臺灣博碩士論文加值系統

本研究合成出含矽氧烷與亞醯胺之氰酸酯V。將商用環氧樹脂Tetraglycidyl meta-xylenediamine ( GA-240 )和含矽氧烷與亞醯胺之氰酸酯V依不同當量比例混合並交聯，由實驗結果來研究氰酸酯V對商用環氧樹脂的改質效果。

　　以FT-IR研究商用環氧樹脂和氰酸酯V反應過程中官能基的變化，以動態DSC在不同升溫速率研究其反應活化能，GA-240和氰酸酯V混合後的活化能，遠低於純GA-240，推測是由於氰酸酯V的三級胺催化所致。用TMA、TGA進行熱機械性質分析。研究結果顯示，交聯產物的玻璃轉移溫度約從199℃至207℃，而起始裂解溫度也比純GA-240的286℃高。交聯產物的介電常數經測試在3.2至4.3間。

　　The research deals with synthesis of cyanate ester V containing siloxane and imide groups , which was then mixed with a commercial epoxy resin “Tetraglycidyl meta-Xylenediamine (GA-240)”, followed by curing in various equivalent ratios of GA-240/V.
Functional group changes during curing reaction were investigated by FT-IR. The curing behavior was studied by dynamic DSC at different rising temperature rate. The curing activation energy of the epoxy resin that containing cyanate ester V was found much lower than the pure epoxy resin , presumably because of the catalysis of tertiary amine in the cyanate ester V. Thermal mechanical properties were measured by TMA and TGA. These cured materials indicate glass transition temperatures ranging from 199℃ to 207℃. On-set of decomposition temperature was found at around 286℃ for the pure GA-240 with improved thermal stability upon incorporation of cyanate ester V. The dielectric constants of the cured materials were in the range of 4.3 to 3.2.

目錄
英文摘要…………………………………………………………………i
中文摘要…………………………………………………………………ii
誌謝 ……………………………………………………………………iii
目錄………………………………………………………………………iv
圖目錄 ……………………………………………….………………viii
表目錄 …………………………………………………………………xii

一、緒論…………………………………………………………………1
1-1 半導體封裝簡介……………………………………………………1
1-2 環氧樹脂簡介………………………………………………………5
1-2-1 環氧樹脂之介紹……………………………………………5
1-2-2 環氧樹脂之特性……………………………………………6
1-2-3 環氧樹脂之硬化……………………………………………7
1-2-4 環氧樹脂與胺類硬化劑……………………………………9
1-3 聚亞醯胺簡介…………………………………………………11
1-4 矽氧烷簡介……………………………………………………14
1-5 含矽氧烷之亞醯胺或環氧樹脂相互間補強材料………………16
1-5-1 含亞醯胺基環氧樹脂相關文獻……………………………16
1-5-2 含矽氧烷聚亞醯胺相關文獻………………………………19
1-5-3 含矽氧烷環氧樹脂相關文獻………………………………21
1-6 氰酸酯簡介…………………………………………………………23
1-6-1 氰酸酯介紹…………………………………………………23
1-6-2 氰酸酯合成原理……………………………………………24
1-6-3 氰酸酯與環氧樹脂之反應機構……………………………25
1-7 研究動機…………………………………………………………27

二、實驗…………………………………………………………………28
2-1 藥品與材料…………………………………………………………28
2-1-1 藥品與材料…………………………………………………28
2-1-2 試藥純化……………………………………………………29
2-2 環氧樹脂系統………………………………………………………30
2-3 儀器與設備…………………………………………………………31
2-4 單體合成……………………………………………………………33
2-5 環氧當量滴定………………………………………………………42
2-6 合成化合物鑑定……………………………………………………44
2-6-1 1H核磁共振光譜……………………………………………44
2-6-2 13C 核磁共振光譜…………………………………………44
2-6-3 紅外線光譜分析……………………………………………44
2-7 交聯行為分析………………………………………………………45
2-7-1 硬化反應配方………………………………………………45
2-7-2 動態DSC 分析………………………………………………45
2-7-3 交聯過程之FT-IR 分析……………………………………46
2-7-4 交聯樣品製作………………………………………………46
2-8 交聯後材料性質測試………………………………………………47
2-8-1 熱膨脹係數測試 ( TMA ) ………………………………47
2-8-2 熱重量分析儀分析 ( TGA ) ……………………………47
2-8-3 凝膠分率測試 ( Gel fraction ) ………………………47
2-8-4 介電常數測試………………………………………………48

三、結果與討論…………………………………………………………49
3-1 合成流程……………………………………………………………49
3-2 單體之鑑定…………………………………………………………51

3-2-1 5,5-(1,1,3,3-tetramethyl-1,1,3,3-disiloxanedialy
l)-bis-norbornane - 2,3-dicarboxylic anhydride
………………………………………………………………51

3-2-2 4-(4-hydroxyphenyl)-8-[1-({1-[4-(4-hydroxyphenyl)- 3,5-dioxo- 4-azatricyclo[5,2,1,0]dec-8-yl]-1,1- dimethylsilyl}oxy)-1,1- dimethylsilyl]-4-azatri
cyclo[5,2,1,0]decane-3,5-dione………………………52

3-2-3 4-[4-(allyloxy)phenyl]-8-{1-[(1-{4-[4-(allyloxy)
phenyl]-3,5- dioxo-4-azatricyclo[5,2,1,0]dec-8-
yl}-1,1-dimethylsilyl)oxy]-1,1-di methylsilyl}-4-
azatricyclo[5,2,1,0]decane-3,5-dione………………53

3-2-4 4-(3-allyl-4hydroxyphenyl)-8-[1-({1-[4-(3-allyl-
4hydroxyphenyl)-3,5-dioxo-4-azatricyclo[5,2,1,0]
dec-8-yl]-1,1-dimethylsilyl}oxy)-1,1-dimethylsi
lyl]-4-azatricyclo[5,2,1,0]decane-3,5-dione ……54

3-2-5 N,N’-bis(3-allyl-4-cyanatophenyl)-5,5’-(1,1,3,3-
tetramethyl- 1,1,3,3-disiloxanedialyl)-bis-norborn
ane-2,3-dicarboximide……………………………………56

3-3 交聯行為討論………………………………………………………58
3-3-1 動態DSC分析 ………………………………………………58
3-3-2 硬化條件……………………………………………………61
3-3-3 硬化過程之紅外線光譜分析………………………………62
3-4 交聯產物性質測試…………………………………………………64
3-4-1 凝膠分率測試………………………………………………64
3-4-2 熱膨脹係數分析……………………………………………65
3-4-3 熱重機械分析………………………………………………66
3-4-4 介電常數測試………………………………………………68
四、結論…………………………………………………………………69
五、參考文獻……………………………………………………………71

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