含有矽氧烷偶合基團之聚醯胺酸及其衍生之聚醯亞胺/二氧化矽混成材料的合成與性質研究

Synthesis and Properties of Polyimide-Silica Hybrid Derived from Alkoxysilane-Containing Poly(amic acid)s

徐毓賢(Yu-Hsien Hsu)

指導教授 ： 鄭俊麟 ； 王立義

中原大學/工學院/化學工程研究所/碩士(2004年)

https://doi.org/10.6840/cycu200400645

摘要

本研究藉由醯氯反應合成出含有silane基團的雙胺單體3,5-diaminobenzamide-n-propyltriethoxylsilane (PTSDA)，然後利用此一新型單體與3,3-4,4-benzophenone tetracarboxylic dianhydride (BTDA)反應形成poly(amic acid)，再進一步加入TEOS前驅物，進行溶凝膠(sol-gel process)反應以製備聚醯亞胺/二氧化矽混成材料。
我們藉由SEM與AFM來觀察材料的表面型態、微觀結構以及SiO2粒子顆粒大小及分佈情形，並從結果得知SiO2粒子最小大約可達20 nm左右，而且能夠均勻的分佈在聚醯亞胺膜內。同時，可觀察到聚醯亞胺混成薄膜均有優良的平坦度。
在合成BTDA-PDA聚醯亞胺薄膜後，由TGA結果顯示，摻合SiO2粒子後之聚醯亞胺，其熱裂解溫度均高於430℃。DSC的量測也顯示，含有SiO2之聚醯亞胺會受到分子中SiO2無機粒子含量的增加，造成分子鏈轉動或移動不易，因而使得玻璃轉移溫度增加;前者與加入偶合試劑PTSDA之BTDA-PDA/PTSDA聚醯亞胺系列比較，由於後者分子鏈間有偶合作用產生而造成Si-O-Si鍵結，因此限制分子鏈的轉動，其分子鏈轉動程度比起摻混SiO2於分子鏈中還要困難，導致其擁有更高的玻璃轉移溫度。另外，實驗結果亦顯示，將無機粒子變小可以有效的提升玻璃轉移溫度，但粒子大小的改變對介電特性並無明顯的幫助。在介電性質測量，本實驗結果顯示，隨著TEOS摻合量的增加，其薄膜介電常數值會呈現增加的趨勢。由TMA數據發現，經由摻混TEOS之聚醯亞胺均會因為無機物的存在，使得分子鏈不易受熱而發生膨脹，因此可降低其膨脹係數。隨著TEOS的增加，膨脹係數有下降的趨勢。此外，在BTDA-PDA/PTSDA系列中，因分子間偶合作用而使得分子鏈受熱轉動機會較小，所以具有較低的膨脹係數。同時，經由UV-vis測定透光性證實，偶合劑PTSDA的加入確實有助於相容性的提升。
同時於本研究中，我們另外開發一種含有silane基團的新型雙胺單體diaminophenyldiethoxysilane，此新型單體擁有較多剛硬性的芳香族環及對稱的分子結構，所以我們預期以此單體合成聚醯亞胺材料會有較高的熱穩定性及機械強度，可更加提升其在微電子工業的應用。

關鍵字

溶凝膠反應 ； 混成材料 ； 聚醯亞胺 ； 二氧化矽

並列摘要

In this study, a silane-containing functional molecule, (3,5-diaminobenzamide-n-propyltriethoxylsilane) was synthesized by the acid chloride reaction and used as diamine monomer to condensate with 3,3-4,4-benzophenone tetracarboxylic dianhydride forming poly(amic acid). And then the syntheses of polyimide-silica hybrid materials were carried out via the sol-gel reaction of TEOS precursor in the presence of the thus-prepared polyamic acids.
The morphology, microstructure and the particle sizes and their distribution of silica in hybrid materials was examined by SEM and AFM. The results showed that the SiO2 nanoparticles were evenly distributed inside the hybrid thin films and the silica particle size increased as the silica content increased. The AFM study demonstrated that the thin hybrid films have excellent planarity.
The thermal properties of these hybrid materials were measured by TGA, DSC, and TMA. The thermal decomposition temperatures (Td) of hybrid thin films are all above 430℃. The thin hybrid films of BTDA-PDA/silica are more thermal stable than the films of BTDA-PDA/PTSDA/silica owing to the higher molecular weight. The glass transition temperature (Tg) in BTDA-PDA/PTSDA series is higher than BTDA-PDA series because of the coupling effect between polymer chains. Moreover, the results also showed that the glass transition temperature (Tg) increased slightly by decreasing the size of silica particle. Besides, the dielectric constant of hybrid thin films was increased by coupling as well as sol-gel effect and the increase of the silica content. However, the decrease of the silica particle size did not result in a significant effect on the dielectric constant.
The coefficient of thermal expansion decreased as the inorganic content increased. Moreover, the coefficient of thermal expansion in BTDA-PDA/PTSDA series was lower than BTDA-PDA series owing to coupling effect. The transparency of the hybrid by UV/vis spectra is also included in this study.
In addition, we designed and synthesized a novel diamine, diaminophenyldiethoxysilane, which contains more aromatic groups and symmetrical structure. Therefore, it is expected that the PI/silica hybrid film derived from this monomer will exhibit higher thermal stability and mechanical properties. Consequently, they could have good opportunities to be used in microelectronic process.

並列關鍵字

sol-gel process ； SiO2 ； hybrid materials ； polyimide

參考文獻

CHAPTER 1

1. T. M. Bogert and R. R. Reshaw, J. Chem. Soc., 30, 1140 (1908).

2. B. C. Auman, Polymer, 36, 651 (1995).

3. C. S. Wang, J. Appl. Polym. Sci., 66, 609 (1997).

4. J. O. Simpson, J. Appl. Polym. Sci., 36, 1717 (1998).