利用原子轉移自由基聚合方式製備刷狀結構的二氧化矽次微米球之研究

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研究生：	蕭智遠 Chih-yuan Hsiao
論文名稱：	利用原子轉移自由基聚合方式製備刷狀結構的二氧化矽次微米球之研究 The Study on Preparation of Brush Submicrospheres byAtom Transfer Radical Polymerization (ATRP)
指導教授：	陳暉 Hui Chen
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程與材料工程學系 Department of Chemical & Materials Engineering
畢業學年度：	98
語文別：	中文
論文頁數：	70
中文關鍵詞：	光子晶體、表面改質、原子轉移自由基聚合、Stöber 、均ㄧ粒徑次微米球
外文關鍵詞：	Stöber, Self-assembly, Monodispersed submicrospheres, ATRP, Surface modification, Photonic crystals
相關次數：	點閱：14 下載：0
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本論文探討利用原子轉移自由基聚合(ATRP)製備高分子刷狀結構之SiO2次微米球，並且探討不同尺寸大小之均一粒徑SiO2次微米球的製備，以及其光子晶體之排列。
首先利用Stöber所提方法，以四乙氧基矽烷(TEOS)作為單體，可成功合成出158 nm ~ 700 nm之均一粒徑的SiO2次微米球，其Cv值皆小於4%，並將此次微米球經由自組裝排列形成光子晶體，其光子能隙(PBG)可涵蓋整個可見光波段及近紅外光範圍，並呈現出不同的結構性色彩。
由於ATRP是利用粒子表面的鹵素基去進行高分子刷狀結構的聚合反應，因此選用286 nm之SiO2次微米球以3-氯丙基三乙氧基矽烷(CPTS)進行表面改質，以形成表面帶有氯基之SiO2次微米球(即SiO2-Cl)，經由化學分析能譜儀(ESCA)進行表面元素的分析，可觀察出約在198ev位置有氯元素鍵結能(binding energy)波峰的出現，顯示氯基確實存在次微米球的表面。
最後將不同氯基濃度之SiO2-Cl粒子利用ATRP聚合反應製備刷狀結構之SiO2次微米球(SiO2-g-PMMA)，反應系統中以氯化亞銅(CuCl)當金屬觸媒，以N,N,N'',N",N"-pentamethyldiethylenetriamine (PMDETA)當作螯合劑，合成出的高分子PMMA重量比率為5.6 % ~ 10.5 %，並經由掃描式電子顯微鏡(SEM)以及穿透式電子顯微鏡(TEM)可證明SiO2-g-PMMA粒子上的PMMA部分約6 nm，由以上結果顯示，本實驗已經可以成功製備出均一粒徑具刷狀結構之SiO2-g-PMMA粒子。

The preparation of highly monodisperse silica submicrospheres (SiO2), SiO2 with Chloro- functional group (SiO2-Cl), and silica-g-poly(methyl methacrylate) submicrospheres (SiO2-g-PMMA) have been discussed.
At first, diameter of 158 to 700 nm were prepared by Stöber method. Three dimensional photonic crystals (PCs) were obtained by self- assembling of SiO2. Experimental λ max, obtained from UV Vis spectrophotometer, were consistent with photonic band gap (PBG), calculated from Bragg''s Law, on 0° to 60°reflection angles. In other words, the structure color of PCs was corresponded to the PBG.
Secondly, SiO2 was modified by (3-Chloropropyl) triethoxysilane (CPTS) to form Cl end-functional group on the surface (SiO2-Cl). The Chloro group was detected at about 198ev position by Electron Spectroscopy for Chemical Analysis (ESCA).
Finally, SiO2-g-PMMA was obtained by atom transfer radical polymerization (ATRP) of SiO2-Cl in the presence of MMA using copper(I) chloride and N,N,N'',N",N"-pentamethyldiethylenetriamine as catalyst precursors. The resulted showed that 5.6 % ~ 10.5 % grafted percentage of PMMA on SiO2-g-PMMA were characterized by Thermogravimetric Analyzer (TGA). In addition, 6 nm thickness of PMMA was observed by SEM and TEM. These results demonstrated that brush submicrospheres were synthesized successfully by ATRP.

摘要..........................................................................................................................................I
Abstract................................................................................................................................... II
謝誌....................................................................................................................................... III
目錄.......................................................................................................................................IV
圖目錄...................................................................................................................................VI
表目錄................................................................................................................................ VIII
第一章 緒論............................................................................................................................ 1
第二章 實驗............................................................................................................................ 7
2-1 實驗藥品....................................................................................................................... 7
2-2 實驗儀器....................................................................................................................... 9
2-3 實驗方法..................................................................................................................... 10
2-3-1 均一粒徑二氧化矽次微米球之製備.................................................................. 10
2-3-2 利用自組裝排列製備光子晶體......................................................................... 10
2-3-3含氯基二氧化矽次微米球(SiO2-Cl)之製備..................................................... 11
2-3-4 以原子轉移自由基聚合方式製備刷狀結構的次微米球................................. 12
2-4 儀器分析..................................................................................................................... 13
2-4-1 傅立葉轉換紅外線光譜儀(FTIR)測試條件...................................................... 13
2-4-2 掃描式電子顯微鏡(SEM)測試條件................................................................... 13
2-4-3 化學分析電子光譜儀(ESCA)測試條件............................................................. 14
2-4-4 熱重損失儀(TGA)測試條件............................................................................... 14
2-4-5 紫外-可見光光譜儀(UV-Vis)測試條件............................................................. 14
2-4-6 動態粒徑分析儀(DLS)測試條件....................................................................... 15
第三章 結果與討論.............................................................................................................. 16
3-1 均一粒徑次微米球之製備.......................................................................................... 16
3-1-1 R值對二氧化矽次微米球之探討........................................................................ 17
3-1-2 R值固定同時提高水與單體含量對二氧化矽次微米球之探討........................ 21
3-1-3 單體含量多寡對二氧化矽次微米球之探討...................................................... 25
3-1-4 NH4OH與溫度對二氧化矽次微米球之探討..................................................... 31
3-1-5 次微米球尺寸改變之探討................................................................................. 33
3-1-6 利用自組裝排列製備光子晶體之研究............................................................. 34
3-1-6-1 反射角為0°時，不同粒徑之次微米球對自組裝排列之影響...................... 34
3-1-6-2 各種反射角下，286 nm之SiO2對自組裝排列之影響.................................. 37
3-2含氯基二氧化矽次微米球(SiO2-Cl)之製備............................................................. 40
3-3 以原子轉移自由基聚合方式製備刷狀結構的次微米球之研究............................. 49
3-3-1 刷狀次微米球粒徑及表面形態之探討.............................................................. 49
3-3-2 刷狀次微米球的高分子接枝含量之探討.......................................................... 58
第四章 結論.......................................................................................................................... 64
參考文獻............................................................................................................................... 66

                                

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