EVOH為乙烯與乙烯醇的共聚物，是一種半結晶的高分子，其相當好的阻氣、阻有機溶劑等性質使其大量被運用在食品包裝跟其他包裝用途上。隨著其共聚單體組成的不同，EVOH基本性質像熱性質跟機械性質會有所不同，使得EVOH產品有著不同乙烯變性度的規格。此外，因為其乙烯醇單體上-OH基的關係，使得其可與高極性的材料形成氫鍵，而有相當好的相容性，故可藉由摻混的方式將EVOH進行改質，來達到應用所需求的性質。
本論文探討不同的乙烯變性度的EVOH產品之基礎結構與物性，作為該高分子結構與性質相關性建立之基礎。我們以微分掃描熱卡計(DSC)來分析其熱性質與結晶行為，並應用核磁共振光譜(NMR)詳細解析EVOH之化學微結構，利用小角度X光散射解析其晶板微結構。
另外，我們藉由摻混小分子甘油及低分子量的聚合物來改質EVOH深入探討摻混組成對於相容性及結晶動力學的影響。

EVOH is a copolymer of ethylene and vinyl alcohol. It is a semicrystalline polymer with superior barrier properties for gases and organic solvents. EVOH has found wide application in packaging of foods and chemicals. The mechanical and physiochemical properties of EVOH are governed by its comonomer composition. There are different types of commercial products of EVOH according to the content of ethylene comonomer. The abundance of hydroxyl group of EVOH renders the polymer the capability of hydrogen bond formation with other materials for good miscibility. Consequently, physical blending may serve as an attractive approach for improving the properties of EVOH for broadening its application window.
This thesis is dedicated to elucidating the structure of EVOHs, with the focus on understanding the key e comonomer composition. We have established the protocol for characterizing the chemical structure and composition of EVOH. Moreover, the glass transition behavior, crystallization behavior, crystal polymorphism and lamellar morphology have been studied by the combination of thermal analysis and X-ray scattering techniques. The effects of the comonomer composition and crystallization history have been resolved.
We proceed one step further to study the blends of EVOH with glycerol and low molecular weight poly(ethylene glycol) (PEG) with the objective of lowering the Tg¬ of EVOH by diluent effect. It was found that both glycerol and PEG were miscible with EVOH in the melt state due to hydrogen bonding interaction. The crystallization kinetics of EVOH could be enhanced by adding a small amount of the diluents due to enhancement of chain mobility. Upon the crystallization of EVOH, the diluent molecules were mainly segregated into the interlamellar region, causing a swelling of the long period of the lamellar stacks.

目錄
第一章EVOH介紹及文獻回顧 10
1.1 EVOH(ethylene-vinyl alcohol)簡介 10
1.2 EVOH混摻Polyamide間物理及化學交互作用力3 12
1.3 Poly(N-vinyl Pyrrolidone)混摻氫鍵塑化劑對玻璃轉化溫度的影響 15
1.4 Random copolymer的結晶型態 17
1.5 300-MHz 1H NMR分析Vinyl Alcohol-Vinyl Acetate Copolymers之組成21, 22 20
1.6 EVOH的不同結晶結構 23
1.7 濕度對EVOH性質的影響17, 28 27
1.8 研究動機 29
第二章 實驗部分 31
2-1 EVOH的基本性質測定 31
2-2 EVOH與甘油及PEG之摻合體的製備 33
2-2-1 溶液摻混法 33
2-2-2 熔融摻混法 35
2-2-3 摻混體的分析 35
2-3 EVOH熔融態後的不同溫度下的等溫結晶 36
第三章 結果與討論 37
3-1 以1H-NMR光譜儀分析EVOH和EVA 37
3-2 13C-NMR來測定EVOH和EVA的的單體序列嵌段性 42
3-3 EVOH的結晶性質分析 48
3-3-1 EVOH的相轉化溫度 48
3-3-2 EVOH之結晶結構變化 52
3-4 EVOH在不同溫度之等溫結晶下基本性質的探討 56
3-4-1 結晶溫度對晶格結構的影響 56
3-4-2 EVOH晶層形態學 60
3-4 EVOH/甘油摻合體之研究 64
3-5 EVOH/PEG摻合體研究 67
3-6 用熔融混摻EVOH與甘油 71
第四章 結論 75
參考文獻References 77

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