快速合成具耐溶劑核心之核殼結構次微米球及其應用於增加光子晶體成膜性質之研究

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研究生：	陳鴻文 Hong-Wen Chen
論文名稱：	快速合成具耐溶劑核心之核殼結構次微米球及其應用於增加光子晶體成膜性質之研究 Rapid synthesis of core-shell submicrospheres with solvent-resistance core and soft shell and its application for Robust Opal Film
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
論文出版年：	2014
畢業學年度：	102
語文別：	中文
論文頁數：	124
中文關鍵詞：	無乳化劑乳化聚合、均ㄧ粒徑次微米球、光子晶體、玻璃轉移溫度、高分子球折射率
外文關鍵詞：	Soap-free emulsion polymerization, Monodisperse submicrospheres, Photonic crystals, Glass transition temperature, Refractive index
相關次數：	點閱：16 下載：0
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本研究乃利用二階段單體添加的製備方式，以無乳化劑乳化聚合法於沸騰狀態下，製備具有交聯結構的耐溶劑核心與軟殼層之核殼結構次微米球。將不同比例的MMA與DVB反應一段時間後，添加二階段單體BA製備出核殼結構次微米球，並於室溫下或壓縮程序進行自組裝，建構三維結構之光子晶體。在實驗探討方面，主要針對第一階段轉化率、核心耐溶劑性、二階段單體添加量對成膜性的影響、核心與殼層折射率差對光子晶體膜光學性質的影響以及不同表面官能基改質的影響做討論。
結果顯示，當核心交聯程度達20%即具有耐溶劑性，並於轉化率為85%時製備P(MMA-co-DVB)/PBA核殼結構次微米球，隨著二階段單體BA添加量由3克添加至10克時，其粒徑由263 nm上升至341 nm，殼層玻璃轉移溫度由-21℃下降至-40℃，核心則因為交聯20%使得Tg變化不明顯。由外觀判斷，二階段單體BA添加量達10克時，自組裝後的光子晶體膜即具有成膜性，但其光學性質仍然微弱，其原因為核心與殼層折射率差異過於相近所造成。
另一部份則藉由St的添加，改變核心的折射率，並於核心轉化率85%時製備P(St-co-MMA-co-DVB)/PBA核殼結構次微米球，並將室溫自組裝後的光子晶膜經由一壓縮程序，使原本微弱的結構性色彩變得更鮮明。隨著核心與殼層折射率差異增加，光子能隙亦從原先1~2%微弱的反射強度提升至25%左右；最後則利用不同官能基之單體進行表面改質，藉由改變球與球之間作用力或殼層折射率，改善光子晶體之光學性質。

In this study, robust opal film has been developed by core-shell submicrospheres. Monodispersed P(MMA-co-DVB) / P(BA) core-shell structure submicrospheres were prepared by two-step soap-free emulsion polymerization at boiling state. MMA and DVB were polymerized during a period of time, and then BA was introduced into the above reaction solution and polymerized. Then the latex was dropped onto substrate and self-assembly in room temperature to fabricate the photonic crystal film. The effect of the conversion of core, the solvent resistance properties of core, the amount of shell monomer, the difference of refractive index between core and shell and kinds of shell monomers on the optical and mechanical properties were discussed.
The results indicated that the monodispersed, solvent-resistant cores were prepared as the DVB content was higher than 20 wt %. The P(MMA-co-DVB) / P(BA) core/shell submicrospheres were easily prepared when the first step conversion was 85%. The diameters of P(MMA-co-DVB) / P(BA) core/shell submicrospheres were changed from 263 nm to 341 nm and the Tg of shell were decreased from -21 oC to -40 oC by adjusting the amount of shell monomer (BA) from 3g to 10g. The photonic crystal had the film-forming property when amount of shell monomer (BA) reached to 10g, but the optical property was still weak.
The optical property can be improved by compressing the photonic crystal film that was self-assembly in room temperature and increasing the difference of refractive index between core and shell by adding styrene at first step. In addition, for the UV-vis result, the reflective intensity were improved from 1~2% to 25%, the photonic crystal film became colorful. On the other hand, the optical properties of photonic crystal film can be improved by adding different monomers into shell to change the interaction between particle to particle and the difference of refractive index between core and shell.

摘要 .......................................... I
Abstract ........................................ II
致謝 ....................................... III
目錄 ....................................... IV
圖目錄 ......................................... VI
表目錄 ......................................... XI
第一章 緒論 ...................................... 1
1-1 均一粒徑高分子球之簡介與文獻回顧 ................. 1
1-2 光子晶體之簡介與文獻回顧 ..................... 4
1-3 提升光子晶體成膜性及機械強度之文獻回顧 ................. 8
1-4 研究動機及目的 ........................... 11
第二章 實驗 ..................................... 12
2-1 實驗藥品 .................................. 12
2-2實驗儀器 ................................... 14
2-3實驗方法 ................................... 15
2-3-1 單體精製 ............................ 15
2-3-2 快速製備具核殼結構之均一粒徑次微米球 .............. 15
2-3-2-1不同交聯程度PMMA核心之製備 ........... 16
2-3-2-2 不同折射率的耐溶劑核心之製備............. 17
2-3-2-3核殼結構次微米球之製備 .................... 18
2-3-3 光子晶體之製備 ............................ 19
2-4 儀器分析 .................................. 19
2-4-1 掃描式電子顯微鏡(SEM)測試條件 ............... 19
2-4-2 動態粒徑分析儀(DLS)測試條件 .................... 19
2-4-3 紫外-可見光光譜儀(UV-vis)測試條件 ................ 19
2-4-4 微差掃描熱分析儀(DSC)測試條件 ............... 20
2-4-5 鉛筆硬度機(Pencil Hardness)測試條件 ............... 20
第三章 結果與討論 ............................... 21
3-1 不同交聯程度PMMA核心之製備 ..................... 22
3-1-1粒徑與表面型態分析 ..................... 22
3-1-2折射率、耐溶劑測試與熱性質分析 ............... 22
3-1-3 轉化率影響 .............................. 23
3-2 P(MMA-co-DVB)/PBA核殼結構球之研究 ............... 29
3-2-1添加不同BA含量作為殼層之研究 ............... 29
3-2-1-1粒徑與表面型態分析 ...................... 29
3-2-1-2 光學性質之討論 ....................... 30
3-2-1-3 熱性質分析 ......................... 32
3-2-2 第二階段不同轉化率下添加BA作為殼層之影響 ........ 44
3-2-2-1表面型態與粒徑分析 ...................... 44
3-2-2-2光學性質之討論 ........................ 45
3-2-2-3熱性質分析 .......................... 45
3-3藉由奈米軟球混合或溶劑添加增加其成膜性 ................ 50
3-3-1奈米軟球混合下之光子晶體特性 ................... 50
3-3-1-1表面型態之探討 ........................ 50
3-3-1-2光學性質之討論 ........................ 51
3-3-1-3鉛筆硬度之測試 ........................ 52
3-3-2溶劑添加下之光子晶體特性 ..................... 60
3-3-2-1表面型態與粒徑分析 ...................... 60
3-3-2-2光學性質之討論 ........................ 61
3-4不同折射率的耐溶劑核心之製備 .................. 69
3-4-1粒徑分析與耐溶劑測試 ....................... 70
3-4-2折射率變化與熱性質分析 ................... 70
3-4-3轉化率影響 ............................... 71
3-5 P(St-co-MMA-co- DVB)/PBA核殼結構球之研究 .......... 77
3-5-1 以室溫為條件下自組裝(壓縮前)之光子晶體膜特性 ..... 77
3-5-1-1 表面型態與粒徑分析 ..................... 77
3-5-1-2 光學性質之討論 ....................... 78
3-5-1-3 熱性質分析 ......................... 79
3-5-2以200bar壓力壓縮為條件下自組裝之光子晶體膜特性 ...... 84
3-5-2-1表面型態分析 ...................... 84
3-5-2-2光學性質之討論 ........................ 85
3-5-2-3 壓縮自組裝機制 ....................... 86
3-5-3 不同表面官能基改質之影響 .................... 94
3-5-3-1表面型態與粒徑分析 ...................... 94
3-5-3-2光學性質之討論 ........................ 94
3-5-3-3熱性質分析 .......................... 96
第四章 結論 ................................... 104
參考文獻 ......................................... 106
                                

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