臺灣博碩士論文加值系統

本研究利用具有多官能基與高反應性之氧氯化磷先與醇類或胺類行氯 基的單取代反應，再與矽氧烷寡聚物進行共聚合反應，合成具有不同官能性懸掛基(-OR，-NR2等)的含磷酯矽氧烷樹脂。然後以高機械強度且多孔性的PVDF薄膜為基材，利用電漿接枝聚合法將三甲氧基乙烯基矽烷單體接在PVDF薄膜表面，再與具不同懸掛基之含磷酯矽氧烷樹脂交聯製成複合薄膜。此一系列不同親疏水性的複合薄膜薄膜應用於酒精/水溶液的滲透蒸發分離實驗進行比較評估。
實驗結果顯示，本質上為疏水性的複合膜對於低酒精濃度有較高之選擇性，選擇係數與滲透通量呈現反比之關係。複合膜中帶乙氧基或苯氧基之複合膜呈現著比較疏水之性質；帶正丁胺基或二乙胺基者會降低疏水性，造成酒精選擇係數降低，滲透通量提高。其中以苯氧基複合膜有著最佳分離效果，酒精選擇係數4.6，滲透通量為2.85 kg/m2-hr，PSI為13110(進料酒精濃度10wt%)。若將苯氧基複合膜的厚度加厚，以單層，兩面塗佈，三層及四層複合進行酒精/水溶液的分離時，厚度及型態皆能有效提昇分離效果，其中以四層複合膜之酒精選擇係數31，滲透通量0.9為 kg/m2-hr，PSI 27900為(進料酒精濃度10wt%)呈現最佳分離效果。

In this study, polysiloxanes containing phosphate esters were synthesized by adding various functional species and PDMS diol in sequence to POCl3. A variety of copolymers could thus be prepared by varying functional species. There were two kinds of functional groups attached to the copolymers, oxy-organic and amino groups. The synthesized copolymers were coated and cured on the porous PVDF membranes to form composite membranes. An interfacial layer between the silicone and PVDF layers was formed through plasma polymerization of trimethoxyvinylsilane on the PVDF surface prior to composite. The composite membranes were applied to the separation of ethanol from water in a pervaporation separation process.
The experimental results showed that these naturally hydrophobic composite membranes were highly ethanol-permselective, especially when the ethanol concentration in feed was low. The composite membranes with ethoxy or benzoxy pending groups exhibited more hydrophobic properties. With amino pending groups, the separation factor was lower while the permeation rate was higher. Benzoxy composite membrane had better performance with the separation factor of 4.6 and the permeation rate of 2.85 kg / m2h at a feed concentration of 10wt﹪ethanol. The membrane performance was further enhanced by increasing the thickness of the PDMS layer. Fixing the total thickness of PDMS layers, membranes with double, triple and quadruple layers were also prepared and tested. The membrane with four layers of PDMS performed the best results with the separation factor of 31 , the permeation rate of 0.9 kg / m2h and PSI of 27900 at a 10wt﹪ethanol feed concentration.

目 錄
中文摘要………………………………………………………………..Ⅰ
英文摘要………………………………………………………..Ⅱ
目錄………………………………………………………………………Ⅲ
表索引…………………………………………………………………...Ⅵ
圖索引…………………………………………………………………...Ⅶ
第一章緒論…………………………………………………………....….1
第二章文 獻 回 顧…..…………………………………………………3
2.1薄膜分離程序………………….…………………………………….…3
2.2 薄膜之製備與結構..………………………………………………….5
2.2.1薄膜之製備…………………………………………………….….5
2.2.2薄膜之結構………………………………………………………..6
2.3 薄膜改質……………………………………………………………….7
2.4 電漿原理………………….……………………………………….….10
2.4.1 電漿………………………………………………………………10
2.4.2 電漿型式…………………………………………………………11
2.4.3 電漿改質…….…………………………………………….……..13
2.5 滲透蒸發..…………………………………………………………….14
2.5.1 滲透蒸發原理……………………………………………………14
2.5.2 薄膜之發展與操作程序…………………………………………15
2.5.3分離成效指標的定義…………………………………………….17
2.6 乙醇/水系統之滲透蒸發的相關研究………………………………..18
第三章實驗裝置與實驗步驟………………………………………….22
3.1 實驗材料……………………………………………………………...22
3.2 實驗儀器……………………………………………………………...24
3.3 實驗步驟……………………………………………………………...27
3.3.1 具有機氧基與胺基之含磷酯矽氧烷化合物……………………27
3.3.2 PVDF薄膜之製備……………………………………………..30
3.3.3 電漿接枝聚合反應………………………………………….…..30
3-3.4 複合薄膜之製備…………………………………………….…..31
3-3.5 滲透蒸發分離程序………………………………………….…..31
第四章結果與討論……………………………………………………...32
4-1不同懸掛基之含磷酯矽酮樹脂的合成………………………………32
4.1.1有機氧基………………………………………………………….32
4.1.2 胺基………………………………………………………………40
4.2滲透蒸發分離程序……………………………………………………47
4.2.1 PVDF薄膜………………………………….…………………….48
4.2.2電漿接枝膜之滲透蒸發分離效果………………………………51
4.2.3 複合薄膜之滲透蒸發分離效果…………………………………55
4.2.4不同厚度的苯氧基複合薄膜對滲透蒸發分離效果的影響…….73
第五章結論與建議……………………………………………………..79
參考文獻…………………………………………………………………...81
附錄…………………………………………………………………………88

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