摘要
本研究探討直接使用元素硫(S8)與高分子反應的可能性，透過硫自由基對高分子的氫進行取代反應，期望以此合成含硫的高分子材料。
本實驗以PPO、PVB、PS、PVDF以及PMMA做為與元素硫反應的高分子，以60wt %的元素硫以及40wt %的高分子做為反應物，溶於Diglyme後在180°C下反應一天，透過離心的方式移除未反應的元素硫後，將反應溶液中的高分子沉澱後，得到硫化的高分子產物。
經過純化後的硫化高分子，透過拉曼光譜觀察到S-S振動的特徵峰，透過DSC和TGA結合元素分析的結果，也證明硫化高分子內確實含有硫元素，並且不含元素硫。久置高元素硫含量的樣品S-PPO後，在熱分析結果以及XRD繞射光譜，觀察到屬於元素硫α-sulfur的特徵峰出現，間接證明硫元素以線性高分子的形式存在於硫化高分子中，而線性硫高分子隨時間逐漸降解為元素硫。
本研究證實元素硫可直接與高分子反應，透過硫自由基攻擊並取代氫原子的機制，可以得到含硫的高分子材料，建立全新含硫材料的合成方法。

Abstract
This study explores the possibility of directly using elemental sulfur as feedstock to react with polymers. It is desirable to synthesize sulfur-derived polymer materials by substituting sulfur for the proton of polymer chain.
60wt% of elemental sulfur and 40wt% of the polymer, PPO, PS, PVB, PVDF and PMMA, were used as reactants. After dissolved in Diglyme, the reaction was carried out at 180°C for a day. The sulfur-derived polymers were obtained by precipitated in methanol or water.
The appearance of sulfur-sulfur bond can be observed on the raman spectrum. The thermal analysis results of Differential scanning calorimetry (DSC) and Thermogravimetric analysis (TGA) prove no elemental sulfur remains in the sulfur-derived polymers, and elemental analysis (EA) results indicate the existence of sulfur element. Moreover, the formation of α-sulfur was observed in S-PPO case, which is storaged in room temperature for a long time. The appearance of α-sulfur supports the existence of linear polymeric sulfur, which will degrade into α-sulfur with time.
This study confirmed that a sulfur-derived polymer material can be obtained by directly reacting elemental sulfur with a polymer through sulfur radical attacking and replacing proton of polymer, and a new synthesis method of a sulfur-derived material is established.

目錄
摘要 I
Abstract II
圖目錄 V
表目錄 VIII
第一章 緒論 1
1-1 前言 1
1-2 元素硫於物理製程的應用簡介 3
1-2.1 熔融擴散法 3
1-2.2 氣相及溶液分散法 6
1-3 元素硫於化學製程的應用簡介 10
1-3.1 陰離子聚合反應 10
1-3.2 自由基反應 12
1-3.3 其他利用元素硫的化學反應 17
1-4 逆硫化反應 19
1-5 研究目的 22
第二章 文獻回顧 24
2-1 硫化與逆硫化反應 24
2-2 具自由基轉移活性高分子 31
2-3 研究方法 34
第三章 實驗方法 36
3-1 實驗藥品及溶劑 36
3-2 分析儀器 40
3-3 實驗步驟 44
3-3.1 S-PPO合成及純化 44
3-3.2 S-PVB合成及純化 46
3-3.3 S-PS合成及純化 48
3-3.4 S-PVDF合成及純化 51
3-3.5 S-PMMA合成 53
第四章 結果與討論 55
4-1 S-PPO結構與性質鑑定 63
4-2 S-PVB結構與性質鑑定 76
4-3 S-PS結構與性質鑑定 88
4-4 S-PVDF結構與性質鑑定 96
4-5 S-PMMA結構與性質鑑定 103
第五章 結論 112
參考文獻 113

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