臺灣博碩士論文加值系統

使用苯胺單體或寡聚體如雙體、四聚體做為起始物，在不添加寡聚物及添加微量(1.4%)寡聚物的條件下，電化學法製作掌性聚苯胺；發現以單獨使用苯胺雙體做為起始物效果較聚合苯胺單體、四聚體更好，並可增加掌性聚苯胺的旋光度、促進聚合速度；本文針對不同環境下聚合掌性聚苯胺進行討論，如聚合時間、苯胺雙體及摻雜酸濃度、聚合溫度以及pH 值的改變，找出聚合掌性聚苯胺的最佳條件，並比較不同寡聚物對掌性聚苯胺的影響。
聚合最佳條件如下：40°C 下，在樟腦磺酸(1.29 M)中加入苯胺雙體(40mM)施加定電壓0.75 V(v.s. Ag/AgCl)，通過122 mC/cm2，可以得到g-factor 0.0105，分子量3928，PDI = 1.40，聚苯胺纖維直徑約80 ~ 100 nm，長度可達幾個μm；掌性聚苯胺透過摻雜(doped)及去摻雜(dedoped)，具有可逆反應；並在室溫及40°C 下聚合可以獲得相反旋光度的掌性聚苯胺；若在不同pH 下，以雙體聚合，可以得到不同外觀形態之聚苯胺。

Aniline or aniline oligomers, such as aniline dimer, tetramer are used as starting materials to prepare chiral polyaniline, electrochemically. Furthermore, aniline oligomers as starting materials with 1.4% other oligomers adding as promoter are exploited for chiral polyaniline nanofiber preparation. The chiral polyaniline made by aniline dimer as a starting material shows the superior anisotropic factor than them by aniline and tetramer.
The optimal condition as follows: 40 mM aniline dimer and 1.29 M camphorsulfonic acid (CSA) as electrolyte, applying potential 0.75 V for 122 mC/cm2 at 40°C. The chiral polyaniline prepared by aniline dimer shows the average molecular weight 3928 (polydispersity index, PDI 1.40) and a g-factor of 0.0105. The diameter of polyaniline fiber is around 80~100 nm and the lengths up to several μm. The doped and dedoped forms of chiral polyaniline prepared at 23°C and 40°C show the inversion of anisotropic factor which may cause by the amount of hydrogen bonding and subsequently changing the helical conformations of polyaniline.

1、 緒論.....................................................................................................1
1.1、導電高分子的簡介與發展近況.....................................................1
1.2、聚苯胺的簡介及發展.....................................................................1
1.3、聚苯胺的合成.................................................................................2
1.4、聚苯胺的氧化還原態.....................................................................5
1.5、聚苯胺的結構與紫外光-可見光光譜(UV-Vis).............................6
1.6、聚苯胺的氧化還原機制.................................................................8
1.7、圓二色極化光譜(circular dichroism，CD) ...................................9
1.7.1、g-factor.......................................................................................13
1.7.2、Bisignate.....................................................................................13
1.8、對掌性導電高分子-聚苯胺...........................................................14
1.9、掌性聚苯胺結構的反轉................................................................16
1.10、寡聚物對導電高分子的影響......................................................17
1.11、雙體聚合聚苯胺..........................................................................19
1.12、研究動機及目的..........................................................................20
2、實驗部分..............................................................................................23
2.1、試藥.................................................................................................23
2.2、試藥結構.........................................................................................24
2.3、儀器設備.........................................................................................25
2.4、實驗步驟.........................................................................................26
2.4.1、聚合方法....................................................................................26
2.4.2、循環伏安法偵測苯胺雙體的氧化電位..................................26
2.4.3、掌性聚苯胺的最佳化................................................................27
2.4.3.1、聚合電壓的最佳化...............................................................27
2.4.3.2、苯胺雙體濃度的最佳化.......................................................27
2.4.3.3、聚合時間的最佳化...............................................................27
2.4.3.4、載體溶液S-CSA 對掌性聚苯胺的影響.............................27
2.4.4、固定酸根濃度改變pH 對掌性聚苯胺的影響.........................27
2.4.5、苯胺四聚體聚合掌性聚苯胺....................................................28
2.4.6、溫度效應....................................................................................28
2.4.6.1、改變聚合溫度對掌性聚苯胺的效應...................................28
2.4.6.2、聚合後經過熱處理對掌性聚苯胺的影響..........................28
2.4.7、掌性聚苯胺經過真空抽氣去除水份對掌性聚苯胺的影響...28
2.4.8、掌性聚苯胺的摻雜(doping)與去摻雜(dedoping) ...................28
2.4.9、利用苯胺雙體加入催化劑下進行聚合....................................28
2.4.10、電化學石英晶體微天秤(EQCM)............................................29
2.4.11、四聚體之合成..........................................................................29
3、結果與討論..........................................................................................33
3.1、利用苯胺、雙體、四聚體在不加入催化劑下進行聚合比較........33
3.1.1、循環伏安法偵測苯胺、雙體、四聚體及八聚體的氧化電位....33
3.1.2、室溫下掌性聚苯胺的最佳化....................................................35
3.1.2.1、聚合電壓的最佳化...............................................................35
3.1.2.2、苯胺雙體濃度的最佳化.......................................................36
3.1.2.3、固定庫侖數對雙體濃度之最佳化.......................................37
3.1.2.4、聚合時間的最佳化...............................................................38
3.1.2.5、載體溶液S-CSA 對掌性聚苯胺的影響..............................39
3.2、pH 對掌性聚苯胺的影響...............................................................41
3.2.1、固定酸根濃度改變pH 對掌性聚苯胺的影響.........................41
3.2.2、不同pH 條件下聚合掌性聚苯胺之FE-SEM..........................42
3.3、苯胺四聚體聚合掌性聚苯胺.........................................................45
3.4、比較苯胺、雙體、苯胺加雙體聚合............................................46
3.4.1、比較苯胺、苯胺加雙體、雙體、四聚體聚合之FT-IR........46
3.4.2、苯胺、雙體、苯胺單體加雙體聚合之FE-SEM....................49
3.5、溫度效應.........................................................................................51
3.5.1、改變聚合溫度對掌性聚苯胺的效應.......................................51
3.5.2、比較苯胺雙體在室溫下及40°C 聚合之FT-IR.......................54
3.5.3、改變環境溫度的聚合過程之電流變化....................................55
3.6、聚合後經過熱處理對掌性聚苯胺的影響.....................................57
3.7、掌性聚苯胺經過真空抽氣去除水份對掌性聚苯胺的影響.........58
3.8、40°C 聚合掌性聚苯胺...................................................................60
3.8.1、掌性聚苯胺的摻雜(doping)與去摻雜(dedoping)之CD 光譜..60
3.8.2、掌性聚苯胺的摻雜與去摻雜之UV-Vis 光譜..........................61
3.9、聚合條件.........................................................................................62
3.10、掌性聚苯胺分子量的探討...........................................................63
3.11、苯胺單體、雙體、單體加雙體及四聚體聚合之導電度及g-factor
比較.............................................................................................64
3.12、苯胺單體及雙體與其它苯胺衍生物之比較...............................66
3.13、電化學石英晶體微天秤(EQCM)................................................68
3.13.1、使用EQCM 做陰離子摻雜之探討........................................68
3.13.2、聚苯胺摻雜掌性陰離子時，頻率變化與質量之關係.........69
3.13.3、利用EQCM 偵測掌性非類固醇類抗發炎藥物fiurbiprofen..69
4、結論與未來展望.................................................................................73
5、參考資料..............................................................................................75

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