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Student Number 87621003
Author Wen-Len Xia(謝文仁)
Author's Email Address No Public.
Statistics This thesis had been viewed 1521 times. Download 1753 times.
Department Chemistry
Year 1999
Semester 2
Degree Master
Type of Document Master's Thesis
Language zh-TW.Big5 Chinese
Title 塞吩-烷基塞吩共聚物之合成與性質探討
Date of Defense 2000-07-18
Page Count 76
Keyword
  • 塞吩
  • Abstract Conducting polymers, polyalkylthiophenes(P3ATs) are attracting extensive attentions, due to their good electrical properties and processability. Enhanced solubilization can be achieved by grafting long alkyl side chains on a polyaromatic backbone as has been demonstrated in P3ATs. However, side chains also decreased the stability of doped polymer, thin films of FeCl3 doped P3ATs dedoped automatically in ambient atmosphere at room temperature. It was believed that the side chain mobility is the major reason in the dedoping reaction of polyalkylthiophene. Therefore, we prepared a series of copolymers consisting of 3-alkylthiophene and thiophene units, such as Poly(3-octylthiophene-co-thiophene)(CPOTH), Poly(3-octyl-2,2’-bithiophene) (PTOT) and Poly(3’-octyl-2,2’;5’2’’-terthiophene)(PTOTT). These copolymers have fair solubility in common solvents, such as chloroform and tetrahydrofuran although not as good as polyalkylthiophene. The mole ratio of Thiophene (TH)/ Octylthiophene (OT) in the copolymers were determined by the infrared spectroscopic and element analysis. It was found that when the TH/OT ratio of the random copolymer is higher than 0.22, the copolymer losts its solubility. The mole ratio of 3-alkylthiophene/thiophene in the backbone of copolymer affects not only its solubility, but also its stability and conductivity. We found that the dedoping rate of CPOTH decreases as the mole ratio of TH/OT increases, and the electric conductivity increases as the mole ratio of TH/OT increases.
    Table of Content 中文摘要--------------------------------------------------------------------------Ⅰ
    英文摘要--------------------------------------------------------------------------Ⅱ
    目錄--------------------------------------------------------------------------------Ⅲ
    圖目錄-----------------------------------------------------------------------------Ⅵ
    表目錄-----------------------------------------------------------------------------Ⅷ
    壹. 緒論--------------------------------------------------------------------------------------------------1
    1-1聚合物------------------------------------------------------------------------------------------1
    1-2有機導電高分子--------------------------------------------------------------------------- 2
    ◎ 有機導電高分子之發展歷史-------------------------------------------------------- 2
    ◎ 有機導電高分子之導電機構-------------------------------------------------------- 5
    ◎ 古典半導體之帶結構理論----------------------------------------------------------- 5
    ◎ 有機導電高分子之導電理論-------------------------------------------------------- 6
    1-3 導電高分子的應用------------------------------------------------------------------------12
    1-4 聚3-烷基?吩系統------------------------------------------------------------------------17
    ◎ 簡介--------------------------------------------------------------------------------------- 17
    ◎ 聚3-烷基?吩的聚合--------------------------------------------------------------- 18
    ◎ 聚3-烷基?吩鏈上的烷基排列方式-------------------------------------------- 21
    ◎ 聚3-烷基?吩的摻雜理論--------------------------------------------------------- 23
    1-5 研究動機------------------------------------------------------------------------------------ 26
    貳、實驗部份------------------------------------------------------------------- 27
    2-1藥品---------------------------------------------------------------------- 27
    2-2 使用儀器及樣品的製備--------------------------------------------- 30
    2-3實驗步驟---------------------------------------------------------------- 37
    ◎3-alklythiophene單體的合成--------------------------------- 37
    ◎化學聚合Poly(3-octylthiophene)--------------------------- 38
    ◎化學聚合Polythiophene------------------------------------------39
    ◎化學聚合Poly(alkylthiophene-co-thiophene)------------39
    ◎合成3-hexynylthiophene----------------------------------------40
    ◎化學聚合3-hexynylthiophene----------------------------------41
    ◎合成2-Bromo,3-octylthiophene-----------------------------------42
    ◎合成2,5-Bromo 3-octylthiophene---------------------------------43
    ◎合成2-thiopheneboronic acid--------------------------------------44
    ◎3’-octyl-2,2’-terthiophene單體的合成--------------------45
    ◎3’-octyl-2,2’;5’,2’’-terthiophene單體的合成-----------46
    ◎化學聚合Poly 3’-octyl-2,2’-terthiophene----------------47
    ◎化學聚合Poly 3’-octyl-2,2’;5’,2’’-terthiophene-------48
    ◎摻雜反應--------------------------------------------------------------49
    ◎利用紫外光可見光近紅外光光譜觀察去摻雜--------------49
    ◎利用GPC測量分子量----------------------------------------------51
    參、結果與討論------------------------------------------------------------------52
    3-1共聚物與聚合物結構的鑑定-----------------------------------------52
    ◎單體的製作方面-----------------------------------------------------52
    ◎合成具有規則性之?吩-烷基?吩共聚物---------------------53
    ◎聚3-烷基?吩之聚合反應和共聚合反應-----------------------56
    ◎共聚物的溶解性質探討--------------------------------------------59
    ◎共聚合物結構的探討-----------------------------------------------61
    ◎由UV-Vis吸收光譜來探討共聚物與POTH結構上的差異--67
    ◎共聚物之螢光性質探討--------------------------------------------70
    ◎所合成共聚物之再現性--------------------------------------------71
    3-2摻雜後的共聚物之性質----------------------------------------------74
    ◎CPOTH摻雜後的紅外光吸收光譜探討---------------------------74
    ◎摻雜後的薄膜之紫外光/可見光/近紅外光吸收光譜--------75
    ◎由SEM來觀察摻雜前後之薄膜表面型態----------------------76
    3-3聚合物的去摻雜現象------------------------------------------------- 78
    3-4 3-己炔?吩的合成及探討--------------------------------------------79
    ◎poly 3-hexynylthiophene(phyth)的結構探討--------------------79
    肆、 結論-------------------------------------------------------------------------81
    伍、參考文獻-------------------------------------------------------------------115
    圖目錄
    圖1-2-1:簡單的能帶示意圖---------------------------------------------------------------------- 6
    圖1-2-2:基態具有同階性的反式-聚乙炔的結構--------------------------------------------7
    圖1-2-3:在帶溝中感應出孤波子態的示意圖------------------------------------------------7
    圖1-2-4:聚3-烷基?吩的芳香與?型式,兩者之間能量不相
    等,所以不能互相轉換-----------------------------------------------------------------8
    圖1-2-5:聚3-烷基?吩形成偏極子的結構---------------------------------------------------8
    圖1-2-6:在聚3-烷基?吩中,偏極子無法發生上述的共振結構式------------------9
    圖1-2-7:聚3-烷基?吩形成雙偏極子的結構------------------------------------------------9
    圖1-2-8:在聚3-烷基?吩中,雙偏極子可在鏈的?吩環之間傳遞電荷------------10
    圖1-2-9:聚3-烷基?吩摻雜時的能階圖------------------------------------------------------11
    圖1-3-1:導電高分子應用在積體電路圖案的製程-----------------------------------------13
    圖1-3-2:導電高分子應用在太陽能電池示意圖---------------------------------------------13
    圖1-3-3:導電高分子應用在感應器的示意圖------------------------------------------------14
    圖1-3-4:鋰-聚苯胺電池裝置圖------------------------------------------------------------------15
    圖1-4-1:聚3-烷基?吩的聚合反應機構(經π自由基)----------------------------------19
    圖1-4-2:聚3-烷基?吩的聚合反應機構(經σ自由基)----------------------------------19
    圖1-4-3:聚合後,聚3-烷基?吩可能發生的化學缺陷與結構缺陷------------------20
    圖1-4-4:兩個?吩環為單元的排列情形------------------------------------------------------21
    圖1-4-5:三個?吩環為單元的排列情形------------------------------------------------------21
    圖1-4-6:不同的排列所造成共平面程度的減少---------------------------------------------22
    圖1-4-7:經氯化鐵摻雜後,聚3-烷基?吩的平面結構示意圖------------------------24
    圖2-1:四點探針導電度測試-------------------------------------------------36
    圖2-2:摻雜之過程示意圖----------------------------------------------------50
    圖2-3:不同分子量之聚苯乙烯與其對應滯留時間的關係圖---------51
    圖3-1-1:3-octylthiophene單體之1H NMR圖譜--------------------------82
    圖3-1-2:共聚物之單體--------------------------------------------------------53
    圖3-1-3:合成溴化烷基?吩的方法-----------------------------------------54
    圖3-1-4:2,5-Dibromo 3-octylthiophene的1H NMR圖譜---------------83
    圖3-1-5:2-Bromo 3-octylthiophene的1H NMR圖譜--------------------84
    圖3-1-6:3’-octyl-2,2’-terthiophene之1H NMR圖------------------------85
    圖3-1-7:3’-octyl-2,2’;5’,2’’-terthiophene之H1 NMR圖----------------86
    圖3-1-8:中性聚合物之IR圖------------------------------------------------87
    圖3-1-9:中性之CP0.21的IR圖--------------------------------------------88
    圖3-1-10:中性共聚物固態薄膜之IR圖-------------------------------------89
    圖3-1-11:PTOTT與PTOT之IR圖----------------------------------------90
    圖3-1-12:CP0.21與CP0.04之1H NMR光譜圖-------------------------91
    圖3-1-13:不同TH/OT比的共聚物之NMR圖---------------------------92
    圖3-1-14:各種不同連接方式的共聚物可能結構------------------------64
    圖3-1-15:PTOT與PTOTT之1H NMR圖--------------------------------93
    圖3-1-16:TH/OT共聚時的莫耳比與共聚物中TH與OT莫耳比的
    關係圖---------------------------------------------------------------94
    圖3-1-17:IR特殊峰型比與元素分析結果之關係圖---------------------95
    圖3-1-18:中性之共聚物固態薄膜之UV/vis圖--------------------------96
    圖3-1-19:所有聚合物之UV/vis圖與螢光光譜圖-----------------------97
    圖3-1-20:相同共聚物濃度下,TH/OT比與螢光強度之關係圖-------98
    圖3-1-21:(a) PTOTT (b) CP0.04 (c) PTH 之熱重分析結果------------99
    圖3-1-22:中性CP0.19之XRD繞射圖------------------------------------100
    圖3-2-1:CP0.21之中性態與氧化態的IR圖------------------------------101
    圖3-2-2:PTOTT之中性態與氧化態的IR圖-----------------------------102
    圖3-2-3:CPOTH2:1之中性態與氧化態的UV/Vis/NIR光譜圖-------103
    圖3-2-4:摻雜前後聚合物之SEM圖(放大200倍)--------------------104
    圖3-2-5:各種不同TH/OT莫耳比之共聚物摻雜後之SEM圖(放大
    5000倍)--------------------------------------------------------------105
    圖3-2-6:摻雜後的共聚物ESCA大範圍掃描圖-------------------------106
    圖3-3-1:CP0.14去摻雜現象------------------------------------------------107
    圖3-3-2:CP0.14平均去摻雜速率對時間的關係------------------------108
    圖3-3-3:平均去摻雜速率對共聚物組成的關係圖----------------------109
    圖3-4-1:3-hexynylthiophene的1H NMR圖譜----------------------------110
    圖3-4-2:PHYTH溶解與不溶部份的IR圖------------------------------111
    圖3-4-3:PHYTH溶解部份之ESCA圖------------------------------------112
    圖3-4-4:PHYTH溶解部份之Cl的ESCA化學位移掃描圖----------113
    圖3-4-5:PHYTH之SEM及EDS圖(放大3000倍)--------------------114
    表目錄
    表1-1:常見的導電高分子-------------------------------------------------------------------------4
    表1-3-1:導電高分子可作成不同類型的感應器---------------------------------------------14
    表1-3-2:導電高分子應用於鋰電池中的各種性質-------------------------16
    表3-1-1:3-烷基?吩的單體產率--------------------------------------------52
    表3-1-2:合成時,所控制的條件--------------------------------------------54
    表3-1-3:聚合物的簡稱及產物(TH/OT)比---------------------------------58
    表3-1-4:聚合物的溶解性測定-----------------------------------------------60
    表3-1-5:由元素分析所測得共聚物中的組成-----------------------------66
    表3-1-6:由IR特殊峰吸收高度比推算TH /OT之莫耳比與元素
    分析結果做比較(可溶部分)---------------------------------------67
    表3-1-7:共聚合物薄膜和溶液的最大吸收波長位置和組成比-------68
    表3-1-8:由不同有機溶液中,所鍍出的聚烷基?吩及?吩-烷
    基?吩共聚物膜的最大吸收波長--------------------------------69
    表3-1-9:聚合物的最大吸收波長與發光波長-----------------------------71
    表3-1-10:共聚物再現性的情形---------------------------------------------72
    表3-1-11:共聚物的裂解溫度比較表與分子量---------------------------73
    表3-1-12:不同TH/OT比之中性共聚物鏈與鏈之間的距離----------72
    表3-2-1:聚合物中性態、氧化態之導電度--------------------------------76
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    Advisor
  • Chun-Guey Wu(吳春桂)
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