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研究生:李國達
研究生(外文):Guo-Da Lee
論文名稱:以靜電紡絲法製備含有苯胺五聚體之電活性聚氨酯纖維之研究
論文名稱(外文):Preparation and Characterization of Electroactive Composite Fibers containing Polyurethane with Amine-capped Aniline Pentamer by Electrospinning
指導教授:林榮顯
指導教授(外文):Rong-Hsien Lin
口試委員:王宗櫚謝永堂何宗漢
口試委員(外文):Tzong-Liu WangYeong-Tarng ShiehTsung-Han Ho
口試日期:2014-07-15
學位類別:碩士
校院名稱:國立高雄應用科技大學
系所名稱:化學工程與材料工程系博碩士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2014
畢業學年度:102
語文別:中文
論文頁數:121
中文關鍵詞:靜電紡絲電活性聚氨酯苯胺五聚體
外文關鍵詞:electrospinningelectroactive polyurethaneamine-capped aniline tetramer
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含有苯胺四聚體( amine-capped aniline tetramer)的電活性聚氨酯( Electroactive polyurethane)所採取的合成方式是先以4,4 Diphenylmethane diisocyanate或1,6-diisocyanatohexane與1,3-propanediol和N-phenyl-p-phenylenediamine合成兩端為苯封端( Phenyl-capped)之含有苯胺四聚體之各類聚氨酯寡聚物,接著再與p-Phenylenediamine進行氧化偶聯聚合( oxidative coupling polymerization)反應而得到含有苯胺五聚體( amine-capped aniline pentamer)之各類電活性的聚氨酯。各系列紡絲液的備製方式是將混合含有苯胺五聚體( amine-capped aniline pentamer)之各類電活性的聚氨酯( Electroactive polyurethane)與Polyvinylpyrrolidone (PVP)溶於Dimethylformamide (DMF)溶劑。緊接著,將所得之的紡絲液進行靜電紡絲之製備,可得到含有苯胺五聚體( amine-capped aniline pentamer)之各系列電活性聚氨酯纖維( electroactive polyurethane fibers)。
此外,以傅立葉轉換紅外線光譜儀(FT-IR)與凝膠滲透層析儀(GPC)量測含苯胺五聚體之各類電活性聚氨酯之特徵峰與分子量,有高分子量的形成,間接證實氧化偶聯聚合反應已成功進行;以SEM觀察各系列電活性聚氨酯奈米複合纖維之表面形態。
本研究除了探討系統的分子量、溶液的黏度、溶液的濃度及系統的組成等參數對靜電紡絲之影響外,本研究亦企圖結合上述各互相干擾之因子成為單一因子,比濃黏度(reduced viscosity),探討此因子對靜電紡絲之影響。結果顯示,不論我們改變溶液的濃度、系統的組成及系統的分子量,只要比濃黏度值大於510 ml/g以上的紡絲液,經由靜電紡絲程序後,都有利於成絲。
最後,利用循環伏特安培法鑑定含苯胺五聚體之各類電活性聚氨酯之電活性性質;使用紫外光光譜儀(UV-Vis)鑑定含苯胺五聚體之各類電活性聚氨酯之氧化還原行為;以四點探針法測試含苯胺五聚體之電活性聚氨酯纖維與薄膜之表面電阻率 (sheet resistivity)。含苯胺五聚體之電活性聚氨酯纖維系列之表面電阻較薄膜系列的表面電阻少於一個級數。

The polyurethane oligomer with amine-capped aniline tetramer was preliminarily synthesized from 4, 4-diphenylmethane diisocyanate or 1, 6-diisocyanatohexane with 1, 3-propanediol and N-phenyl-p-phenylene diamine. Subsequently, a series of electroactive polyurethanes (PU) with amine-capped aniline pentamer were successfully synthesized by reacting the synthesized polyurethane oligomers with amine-capped aniline tetramer with p-phenylenediamine via oxidative coupling polymerization.
Various spinning solutions were prepared by mixing the electroactive polyurethanes and polyvinylpyrrolidone (PVP) in the solvent of Dimethylformamide (DMF). Subsequently, a series of electroactive composite fibers containing polyurethane with amine-capped aniline pentamer were obtained from the resulting spinning solution by electrospinning.
In addition, the resulting polyurethane oligomer were identified by FT-IR. The molecular weight of various types of the electroactive polyurethane were measured by GPC (gel permeation chromatography), and the resulting high molecular weight circumstantially confirmed that oxidative coupling polymerization has indeed carried out. The surface morphology of electroactvie polyurethane fibers were observed by SEM.
The factors for successful electrospinning, such as system molecular weight, solution viscosity, solution concentration and system constitution were also thoughtfully investigated. In order to combine various above-mentioned factors, a newly promising factor, reduced viscosity (red) for successful electrospinning was attemptly introduced in this paper to combine those interrelationship factors.
Finally, electrochemical activity of electroactive PUs were conducted in 1.0 M H2SO4 aqueous solution by a cyclic voltammetry. UV-Vis spectra were showed that electroactive polyurethane had redox behavior. The sheet resistivity of obtained PUs fiber or film were measured by four-probe apparatus. The sheet resistivity of fiber type was less magnitude of one order than that of the film type.

摘要 I
Abstract III
誌謝 V
總目錄 VI
流程目錄(Scheme) IX
表目錄(Table) X
圖目錄(Figure) XI
第一章 前言 1
第二章 基本原理 3
2-1聚氨酯(polyurethane)之簡介 3
2-1-1聚氨酯(polyurethane)的化學反應性 4
2-1-2聚氨酯(PU)之合成 6
2-2導電高分子之簡介及種類 8
2-2-1導電高分子之簡介 8
2-2-2聚苯胺(Polyaniline)之簡介 10
2-2-3聚苯胺(Polyaniline)的合成 11
2-3靜電紡絲(Electrospinning)之簡介 14
2-3-1 臨界電位理論 17
2-3-2 靜電紡絲射流剖面分析 17
2-3-3 靜電紡絲邊動理論 18
2-3-4 靜電紡絲參數 19
第三章 文獻回顧與研究動機 23
3-1電活性高分子相關文獻回顧 23
3-2苯胺片段之電活性高分子之文獻回顧 26
3-3以靜電紡絲法製備高分子奈米纖維之文獻回顧 32
3-4 研究動機與目的 34
第四章 材料設備與研究方法 36
4-1 實驗材料 36
4-2 實驗儀器 38
4-3 實驗步驟 42
4-3-1 以芳香族類二異氰酸酯單體製備含苯胺四聚體之聚氨酯寡聚物(polyurethane oligomer with phenyl-capped aniline tetramer, M-PU-AN4 oligomer)之合成及結構鑑定 43
4-3-2 以脂肪族類二異氰酸酯單體製備含苯胺四聚體之聚氨酯寡聚物( polyurethane oligomer with amine-capped aniline tetramer, H-PU-AN4 oligomer)之合成及結構鑑定 44
4-3-3 主鏈上具苯胺五聚體之各類電活性聚氨酯的合成及結構鑑定 45
第五章 結果與討論 47
5-1 各類電活性聚氨酯之電性質探討 47
5-1-1 主鏈上具苯胺五聚體之各類聚氨酯之電活性之探討 47
5-1-2 主鏈上具苯胺五聚體之各類聚氨酯之氧化還原之探討 49
5-2 各系列電活性聚氨酯複合材料之電紡絲纖維的表面形態觀察 51
5-2-1 不同組成之電紡液對纖維表面形態之影響 53
5-2-2 不同濃度之高分子溶液對靜電紡絲纖維表面形態之影響 56
5-2-3 不同分子量的電活性聚氨酯之紡絲液對纖維表面型態之影響 58
5-3各系列電活性聚氨酯複合材料之成絲性之探討 61
5-3-1 含苯胺五聚體之芳香族電活性聚氨酯複合材料之成絲性之探討 62
5-3-2 含苯胺五聚體之脂肪族電活性聚氨酯複合材料之成絲性之探討 66
5-4 主鏈上具苯胺五聚體之各系列聚氨酯複合材料之表面電阻率之探討 71
第六章 結論 73
第七章 參考文獻 75
自傳簡歷 121

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