臺灣博碩士論文加值系統

經鹼液(NaOH)水解反應後的離子化PAN(Polyacrylonitrile)薄膜，會在薄膜表面成PAA(Polyacrylic acid)凝膠層，此一凝膠層具有pH敏感性，可進一步與異丙胺(Isopropylamine)經由醯胺反應來與PAN薄膜表層產生作用，形成一具pH、溫度感應性之聚異丙基丙醯胺（Poly(N-isopropylacrylamide)）(PNIPAAm)。
聚異丙基丙醯胺（Poly(N-isopropylacrylamide)）(PNIPAAm)，它的水溶液在室溫( 25°C )下是澄清且低濃度；當溶液溫度接近31°C時會因去水合作用而有溶膠相轉移的現象。若在離子溶液裡，將會集結沈澱而成一高分子膜。此水膠薄膜具有高孔洞、高的膨潤數(swelling ratio)和低極限溫度(LCST)等特性，並且此薄膜在與一般傳統薄膜比較時，其具有較快的可逆的溫度應答性，藉著這些特性來改善分離效果和加速反應器的效率。
本實驗經由改變濃度、溫度、pH值的改變，探討反應條件對薄膜表面形態的影響。並經由透過性實驗來鑑定此水膠薄膜的性質。反應結果顯示當溫度低於相轉換溫度時高分子鏈與周遭水分子以分子間氫鍵存在，呈柔曲狀可溶於水中；溫度達相轉換溫度以上時轉而以分子內氫鍵及末端基疏水性作用力存在，致使分子鏈凝集而收縮呈相分離。經改質之PNIPAAm薄膜，其相轉換溫度隨反應物之增加而升高，約為50°C；當溫度低於相轉換溫度時，因分子鏈為親水性而使薄膜呈膨潤狀態；溫度高於相轉換溫度時則因末端基之疏水性作用力，使薄膜體積產生急速收縮變化，但是具良好可逆性；在pH一方面，隨著pH由6增加至8之間，薄膜之膜透過率Lp將降低約1/10。

Polyacrylonitrile (PAN) membranes were hydrolyzed with NaOH(aq) to convert the surface into polyacrylic acid (PAA). The surface was then reacted with isopropylamine and produced a layer of poly(N-isopropyl acrylamide) (PNIPAAm). Because of the PAA surface, the membrane is sensitive to pH. Because of the PNIPAAM layer, the membrane is sensitive to temperature. The separation performance of the membranes was evaluated with the hydraulic permeability (Lp) and the retention (R%) of dextran under varying temperature and pH. The results show that the Lp dropped at around 50°C. In addition, the Lp decreased by 10% when the pH increased from 6 to 8.

摘要I
AbstractIII
誌謝IV
目錄V
表目錄IX
第1章.緒論1
1.1.前言1
1.2.膜(membrane)的定義：3
1.3.膜的分類和特性4
1.4.水膠的定義與分類6
1.5.LCST形成原理7
1.6.研究動機及目的8
第2章.文獻回顧10
2.1.環境敏感性的聚合物10
2.2.酸鹼敏感性性薄膜12
2.3.溫度敏感性性薄膜16
2.4.超過濾和微濾20
2.5.超濾和微濾程序中使用的膜25
2.6.微濾膜26
2.7.超濾膜28
第3章.實驗步驟31
3.1.實驗材料31
3.2.實驗儀器及設備33
3.3.實驗流程34
3.4.實驗步驟及方法35
3.4.1.PAN薄膜製作：35
3.4.2.PAN薄膜改質：35
3.4.3.離子基密度測試[57-58]35
3.4.4.溫度敏感性薄膜製作：36
3.4.5.pH敏感性薄膜性質測定：36
3.4.6.溫度敏感性薄膜性質測定：38
3.4.7.pH及溫度敏感性薄膜性質測定：38
3.5.實驗裝置圖40
第4章.結果與討論41
4.1.離子基密度測定41
4.2.醯胺的合成44
4.3.Dextran透過實驗45
第5章.結論51
第6章.參考文獻52
圖目錄
Fig. 11膜的分類5
Fig. 12 NIPAAm交聯共聚合物吸水原理示意圖7
Fig. 21壓力推動的膜工業分類20
Fig. 22不同微粒的大小範圍21
Fig. 23超濾和微濾工業中的靜態和動態操作法22
Fig. 24在超濾和微濾程序中可能出現的滲透通量隨時間的變化曲線23
Fig. 25微濾膜的孔徑分怖26
Fig. 26多孔膜的分離曲線28
Fig. 31實驗流程圖34
Fig. 32實驗裝置圖40
Fig. 41不同溫度下，改質後PAN之離子基密度與時間關係圖43
Fig. 42不同溫度下，反應25分鐘，NaOH濃度對PAN表面離子化之關係圖43
Fig. 43 PAN系列薄膜之透過率與pH關係圖47
Fig. 44 PAN系列薄膜之透過率與溫度關係圖47
Fig. 45 PAN系列薄膜對Dextran溶液之截留率與溫度關係圖47
Fig. 46不同pH環境下，PAN薄膜對Dextran溶液之截留率與溫度關係圖48
Fig. 47不同pH環境下，具PAA之PAN薄膜對Dextran溶液之截留率與溫度關係圖48
Fig. 48不同pH環境下，具PNIPAAm之PAN薄膜對Dextran溶液之截留率與溫度關係圖49
Fig. 49不同pH環境下，PAN薄膜之透過率與溫度關係圖49
Fig. 410不同pH環境下，具PAA之PAN薄膜之透過率與溫度關係圖50
Fig. 411不同pH環境下，具PNIPAAm之PAN薄膜之透過率與溫度關係圖50
表目錄
表格 21超濾膜的結構和特性30
表格 31 500ml pH緩衝溶液配製表37
表格 32不同pH條件之葡據糖溶液配製表39

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