結晶性對可摻雜電活性聚亞醯胺薄膜用於O2/N2氣體分離之影響研究

Effect of Crystallinity on O2/N2 Gas Separation of Doped Electroactive Polyimide Films

藍云襄(Yun-Xiang Lan)

指導教授 ： 葉瑞銘

中原大學/理學院/化學研究所/碩士(2020年)

https://doi.org/10.6840/cycu202000453

摘要

本研究論文的研究主軸為研究利用不同調控方式來調整聚亞醯胺薄膜之結晶度，並研究不同結晶度之聚亞醯胺薄膜在氣體滲透性及氣體選擇性質之影響。
首先，製備不同結晶度的聚亞醯胺氣體分離薄膜，利用氧化偶合一步法合成穩定的半氧化半還原態之胺基封端苯胺三聚體 (Amine-capped aniline trimer；ACAT) ，並選為製備聚亞醯胺 (PI) 之雙胺單體，分別與二酸酐 ( 3,3′,4,4′-Biphenyltetracarboxylic dianhydride，BPDA) 及 ( 4,4’- ( 4,4’– Isopropylidene – diphenoxy ) bis ( phthalic anhydride)，BSAA ) 進行預聚合，合成電活性聚醯胺酸 (Electroactive Poly(amic acid)，EPAA) ，再以熱縮合方式進行閉環製備出電活性聚亞醯胺薄膜 (Electroactive Polyimide Membranes，EPI)，並與分別摻雜鹽酸及硫酸後之 EPI 薄膜做比較，藉由 TGA 可知所製備之 EPI 薄膜的熱裂解溫度 (Td) 皆高於 400℃ ，表示這些 EPI 薄膜皆有良好的耐熱性，接著利用動態機械分析儀 (DMA) 可知所製備之 EPI 薄膜皆有良好的機械強度，再由 XRD 及 DSC 可發現此電活性聚亞醯胺薄膜具有不同的結晶度，最後，藉由GPA測得在摻雜前 HC-EPI 有較好的氧氮氣體分離能力為20.15，分別為 A-EPI 和 LC-EPI 的1.48倍和1.12倍。在經過鹽酸摻雜後， A-EPI 、 LC-EPI 和 HC-EPI 的氧氮氣體分離效果分別提升 1.23、1.12 及 1.10 倍；而在經過硫酸摻雜後， A-EPI 、 LC-EPI 和 HC-EPI 的氧氮氣體分離效果分別提升 1.61、1.27 及 1.27 倍。

關鍵字

氣體分離 ； 結晶度 ； 電活性 ； 聚亞醯胺

並列摘要

The main axis of this research paper is to prepare and characterize undoped and doped polyimide membranes with different crystallinities and study the effect of crystallinities on gas permeability and gas selectivity of as-prepared undoped and doped polyimide membranes.
First, prepare polyimide gas separation membranes with different crystallinities, and use a one-step oxidation coupling method to synthesize a stable semi-oxidized and semi-reduced amine-terminated aniline trimer (ACAT), and select as Preparation of diamine monomers of polyimide, respectively with dianhydride (3,3′,4,4′-Biphenyltetracarboxylic dianhydride, BPDA) and (4,4'- (4,4'– Isopropylidene – diphenoxy) bis ( phthalic anhydride), BSAA) pre-polymerization to synthesize Electroactive Poly (amic acid) (EPAA), and then cyclization and ring closure by high-temperature heat condensation to prepare electroactive polyimide film (Electroactive) Polyimide Membranes (EPI), and compared with the EPI film doped with hydrochloric acid and sulfuric acid respectively. According to TGA, the thermal cracking temperature (Td) of the prepared EPI film is higher than 400℃, indicating that these EPI films are good Heat resistance, and then using dynamic mechanical analyzer (DMA), the prepared EPI film has good mechanical strength, and then XRD and DSC can be found that this electroactive polyimide film has different crystallinity, and finally, by According to GPA, the HC-EPI has a good oxygen and nitrogen gas separation capacity of 20.15 before doping, which is 1.48 times and 1.12 times of A-EPI and LC-EPI, respectively. After doping with hydrochloric acid, the separation effect of oxygen-nitrogen gas of A-EPI, LC-EPI and HC-EPI is increased by 1.23, 1.12 and 1.10 times respectively; and after doping with sulfuric acid, A-EPI, LC-EPI and HC -EPI's oxygen-nitrogen gas separation effect is improved by 1.61, 1.27 and 1.27 times respectively.

並列關鍵字

Gas separation ； Crystallinity ； Electroactive ； Polyimide

參考文獻

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