本研究乃提高無乳化劑乳化聚合之反應溫度至100 ℃，以快速反應來製備具均ㄧ粒徑特性之次微米球，並利用自組裝之方法將其應用於三維光子晶體之組建。 首先，製備聚苯乙烯(PS)及聚甲基丙烯酸正丁酯(PBMA)之均ㄧ粒徑次微米球，且利用共聚合反應合成出具有不同玻璃轉移溫度(Tg)之甲基丙烯酸(MAA)、苯乙烯與甲基丙烯酸正丁酯三元共聚合物次微米球，當苯乙烯單體之重量百分比增加時，便可使高分子之玻璃轉移溫度由30.3 ℃提升至111.6 ℃，另外亦合成具有20%交聯密度之不同玻璃轉移溫度高分子次微米球。另一方面，在第一階段單體轉化率為80%時，進行添加第二階段單體，可製備出具有不同核殻結構之次微米球，包含有P(MAA-co-St)/P(St-co-NaSS)、P(MAA-co-BMA)/P(BMA-co-MMA)、P(MAA-co-BMA)/P(BMA-co-St)及P(MAA-co-BMA)/P(BMA-co-NIPAAm)之核/殼結構次微米球，且其粒徑範圍皆在數百奈米之間。 最後利用溶劑導入法將黑色染料Solvent black 34導入均ㄧ粒徑(Cv值小於4%)次微米球中，製成染料球。以不同粒徑之次微米球或染料球，經毛細力趨動後，可使其自組裝排列形成光子晶體，且其光子能隙(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。在紫外線-可見光光譜儀鑑定之下，次微米球及染料球以面心立方(FCC)最密堆積後所形成之光子能隙位置與布拉格定律計算之理論值相符合。此外染料球會使光子晶體之結構色彩能更加鮮明；且當乳液以濃縮之方式提升固含量後亦可讓次微米球排列整齊。 Preparation of monodispersed polystyrene (PS), poly(n-butyl methacrylate) (PBMA), various glass transition temperature (Tg) of P(MAA-co-St-co-BMA), and various core/shell submicrospheres by soap-free emulsion polymerization at 100 ℃ have been developed. The application of these monodispersed submicrospheres self-assembled to three dimensional photonic crystals (PCs) has also discussed. Above all, The various Tg of monodispersed P(MAA-co-St-co-BMA) submicrospheres were successively prepared by copolymerization, the Tg increased from 30.3 ℃ to 111.6 ℃ with increasing the weight fraction of St monomer. Afterward, the various types of core/shell submicrospheres were successfully prepared. The monomer addition experiment was carried out when the conversion was 80%, then, a number of surface modification submicrospheres with a size of several hundreds nanometer were synthesized, such as P(MAA-co-St)/P(St-co-NaSS), P(MAA-co-BMA)/P(BMA-co-MMA), P(MAA-co-BMA)/P(BMA-co-St) and P(MAA-co-BMA)/P(BMA-co-NIPAAm) core/shell submicrospheres. Finally, the highly monodispersed (Cv value < 4%) dye-containing (≦1.0 wt%, based on polymer) submicrospheres latexes were prepared by introducing the solvent black 34 dye in acetone solution. High quality polymer PCs with one photonic band gap (PBG) that can be controlled in the whole range of the visible and near infrared lights. When the various sizes of monodispersed submicrospheres were self-assembled by capillarity driven, the vivid structure colors were observed. In UV-Vis spectra, the reflection of self-assembled PCs of submicrospheres and dye-containing submicrospheres with the (111) planes in face-centered cubic (FCC) arrangement to confirm with the theoretical value calculated by Bragg’s law. Moreover, the structure color of dye-containing submicrospheres would be more brightly. Comparing with the general case of the solid state PCs, the latex with higher solid content obtained through a centrifugal process would be more helpful to form ordered periodic structure in the aqueous medium.
