含有線性側鏈的芳香族二胺及其衍生之聚醯亞胺的合成與性質研究

Syntheses and Properties of Polyimides Containing Linear Alkyl Side Chain

陳世學(CHEN SHIH HSUEN)

指導教授 ： 鄭俊麟

中原大學/工學院/化學工程研究所/碩士(2001年)

https://doi.org/10.6840/cycu200100450

摘要

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、航太其他相關產業所採用。本研究使用1,1’-diphenyl bromomethane與alkyl bromide進行Grigrand 鍵結反應而合成一系列具有不同長度之烷基側鏈的雙胺，再與3,3’-4,4’-benzophenone tetracarboxylic dianhydride (BTDA)和hexafluoroisopropylidene diphthalic dianhydride (6FDA)兩種，以兩步驟方法來高溫閉環脫去水分形成聚醯亞胺(polyimide)。
我們利用歐斯特瓦爾德－馮士克黏度計來測量聚醯胺酸黏度值，結果顯示雙胺上所接的側鏈烷基鏈愈長時，黏度值有下降的趨勢，推測這是由於烷基長鏈會降低雙胺反應性所造成。對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增加而微幅下降，然而所有樣品裂解溫度仍均高於400℃。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，並隨著鏈長的增加而下降。同時，TMA所測的熱膨脹係數隨側鏈烷基鏈愈長而增大，但BTDA系列聚醯亞胺是比6FDA系列有較低的熱膨脹係數其值最低可達到20(μm/m℃)。在電性測量方面，量測數據顯示烷基側鏈鏈段接的愈長時，其介電常數值呈現下降趨勢，其中6FDA-DDA之介電常數值可降至2.3左右。

關鍵字

烷基側鏈 ； 聚醯亞胺

並列摘要

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, a series of diamines containing alkyl side arm in varying chain length has been synthesized by the Grignard coupling reaction of 1,1’-diphenylbromomethane and linear alkyl bromide. Then, two series of polyimides were fabricated by thermal imidization of the poly (amic acid)s prepared from the polyaddition of these novel diamines with benzo- phenoneteracarboxylic dianhydride (BTDA) and hexafluoroisopropylidene bis (phthalic anhydride) (6FDA).
The influence of alkyl 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 400℃. Furthermore, the dielectric constant also shows greatly dependent on the length of alkyl chain and the chemical composition. It decreases with the increasing size of side group and the replacement of hydrogen with CF3 groups.

並列關鍵字

linear alkyl side chain ； polyimide

參考文獻

3. G. Hougham, G. Tesoro, and J. Shaw, Macromolecules, 27, 3642-3649, (1994).

8. Bernardo Masci, J. Org. Chem., 50, 4081, (1985).

10. B. E. Leggetter, and R. K. Brown, Can. J. Chem., 38, 2363, (1960).

11. F. P. Robinson, and R. K. Brown, Can. J. Chem., 39, 1171, (1961).

14. S. I. Kim, T. J. Shin, Y. H. Park, and M. Ree, J. Polym. Sci.: Part A: Polym. Chem., 37, 937, (1999).