透過您的圖書館登入
IP:54.144.233.198
  • 學位論文

(a)含氟鏈之銅觸媒在熱控制下之原子轉移自由基聚合研究 (b)含氟化合物之合成與聚合

(a) Novel Cu Complexes with Fluoro-ponytailed for the ATRP under the Thermomorphic Mode (b) Synthesis and Polymerization of Fluorine-containing Compounds

指導教授 : 呂良賜
若您是本文的作者,可授權文章由華藝線上圖書館中協助推廣。

摘要


(a) 目前的原子轉移自由基聚合反應常在均相催化條件下進行,但是反應中之金屬觸媒會殘留於產生的高分子中,常會造成污染影響品質,這也是目前原子轉移自由基聚合法最關切的問題。因此本實驗室利用所合成之含氟長鏈吡啶觸媒與銅金屬形成錯合物,在於低溫或室溫下銅金屬錯合物不溶解因而會沉澱分開,形成異相環境,但溫度加高後;銅金屬錯合物又可溶解形成均相而進行聚合反應(溫度控制),故以此方法可輕易分離高分子與金屬觸媒,從而得到金屬殘留量非常少而產率高的高分子產物。我們在研究中所開發出之方法,可以解決目前高分子產物中金屬殘留的問題,開創了一個新的聚合方法。 (b) 在此研究主題中,我們利用含氟元素的醇類(RfCH2OH)做起始物,合成出一系列含氟元素之化合物,其中包括含氟長鏈的壓克力單體。能以簡單的實驗步驟將氟醇形成具有親核基的氟醇鈉基團,以用來合成一系列化合物,純化容易產率高。以核磁共振儀(NMR)、氣相質譜儀(GCMS)與FT-IR進行樣品鑑定。利用自由基聚合法(AIBN)在超臨界二氧化碳流體中聚合壓克力單體,藉由控制單體之間莫耳比例進行共聚合反應,改善高分子的溶解度。聚合出的高分子利用核磁共振儀(NMR)、膠體滲透層析儀(GPC)、熱重分析儀(TGA)、 Abbe屈折度計量測折射率,分析樣品性質。含氟的壓克力高分子具有不同的折射率性質,能為高科技如面板產業帶來新的材料。

並列摘要


(a)The ATRP reaction often takes place under the homogeneous condition, so the residual metal catalyst that often causes pollution or influences the quality of compounds remains in the polymer at the end of reaction. This is the most serious problem associated with ATRP for the time being. The novel copper complexes are insoluble in the solvent at room temperature or below. However, these complexes are dissolved when we moderately raise temperature to form homogeneous phase. When the reaction mixtures are cooled down, the metal complexes precipitate again. Thus, we can easily separate the metal complex from product by liquid/solid method. We hope that this new method can solve the problem of residual metal contamination in the polymer by carrying out the ATRP under the thermomorphic mode. (b) This research is mainly to use the fluorinated alcohols as useful starting materials to synthesize a series of fluorine-containing compounds including acrylate or methacrylate monomers. The basic procedure is to easily prepare the fluorinated alkoxide which acts as the versatile nucleophile from the corresponding alcohol. The fluorinated alkoxide can then react with a variety of substrates. The fluorinated monomers obtained by the above method are then polymerized by the free radical polymerization (using AIBN) method in super critical carbon dioxide (ScCO2). By controlling the molar ratios of fluorinated monomers to MMA the solubility of these polymers improved greatly. We hope that these polymers which usually have tunable or low refraction indexes could serve as the new materials for LCD industry.

並列關鍵字

ATRP thermomorphic

參考文獻


32.陳政湧,PdCl2[4,4′-bis(RfCH2OCH2)-2,2′- bipyridine] (Rf=HC4F8, HC8F16, C3F7及C10F21)之合成、構造及反應性(在氟有機二相的應用),碩士論文,國立台北科技大學有機高分子研究所,台北,2006。
3.(a) I.T. Horvàth, J. Rábai, "Facile catalyst separation without water: Fluorous biphase hydroformylation of olefins", Science, 1994, 266, 72-75 (b)I.T. Horvàth, "Fluorous Biphase Chemistry", Acc. Chem. Res.,1998, 31, 641-650
4.M. Wende, R. Meier, J.A. Gladysz, J. Am. Chem. Soc. 2001, 123, 11490.
8.S. Gaynor, J. S. Wang, K. Matyjaszewski, Macromolecules, 1995, 28, 8051.
11.H. Fischer, Macromolecules, 1997, 30, 5666-5672

被引用紀錄


侯曦鈞(2008)。特殊含氟鏈聯吡啶鈀及鉑錯合物的合成、結構及電化學研究〔碩士論文,國立臺北科技大學〕。華藝線上圖書館。https://doi.org/10.6841%2fNTUT.2008.00338

延伸閱讀