane coupling agent; it can rise up hybrid’s heat-resistant property.
Besides, resulted from DSC and TGA test, the quantity of the inorganic SiO2 has increase in hybrid it can help to transfer temperature from hybrid glass and promote the heat-resistant property. In addition from FTIR has shown in inside the organic-inorganic hybrids has two elements which is SiO2 and epoxy.
In conclusion, this graph shows it has move on high temperature by using different silane-coupling agent to produce hybrid and through the TGA method, it is shown there all can achieved the efficiency of heat-resistant property, by add two kinds of silane-coupling agent.

關鍵字(中)

★ 耐熱性質
★ 混成體
★ 溶膠-凝膠法
★ 環氧樹脂

關鍵字(英)

★ epoxy
★ heat-resistant property
★ hybrids
★ sol-gel

論文目次

目錄
目錄…………………………………………………………………….Ⅰ
表索引………………………………………………………………….Ⅱ
圖索引………………………………………………………………….Ⅳ
第一章緒論…………………………………………………………….1
第二章實驗……………………………………………………………19
2-1 實驗藥品..………………………………………………………20
2-2 實驗儀器..………………………………………………………21
2-3 有機無機混成體之製備…..……………………………………22
2-3-1 前置物之製備(無機部分)…………………………………22
2-3-2 自製無機二氧化矽粉體.………………………………….22
2-3-3 環氧樹脂含浸液之製備(有機部分)………………………22
2-3-4 環氧樹脂/二氧化矽混成體之製備……………………….22
2-4 產物測試條件…………………………………………………..24
2-4-1 熱重損失測試……………………………………………..24
2-4-2 DSC 測試條件……………………………………………..24
2-4-2-1 升溫式DSC測試條件………………………………...24
2-4-2-2 恆溫式DSC測試條件………………………………...24
2-4-2-3 玻璃轉移溫度測試 ………………………………….24
2-4-3 紅外線光譜儀分析 ……………………………………….25
2-4-4 二氧化矽粉體粒徑鑑定…………………………………..25
第三章結果與討論……………………………………………………26
3-1無機部分製備條件的探討探討………………………………….27
3-2有機部分製備條件的探討探討………………………………….35
3-2-1促進劑添加量的影響……………………………………….35
3-2-2恆溫硬化分析……………………………………………….41
3-3環氧樹脂/二氧化矽混成體的製備探討………………………..50
3-3-1矽偶合劑添加量對混成體的影響………………………….50
3-3-2改變前置物添加量對混成體的影響……………………….56
3-3-3不同矽偶合劑對混成體的影響…………………………….64
3-4環氧樹脂/二氧化矽混成體定性分析…………………………..69
第四章結論……………………………………………………………71
參考文獻……………………………………………………………….73

參考文獻

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指導教授

陳暉(Hui Chen)

審核日期

2002-6-18

推文