酸鹼敏感型聚乙烯醇/海藻酸鹽混摻薄膜之膨潤及控制釋放行為探討

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研究生：	劉欣維 Hsin-wei Liu
論文名稱：	酸鹼敏感型聚乙烯醇/海藻酸鹽混摻薄膜之膨潤及控制釋放行為探討 Investigation of swelling and controlled-release behaviors of pH-sensitive poly(vinyl alcohol)/ sodium alginate blend hydrogel membranes
指導教授：	楊銘乾 Min-chien Yang
口試委員:	李振綱 none 王大銘 none
學位類別：	碩士 Master
系所名稱：	工程學院 - 材料科學與工程系 Department of Materials Science and Engineering
論文出版年：	2007
畢業學年度：	95
語文別：	中文
論文頁數：	69
中文關鍵詞：	海藻酸、聚乙烯醇、混摻、控制釋放
外文關鍵詞：	sodium alginate (SA), polyvinyl alcohol (PVA), blend, controll release
相關次數：	點閱：260 下載：0
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本實驗先以海藻酸(SA)與聚乙烯醇(PVA)製作出各種混摻比例PVA/SA薄膜，再以不同濃度之CaCl2進行交聯。藉由UV紫外光/可見光光譜儀等儀器，研究不同混摻比例以及交聯度薄膜在不同pH(pH4、pH7、pH10)中orange II的釋放行為探討。結果顯示溶質之釋放速率，在溶液pH4中，隨SA混摻比例之增加而下降，隨交聯度之增加而下降。其膨潤度(Swelling)隨pH變化之順序為pH10>pH4>pH7。推測應為海藻酸中的-COOH官能基在遇到不同的pH值溶液，產生不同程度之排斥現象，使PVA/SA薄膜內之孔隙有了大小不同變化，影響了不同交聯成分之PVA/SA薄膜的吸收以及釋放。

In this work, sodium alginate (SA) was blended with polyvinyl alcohol (PVA) at various ratios, and then the solution was cast into membranes. The resulting membranes were then crosslinked with CaCl2 of various concentrations. The releasing behavior of these PVA/SA hydrogels was studied using orange II as the model drug. The swelling ratio varied with the pH in the following order: pH 10 > pH 4 > pH 7. This suggested that the repelling of those carboxyl groups was affected by the pH. The releasing rate of the dye decreased with the increase of the blending ratio of SA and the crosslinking degree. This can be related to the swelling ratio of the PVA/SA hydrogel membranes.

摘要.............................................................................................. I
Abstract....................................................................................... II
致謝.............................................................................................III
目錄.............................................................................................IV
圖目錄..........................................................................................V
表目錄.........................................................................................VI
第1 章. 緒論.................................................................................1
第2 章. 文獻回顧........................................................................ 2
2.1. 水膠的定義........................................................................... 2
2.2 水膠之分類.............................................................................3
2.3. 功能性水膠............................................................................6
2.4. PVA的簡介...............................................................................9
2.5. Alginate簡介.......................................... ………………….12
2.6. 控制釋放............................................................................ ..16
第3 章. 實驗材料與方法........................................................... 24
3.1. 實驗步驟........................................................................ …..24
3.2. 實驗材料...............................................................................26
3.3. 實驗設備........................................................................ …..27
3.4. 實驗儀器原理............................................................. …….27
3.5. 實驗原理.................................................................... ……..29
第4 章. 結果與討論....................................................................32
4.1. 控制釋放............................................................. ………….32
4.2. Swelling..................................................................................51
4.3.吸附效應................................................................................ 54
第5 章. 結論................................................................................63
第6 章. 參考文獻........................................................................64











圖目錄
Fig. 2.1水膠交鏈方式..................................................................3
Fig. 2.2敏感性水膠於不同PH下之變化......................................6
Fig. 2.3溫度敏感型高分子poly( NIPAAM )於高低溫下之結構變化................................................................................................. 7
Fig. 2.4光敏感性高分子之結構............................................... ...8
Fig. 2.5聚乙烯醇之化學式...........................................................9
Fig. 2.6 Alginate 單位化學式....................................................12
Fig. 2.7 Alginate的結構....................................................……..14
Fig. 2.8二價陽離子對海藻膠結合之“egg box”結構…………...15
Fig. 2.9氫離子和鈉離子而轉化為海藻酸鈣分子反應式……...15
Fig. 2.10 Cross-section of spheres or cylinder of reservoir devices....................................................................................... 18
Fig. 2.11 Matrix diffusion systems..............................................19
Fig. 2.12 Swelling-controlled systems.........................................20
Fig. 2.13腸衣（Enteric coating）劑型為溶蝕控制系統............21
Fig. 2.14生物可分解性（Biodegradable）系統圖.....................21
Fig. 2.15 Chemical bonding systems.......................................... .22
Fig. 2.16 Structure of the osmotic pumps sys.............................. 23
Fig. 3.1雙光紫外光/可見光光譜儀原理.................................... 28
Fig. 3.2電磁波能量範圍圖.........................................................29
Fig. 3.3聚丙烯酸鈉(PAAS).........................................................30
Fig. 3.4吸水原理示意圖..............................................................30
Fig. 3.5二價陽離子對海藻膠結合之“egg box”結構...................31
Fig. 4.1 2×2 cm2Alginate與1% CaCl2交聯之PVA/SA薄膜在pH=4 溶液中釋放之結果..................................................................................33
Fig. 4.2 2×2 cm2Alginate與3% CaCl2交聯之PVA/SA薄膜在pH=4 溶液中釋放之結果..................................................................................33
Fig. 4.3 2×2 cm2Alginate與5% CaCl2交聯之PVA/SA薄膜在pH=4 溶液中釋放之結果..................................................................................34
Fig. 4.4 pH4 orange II溶液1％交聯之 Fickian diffusion equation圖..................................................................................................35
Fig. 4.5 pH4 orange II溶液3％交聯之 Fickian diffusion equation圖..................................................................................................35

Fig. 4.6 pH4 orange II溶液5％交聯之 Fickian diffusion equation圖......................................................................................................36
Fig. 4.7 2×2 cm2Alginate與1% CaCl2交聯之PVA/SA薄膜在pH=7 溶液中釋放之結果......................................................................................39
Fig.4.8 2×2 cm2Alginate與3% CaCl2交聯之PVA/SA薄膜在pH=7 溶液中釋放之結果......................................................................................39
Fig.4.9 2×2 cm2Alginate與3% CaCl2交聯之PVA/SA薄膜在pH=7 溶液中釋放之結果......................................................................................40
Fig. 4.10 pH7 orange II溶液1％交聯之 Fickian diffusion equation圖......................................................................................................41
Fig. 4.11 pH7 orange II溶液3％交聯之 Fickian diffusion equation圖......................................................................................................42
Fig. 4.12 pH7 orange II溶液5％交聯之 Fickian diffusion equation圖......................................................................................................42
Fig. 4.132×2 cm2Alginate與1% CaCl2交聯之PVA/SA薄膜在pH=10 溶液中釋放之結果...................................................................................45
Fig. 4.142×2 cm2Alginate與3% CaCl2交聯之PVA/SA薄膜在pH=10 溶液中釋放之結果...................................................................................46
Fig. 4.152×2 cm2Alginate與5% CaCl2交聯之PVA/SA薄膜在pH=10 溶液中釋放之結果...................................................................................46
Fig. 4.16 pH10 orange II溶液1％交聯之 Fickian diffusion equation圖.......................................................................................................47
Fig. 4.17 pH10 orange II溶液3％交聯之 Fickian diffusion equation圖.......................................................................................................48
Fig. 4.18 pH10 orange II溶液5％交聯之 Fickian diffusion equation圖.......................................................................................................48
Fig. 4.19 CaCl2 1%交聯下，PVA/SA薄膜跟SR及pH之關係..........52
Fig. 4.20 CaCl2 3%交聯下，PVA/SA薄膜跟SR及pH之關係..........53
Fig. 4.21 CaCl2 5%交聯下，PVA/SA薄膜跟SR及pH之關係..........53
Fig. 4.22 CaCl2 1% pH=4 溶液中以Langmuir 吸附方程式作圖.....55
Fig. 4.23 CaCl2 3% pH=4 溶液中以Langmuir 吸附方程式作圖.....55
Fig. 4.24 CaCl2 5% pH=4 溶液中以Langmuir 吸附方程式作圖.....56
Fig. 4.25 CaCl2 1% pH=7 溶液中以Langmuir 吸附方程式作圖.....56
Fig. 4.26 CaCl2 3% pH=7 溶液中以Langmuir 吸附方程式作圖.....57
Fig. 4.27 CaCl2 5% pH=7 溶液中以Langmuir 吸附方程式作圖.....57
Fig. 4.28 CaCl2 1% pH=10 溶液中以Langmuir 吸附方程式作圖....58
Fig. 4.29 CaCl2 3% pH=10 溶液中以Langmuir 吸附方程式作圖....58
Fig. 4.30 CaCl2 5% pH=10 溶液中以Langmuir 吸附方程式作圖....59













表目錄
Table.3.1 PVA/SA不同比例之成份混摻...............................................25
Table.4.1 pH 4  1%控制釋放之速率................................................... 37
Table.4.2 pH 4  3%控制釋放之速率............................................. …..37
Table.4.3 pH 4  5%控制釋放之速率............................................. …..37
Table.4.4 pH 7  1%控制釋放之速率................................................... 43
Table.4.5 pH 7  3%控制釋放之速率............................................. …..44
Table.4.6 pH 7  5%控制釋放之速率............................................. …..44
Table.4.7 pH 10  1%控制釋放之速率..................................................50
Table.4.8 pH 10  3%控制釋放之速率..................................................50
Table.4.9 pH 10  5%控制釋放之速率..................................................50
Table.4.10 CaCl2 1% pH=4溶液中Langmuir方程式作圖所得之S及K..60
Table.4.11 CaCl2 3% pH=4溶液中Langmuir方程式作圖所得之S及K..60
Table.4.12 CaCl2 3% pH=4溶液中Langmuir方程式作圖所得之S及K..60
Table.4.13 CaCl2 1% pH=7溶液中Langmuir方程式作圖所得之S及K..61
Table.4.14 CaCl2 3% pH=7溶液中Langmuir方程式作圖所得之S及K..61
Table.4.15 CaCl2 3% pH=7溶液中Langmuir方程式作圖所得之S及K..61
Table.4.16 CaCl2 1% pH=10溶液中Langmuir方程式作圖所得之S及K62
Table.4.17 CaCl2 3% pH=10溶液中Langmuir方程式作圖所得之S及K..62
Table.4.18 CaCl2 3% pH=10溶液中Langmuir方程式作圖所得之S及K..62

                                

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