淡色之聚醚醯亞胺與聚醯亞胺/二氧化矽混成薄膜之合成與性質

SYNTHESIS AND PROPERTIES OF LOW COLOR POLY(ETHER IMIDE)S AND PI/SiO2 HYBRID FILMS

黃盛裕(Sheng-Yu Huang)

指導教授 ： 蕭勝輝

大同大學/工程學院/化學工程學系所/碩士(2006年)

摘要

摘要
在第一部份中，一系列有機可溶淡色之新型含氟聚醚醯亞胺(IV)是由二醚二酐(4,4’-[1,4-phenylenbis(isopropylidene-1,4-phenyleneoxy)]diphthalic anhydride) (I)與ㄧ系列含氟之二醚二胺利用二步驟法經熱烤及化學閉環所合成，其固有黏度在0.43-0.59 dL/g之間。這些聚醚醯亞胺在數種有機溶劑中有良好的溶解性，且可製成透明、可撓曲且強韌的薄膜。這些薄膜在UV-visible光譜測定中，其截止波長在361-375 nm之間，而在色差計測定下也具有低的b*值，其範圍在15.3-17.0之間。所有薄膜都具有好的熱穩定性，且玻璃轉移溫度在191-248 ℃之間，10% 熱重損失溫度皆高於494 ℃，在800 ℃氮氣下之熱重殘餘率皆高於39%。使用熱烤閉環之V系列具有良好的機械性質，其抗張強度在83-96 MPa之間，起始模數在1.7-2.0 GPa之間。這些薄膜具有較低的介電常數，其範圍在3.25-3.72 (1MHz)之間。比較不含氟之V系列與含氟之IV系列，IV系列具有較好之溶解性較低的介電常數及較淡的顏色。
第二部份之聚醯亞胺二氧化矽有機無機混成材料是由hydrolysed tetramethoxysilane (TMOS)及aromatic poly(amic acid) ，利用sol-gel方法並分別加入或不加入偶合劑3-aminopropyltrimethoxysilane (APrTMOS) 所合成，其中poly(amic acid)是由4,4’-oxydiphthalic dianhydride (ODPA) 及 4,4’-bis(4-aminophenoxy)biphenyl (I”)反應生成。加入偶合劑的V系列在二氧化矽濃度40 wt% 仍具有強韌的機械性質與光學穿透度。而V系列的混成薄膜比VI系列(不含偶合劑)擁有更高的光學穿透度。所有的混成薄膜具有良好的熱穩定性，包括適當的玻璃轉移溫度在243-254 ℃之間，10 %熱重損失溫度在560 ℃以上，在氮氣下，800 ℃熱重殘餘率大於60 %。
第三部份是由4,4’-bis(4-aminophenoxy)biphenyl (I”) 或 4,4’-bis(4-amino-2-trifluoromethylphenoxy)biphenyl (I’) 與 4,4’-oxydiphthalic dianhydride (ODPA) 使用 3-aminopropyltrimethoxysilane (APrTMOS)為偶合劑，使用sol-gel方法，所製成兩端為矽氧烷結構之聚醯胺酸。兩系列的混成薄膜式利用兩端的矽氧晚結構與TMOS及水反應，利用sol-gel方法在PAA與TMOS間產生化學鍵結，再經過多段熱烤閉環所製成。混成薄膜在二氧化矽濃度增加到40 wt%時仍為具有強韌的機械性質、良好的穿透度以及色淡之薄膜。含氟之混成薄膜(IX系列)比不含氟的VIII系列，擁有較高的光學穿透性以及較淡的顏色。所有的混成薄膜皆具有良好的熱穩定性，包括適當的玻璃轉移溫度在242-266 ℃之間，10 %熱重損失溫度在535 ℃以上，在氮氣下，800 ℃熱重殘餘率則皆高於54 %。

關鍵字

聚醚醯亞胺 ； 有機無機混成材料 ； 淡色 ； 混成材料

並列摘要

ABSTRACT
In part I, a series of novel organosoluble and light-colored fluorinated poly(ether imide)s (IV) having inherent viscosities of 0.43-0.59 dL/g were prepared from 4,4’-[1,4-phenylenbis(isopropylidene-1,4-phenyleneoxy)]diphthalic anhydride (I) and various trifluoromethyl-substituted aromatic bis(ether amine)s by a standard two-step process with thermal and chemical imidization of poly(amic acid) precursors. These poly(ether imide)s showed excellent solubility in many organic solvents and could be solution-cast into transparent, flexible, and tough films. These films were essentially colorless, with an UV-visible absorption edge of 361-375 nm and a very low b* value (a yellowness index) of 15.3 to 17.0. They series also showed good thermal stability with glass-transition temperature of 191-248oC, 10% weight loss temperature in excess of 494oC, and char yields at 800oC in nitrogen more than 39%. The thermally cured poly(ether imide) films showed good mechanical properties with tensile strengths of 83-96 MPa, elongations at break of 8-11%, initial moduli of 1.7-2.0 GPa. They possessed lower dielectric constants of 3.25-3.72 (1MHz). In comparison with the V series nonfluorinated poly(ether imide)s, the IV series showed better solubility, lower color intensity and lower dielectric constants.
In part II, hybrid organic-inorganic materials based on polyimide-silica system have been produced by the sol-gel route from solution mixture of hydrolysed tetramethoxysilane (TMOS) and an aromatic poly(amic acid) prepared from 4,4’-oxydiphthalic dianhydride (ODPA) and 4,4’-bis(4-aminophenoxy)biphenyl (I”) with or without the use of 3-aminopropyltrimethoxysilane (APrTMOS) as a chain-end capper. The APrTMOS-modified hybrid films (V series) containing up to 40 wt% silica were mechanically robust and optically transparent. The V series hybrid films showed a higher optical transparency than the VI series analogs (without APrTMOS as the coupling agent). All the hybrid films showed excellent thermal stability, including moderately high Tgs of 243-254℃, 10% weight loss temperatures higher than 560 oC, and high char yields at 800oC in nitrogen (＞60%).
In part III, an alkoxysilane terminated amide acid prepolymer was prepared from 4,4’-bis(4-aminophenoxy)biphenyl (I”) or 4,4’-bis(4-amino-2-trifluoromethylphenoxy)- biphenyl (I’) with 4,4’-oxydiphthalic dianhydride (ODPA) using 3-aminopropyltrimethoxysilane (APrTMOS) as an end capper. Two series of polyimide/silica (PI/SiO2) hybrid films with chemical bonding between the polyimide backbone and silica network have been prepared from the mixture of APrTMOS-terminated prepolymer, tetramethoxysilane (TMOS), and water via a sol-gel reaction, followed by solution casting and multistep heating. The hybrid films containing up to 40 wt% silica were mechanically robust, transparent, and light-colored. The fluorine-containing PI/SiO2 hybrid films (IX series) showed a higher optical transparency and less color intensity than the non-fluorinated (VIII series). All the hybrid films showed excellent thermal stability, including moduately high Tgs of 242-266 ℃, 10% weight loss temperatures higher then 535 ℃, and high char yield at 800 ℃ in nitrogen (＞ 54%).

並列關鍵字

poly(ether imide) ； organic-inorganic material ； hybrid material ； low color

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