臺灣博碩士論文加值系統

本篇論文主要在研究末端具有硫醇官能基的聚苯乙烯高分子(ｐ
ｓ－ｓｈ)與原位合成大小不同的金奈米顆粒所構築成的高分子複合
材料。本研究的方法是利用環硫乙烷(Ethlyene sulfide)將聚苯乙烯
(PS)末端官能化後，使其成為末端帶有硫醇基(thiol)的官能化高分
子。然後再將金離子(Au+)在含有官能化高分子的均相有機溶液中以
還原劑Super Hydride還原成金原子。在金原子還原堆積過程中，高
分子末端的硫醇基會行化學反應鍵結上金顆粒的表面，成為外層包覆
著高分子之金奈米顆粒複合材料。透過加入的官能化高分子之莫耳數
以及高分子分子量的改變，我們可以控制金奈米顆粒的大小在3~30
奈米之範圍並且均勻分佈在高分子材料之中沒有聚集的現象。此外，
結合1H-NMR、13C-NMR、TEM、XPS、TGA、DSC、UV-VIS各種儀器來做產
物物性方面的探討。

The aim of this work is to prepare the polystyrene with thiol
terminal group (PS-SH) and use this functionalized polystyrene
to stabilize and control the size of gold nanoparticles. The
PS-SH was first synthesized via an anionic polymerization. Then,
PS-SH was mixed with HAuCl4·3H2O in THF solvent in the presence
of a reducing agent, super hydride. Upon the reduction of Au+
to Au atoms, the thiol groups of the polymer molecules were
bonded onto the gold surface and a polymeric nanocomposite with
well-distribute nanogold particles material was thus formed.
Depending on the molar ratio of thiol to Au+ and the
molecular weight of the polymer, the particle size was
controlled within a range of 3~30nm with little aggregation.
1H-NMR、13C-NMR、TEM、XPS、TGA、DSC and UV-VIS were used to
investigate the physical properties of the nanocomposite.

圖目錄⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯V
表目錄⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯VIII
Abstract⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯X
中文摘要⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯XI
第一章 緒論⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯1
1.1 研究動機與目的⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯1
1.2 文獻回顧⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯4
1.2-1 PS-SH(polystyrene with thiol terminated)
之聚合⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯4
1.2-2 (高分子/奈米金)奈米複合材料⋯⋯⋯⋯⋯⋯⋯⋯⋯5
第二章 原理介紹⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯9
2.1 陰離子聚合反應原理⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯9
2.1-1 起始劑種類與起始反應⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯10
2.1-2 成長反應⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯18
2.1-3 鏈轉移反應⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯19
2.1-4 無終止反應與其特色⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯21
2.2 高分子硫醇官能基與金的自組裝薄膜⋯⋯⋯⋯⋯⋯⋯22
I
第三章 實驗部分以及儀器分析⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯27
3.1 實驗藥品⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯27
3.2 聚合反應設備與分析儀器⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯30
3.3 實驗步驟⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯32
3.3-1 陰離子聚合Living Polystyrene⋯⋯⋯⋯⋯⋯⋯⋯32
3.3-2 Living polystyrene 之末端官能化(硫醇化)⋯⋯⋯33
3.3-3 以官能化高分子PS-SH 與金離子溶液形成外層包覆高
分子之金奈米顆粒⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯34
3.4 儀器分析⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯36
3.4-1 凝膠滲透層析儀
(Gel Permeation Chromatography, GPC)⋯⋯⋯⋯36
3.4-2 調幅式微差掃描熱分析儀(Modulated Differential
Scanning Calorimetry,MDSC)⋯⋯⋯⋯⋯⋯⋯⋯38
3.4-3 熱重分析儀(Thermogravimetric Analyzer,TGA)⋯44
3.4-4 核磁共振儀(Nuclear Magnetic Resonance
Spectrometer,NMR)⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯44
3.4-5 紫外光-可見外吸收光譜儀(UV/Vis spectroscopy,
UV/Vis)⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯45
3.4-6 穿透式電子顯微鏡(Transmission Electron
II
Microscope,TEM)⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯47
3.4-7 能量散佈分析儀(Energy Dispersive X-ray
Spectrometer,EDS)⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯48
3.4-8 X 光光電子能譜儀(X-ray Photoelectron
Spectrometer,XPS)⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯50
第四章 結果與討論⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯53
4.0 定量校正⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯54
4.1 聚苯乙烯的官能化⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯55
4.1-1 溫度環境對官能化程度的影響⋯⋯⋯⋯⋯⋯⋯⋯57
4.1-2 1H-NMR氫譜分析⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯60
4.1-3 13C-NMR碳譜分析⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯66
4.2 官能化高分子PS-SH 與金離子溶液形成外層包覆高分子之
金奈米顆粒⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯69
4.2-1 加入不同重量但同樣分子量的高分子對PS-SH 所包
覆之金顆粒大小之影響⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯70
4.2-2 加入不同分子量但同樣重量的高分子對PS-SH 所包
覆之金顆粒大小之影響⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯74
4.3 使用XPS(X-ray photoelectron spectroscopy)來測定高
分子PS-SH 與金(Au)的鍵結⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯80
III
4.4 TGA 熱性質分析PS-SH 官能化高分子與(高分子/金奈米顆
粒)⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯84
4.5 DSC(微差掃瞄熱卡計)熱性質分析⋯⋯⋯⋯⋯⋯⋯⋯⋯89
4.6 以UV-Vis 紫外光-可見光吸收光譜儀測定金奈米顆粒大小
分佈⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯91
第五章 總結與後續研究⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯95
參考文獻⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯⋯97
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