Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3576
標題: 可應用於低軌太空材料之聚醯亞胺/聚醯胺/聚醯胺醯亞胺之合成與性質探討
Polyimides/polyamides/poly(amide-imide)s for Potential Low Earth Orbit Applications
作者: 林俊宏
Lin, Chun-Hung
關鍵字: Polyimides;聚醯亞胺;polyamides;poly(amide-imide)s;聚醯胺;聚醯胺醯亞胺
出版社: 化學工程學系所
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摘要: 
本論文分成二個部分,第一部份在探討含磷結構之二胺所衍生的新型芳香族polyimides (PI)之合成與性質。一種新型含磷的二胺1,4-bis(4-aminophenoxy)-2-(6-oxido-6H-dibenz <1,2> oxaphosphorin-6-yl) phenylene (3)是由2-(6-oxido-6H-dibenz <1,2> oxaphosphorin-6-yl)-1,4-dihydroxy phenylene (1)和4-fluoronitrobenzene 進行芳香親核取代反應,生成二硝化合物後,再以氫氣和Pd/C 催化還原反應而得到。而一系列色淡、具撓曲性、高分子量、高玻璃轉移溫度、高熱安定性、有機可溶性、耐氧電漿特性之polyimides,是由上述含磷之二胺單體(3)和市售六種芳香族二酐溶於DMAc,再經由熱閉環法聚縮合製得。這些polyimides 的數目平均分子量( )在7.0到8.3 x104 g/mol 之間、重量平均分子量( )在12.5到16.5 x104 g/mol 之間。其熱性質由DSC 測定之玻璃轉移溫度(Tg)在230到304 oC之間,經由DMA 測定之玻璃轉移溫度(Tg)在228到305 oC之間,由TGA 之分析,在氮氣中之5 %重量損失及800 oC之熱重殘餘率分別為544到597 oC和59到65 wt%之間,顯示這些polyimides 具有良好的熱穩定性。測得的polyimides 薄膜之機械性質具有強韌性,抗張強度約在100 MPa。Polyimides 5c 及5e (分別由ODPA 及6FDA 製備而得)之截止波長(cutoff wavelength)分別在347及342 nm,顯示出具有非常淡的顏色。這些polyimides 也顯示出良好的耐氧電漿特性。
本論文第二部份論及了以含磷二胺(3)為主體的新型芳香族polyamides (PA)與poly(amide-imide)s (PAI)的合成與性質,這些PA 與PAI 是由二胺(3)單體與芳香族二羧酸和芳香族二醯亞胺二羧酸經由磷酸化聚縮合反應所合成,又為比較含磷之二胺(3)在PAI 中之位置對於聚合物物性之影響,特別用(3)與TMA 合成二醯亞胺二羧酸(9),再以(9)分別與芳香族二胺合成PAI,以便可與同分異構之PAI 比較。大多數之聚合物可以經由溶液鑄膜法塗製成強韌且具可撓曲性的薄膜。其熱性質由DSC 測定之玻璃轉移溫度(Tg)部分,PA 在209到260 oC之間,PAI 在224到262 oC之間。經由DMA 測定之玻璃轉移溫度(Tg)部分,PA 在210到255 oC之間。由TGA 之分析,PA 在氮氣中之5%重量損失及800 oC之熱重殘餘率分別為460到486 oC和59到68 wt% 之間,PAI 在氮氣中之5 %重量損失及800 oC之熱重殘餘率分別為461到505 oC和61到64 wt%之間,顯示這些PA 及PAI 具有良好的熱穩定性。這些PA 及PAI 也顯示出良好的耐氧電漿特性。
為了與上述含磷的聚合物的性質做比較,另一系列不含磷之PI、PA 及PAI 是由不含磷的二胺單體1,4-bis(4-aminoophenoxy)benzene (BAB)製備而得,其合成與性質測定方法類似於含磷之PI、PA 及PAI 所使用之方法。

Part I, A new phosphorus-containing aromatic diamine, 1,4-bis(4-aminophenoxy)-2-(6-oxido-6H-dibenz <1,2> oxaphosphorin-6-yl) phenylene (3) was synthesized by the nucleophilic aromatic substitution of 2-(6-oxido-6H-dibenz <1,2> oxaphosphorin-6-yl)-1,4-dihydroxy phenylene (1) with 4-fluoronitrobenzene, followed by catalytic hydrogenation. Light color, flexible and creasable polyimides with high molecular weight, high glass transition, high thermal stability, improved organo-solubility, and good oxygen plasma resistance were synthesized from the condensation of (3) with various aromatic dianhydrides in DMAc, followed by thermal imidization. The number-average molecular weights of polyimides are in the range of 7.0-8.3 x104 g/mol, and the weight-average molecular weights are in the range of 12.5-16.5 x104 g/mol. The Tgs of these polyimides range from 230 oC to 304 oC by DSC and from 228 to 305 oC by DMA. These polyimides are tough and flexible with tensile strength at around 100 MPa. The degradation temperatures (Td 5%) and char yields at 800 oC in nitrogen range from 544 to 597 oC and 59-65 wt %, respectively. Polyimides 5c and 5e, derived from ODPA and 6FDA respectively, with the cutoff wavelength of 347 and 342 nm, respectively, show very light color. These polyimides also exhibit good oxygen plasma resistance. Part II, reports the synthesis and properties of new aromatic polyamides and poly(amide-imide)s based on phosphorus-containing aromatic diamine (3). A set of phosphorus-containing polyamides and poly(amide-imide)s were synthesized by the phosphorylation
polyamidation of diamine (3) with aromatic dicarboxylic acids and the imide-containing diacids, and generality of them could afford flexible and tough film via solution casting. The Tgs of these polyamides and poly(amide-imide)s range from 209 oC to 260 oC and 224 oC to 262 oC by DSC, respectively, respectively, and the imide-containing PAIs had better thermal stability than PAs. PAs showed higher transparency and were much lighter in color than PAIs, and their cutoff wavelength (λ0) were below 400 nm. These polyamides and poly(amide-imide)s also exhibit good oxygen plasma resistance. In each part of the thesis, a comparative study of the properties with the corresponding polyimides, polyamides and poly(amide-imide)s prepared from a non-phosphorus diamine, 1,4-bis(4-aminoophenoxy)benzene (BAB) was also made.
URI: http://hdl.handle.net/11455/3576
其他識別: U0005-2007200618125100
Appears in Collections:化學工程學系所

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