新型含三氟甲基取代之萘環結構的芳香族二醚二胺所衍生之有機可溶性及低介電常數之聚醯亞胺之合成與性質

SYNTHESIS AND PROPERTIES OF ORGANOSOLUBLE, LOW DIELECTRIC CONSTANT POLYIMIDES BASED ON NEW TRIFLUOROMETHYL SUBSTITUTED AROMATIC BIS(ETHER AMINE)S CONTAINING NAPHTHALENE UNITS

鍾成林(Cheng-Lin Chung)

指導教授 ： 蕭勝輝

大同大學/工程學院/化學工程學系所/博士(2009年)

摘要

本論文在探討含有三氟甲基取代及具萘環結構之芳香族二醚二胺所衍生出四個系列具有有機可溶性、色淡及低介電常數性質的聚醯亞胺之合成與性質探討。
四種含三氟甲基結構之二胺單體是經由相對應的萘二酚單體 (如2,6-，1,6-，1,7-，及1,3- 取代) 與含三氟甲基基團的對氯硝基苯於碳酸鉀(K2CO3)的存在下，以N,N-dimethylformamide (DMF)、dimethyl sulfoxide (DMSO) 或 N-methyl-2-pyrrolidone (NMP) 作為溶劑進行親核取代反應，合成出二硝基化合物之後，再經由聯胺在Pd/C的環境中以乙醇為溶劑還原而成。這些新型具有醚鏈之含氟聚醯亞胺是由上述這些二胺分別與市售六種不同的芳香族二酐，以兩個步驟的開環聚加成反應再以熱烤或化學閉環法的方式製得。第一步驟製得之聚醯胺酸前驅物的固有黏度介於0.66~2.16 dL/g之間，它們均可以熱轉化成可撓曲強韌的薄膜，而且這些薄膜在所有測試的溶劑中具有優異的有機可溶性，如NMP、DMF及DMAc (N,N-dimethylacetamide)。這些聚醯亞胺維持一定的玻璃轉移溫度和優良的熱性質，其玻璃轉移溫度和軟化溫度分別介於222~311 oC和210~286 oC，它們在空氣或氮氣中皆在500 oC以上才有明顯的熱分解。它們亦具有低的吸濕性 (0.12~0.85%)、低的介電常數值 (2.49~3.59 at 10 kHz)以及高的光學透過性 (cutoff wavelength at 358~430 nm)。此外，相類似結構以及相對應不含氟之聚醯亞胺亦被合成與製備，並與含氟之聚醯亞胺在一些性質上做比較與探討。

關鍵字

有機可溶性 ； 低介電常數 ； 聚醯亞胺

並列摘要

Synthesis and properties of organosoluble, low colored and low dielectric constant polyimides based on new trifluoromethyl-substituted aromatic bis(ether amine)s containing naphthalene units were investigated in this dissertation.
Four trifluoromethyl-substituted aromatic diamine monomers m,n-bis(4-amino-2-trifluoromethylphenoxy)naphthalene, were prepared through the nucleophilic substitution reaction of 2-chloro-5-nitrobenzotrifluoride and corresponding m,n-dihydroxynaphthalenes (such as 2,6-, 1,6-, 1,7-, 1,3-substitution) in the presence of potassium carbonate (K2CO3) in N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or N-methyl-2-pyrrolidone (NMP), followed by catalytic reduction with hydrazine and Pd/C in ethanol. These series of novel fluoroinated aromatic polyimides containing ether segment were synthesized from these bis(ether amine)s with various commercially available aromatic tetracarboxylic dianhydrides using a two-stage process with thermal or chemical imidization method. The poly(amic acid) precursors had inherent viscosity of 0.66~2.16 dL/g, and all of them could be cast and thermally converted into transparent, flexible, and tough polyimide films. These polyimide films were highly soluble in a variety of organic solvents such as NMP, DMF, and DMAc (N,N-dimethylacetamide), the glass-transition temperatures of these polyimides were recored between 222~311 oC by differential scanning calorimetery and the softening temperatures of the polyimide films were in the range of 210~286 oC according to thermomechanical analysis. These polyimides showed insignificant decomposition before 500 oC in air or nitrogen. They also revealed low moisture absorptions (0.12~0.85%), low dielectric constant (2.49~3.59 at 10 kHz), and high optical transparency (cutoff wavelength at 358~430 nm). For a comparative study, some properties of the present polyimides will be compared with those of the corresponding analogous non-fluorinated or structurally related ones.

並列關鍵字

organosoluble ； polyimide ； low dielectric constant

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