研究生: |
陳思瑾 Ssu-Chin Chen |
---|---|
論文名稱: |
利用電漿技術與點擊化學方法接枝poly(2-ethyl-2-oxazoline) 於聚甲基丙烯酸甲酯高分子及不鏽鋼基材表面並探討其應用 Plasma induced grafting and click chemistry methods for the immobilization of poly(2-ethyl-2-oxazoline) on the surfaces of polymethyl methacrylate (PMMA) and stainless steel and to study the related applications |
指導教授: |
王孟菊
Meng-Jiy Wang |
口試委員: |
徐振哲
Cheng-Che Hsu 王勝仕 Sheng-Shin Wang 何明樺 Ming-Hua Ho 劉懷勝 Hwai-Shen Liu 蔡偉博 Wei-Bor Tsai 魏大欽 Ta-Chin Wei |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2014 |
畢業學年度: | 102 |
語文別: | 中文 |
論文頁數: | 105 |
中文關鍵詞: | 電漿誘導接枝法 、點擊化學中環加成反應法 、甲基丙烯酸甲酯 、不鏽鋼 |
外文關鍵詞: | plasma induced grafting, azide-alkyne cycloaddition reaction, poly(2-ethyl-2-oxazoline), polymethyl methacrylate |
相關次數: | 點閱:231 下載:0 |
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本研究主要目的以陽離子開環聚合法製備poly(2-ethyl-2-oxazoline) 高分子 (PEOXA),並分別以電漿誘導接枝方法及點擊化學中的環加成反應方法,接枝於甲基丙烯酸甲酯 (poly(methyl methacrylate), PMMA) 及不鏽鋼 (stainless steel, SS) 等兩種基材表面,並測試改質後的PMMA與不鏽鋼的抗細胞貼附的性質。PEOXA高分子合成的部分以傅立葉轉換紅外光光譜儀 (Fourier Transform Infrared Spectroscopy, FTIR) 及液態核磁共振儀 (1H NMR) 進行結構分析,另外,高分子改質於基材表面之結果,以量測水接觸角探討改質前後基材表面親水性質的改變,ATR-FTIR及化學分析電子能原子能譜儀 (Electron spectroscopy for chemical analyzer, ESCA) 分析表面官能基和元素鍵結,並以表面掃描示電子顯微鏡 (Scanning Electron Microscope, SEM) 觀察基材改質前後的表面形態之變化,最後,利用老鼠纖維母細胞 (L929-fibroblast) 進行細胞貼附實驗,驗證抗細胞貼附的效率。本論文將分別就電漿誘導接枝與點擊化學中環加成反應方法兩部分進行討論。
第一部分,是合成末端基為乙烯的PEOXA分子 (PEOXA—C=C),並以電漿誘導接枝法,接枝所合成的高分子於甲基丙烯酸甲酯與不鏽鋼基材表面。本研究合成兩種不同數量平均分子量 (Mn) 的PEOXA—C=C,Mn分別為1790與2603。接枝的方法,則是先利用氬氣電漿預處裡PMMA基材表面,並以旋轉塗佈法塗佈不同濃度的PEOXA—C=C高分子 (0.01- 0.15 M) 於基材上,再以氬氣電漿處理已經過預處理的PMMA基材。另一方面,不鏽鋼基材的預處理是以矽烷化法修飾矽烷有機層於不鏽鋼基材之上,誘導高分子接枝的步驟則是與前述接枝於PMMA基材的方法相同。實驗結果顯示,未改質的PMMA和不鏽鋼基材的靜態水接觸角分別為80°和52.7°,經PEOXA¬C=C修飾後,水接觸角皆為60°。並以ATR-FTIR分析兩種基材表面官能基,可在波數1627 cm-1處發現PEOXA¬C=C的訊號,接枝不同數量平均分子量 1790和2603 PEOXA—C=C於PMMA基材上,抗細胞沾黏的效率可達56 %及65 %,於不鏽鋼基材表面抗細胞沾黏的效率則分別為55 %及60 %。
第二部分,是合成末端基為乙炔的PEOXA分子 (PEOXA¬C≡C),並以點擊化學中的環加成反應法,接枝於不鏽鋼基材表面。將數量平均分子量為1548和4262的 PEOXA¬C≡C的高分子接枝於不鏽鋼基材表面。在不鏽鋼的預處理方面,先以矽烷化法修飾疊氮官能基於不鏽鋼表面,此時靜態水接觸角為92°,由ATR-FTIR分析2106 cm-1波峰為疊氮官能基的訊號,將PEOXA¬C≡C與經由預處理的不鏽鋼基材反應後,以數量平均分子量 (Mn) 為4262的 PEOXA—C≡C與不鏽鋼反應, 當反應量為11 mM時,抗細胞沾黏效率達63 %,以數量平均分子量 (Mn) 為 1548 的PEOXA—C≡C與不鏽鋼反應,當濃度為 64 mM,抗細胞貼附效率達48 %,結果顯示Mn為4262的長鏈高分子,於低濃度反應量時,具有較佳的抗細胞貼附之效果。
In this thesis, poly(2-ethyl-2-oxazoline) (PEOXA) was synthesized by cationic ring opening polymerization. The synthesized PEOXA was further used to be altered with different end functional groups in order to be incorporated on polymethyl methacrylate (PMMA) and stainless steel (SS) surfaces by plasma induced grafting and cycloaddition reaction methods, respectively. The synthesized PEOXA molecules were evaluated by Fourier Transform Infrared Spectroscopy (FTIR) and 1H NMR. The effects of surface modifications on surface of PMMA and stainless steel were characterized by ATR-FTIR, water contact angle (WCA), and Electron Spectroscopy for Chemical Analysis (ESCA). The surface morphology was evaluated by scanning electron microscopy (SEM). The cell adhesion was evaluated by directly cultivating L-929 fibroblasts on the samples.
For the first part of this thesis, PEOXA was altered to possess alkene end groups to form PEOXA¬C=C. Two different number average molecular weight (Mn), 1790 and 2603, of PEOXA-C=C were synthesized and were firstly immobilized on plasma pretreated PMMA and stainless steel, which was followed by Ar plasma induced grafting. The outcome of PEOXA¬C=C grafting was clearly demonstrated by the change of water contact angle from 80° (PMMA) and 52.7° (SS) to 60°, on both substrates. Moreover, the ATR-FTIR results revealed that a C-C-N peak appeared at 1627 cm-1, confirming the incorporation of PEOXA moieties on substrates. The efficiency for resisting cell adhesion of L-929 fibroblasts reached up to 55 % for 0.15 M of PEOXA¬C=C polymer grafted on PMMA and stainless steel surfaces.
For the second part of the thesis, the end groups of PEOXA was altered to be alkyne to form PEOXA¬C≡C. Two different molecular weight of PEOXA¬C≡C, 1548 and 4262, were synthesized. In addition, the azide functional groups were incorporated on stainless steel by silanization approach. Then the two different molecular weight of PEOXA¬C≡C were immobilized on stainless steel with azide groups which were further underdgone the azide-alkyne cycloaddition reactions. The incorporation of PEOXA¬¬—C≡C on stainless steel resulted in change of water contact angle from 52.7° to 60°. Moreover, the functionalities were also verified by ATR-FTIR. The N-C=O and C-N bonds were detected after PEOXA¬¬—C≡C incorporated on stainless steel surfaces according to the results of ESCA analyses. The efficiency of anti-cell adhesion was up to 63 % by using 11 mM of PEOXA¬¬—C≡C with Mn of 4262 on stainless steel surface.
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