均一粒徑次微米染料球之合成與其自組裝排列之研究

The study on preparation and self-assembly of monodispersed dye-containing smbmicrospheres

林惠敏(Hui-min Lin)

指導教授 ： 陳暉

國立中央大學/工學院/化學工程與材料工程學系/碩士(2008年)

摘要

本論文主要探討具有不同表面官能基、形態、結構均一粒徑染料球之合成，以及其自組裝排列形成光子晶體之研究。
首先利用無乳化劑乳化聚合以苯乙烯(St)或甲基丙烯酸甲酯(MMA)做為單體，添加共單體：對-苯乙烯硫酸鈉鹽(NaSS)、甲基丙烯酸(MAA)或甲基丙烯酸羥乙酯(HEMA)合成均一粒徑次微米球。其中P(St+NaSS)經溶脹聚合法導入光起始劑4-乙烯基苯基N,N-二乙基硫代氨基甲酸酯(VBDC)於次微米球中，再以光誘導原子轉移自由基聚合(ATRP)製備刷狀次微米球。本研究並以溶劑導入法將solvent black 34黑色染料導入特定粒徑之次微米球中製成染料球，最後利用自組裝法使次微米球排列成光子晶體。
次微米染料球以傅立葉轉換紅外線光譜儀(FTIR)確認特性，以掃描式電子顯微鏡(SEM)觀測表面形態與粒徑，及動態粒徑分析儀(DLS)量測水力粒徑，而光子晶體之光學特性則利用紫外線-可見光光譜儀(UV-Vis)來鑑定。
結果顯示藉由共單體的種類與添加量可控制次微米球粒徑大小，成功合成出100-600 nm之均一次微米球。經由光誘導ATRP也可成功製備出具有PMMA鏈之刷狀次微米球。在導入染料部分，次微米染料球之粒徑(200-300 nm)並不會因添加染料而改變且Cv值(小於4 %)，而染料最多可導入1 wt%。以PS次微米球自組裝排列之光子晶體顯示對應其粒徑之結構性色彩，而PMMA次微米球排列之光子晶體，由於PMMA本身有頸收的特性使得實際能隙位置會比由粒徑計算理論值大；提升乳液固含量與添加染料皆會使光子晶體結構色彩更加鮮明；此外刷狀次微米球可提升成膜性。

關鍵字

均一粒徑次微米球 ； 無乳化劑乳化聚合 ； 光誘導原子轉移自由基聚合 ； 溶劑導入法 ； 自組裝排列 ； 光子晶體

並列摘要

The synthesis and self-assembly of monodispersed dye-containing submicrospheres with different functional group and morphology were studied in this thesis.
First of all, monodispersed submicrospheres were prepared by soap-free emulsion polymerization in the present of styrene (St) or methyl methacrylate (MMA) as monomer and sodium p-styrenesulfonate (NaSS), methacrylic acid (MAA) or hydroxyethyl methacrylate (HEMA) as comonomer. Afterward, the ATRP initiator 4-vinylbenzyl N,N-diethyldithiocarbamate (VBDC) were introduced to P(St+NaSS) submicrospheres by swelling polymerization, then utilizing photo-induced atom transfer radical polymerization (ATRP) to prepare PMMA brush. The dye-containing submicrospheres were prepared by solvent introducing method with different content of solvent black 34. Finally, photonic crystals were obtained by self-assembly of submicrospheres.
The functional groups of submicrospheres were confirmed by Fourier Transform Infrared Spectroscopy (FTIR). The diameters and hydrodynamic diameter were observed from Scanning electron microscope (SEM) and Dynamic light scattering (DLS), respectively. The photonic bandgap (PBG) were measured by Ultraviolet-visible spectroscopy (UV-Vis).
The results showed that 100-600 nm submicrospheres can be synthesized by adding different types and amount of comonomer. Submicrospheres with PMMA brush can be prepared successfully by photo-induced ATRP. For dye-containing submicrospheres, submicrospheres maintain their diameters with low Cv value(< 4 %), the maximum content of solvent black 34 in these was 1 wt%. The experimental PBG of photonic crystals in PS series were consistent with calculated PBG. Nevertheless, PBG in PMMA series weren’t corresponding because of necking. The structure color would be more vivid when submicrospheres with dye or higher solid content. In addition, brush submicrospheres can promote the film-forming ability.

並列關鍵字

Monodispersed submicrospheres ； Soap-free emulsion polymerization ； Photo-induced ATRP ； Solvent inducing method ； Self-assembly ； Photonic crystals

參考文獻

[8] 張明仁 “聚烯烴/氫氧化鎂奈米複合材料之合成與應用” 中原大學化學系博士論文 (2007)

[31] 郭政雨 “膠體粒子系統於光子晶體、光催化與染料敏化太陽能電池之應用” 國立成功大學材料科學及工程研究所博士論文 (2007)

[2] 川瀬進, Sen’i Gakkaishi, 60(7) (2004) 371

[3] T. Matsumoto, A. Ochi, Kobunshi Kagaku, 22 (1965) 481

[6] T. Gong, C. C. Wang, Journal of Materials Science, 43 (2008) 1926