臺灣博碩士論文加值系統

本論文是利用UV光照射法（UV radiation）製備不同比例的聚乙烯醇/聚甲基丙烯酸二甲胺乙酯, poly（vinyl alcohol）/poly（dimethyl aminoethyl methacrylate）, PVA/poly（DMAEMA）薄膜並且以戊二醛處理，討論PVA分子量、poly（DMAEMA）含量以及交聯度的影響。由FTIR光譜圖，C＝O隨著poly（DMAEMA）含量增加而增加。由DSC，發現只有一個Tg，所以PVA與poly（DMAEMA）相容性佳。同時發現poly（DMAEMA）含量愈多Tm愈小，原因是poly（DMAEMA）會降低PVA的結晶度，可以由XRD來印證。PVA薄膜經過戊二醛交聯後氧含量減少，而且發現抗拉強度與伸長率增加，熱性質增加。討論poly（DMAEMA）的含量以及交聯度對接觸角、含水率、溶質透過的影響，發現poly（DMAEMA）含量愈多接觸角愈小，含水率愈高，溶質透過愈好，同時發現交聯度愈低含水率愈高，溶質透過愈好。

In this study the preparation of various poly（vinyl alcohol）/poly（dimethylaminoethyl methacrylate）, PVA/poly（DMAEMA）membranes by UV radiation and treated with glutaraldehyde is reported. The influences of PVA molecular weight, poly（DMAEMA）content and various crosslinking ratio were discussed. From the FTIR spectra, the peak of C＝O increased with the increasing poly（DMAEMA）content. In the results of DSC, it was found there was one Tg, so the compatibility between PVA and poly（DMAEMA）was good. It was also found Tm decreased with the increaseing poly（DMAEMA）content cause poly（DMAEMA）could decrease the crystallinization of PVA, as the results of XRD. From the results of elemental analysis, the oxygen content in the PVA membranes decreased after treated with glutaraldehyde. It was also found that tensile strength, elongation and thermal stability increased. The effects of poly（DMAEMA）content and crosslinking ratio on the contact angle, water content and permeability of solute were determined. It was found that with an increase in the poly（DMAEMA）content, the contact angle decreased whereas the water content increased, and the higher permeability of solute. It was also found that with an decrease crosslinking ratio, the water content increased, and the higher permeability of solute.

指導教授推薦書
口試委員會審定書
博碩士論文授權書....................................................iii
博碩士紙本論文著作授權書...............................................iv
誌謝.................................................................v
中文摘要.............................................................vi
英文摘要............................................................vii
圖目錄.............................................................xii
表目錄.............................................................xvi
第一章 前言..........................................................1
1.1 薄膜..........................................................1
1.1.1 定義與種類.................................................1
1.1.2 分離程序...................................................2
1.1.3 非孔洞性薄膜的製備方法......................................3
1.2 水膠..........................................................4
1.2.1 定義與種類.................................................4
1.2.2 吸水理論與計算.............................................6
1.2.3 溶質透過理論與計算..........................................8
1.2.4 應用.....................................................14
1.3 UV光與UV光照射法..............................................15
1.3.1 UV光.....................................................15
1.3.2 UV光照射法................................................16
第二章 文獻回顧......................................................18
2.1 聚乙烯醇......................................................18
2.1.1 介紹與用途................................................18
2.1.2 聚乙烯醇的交聯研究.........................................20
2.1.3 聚乙烯醇水膠在溶質透過的研究................................21
2.2 甲基丙烯酸二甲胺乙酯...........................................23
2.2.1 介紹與用途................................................23
2.2.2 甲基丙烯酸二甲胺乙酯的光聚合的研究...........................24
2.3 IRGACURE 2959................................................25
2.4 Creatinine...................................................25
2.5 5-FU.........................................................26
2.6 Uric acid....................................................26
2.7 UV光照射法....................................................27
第三章 研究方法......................................................30
3.1 實驗藥品......................................................30
3.2 實驗儀器......................................................32
3.3 實驗流程......................................................34
3.4 實驗方法......................................................36
3.5 實驗步驟......................................................37
3.5.1 製備PVA/poly（DMAEMA）的薄膜..............................37
3.5.2 製備PVA的交聯液...........................................39
3.5.3 製備PVA/poly（DMAEMA）的交聯薄膜...........................39
3.5.4 繪製藥物的UV-Vis圖譜及檢量線...............................42
3.6 測試方法......................................................43
3.6.1 富立葉轉換紅外線光譜儀（FTIR）..............................43
3.6.2 元素分析（EA）............................................43
3.6.3 X光射線繞射（XRD）........................................43
3.6.4 接觸角（contact angle）...................................44
3.6.5 含水率（water content）.................................44
3.6.6 熱重量分析（TGA）.........................................45
3.6.7 微差掃描卡計（DSC）........................................45
3.6.8 拉伸測試（tensile strength test）.........................45
3.6.9 溶質透過（permeability of solute）........................46
第四章 結果與討論....................................................48
4.1 富立葉轉換紅外線光譜儀（FTIR）..................................48
4.2 元素分析（EA）................................................48
4.3 X光射線繞射（XRD）............................................49
4.4 接觸角（contact angle）.......................................49
4.5 含水率（water content）.......................................50
4.6 熱重量分析（TGA）.............................................51
4.7 微差掃描卡計（DSC）............................................52
4.8 拉伸測試（tensile strength test）.............................53
4.9 溶質透過（permeability of solute）............................54
第五章 結論.........................................................56
參考文獻 ............................................................57

圖 目 錄

Fig. 1-1. Schematic representation of various membrane cross-
sections....................................................2
Fig. 1-2. Schematic representation of two-phase system separated by
membrane....................................................2
Fig. 1-3. A typical hand-casting knife...............................3
Fig. 1-4. Machinery used to make solution-cast film on a commercial
scale........................................................3
Fig. 1-5. Illustrations of hydrogel chemically crosslinked network and
hydrogel physically crosslinked network......................5
Fig. 1-6. Schematic representation of the cross-linked structure of a
hydrogel.....................................................6
Fig. 1-7. Depiction of polymer relaxation during water sorption into
a slab geometry（A）, and on the molecular level.（B）Shaded
areas represent glassy polymer regions.......................7
Fig. 1-8. Swelling of a hydrophilic, glassy polymer by water.........7
Fig. 1-9. Cross-linked structure of a polymer gel....................9
Fig. 1-10. Experimental apparatus for permeation studies............10
Fig. 1-11. Schematic diagram of stirred diffusion cell..............11
Fig. 1-12. Regions of the electromagnestic spectrum.................15
Fig. 1-13. The flow chart of UV radiation process...................17
Fig.1-14. The mechanism for UV radiation............................17
Fig. 2-1. The hydrolysis of polyvinyl acetate to polyvinyl alcohol..18
Fig. 2-2. The structural of PVA: （a）partially hydrolyzed, （b）fully
hydrolyzed................................................18
Fig. 2-3. Continuous process for the preparation of polyvinyl
alcohol...................................................19
Fig. 2-4. Crosslinked PVA formed by reaction between PVA and GA.（a）
Acetal ring group or ether linkage formation.（b）Aldehyde
formation by monofunctional reaction........................21
Fig. 2-5. The structure of DMAEMA...................................23
Fig. 2-6. The structure of IRGACURE 2959............................25
Fig. 2-7. The structure of creatinine...............................25
Fig. 2-8. The structure of 5-Fu.....................................26
Fig. 2-9. The structure of uric acid................................26
Fig. 3-1. （a）The UV radiation facility（b）The illustration of UV
radiation..................................................33
Fig. 3-2. The illustration of content angle.........................44
Fig. 3-3. The illustration of tensile strength test.................46
Fig. 3-4. The illustration of permeability of solute................47
Fig. 4-1. The FTIR spectra of various samples（PVA Mw=30,000~70,000）
.........................................................65
Fig. 4-2. The XRD curves of various PVA/poly（DMAEMA）membranes
（PVA Mw=30,000~70,000）...................................66
Fig. 4-3. The XRD curves of various PVA/poly（DMAEMA）membranes
（PVA Mw=70,000~100,000）..................................67
Fig.4-4. The water content of various PVA/poly（DMAEMA）membranes
（PVA Mw=70,000~100,000）..................................68
Fig. 4-5. The water content of various crosslinked PVA membranes
（PVA Mw=30,000~70,000）...................................69
Fig. 4-6. The thermogravimetric curves of various PVA/poly（DMAEMA）
membranes（PVA Mw=30,000~70,000）.........................70
Fig. 4-7. The thermogravimetric curves of various PVA/poly（DMAEMA）
membranes（PVA Mw=70,000~100,000）........................71
Fig.4-8. The thermogravimetric curves of various PVA membranes......72
Fig. 4-9. The derivative thermogravimetric curves of various PVA/poly
（DMAEMA）membranes（PVA Mw=30,000~70,000）..................73
Fig. 4-10. The derivative thermogravimetric curves of various PVA/poly
（DMAEMA）membranes（PVA Mw=70,000~100,000）.................74
Fig. 4-11. The derivative thermogravimetric curves of various PVA
membranes.................................................75
Fig. 4-12. The DSC curves of various PVA/poly（DMAEMA）membranes
（PVA Mw=30,000~70,000）...................................76
Fig. 4-13. The DSC curves of various PVA/poly（DMAEMA）membranes
（PVA Mw=70,000~100,000）..................................77
Fig. 4-14. The DSC curves of various PVA membranes..................78
Fig. 4-15. The stress-strain curves of various PVA/poly（DMAEMA）
membranes（PVA Mw=30,000~70,000）.........................79
Fig. 4-16. The stress-strain curves of various PVA/poly（DMAEMA）
membranes（PVA Mw=70,000~100,000）........................80
Fig. 4-17. The stress-strain curves of various crosslinked PVA/poly
（DMAEMA）membranes, crosslinking ratio=0.003
（PVA Mw=30,000~70,000）.....................................81
Fig. 4-18. The stress-strain curves of various crosslinked PVA/poly
（DMAEMA）membranes, crosslinking ratio=0.012
（PVA Mw=30,000~70,000）.....................................82
Fig. 4-19. The stress-strain curves of various PVA membranes........83
Fig. 4-20. Permeation of creatinine through various membranes ......84
Fig. 4-21. Permeation of 5-Fu through various membranes.............85
Fig. 4-22. Permeation of uric acid through various membranes........86

表 目 錄

Table 2-1 Solvents and non-solvents for PVA.........................20
Table 3-1 The solubility of PVA and poly（DMAEMA）..................87
Table 3-2 Regression result of various solutes......................88
Table 4-1 The elements analysis of various membranes................89
Table 4-2 The contact angle of various PVA/poly（DMAEMA）membranes..90
Table 4-3 The water content of various membranes....................91
Table 4-4 The degradation temperature of variousPVA/poly（DMAEMA）
membranes................................................92
Table 4-5 The Tg and Tm of various PVA/poly（DMAEMA）membranes......93
Table 4-6 The tensile strength and elongation of various
PVA/poly（DMAEMA）membranes..............................94
Table 4-7 Regression result of -（V/2A）ln〔1-2Ct/C0〕versus time
（min）of various PVA/poly（DMAEMA）membranes...............95

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