臺灣博碩士論文加值系統

本研究致力於主鏈硬桿狀環氧樹脂與氰酸酯固化後性質探討。以合成出之硬桿狀並呈液晶態之環氧樹脂：azomethine linkage epoxy resin (AM)，biphenol epoxy resin (BP)，及商業用硬桿狀環氧樹脂：tetramethyl biphenyl epoxy (TMBP)，對酚型環氧樹脂：diglycidyl ether of bisphenol A (DGEBA)分別與氰酸酯類： 2,2’-bis(4-cyanatophenyl) propane(B10)硬化劑以當量比為1：0.5；1：1；1：2三種比例混合反應以微差熱分析儀(DSC)，動態升溫的方式找出硬化的條件，並以熱重分析儀(TGA)、動態機械分析儀(DMA)、熱機械分析儀(TMA)、介電分析儀(DEA)探討其性質、混合比例與結構的關係。
在熱裂解行為方面，氰酸酯比例較高時，其450℃殘餘量增多；在同一種比例時，以AM殘餘量最大，TMBP有最高的裂解溫度。就玻璃轉移溫度而言，當氰酸酯比例增加時，玻璃轉移溫度提高；在同一種比例時，AM擁有較高的玻璃轉移溫度，其次為TMBP和DGEBA。氰酸酯的含量則對於各環氧樹脂的熱膨脹係數的影響不大，除了DGEBA以外。關於氰酸酯測得之介電常數，隨著氰酸酯含量增加而減少。環氧樹脂的熱性與介電性隨著氰酸酯的含量增加而改進，可由形成熱穩定性交聯的三氮雜環(Trizine)結構來解釋。
本系列材料呈現高耐熱性，低介電值，非常適用於電子用高密度印刷電路板，封裝材料及航太用複合材料。

This research project is to investigate the curing properties of main chain rigid-rod epoxy resin cured by cyanate ester. Rigid rod resin with liquid crystalline properties: azomethine epoxy resin (AM), biphenol epoxy resin (BP), rigid rod resin of tetramethyl biphenyl epoxy resin (TMBP), and conventional epoxy resin of diglycidyl ether of bisphenol A (DGEBA), were cured by 2,2’-bis(4-cyanatophenyl) propane (B10) with the ratio of 1:0.5, 1:1, and 1:2 respectively. The curing conditions were studied by using differential scanning calorimetry (DSC). The cured samples were examined by thermogravimetric analyzer (TGA), dynamic mechanical analyzer (DMA) and thermomechanical analyzer (TMA).
The TGA results show that the ratio of cyanate ester increases, the char yield will increase at 450℃. At the same ratio, AM has the highest residual weight, and TMBP has the highest thermal decomposition temperature. When the ratio of cyanate ester increases, the glass transition temperature of cured resin increases. At the same ratio, AM exhibits the highest glass transition temperature, TMBP and DGEBA are in the second and third place respectively. Regardless the ratio of cyanate ester, the effects on the value of thermal expansion coefficient are not obvious expect DGEBA. The dielectric constant of cyanate ester cured epoxies decreases when the ratio of cyanate ester increase. The improvement in thermal and dielectric properties for high cyanate ester ratio sample can be explained by the formation of high concentration of crosslinked triazine structure.
Cyanate ester cured rigid rod epoxies exhibit high temperature resistance and low dielectric constant. They are useful in the application of high density printed wiring boards, high performance integrated circuited encapsulation compounds and aerospace composites.

第一章 緒論
1-1前言…………………………………………………………………………1
1-2液晶簡介……………………………………………………………………2
1-3液晶與液晶相排列…………………………………………………………2
1-4 環氧樹脂…………………………………………………………………7
1-5 氰酸酯……………………………………………………………………9
第二章 文獻回顧………………………………………………………12
2-1 Biphenyl 系統…………………………………………………………13
2-2 a-Methylstilbene系統………………………………………………15
2-3 Phenylbenzoate 系統…………………………………………………18
2-4 Binaphthyl系統…………………………………………………………19
2-5 Azomethine (Schiff base)系統………………………………………20
2-6 其他………………………………………………………………………20
第三章 實驗部分………………………………………………………22
3-1實驗藥品…………………………………………………………………22
3-2實驗儀器…………………………………………………………………25
3-3實驗步驟…………………………………………………………………28
3-3.1實驗流程………………………………………………………………28
3-3.2液晶環氧樹脂的合成…………………………………………………29
3-3.2.1合成4,4''-dihydroxy benzylideneaniline………………………29
3-3.2.2合成4,4''-bis(2,3-epoxypropoxy)benzylideneaniline………29
3-3.2.3合成 4,4’-bis(2,3-epoxypropoxy)biphenyl…………………30
3-3.3環氧當量滴定…………………………………………………………31
3-3.4環氧樹脂的硬化………………………………………………………32
3-3.5測試項目………………………………………………………………33
第四章 結果與討論………………………………………………………36
4-1 液晶環氧樹脂的合成……………………………………………………36
4-1.1含azomethine linkage 單體的合成…………………………………36
4-1.2含azomethine linkage 環氧樹脂的合成……………………………37
4-1.3含biphenol環氧樹脂的合成…………………………………………38
4-2 環氧樹脂與氰酸酯之反應機構…………………………………………40
4-3 TGA分析…………………………………………………………………41
4-3.1環氧樹脂DGEBA…………………………………………………………41
4-3.2環氧樹脂TMBP…………………………………………………………42
4-3.3環氧樹脂BP……………………………………………………………43
4-3.4環氧樹脂AM……………………………………………………………45
4-3.5環氧樹脂DGEBA，TMBP，BP，AM的比較………………………………46
4-4 DMA分析…………………………………………………………………49
4-4.1環氧樹脂DGEBA…………………………………………………………50
4-4.2環氧樹脂TMBP…………………………………………………………51
4-4.3環氧樹脂BP……………………………………………………………52
4-4.4環氧樹脂AM……………………………………………………………54
4-4.5環氧樹脂DGEBA，TMBP，BP，AM的比較……………………………55
4-5 IR分析……………………………………………………………………57
4-6 TMA分析…………………………………………………………………60
4-7 DEA分析…………………………………………………………………62
第五章 結論…………………………………………………………………65
第六章 參考文獻……………………………………………………………67

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