臺灣博碩士論文加值系統

聚苯胺（polyaniline，PAn）因具價格低廉、在空氣中穩定性佳及可進行酸摻雜之特性，在學術研究上及實際應用上均有極大的價值。由於聚苯胺具有剛性的共軛主鏈，無法溶於一般的有機溶劑或被熔融加工，故本文目的擬探討在二甲亞碸（dimethyl sulfoxide，DMSO）溶劑中，利用丙烯醯胺（acrylamide，AAm）單體、2,2'-偶氮雙異丁腈（2,2'-azobis-isobutyronitrile，AIBN），在聚苯胺中進行聚合反應生成聚苯胺/丙烯醯胺（PAn/AAm）聚合體，並以各種光譜分析法（UV-Vis，IR，X-ray 繞射，GPC，13C-NMR）、熱分析法（TGA，DSC，DMA）及導電度測量法來探討PAn/AAm聚合體溶液與薄膜之結構及物性關係。
在溶解度測試上，一般聚苯胺在經酸摻雜後，極易凝集而沈澱下來，而本論文中所合成PAn/AAm聚合體，不僅在未摻雜前可溶於水，且經酸摻雜後亦溶於水；由GPC結果可知有二組聚合體分佈存在，其一為PAn本身所造成，另一為在反應中當AAm增加時會有另一組不同於PAn之聚合體；而且分子量會受溫度與AIBN量的影響。結構鑑定上，由13C-NMR可以得知AAm基團有接在PAn之amine的N上，而非苯環或醌環上；另外，由IR也亦得知，當隨聚合體內AAm含量增加，會使得PAAm之C=O吸收峰（1661 cm-1）、PAAm之N-H吸收峰（3185 cm-1）、PAn之N-H吸收峰（3274 cm-1）與PAn之Caromatic-N吸收峰（1306 cm-1）分別都有往低波數偏移的趨勢，這證明了上述各吸收峰之間有氫鍵作用力的存在。在UV-Vis光譜分析上，含有AAm基團的聚合體可顯察出在355 nm及610 nm有吸收峰，分別為amine及imine之特性峰，唯imine ring的吸收較pure PAn弱，這是因PAn/DMSO在高溫時，DMSO會因熱裂解而游離出proton自由基（H·），而此自由基會去攻擊PAn之imine form，使可供摻雜的imine結構變少，以致摻雜程度變低，造成導電度不高。就結構與物性分析上，由X-ray，DSC，DMA結果綜合可以得知，AAm可幫助PAn有較規則的排列，使得有新的規則相生成。

Polyaniline (PAn) is currently considered to have high potentiality toward practical applications due to its cheap, good environmental stability and protonation with a protonic acid. However, it is very difficult to be dissolved in common organic solvents owing to its inherent rigid backbone. Thus, the aim of this research is to study the mechanism of PAn by react with 2,2¢-azobis-isobutyronitrile (AIBN) and acrylamide (AAm) in dimethylsulfide (DMSO) solution, and to investigate structure of the polymers. After the modification of PAn, water soluble occurs. The tools used for the studied are gel permeation chromatograph (GPC), nuclear magnetic resonance spectrometer (13C-NMR), ultraviolet-visible spectroscopy (UV-Vis), infrared spectroscopy (IR), X-ray diffractometer (XRD), differential scanning calorimeter (DSC), dynamic mechanical analyzer (DMA), thermogravimetric analyzer (TGA), and conductivity measurements.
In the true solution test, it was found that undoped and acid-doped PAn/AAm polymer could be dissolved in H2O. Results of GPC evidenced PAn/AAm polymers have two molecular weight distributions. One is caused by poly(acryl amide) (PAAm) and the other is due to the addition of AAm into PAn main chain, and their molecular weights are influenced by temperature and the amount of AIBN. 13C-NMR Results indicated that the AAm group is bonding with the nitrogen atom (N) of amine ring of PAn chain. For IR spectra, all the absorption bands at 1661 and 3185 cm-1 of C=O and N-H stretching vibration of PAAm, respectively, and at 3274 and 1306 cm-1 of N-H and Caromatic-N stretching vibration of PAn, respectively, shifted toward low frequency. These results indicate the presence of hydrogen-bond interactions of PAn added with AAm. For PAn/AAm DMSO solution, two absorption peaks exist at 355 nm (π-π* transition of the benzenoid ring) and 610 nm (excition absorption of the quinoid ring) but the decreasing of ratio of lmax,imine/lmax,amine. It is due to the thermal dissociation of DMSO into proton radical(H·), which will attack imine form of PAn to amine form, causing the decreasing of imine structure. XRD results indicate AAm group help PAn chain to form a more regular phase resulting in the formation of a new phase at 2q= ~10°. The co-existence of two-phase strongly supports those hydrogen-bond interactions between the two components. For conductivity measurement as measured using the four-probe method, the decreasing of conductivity of PAn with the increasing of AAm is due to the decreasing of imine in the reaction and the dropping of doping level.

摘要（中文）-------------------------------------------------------------------VIII
摘要（英文）------------------------------------------------------------------X
圖目錄---------------------------------------------------------------------------XII
表目錄---------------------------------------------------------------------------XIV
第一章 緒 論---------------------------------------------------------------------1
1-1 前言-------------------------------------------------------------------------1
1-2 本文研究目的-------------------------------------------------------------4
第二章 文 獻 回 顧------------------------------------------------------------5
2-1 聚苯胺之簡介-------------------------------------------------------------5
2-2 聚苯胺之合成及摻雜----------------------------------------------------6
2-2-1 聚苯胺之合成-------------------------------------------------------6
2-2-2 聚苯胺之合成機構-------------------------------------------------7
2-3 聚苯胺之結構與物性----------------------------------------------------8
2-3-1 聚苯胺之摻雜-------------------------------------------------------8
2-3-2 紅外線光譜分析---------------------------------------------------11
2-3-3 紫外光-可見光（UV-Vis）吸收光譜分析--------------------11
2-4 聚苯胺之電化學現象--------------------------------------------------13
2-5 聚丙烯醯胺（polyacrylamide，PAAm）--------------------------14
2-5-1 聚丙烯醯胺之合成------------------------------------------------17
2-5-2 聚丙烯醯胺之紅外線光譜分析---------------------------------17
2-6 聚苯胺複合膜-----------------------------------------------------------19
第三章 實 驗 內 容-----------------------------------------------------------22
3-1 藥品-----------------------------------------------------------------------22
3-2 合成-----------------------------------------------------------------------23
3-2-1 二甲亞碸（Dimethyl sulfoxide，DMSO）溶劑之純化----23
3-2-2 聚苯胺（polyaniline，PAn）之合成---------------------------23
3-2-3 聚丙烯醯胺（polyacrylamide，PAAm）合成----------------24
3-2-4 聚（丙烯醯胺-苯胺）之合成------------------------------------25
3-2-5 聚苯胺/聚丙烯醯胺（PAn/PAAm）摻合體之製備-----------26
3-3 真實溶液（true solution）之鑑定------------------------------------26
3-3-1 聚（丙烯醯胺-苯胺）聚合體溶液分別滴入H2O中
之真實溶液鑑定-----------------------------------------------------------26
3-3-2 聚（丙烯醯胺-苯胺）聚合體H2O溶液經酸摻雜後
之真實溶液鑑定-----------------------------------------------------------27
3-4 儀器設備-----------------------------------------------------------------27
第四章 聚（丙烯醯胺-苯胺）聚合體之結構鑑定之研究--------------33
4-1 前言-----------------------------------------------------------------------33
4-2 溶解度--------------------------------------------------------------------33
4-3 凝膠滲透層析法（GPC）--------------------------------------------36
4-4 核磁共振光譜（13C-NMR）------------------------------------------44
4-5 紅外線光譜（IR）分析------------------------------------------------46
4-6 紫外光-可見光光譜（UV-Vis）分析--------------------------------50
4-7 熱性質分析（Thermal analysis）-------------------------------------59
4-7-1 熱重量分析（TGA）----------------------------------------------59
4-7-2 微差掃描熱卡分析（DSC）與動態機械分析（DMA）---61
4-8 X-ray 繞射分析（XRD）----------------------------------------------65
4-9 導電度（Conductivity）分析------------------------------------------67
4-10 酸摻雜之溶解度分析-------------------------------------------------68
4-11 反應機構推導----------------------------------------------------------74
第五章 結 論--------------------------------------------------------------------75
參考文獻--------------------------------------------------------------------------79

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