臺灣博碩士論文加值系統

由於聚醯亞胺具有製備方便、材料變化多元性、化學安定性、熱安定性與機械安定性等優點，故長久以來為電子、航太等高科技產業所採用。本研究內容主要分為兩部分，第一部份，是在雙胺主鏈側邊導入長鏈的烷基團，並以此雙胺單體與雙酐單體合成聚醯亞胺。第二部分，是在雙胺主鏈側邊導入長鏈的不飽和烯基團，並以此新型雙胺單體與雙酐單體製備成光敏感性聚醯胺酸及交聯性聚醯亞胺。
研究中，我們利用歐斯特瓦爾德－馮士克黏度計來測量所製備之各種聚醯胺酸的黏度值，結果顯示長鏈烷基與烯基側鏈的導入，將導致時黏度值呈現下降的趨勢。關於聚醯亞胺熱性質方面，我們分別應用熱重分析儀(TGA)、差式掃描熱量分析儀(DSC)及熱機械性質分析儀(TMA)來探討其熱穩定性、相轉變行為及熱膨脹係數。TGA數據顯示聚醯亞胺的熱裂解溫度隨著烷基側鏈的導入而下降，然而其裂解溫度仍皆可高於450℃。由DSC量測所得之玻璃轉化溫度亦顯示其數值深受烷基側鏈存在的影響，而隨著鏈長的增加而下降。同時，TMA所測的熱膨脹係數則隨側鏈烷基鏈導入，而加大。在電性測量方面，量測數據顯示烷基側鏈鏈段的導入，可有效降低材料的介電長數，如BTDA-HADA之介常數值可降至3.3。
由於具有不飽和烯基側鏈的雙胺與BTDA與6FDA聚合生成的聚醯胺酸，經添加Diphenyl (2,4,6-trimethyl-benzoyl) phosphine oxide為光起始劑，在紫外光照射下的交聯作用，可藉由紅外線光譜在918㎝-1處吸收峰的減小來觀測其反應程度。TGA數據顯示經交聯後的聚醯亞胺的熱裂解溫度較具有相同長度烷基側鏈的雙胺單體所衍生之聚醯亞胺者略高。由DSC量測所得之玻璃轉化溫度亦顯示交聯作用將導致其溫度的上升。同時，聚醯亞胺的熱膨脹係數也隨著交聯反應而下降。在電性測量方面，量測數據顯示烯基側鏈鏈段的導入，同樣能有效降低聚醯亞胺的介電常數，其中6FDA-BEDA之介電數值為3.0。

Aromatic polyimides have been widely used in microelectronic and space industries due to their excellent thermal stability, good electronic properties and easy preparation. In this study two aromatic diamins containing either linear alkyl side chain or alkylene side group were successfully synthesized and characterized by NMR and FTIR methods. These new monomer were then reacted with benzophnenetetracrboxylic dianhydride (BTDA) or hexafluoroisopropylidene bis(phthalic anhydride) (6FDA) to prepare novel side-chain-containing polyimides.
The influence of alkyl group and alkyene group substitutes on the thermal properties of polyimides was investigated by differential scanning calorimetry, thermomechanical analyzer, and thermogravimetric analyses techniques. Experimental results indicate that the incorporation of alkyl moieties leads to a moderate increase in the coefficient of thermal expansion and a slight decrease in glass transition temperature and thermal stability, but all polymers still posses a decomposition temperature higher than 450℃. Furthermore, the dielectric constant also shows greatly dependent on the length of alkyl chain and the chemical composition.
Morover, experimental results also indicate that the incorporation of alkylene moieties results in a moderate decrease in the coefficient of thermal expansion and a slight increase in glass transition temperature and thermal stability. More importantly, the presence of alkylene side-chain effectively decrease the dielectric constant of polyimide. The dielectric constant of 6FDA-BEDA was found to be 3.0.

目錄…………………………………………………………..…………4
圖目錄…………………………………………………………..………7
表目錄…………………………………………………………………..10
第一章：緒論……………………………………………………………..11
1-1：引言…………………………………………………………….1
1-2：積體電路多層化與訊號延遲（RC延遲）……………………...12
第二章：文獻回顧………….……………...……………………………..15
2-1：聚醯亞胺之優點……………………………………………….15
2-2：聚醯亞胺在微電子工業之運用……………………………….19
2-3：降低聚醯亞胺之介電值的方法……………………………...23
2-4：光敏感聚醯亞胺之特性與應用……………………………...24
2-5：研究目的……………………………………………………..30
第三章：含有直鏈烷基側鏈之聚醯亞胺介電材料的合成……………31
3-1：前言……………………………………………………...……31
3-2：1,1-di-p-aminophenyl pentane的合成與結構鑑定…………31
3-2-1：1,1-diphenyl hexane之合成…………………………….31
3-2-2：1,1-di-nitrophenyl hexane之合成………………………33
3-2-3：1,1-di-p-aminophenyl hexane之合成…………..………..33
3-2-4：1,1-di-p-aminophenyl hexane（HADA）之結構分析…….35
3-3：聚醯胺酸的合成與聚醯亞胺薄膜之製備…………………...38
3-3-1：聚醯胺酸的合成………………………………...………38
3-3-2：聚醯亞胺薄膜之製備……………………………...……39
3-4：結果與討論…………………………………………………..41
3-4-1：分子量量測（黏度分析）…………………………..……42
3-4-2：聚醯胺酸的醯亞胺化合物結構分析……………...……44
3-4-3：熱性質量測……………………………………………...45
3-4-4：介電值量測……………………………………………...49
3-5：結論………………………………..…………………………52
第四章 ：含有烯基側鏈之光敏感聚醯亞胺的合成…………..………53
4-1：前言………………………………………………..…………53
4-2：1,1’-di-aminophenyl butene的合成與結構鑑定…….………53
4-2-1：1,1-diphenyl butene之合成…………………….………..53
4-2-2：1,1’-diphenyl bromobutane之合成…………..…………54
4-2-3：1,1’-di-nitrophenyl brombutane之合成…………………55
4-2-4：1,1-di-aminophenyl butene（BEDA）之合成…...……….55
4-2-5：1,1-di-aminophenyl butene之結構分析…………………57
4-3：聚醯胺酸的合成與聚醯亞胺薄膜之製備…………...………60
4-3-1：聚醯胺酸的合成…………………………………….…..60
4-3-2：聚醯亞胺薄膜之製備…………………………….……..61
4-4：結果與討論……………………………………………….…..61
4-4-1：分子量量測（黏度測量）………………………………..62
4-4-2：光起始劑的選擇………………………………..……….64
4-4-3：聚醯胺酸之光交聯反應與醯亞胺化之分析…………...66
4-4-4：熱性質測量……………………………………..……….69
4-4-5：介電值量測…………………………………..…………73
4-6：結論…………………………………………………….…….75
參考文獻..……………………..……………………………………..…78

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