本實驗採用具生物分解性的天然高分子聚羥基丁酯(Polyhydroxybutyrate，PHB)，添加聚乙二醇(Poly(ethylene oxide)，PEO)製成薄膜後，以DSC探討兩高分子之間相容性。再將帶有抗菌功能的幾丁聚醣(Chitosan，CS)，溶於內含丙烯酸(Acrylic acid，AA)、聚乙二醇雙丙烯酸酯(Poly(ethylene glycol)diacrylate，PEGDA)及光起始劑(HMPP)水溶液，塗布於PHB/PEO薄膜，經PEO滲進薄膜內，再由UV光硬化，製成帶有CS的PHB薄膜。以大腸桿菌及金黃葡萄球菌測試其抗菌功能，發現對於大腸桿菌沒有顯著的抗菌活性，但在CS含量達0.83%時，對於金黃葡萄球菌有15.89 %的抑菌性。以76T-3分解的測試中，發現大多數的薄膜皆有良好的分解性，唯獨PHB/PEO比例為85/15，經塗布且光硬化的薄膜，沒有分解的跡象，是因為其表面的化學結構及型態所致。

In this study, the biodegradable polymer Poly(hydroxybutyrate) (PHB) was blended with Poly(ethylene oxide) (PEO) to preparation composite films. Measurement with Differential scanning calorimetry (DSC) to investigate the compatibility of PHB and PEO. Chitosan (CS) solution include Acrylic acid (AA), Poly(ethylene glycol) diacrylate (PEGDA) and photoinitiator (HMPP), coating on PHB/PEO films, and then curing with UV light. The antibacterial activity was tested with E.coli and S.aureus. It’s not distinguished antibacterial activity to E. coli, but the antibacterial activity of S. aureus is 15.89% when CS content is 0.83%. The most films was degraded by 76T-3. But the film B85CS was undegraded by 76T-3, due to the difference structure and morphology of the films surface.

中文摘要：	I
目錄	III
圖目錄	VI
表目錄	IX
 第一章 緒論	1
1.1 前言	1
1.2 研究目的與動機	1
 第二章 文獻回顧	2
2.1 生物可分解高分子	2
2.1.1 依製造程序分類	2
2.1.2 依官能基分類	4
2.2 聚羥基丁酯(Poly(3-hydroxybutyrate)，PHB)	6
2.2.1 聚羥基丁酯的歷史	7
2.2.2 聚羥基丁酯的生化合成過程	7
2.2.3 聚羥基丁酯的性質	9
2.2.4 聚羥基丁酯與其摻合物的研究	10
2.3 幾丁聚醣	11
2.3.1 幾丁聚醣的抗菌機制	12
2.3.2 幾丁聚醣的應用	14
2.4 高分子摻合	16
2.4.1 摻合方法	16
2.4.2 摻合物之相容性	18
2.5 紫外光硬化塗膜之原理	21
2.5.1 光聚合反應之原理	21
2.5.2 光的特性及光架橋反應	23
2.5.3 紫外光硬化塗膜的組成及優點	25
 第三章 實驗方法	26
3.1 實驗藥品	26
3.2 實驗儀器	30
3.3 實驗步驟	33
3.3.1 製備PHB/PEO摻合薄膜及性質分析	33
3.3.1.1 PHB純化步驟	33
3.3.1.2 製備PHB/PEO摻合薄膜	34
3.3.1.3 熱重損失測試 (TGA)	35
3.3.1.4 熱轉移溫度及相容性測試 (DSC)	35
3.3.1.5 薄膜形態觀察 (SEM)	35
3.3.2 幾丁聚醣結構鑑定	36
3.3.2.1 幾丁聚醣去乙醯度檢測	36
3.3.3 製備光硬化材料塗佈於PHB/PEO薄膜及性質分析	37
3.3.3.1 製備光硬化材料塗佈於PHB/PEO薄膜	37
3.3.3.2 化學結構鑑定 (FTIR-ATR)	38
3.3.3.3 薄膜形態觀察 (SEM)	38
3.3.3.4 抗菌測試	38
3.3.3.4.1 培養基製備	38
3.3.3.4.2 大腸桿菌及金黃色葡萄球菌之抗菌測試	38
3.3.3.5 分解測試	40
3.3.3.5.1 培養基製備	40
3.3.3.5.2 76T-3分解測試	42
 第四章 結果與討論	43
4.1 PHB/PEO薄膜性質與分析	43
4.1.1 PHB/PEO薄膜熱重損失分析(TGA)	43
4.1.2 PHB/PEO薄膜熱轉移溫度及相容性的研究(DSC)	46
4.1.3 薄膜型態觀察(SEM)	50
4.2 幾丁聚醣結構鑑定	57
4.3 光硬化材料塗布PHB/PEO薄膜性質與分析	58
4.3.1 光硬化薄膜重量的改變	58
4.3.2 薄膜化學結構的鑑定(FTIR-ATR)	60
4.3.3 薄膜型態觀察(SEM)	63
4.3.4 薄膜抗菌分析	69
4.3.5 分解測試	72
 第五章 結論	76
 第六章 參考文獻	77


圖目錄
圖2 1 聚乙烯醇(PVA)的分解機制[2]	4
圖2 2 生物可分解高分子的分解機制[3]	5
圖2 3聚羥基烷酯(PHAs)的結構式(R為取代基團)	6
圖2 4 聚羥基烷酯(PHB)的結構式	6
圖2 5 微生物生化合成PHB及酵素解聚合的過程[5]	8
圖2 6(a)幾丁質(Chitin) (b)幾丁聚醣(Chitosan) 的結構式	11
圖2 7 幾丁聚醣寡聚物對B. cereus及E. coli的抗菌反應機制模擬[29]	13
圖2 8 互穿網狀高分子的示意圖	18
圖2 9 DSC熱分析Tg與摻合物成分間相容性關係圖	20
圖2 10 光化學反應概念圖[37]	21
圖2 11 雙原子分子的位能曲線與電子遷移	22
圖2 12 光的波長及能量範圍	23
圖2 13 光架橋反應示意圖[38]	24
圖3 1 製備PHB/PEO薄膜流程圖	34
圖3 2製備光硬化材料塗佈於PHB/PEO薄膜流程圖	37
圖3 3 四區劃線塗盤示意圖	39
圖4 1 不同比例PHB/PEO薄膜熱重損失圖	44
圖4 2 不同比例PHB/PEO薄膜溫度對重量熱微分圖	45
圖4 3 不同比例PHB/PEO摻合膜的DSC一次升溫圖	47
圖4 4 不同比例PHB/PEO摻合膜的DSC二次升溫圖	48
圖4 5不同比例PHB/PEO摻合膜的DSC二次升溫局部放大圖	48
圖4 6 實驗Tg與Fox eq.Tg比較圖	49
圖4 7 PHB薄膜不同倍率上下表面型態	52
圖4 8 PHB薄膜不同倍率截面型態	52
圖4 9 PHB/PEO(95/5)薄膜不同倍率上下表面型態	53
圖4 10 PHB/PEO(95/5)薄膜不同倍率截面型態	53
圖4 11 PHB/PEO(90/10)薄膜不同倍率上下表面型態	54
圖4 12 PHB/PEO(90/10)薄膜不同倍率截面型態	54
圖4 13 PHB/PEO(85/15)薄膜不同倍率上下表面型態	55
圖4 14 PHB/PEO(85/15)薄膜不同倍率截面型態	55
圖4 15 PHB/PEO(80/20)薄膜不同倍率上下表面型態	56
圖4 16 PHB/PEO(80/20)薄膜不同倍率截面型態	56
圖4 17 幾丁聚醣之1H-NMR光譜圖	57
圖4 18 不同PHB/PEO薄膜塗布光硬化材料經光硬化後重量增加比例	59
圖4 19 不同PHB/PEO薄膜塗布光硬化材料經光硬化後CS含量	59
圖4 20 AA/PEGDA/CS經光硬化後FTIR-ATR	61
圖4 21 PHB及不同PHB/PEO/CS薄膜經光硬化後上表面FTIR-ATR圖	61
圖4 22 PHB及不同PHB/PEO/CS薄膜經光硬化後下表面FTIR-ATR圖	62
圖4 23 B100CS不同倍率上下表面型態	64
圖4 24 B100CS薄膜不同倍率截面型態	64
圖4 25 B95CS不同倍率上下表面型態	65
圖4 26 B95CS薄膜不同倍率截面型態	65
圖4 27 B90CS薄膜不同倍率上下表面型態	66
圖4 28 B90CS薄膜不同倍率截面型態	66
圖4 29 B85CS薄膜不同倍率上下表面型態	67
圖4 30 B85CS薄膜不同倍率截面型態	67
圖4 31 B80CS薄膜不同倍率上下表面型態	68
圖4 32 B80CS薄膜不同倍率截面型態	68
圖4 33 不同樣品實驗後大腸桿菌活性	70
圖4 34 不同樣品實驗後金黃色葡萄球菌活性	71
圖4 35 以76T-3分解PHB薄膜在不同時間之重量變化	73
圖4 36 以76T-3分解B100CS薄膜在不同時間之重量變化	73
圖4 37 以76T-3分解B95CS薄膜在不同時間之重量變化	74
圖4 38 以76T-3分解B90CS薄膜在不同時間之重量變化	74
圖4 39 以76T-3分解B85CS薄膜在不同時間之重量變化	75
圖4 40 以76T-3分解B80CS薄膜在不同時間之重量變化	75
表目錄
表2 1 聚羥基烷酯類的取代基團與其命名	6
表2 2 PHB與聚丙烯於25oC下的物理性質與機械性質之比較[6]	9
表2 3 熔融摻合、溶液摻合、乳膠摻合及互穿型摻合之優缺點比較	18
表3 1 PHB/PEO配方	34
表3 2 光硬化材料塗佈於PHB/PEO薄膜配方	37
表3 3 PHB/PEO薄膜經光硬化後命名	37
表3 4 固體培養基配方	40
表3 5 液體培養基配方	40
表3 6 BMES配方	41
表3 7 Phosphate buffer配方	41
表3 8 基礎培養基配方	41
表4 1 不同比例PHB/PEO薄膜的起始熱裂解溫度(Tonset)、最大裂解速率溫度(Tmax)以及700oC時炭渣比率(Char Yield)	45
表4 2 不同比例PHB/PEO摻合膜在DSC一次升溫圖的熔點數據	47
表4 3 不同比例PHB/PEO的DSC二次升溫圖的玻璃轉移溫度及熔點數據	49
表4 4 不同PHB/PEO薄膜光硬化後重量增加比例及CS含量	58
表4 5 不同樣品CS含量對於大腸桿菌抗菌活性	70
表4 6 不同樣品CS含量對於金黃色葡萄球抗菌活性	71

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