本研究是將幾丁聚醣溶於甲酸溶劑中，再加到N,N-二甲基甲醯胺與鄰苯二甲酸酐的溶液系統中，進行均相的化學反應修飾，利用鄰苯二甲酸酐與幾丁聚醣的胺基反應，藉此保護胺基及改善其有機溶劑溶解性。分別利用元素分析與紫外線可見光光譜分析求出鄰苯二甲酸酐之取代度，在相同反應的條件下，兩種不同方法求出來的結果彼此吻合。利用紅外線光譜及固態核磁共振光譜針對產物作結構分析，結果顯示在高溫反應下，幾丁聚醣確實與鄰苯二甲酸酐有化學反應，且隨著反應時間的增加而有取代度增加的趨勢。反應後之產物可溶於如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺和二甲亞碸有機溶劑。再利用幾丁聚醣上的氫氧基與二環氧基醚聚乙二醇進行接枝反應，並加入陽離子型光起始劑，以UV光交聯得到幾丁聚醣二環氧基醚聚乙二醇接枝的產物，利用元素分析求出取代度。之後再利用聯胺去保護還原幾丁聚醣的胺基，並針對產物作結構分析、熱分析以及澎潤比等測試，藉以評估聚乙二醇接枝幾丁聚醣材料的性質和其它方面的應用性。

In this study, chitosan was dissolved in formic acid and modified with phthalic anhydride in N,N-dimethylformamide (DMF), through the reaction of amino group with anhydride group. In this way, chitosan can be dissolved in organic solvent. The results show that the degree of substitution increased with reaction time. In addition, the modified chitosan could be dissolved in several organic solvents, such as DMF、DMAc and DMSO. After reaction, the available hydroxyl group in the chitosan was used to graft synthetic polymers onto chitosan chains with poly(ethylene glycol) diglycidyl ether. Photoinitiator (UVI-6992) was added to prepare PEG-graft-PACS copolymers by UV radiation. Then hydrazine monohydrate was employed to deprotect the phthaloyl group. FTIR and NMR were used to analyze the chemical structures of copolymers. DSC and TGA were employed to measure the thermal properties of the prepared copolymers. Swelling ratio was measured to understand the swelling behaviors at different pH values in order to evaluate potential applications of PEG-graft-CS copolymers .

目    錄
中文摘要	I
ABSTRACT:	II
目    錄	III
圖  目  錄	VII
表  目  錄	X
第ㄧ章 序論	1
1.1前言	1
1.2研究動機	3
1.3研究目標	3
第二章 文獻回顧	5
2.1幾丁質與幾丁聚醣	5
2.1.1來源	5
2.1.2結構	6
2.1.3排列方向	8
2.1.4幾丁質與幾丁聚醣的製備	11
2.2幾丁聚醣基本性質測定	14
2.2.1分子量的測定	14
2.2.2去乙醯度的測定	16
2.3幾丁聚醣的化學改質	20
2.3.1磺化反應	20
2.3.2接枝聚合作用	21
2.3.3幾丁聚醣與甲基丙烯酸環氧丙酯反應	22
2.3.4羧甲基化反應	23
2.4智慧型高分子水膠概述	25
2.4.1溫度敏感型高分子	25
2.4.2酸鹼敏感型高分子	27
2.4.3離子強度敏感型高分子	28
第三章 研究目的與方法	29
3.1幾丁聚醣與鄰苯二甲酸酐反應	29
3.2幾丁聚醣與二環氧基醚聚乙二醇(PEGDGE)反應	30
3.3幾丁聚醣與聚氮-異丙基丙烯醯胺反應	30
第四章 實驗	33
4.1實驗藥品	33
4.2實驗儀器	38
4.3實驗步驟	40
4.3.1幾丁聚醣與鄰苯二甲酸酐的反應	40
4.3.2苯酸酐修飾幾丁聚醣與二環氧基醚聚乙二醇反應	40
4.3.3去保護反應	43
4.4結構鑑定	44
4.4.1傅氏紅外線吸收光譜儀(FTIR)	46
4.4.2固態13C-NMR光譜	47
4.4.3 X-ray繞射光譜分析儀(XRD)	47
4.5鄰苯二甲酸酐取代度的測定	47
4.5.1元素分析	47
4.5.2產率(%)	48
4.5.3 紫外光/可見光光譜測定	48
4.6二環氧基醚聚乙二醇取代度的測定	49
4.6.1元素分析	49
4.7熱性質分析	49
4.7.1熱重分析(Thermal Gravimetric Analysis, TGA)	49
4.7.2微差掃描熱分析儀(Differential Scanning Calorimeter，DSC)	50
第五章 結果與討論	51
5.1幾丁聚醣與鄰苯二甲酸酐的反應	51
5.1.1樣品之紅外線吸收光譜儀(FTIR)分析	51
5.1.2樣品之固態13C-NMR光譜分析	57
5.1.3 X-ray繞射光譜分析儀(XRD)	61
5.2取代度(DS)的測定	63
5.2.1元素分析	63
5.2.2產率(%)	65
5.2.3紫外光/可見光光譜吸收	66
5.3二環氧基醚聚乙二醇改質幾丁聚醣之合成及其性質	72
5.3.1二環氧基醚聚乙二醇改質幾丁聚醣之合成	72
5.3.2以元素分析法測定二環氧基醚聚乙二醇之取代度	75
5.4性質分析	75
5.4.1熱重分析(TGA)	75
5.4.2微差掃描熱分析(DSC)	80
第六章 結論	84
第七章 建議事項	86
第八章 參考文獻	88




圖  目  錄

圖2-1 纖維素、幾丁質、幾丁聚醣之化學結構	7
圖2-2 α型幾丁質的排列	9
圖2-3 β型幾丁質的排列	10
圖2-4 幾丁質、幾丁聚醣之製程	13
圖2-5 羧甲基幾丁聚醣的製備	24
圖2-6 (a)PNIPAAm結構(b)利用溫度敏感特性貼附及脫附細胞	26
圖4-1 環氧樹脂之光起始反應及交聯反應機制	42
圖4-2 PACS的反應結構式	44
圖4-3 PEG-g-PACS的反應結構式	45
圖4-4 去保護後之PEG-g-CS結構式	46
圖5-1 純幾丁聚醣(a)及高溫酸解後的純幾丁聚醣(b)之FTIR吸收光譜圖	52
圖5-2 鄰苯酸酐修飾幾丁聚醣樣品PACS1及PACS2之FTIR吸收光譜圖	53
圖5-3 鄰苯酸酐修飾幾丁聚醣樣品PACS3及PACS4之FTIR吸收光譜圖	53
圖5-4 鄰苯酸酐修飾幾丁聚醣樣品PACS5之FTIR吸收光譜圖	54
圖5-5 純幾丁聚醣13C-NMR光譜圖	57
圖5-6 樣品PACS1 13C-NMR光譜圖	58
圖5-7 樣品PACS2 13C-NMR光譜圖	58
圖5-8 樣品PACS3 13C-NMR光譜圖	59
圖5-9 樣品PACS4 13C-NMR光譜圖	59
圖5-10 樣品PACS5 13C-NMR光譜圖	60
圖5-11 純幾丁聚醣與不同反應時間之XRD圖	62
圖5-12 不同濃度鄰苯甲醯胺酸之UV光譜圖	67
圖5-13 不同濃度鄰苯二甲醯甲胺之UV光譜圖	67
圖5-14 鄰苯甲醯胺酸在吸收峰275nm的檢量線(λmax=275nm)	68
圖5-15 鄰苯甲醯胺酸在吸收峰291nm的檢量線(λmax=291nm)	68
圖5-16 鄰苯二甲醯甲胺在吸收峰275nm的檢量線(λmax=275nm)	69
圖5-17 鄰苯二甲醯甲胺在吸收峰291nm的檢量線(λmax=291nm)	69
圖5-18 鄰苯二甲酸酐修飾幾丁聚醣樣品(PACS5)之UV光譜圖	70
圖5-19 苯酸酐修飾幾丁聚醣之反應時間與取代度作圖	71
圖5-20 PEG、PACS、PEG-g-PACS和PEG-g-CS之FTIR光譜圖	74
圖5-21 純幾丁聚醣、低分子量幾丁聚醣與鄰苯二甲酸酐修飾幾丁聚醣樣品PACS1~PACS5的熱重分析圖	77


圖5-22 純幾丁聚醣、低分子量幾丁聚醣與鄰苯二甲酸酐修飾幾丁聚醣樣品PACS1~PACS5的DTG圖	77
圖5-23 純幾丁聚醣、苯酸酐修飾幾丁聚醣與聚乙二醇接枝幾丁聚醣樣品(PEG-g-CS)的熱重分析圖	79
圖5-24 純幾丁聚醣、苯酸酐修飾幾丁聚醣與聚乙二醇接枝幾丁聚醣樣品(PEG-g-CS)的DTG圖	79
圖5-25 純幾丁聚醣、低分子量幾丁聚醣與苯酸酐修飾幾丁聚醣PACS1、PACS3和PACS5樣品於DSC中的第一次升溫曲線圖	81
圖5-26 純幾丁聚醣、低分子量幾丁聚醣與苯酸酐修飾幾丁聚醣PACS1、PACS3和PACS5樣品於DSC中的第二次升溫曲線圖	81
圖5-27 純幾丁聚醣、苯酸酐修飾幾丁聚醣與聚乙二醇接枝幾丁聚醣(PEG-g-CS)樣品於DSC中的第一次升溫曲線圖	82
圖5-28 純幾丁聚醣、苯酸酐修飾幾丁聚醣與聚乙二醇接枝幾丁聚醣(PEG-g-CS)樣品於DSC中的第二次升溫曲線圖	83
圖A-1 GMA接枝PACS之FTIR吸收光譜圖	98
圖B-1 GMAPC與NIPAAm經紫外線硬化後之FTIR吸收光譜圖	100


表  目  錄
表2-1 常見的黏度常數K與a值	15
表 2-2 文獻上曾使用過的吸收比以測量幾丁聚醣的去乙醯	19
表2-3 常見的溫度敏感聚合物及其LCST	27
表4-1 幾丁聚醣與鄰苯二甲酸酐於不同反應時間之反應條件	40
表4-2 PEG-g-PACS反應條件	43
表5-1 產物在不同溶劑中的溶解性測試	51
表5-2 FTIR吸收峰之位置表	56
表5-3 純幾丁聚醣和鄰苯二甲酸酐修飾幾丁聚醣上碳的化學位移	60
表5-4 鄰苯二甲酸酐修飾幾丁聚醣樣品PACS1~PACS5苯環(Phth)及羧基(C=O)與幾丁聚醣乙醯胺基上甲基的積分比值	61
表5-5 各結晶峰之吸收角度	63
表5-6 不同反應時間所測得的C、N含量百分比及取代度	63
表5-7 不同反應時間的產率(%)	65
表5-8 樣品之UV吸光度值	70
表5-9 在胺基上的鄰苯甲醯胺酸與鄰苯二甲醯甲胺的取代度	70
表5-10 PEG-g-CS的C、N含量百分比及取代度	75
表5-11 純幾丁聚醣(CS)、低分子量幾丁聚醣(CSO)及苯酸酐修飾幾丁聚醣(PACS1~PACS5)的最大速率裂解溫度值(Tmax)	76
表5-12 純幾丁聚醣(CS)、苯酸酐修飾幾丁聚醣(PACS5)及PEG-g-CS的最大速率裂解溫度值(Tmax)	78
表A-1 元素分析所得到的取代度(DS)與產率(Yield,%)	98
表B-1 PNIPAAm-PC樣品的單體轉化率(X,%)、接枝效率(GE,%)及接枝比值(GR)	101

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