新型聚醯胺醯亞胺及聚醯亞胺-二氧化矽奈米混成材料之合成與性質研究

第一部份中：二醯亞胺二羧酸(DIDA I)是由trimellitic anhydride (TMA)和3,4’-oxydianiline (3,4’-ODA)以2:1之比例；四醯亞胺二羧酸(TIDA II)是由4,4’-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)， TMA和3,4’-ODA 以1:2:2之比例縮合而得，然後再與各種芳香族二胺以Yamazaki磷酸化反應法直接聚縮合成二系列聚醯胺醯亞胺(PAIs；IVak)和聚醯胺醯亞胺醯亞胺(PAIIs；Vak)。大部份的PAIs和所有的PAIIs皆具有良好的溶解性且皆可鑄成透明強韌之薄膜，具優異之機械性質。熱性質測試結果顯示，PAIs IVak和PAIIs Vak之玻璃轉移溫度(Tg)分別介於242-274 ℃與264-295 ℃之間，它們在氮氣與空氣中10%重量損失溫度皆在500 ℃以上。第二部份中：以四種組成合成PI / SiO2 hybrids，並以BPDA/BAPP為PI成份在DMAc中生成PAA後，加入Si(OCH3)4/H2O進行sol-gel反應後鑄膜醯亞胺化生成。前三種hybrids(IV、V及VI)是使用APrTMOS為coupling agent：其中IV系列是改變PI之鏈段長，V系列是改變SiO2含量。並以IR、UV-vis、掃描式電子顯微鏡(SEM)、DSC、TGA及萬能拉力機等測定光學、熱性質與機械等物性之變化。結果顯示使用APrTMOS為耦合劑之PI/SiO2(IV和VI系列)，SiO2含量達30wt%的混成膜仍具有良好的透明性及機械強度，而不加耦合劑之VI’皆呈霧狀不透明之薄膜。含耦合劑合成之IV和VI兩系列和不加耦合劑之VI’ 系列比較性質，實驗證明含耦合劑可有效明顯改善薄膜光學透明度。在實驗中，所有的PI/SiO2混成薄膜皆具優異之熱穩定性，熱性質經由DSC測得玻璃轉移溫度(Tg)在237-266 ℃之間，由TGA之分析在氮氣與空氣中10%重量損失皆在554 ℃以上，在氮氣中800 ℃測得之熱重殘餘率皆在56% 以上。

關鍵字

聚醯胺醯亞胺；磷酸化反應法；聚醯亞胺-二氧化矽奈米混成材；耦合劑

並列摘要

Part 1: A diimides-dicarboxylic acid (DIDA) (I) was synthesized from the condensation reaction of trimellitic anhydride (TMA) and 3,4’-oxydianiline (3,4’-ODA) in a 2:1 molar ratio, and a tetraimide-dicarboxylic acid (TIDA) (II) was prepared from 4,4’-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), TMA, and 3,4’-ODA in a 1:2:2 molar ratio. Several poly(amide-imide)s (PAIs) (IVak) and poly(amide-imide-imide)s (PAIIs) (Vak) were synthesized by Yamazaki phosphorylation polyamidation reactions of DIDA I and TIDA II, respectively, with various aromatic diamines. Due to a highly random segmental sequence in the polymer chain (for both series) and the incorporation of 6FDA moieties (for the V series), most of the IV series PAIs and all the V series PAIIs were readily soluble in many organic solvents and could be solution-cast into transparent, flexible, and tough films with good mechanical properties. Glass-transition temperature (Tgs) of the IV series PAIs and the V series PAIIs were recorded in the range of 242-274℃ and 264-295℃. Almost all these amide-imide polymers showed 10% weight loss temperatures higher than 500℃ under a nitrogen or an air atmosphere. Part 2 : Four series (IV, V, VI, and VI’) of polyimide-silica hybrid (PI/SiO2) were prepared by the sol-gel reaction and characterized in this study. They were synthesized from 3,3’,4,4’-biphenyltetracarboxylic dianhydride (BPDA) and 2,2-bis-[4-(4-aminophenoxy)pheny]propane (BAPP) to obtain viscous poly(amic acid)s, then the hybrid composite films were obtained by the hydrolysis and polycondensation of tetramethylorthosilicate (TMOS) and H2O in N,N-dimethylacetamide (DMAc), following by spin coating and multistep heating. The former three series hybrids were prepared using 3-aminopropyltrimethoxysilane (APrTMOS) as coupling agent. The IV series had dufferent chain length in PI segment; the V series was designed with various contents of silica. The optical, thermal and mechanical properties of the PI/SiO2 hybrids were investigated. All the APrTMOS-modified hybrid films (V and VI series) containing up to 30 wt% silica were mechanically robust and optically transparent. The V and VI series hybrid films showed a higher optical transparency than the VI’ series (without APrTMOS as the coupling agent). All the hybrid films showed excellent thermal stability, including moderately high Tgs of 237-266℃, 10% weight loss temperatures higher than 554 oC, and high char yields at 800oC in nitrogen (＞56%).

並列關鍵字

poly(amide-imide)s ； Yamazaki phosphorylation polyamidation reactions ； PI/SiO2 hybrids ； coupling agent

參考文獻

5. Yang, C.-P.; Lin, J.-H.; Hsiao, S.-H. J Polym Sci Part A: Polym Chem 1991, 29, 1175

6. Yang, C.-P.; Lin, J.-H.; Hsiao, S.-H. J Polym Sci Part A: Polym Chem 1992, 30, 1865

8. Yang, C.-P.; Hsiao, S.-H.; Lin, J.-H. J Polym Sci Part A: Polym Chem 1993, 31, 2995.

9. Yang, C.-P.; Lin, J.-H. J Polym Sci Part A: Polym Chem 1994, 32, 2653.

10. Yamazaki, N.; Matsumato, M.; Higashi, F. J Polym Sci Polym Chem Ed 1975, 13, 1373.

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新型聚醯胺醯亞胺及聚醯亞胺-二氧化矽奈米混成材料之合成與性質研究

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