原子轉移自由基聚合反應的配基開發與高分子結構對螢光放光的影響

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研究生：	韓蕙安 Han, Hui-An
論文名稱：	原子轉移自由基聚合反應的配基開發與高分子結構對螢光放光的影響 Development of Pyridyl-Imine Ligand Used in Atom Transfer Radical Polymerization and The Structural Effect to Fluorescent Intensity of Dye-labeled Polymers
指導教授：	彭之皓 Peng, Chi-How
口試委員:	韓建中 Han, Chien-Chung 陳俊太 Chen, Jiun-Tai 彭之皓 Peng, Chi-How
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2014
畢業學年度：	102
語文別：	中文
論文頁數：	120
中文關鍵詞：	原子轉移自由基聚合反應、甲基丙烯酸甲酯、苯乙烯、星狀聚合物、網狀聚合物、螢光
外文關鍵詞：	ATRP, Methyl methacrylate, Network polymer, Styrene, Star polymer, Fluorescence
相關次數：	點閱：3 下載：0
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本論文主要分為三部分，第一部份是利用新穎的砒碇-亞胺銅金屬錯合物成功聚合甲基丙烯酸甲酯，將吡啶-亞胺銅金屬錯合物 CuII(paenMe2)Br2，以原子轉移自由基聚合 (ATRP) 與電子轉移活化原子轉移自由基聚合 (AGET ATRP) 的方法成功地控制甲基丙烯酸甲酯聚合反應的分子量分布 (Mw/Mn = 1.14 ~ 1.18) ，且實際分子量符合理論分子量 (Mn ~ Mn,th)。
第二部份是利用AGET ATRP的技術合成嵌有芘 (Pyrene) 螢光團的鏈狀、星狀及網狀聚苯乙烯，探討結構的變化對螢光強度的影響。實驗結果發現鏈狀及網狀聚苯乙烯其螢光強度皆會隨著單體轉換率的增加而上升，但網狀聚合物的螢光上升幅度較鏈狀聚合物小，推測可能是因為受到交聯劑 (Cross-linker) 的束縛，使得網狀聚苯乙烯的結構較固定，芘與芘、苯乙烯和苯乙烯之間的π-π作用力較小，因此螢光上升幅度較小。而星狀聚合物的螢光強度則是在聚合初期先下降，爾後上升，推測可能是因為在反應初期星狀聚合物的側鏈 (Arm) 會與大量的交聯劑進行反應，側鏈上的螢光團被大量的交聯劑包圍使得螢光強度下降; 在形成星狀聚苯乙烯後，可能因為星狀聚苯乙烯側鏈數目的增加以及星狀聚苯乙烯間耦合的現象，使得不論分子內及分子間，側鏈與側鏈、芘與芘的π-π作用力增強，因此螢光強度上升。
第三部份則是探討末端嵌有螢光團嵌段共聚物 (Block copolymer) 的自組裝情形。合成pyrene-PMMA-b-PSt、naphthalene-PMMA-b-PSt、pyrene-PSt-b-PMMA及 naphthalene-PSt-b-PMMA，但利用小角度X光散射儀和穿透式電子顯微鏡並未觀察到明顯的相分離效果，推測可能是因為螢光團間的π-π作用力影響了自組裝的效果，或是聚苯乙烯 (PSt) 與聚甲基丙烯酸甲酯 (PMMA) 間的溶解參數太相近 (δPSt = 9.1, δPMMA = 9.2-9.4 cal/cm3)，使得相分離效果不佳，導致沒有明顯的自組裝發生。

Pyridyl-imine copper complex, CuII(paenMe2)Br2, was used to mediate the normal and AGET (Activators generated by electron transfer) ATRP of methyl methacrylate. The different initiators, ratios of ligand and the lengths of copper wires were tuned. The polymeric products showed a low polydispersity (Mw/Mn = 1.14 ~ 1.18) and the molecular weight matched the theoretical values.
Besides, the pyrene-labeled polymers with structure of linear, star and network were synthesized by AGET ATRP. Observing the fluorescent intensity changes of polymers by PL, we found the fluorescent intensity of star polymer decreased at the beginning and increased afterwards. For linear and network polymers, the fluorescent intensity increased with conversion increasing.
The block copolymers of pyrene-PMMA-b-PSt, naphthalene-PMMA-b-PSt, pyrene-PSt-b-PMMA and naphthalene-PSt-b-PMMA were synthesized to observe their self-assembly effect. However, using SAXS (Small angle x-ray scattering) and TEM (Transmission electron microscopy) to observe the structure of block copolymers, the ordered arrangement and microphase separation were not found.

Abstract...................................................................................................................................i
摘要........................................................................................................................................ii
謝誌.......................................................................................................................................iv
目錄........................................................................................................................................v
圖...........................................................................................................................................ix
表.........................................................................................................................................xiii
流程圖..................................................................................................................................xv
附錄....................................................................................................................................xvi
第一章 緒論..........................................................................................................................1
    1-1 可控自由基聚合反應原理.....................................................................................2
    1-2 可控自由基聚合反應方法.....................................................................................4
        1-2-1 氮氧自由基聚合反應 (NMP) ...................................................................4
        1-2-2 可逆加成-斷裂鏈轉移聚合反應 (RAFT polymerization) .......................5
        1-2-3 原子轉移自由基聚合反應 (ATRP) ..........................................................6
  1-2-4 電子轉移活化(再生)原子轉移自由基聚合反應 (A(R)GET   ATRP).....................................................................................................................10                                             
        1-2-5 起始劑持續活化再生原子轉移自由基聚合反應 (ICAR ATRP) ..........11
        1-2-6 補充活化劑與還原劑原子轉移自由基聚合反應 (SARA ATRP) .........12
        1-2-7 電化學引發原子轉移自由基聚合反應 (eATRP).................................14
    1-3利用可控自由基聚合反應方法製備枝狀聚合物...............................................16    
        1-3-1星狀聚合物...............................................................................................17
        1-3-2 網狀聚合物..............................................................................................19
    1-4 研究目的與動機.................................................................................................20
第二章 亞胺銅錯合物催化原子轉移及電子轉移活化原子轉移自由基聚合反應.......21
    2-1 前言.....................................................................................................................22
    2-2 實驗部分.............................................................................................................23
        2-2-1 化學藥品..................................................................................................23
        2-2-2 合成..........................................................................................................24
        2-2-3 聚合反應..................................................................................................25
    2-3晶體鑑定與構造討論...........................................................................................27
    2-4原子轉移自由基聚合甲基丙烯酸甲酯..............................................................30
    2-4-1 不同起始劑測試CuI(paenMe2)Br催化原子轉移自由基聚合甲基丙烯酸甲酯................................................................................................................30
2-4-2 不同配位基比例測試CuI(paenMe2)Br催化原子轉移自由基聚合甲基丙烯酸甲酯........................................................................................................32
    2-5 不同銅線長度測試CuI(paenMe2)Br催化電子轉移活化原子轉移自由基聚合 甲基丙烯酸甲酯..........................................................................................................33
    2-6 結論....................................................................................................................35
第三章 嵌有螢光團之聚合物的結構變化對螢光強度的影響.....................................36
    3-1 前言....................................................................................................................37
    3-2 實驗部分............................................................................................................39
        3-2-1 化學藥品.................................................................................................39
        3-2-2 螢光團起始劑的合成.............................................................................40
        3-2-3 聚合反應.................................................................................................42
    3-3 電子轉移活化原子轉移自由基聚合嵌有芘之鏈狀聚苯乙烯........................44
    3-4 電子轉移活化原子轉移自由基聚合嵌有芘之星狀聚苯乙烯........................46
    3-5利用掃描穿隧式電子顯微鏡觀察嵌有芘之星狀聚苯乙烯.............................52
    3-6 電子轉移活化原子轉移自由基聚合嵌有芘之網狀聚苯乙烯........................54
    3-7 比較嵌有芘之鏈狀聚苯乙烯和網狀聚苯乙烯在螢光強度上之變化............58
    3-8 結論....................................................................................................................60
第四章 探討嵌有螢光團之嵌段共聚物的自組裝行為.................................................61
    4-1前言.....................................................................................................................62
    4-2實驗部分.............................................................................................................65
        4-2-1 化學藥品................................................................................................65
        4-2-2 螢光團起始劑的合成............................................................................66
        4-2-3 聚合實驗步驟........................................................................................68
    4-3 嵌段共聚物之合成...........................................................................................71
    4-4 觀察嵌有螢光團之嵌段共聚物的相分離變化.................................................81
    4-5 結論.....................................................................................................................85
儀器....................................................................................................................................86
參考文獻............................................................................................................................90
附錄....................................................................................................................................94

                                

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