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研究生:安家幸
研究生(外文):Kevin Gerhana
論文名稱:含偶氮側鏈基嵌段共聚物之合成及自組裝特性研究
論文名稱(外文):Synthesis and Characterization of Self-assembled Diblock Copolymers Containing Azo Pendant Groups
指導教授:劉瑞祥
指導教授(外文):Jui-Hsiang Liu
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系碩博士班
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:2008
畢業學年度:96
語文別:英文
論文頁數:88
中文關鍵詞:兩嵌段式共聚物自組裝原子轉移自由基聚合
外文關鍵詞:diblock copolymerself-assemblyATRP
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在本研究中,成功的利用原子轉移自由基聚合法合成一系列兩嵌段式共聚物,並於其中一嵌段中導入具光學異構化之偶氮苯官能基。研究中所合成之兩嵌段式共聚物均以NMR、GPC、DSC、TGA及UV-vis鑑定分析。由GPC分析結果可知,其數目平均分子量(Mn)範圍為1.23×103-2.77×104及具有窄分子量分佈指數 (PDI) 1.02-1.51。在兩嵌段式共聚物自組裝行為的研究上,因不同環境下可誘導出不同的微結構,可分為薄膜及溶液兩種製程。於薄膜製程中,於高溫真空環境下讓兩嵌段式高分子具有足夠時間排列,經AFM表面型態分析可知,薄膜轉變成均勻且規則排列之微米級的凸狀結構;另外,若將合成之高分子薄膜置於適當溶液蒸氣中,亦可得到規則排列之微米級孔洞。在溶液系統中兩嵌段式共聚物亦會有自組裝行為,於實驗中發現在適當極性之溶液狀態下,含偶氮光異構化官能基之兩嵌段式共聚物可自組裝成球狀之微胞構形,經UV光誘導光異構化時,由於N=N官能基可進行E-Z構形變化,因而讓高分子之形狀由球狀之微胞轉變成棒狀。
A series of monomers and AB diblock copolymers incorporating azobenzene group as photochromic segment were successfully synthesized and polymerized using atom transfer radical polymerization (ATRP). The synthesized asymmetric AB diblock copolymers were characterized by NMR, GPC, DSC, TGA, and UV-vis. The number-average molecular weights (Mn) of the synthesized polymers were estimated by GPC using mono-dispersed polystyrene as standard, and were found in the range of 1.23×103 - 2.77×104 gmol-1 with polydispersity indexes (PDI) lying between 1.02 and 1.51. The morphologies with bump construction under thermal annealing were confirmed by AFM. Self-assembled diblock copolymer nano-particles which were fabricated in THF/H2O mixture and mesoporous structure under solvent annealing were investigated by TEM. UV irradiation caused photoisomerization at N=N segment of the synthesized copolymers leading to a construction from sphere to rod. The photo-induced construction variation is expected to be used in transformation of photo energy to mechanical forces. The results of this investigation present significant scientific and practical contributions with respect to the preparation of various morphologies of the diblock copolymer in the supramolecular chemistry.
Abstract i
中文摘要 ii
Acknowledgements iii
Contents iv
List of Figures vii
List of Schemes x
List of Tables xi
Chapter 1 Introduction 1
1.1 Preface 1
1.2 Block Copolymer 2
1.3 Self-Assembly of Block Copolymer 4
1.4 Synthesis of Block Copolymer 5
1.5 Application of Block Copolymer 6
1.6 Research Motivation 7
Chapter 2 General Introduction and Theoretical Background 8
2.1 Self-Assembly 8
2.1.1 Block Copolymer Self-Assembly 10
2.1.2 Phase Separation 12
2.1.3 Block Copolymer in Solution 13
2.1.4 Thermal and Solvent Treatment 15
2.2 Atom Transfer Radical Polymerization (ATRP) 21
2.3 Azo Monomer 27
Chapter 3 Experimental 29
3.1 Materials 29
3.2 Measurement 30
3.3 Preparation of Materials 31
3.3.1 Reactants 31
3.3.2 CuIBr and CuICl 32
3.3.3 Solvents 32
3.3.4 Silicon Substrate 32
3.4 Synthesis of Monomers 33
3.4.1 Ethyl 4-(4-hydroxyphenylazo) benzoate (1) 33
3.4.2 Ethyl 4-[4-(6-hydroxyundecyl) phenylazo] benzoate (2) 33
3.4.3 Ethyl 4-[4-(11-methacryloyloxyundecyloxy) phenyl azobenzoyloxyl] benzoate (M1) 33
3.4.4 4-cyanophenyl methacrylate (M2) 34
3.4.5 4-Hydroxy-4’-cyano-azobenzene (3) 35
3.4.6 4-Methacryloyloxy-4’-cyano-azobenzene (M3) 35
3.4.7 Butyl (s)-(-) methacryloyloxy-isopropanoate (M4) 36
3.5 Synthesis of Homopolymers 37
3.5.1 PMMA-Br Macroinitiator 37
3.5.2 Poly-ethyl-4-[4-(11-methacryloyloxyundecyloxy)phenyl azobenzoyloxyl] benzoate (P1) 38
3.5.3 Poly-4-cyanophenyl methacrylate (P2) 39
3.5.4 Poly-4-methacryloyloxy-4’-cyano-azobenzene (P3) 39
3.6 Synthesis of Diblock Copolymers 41
3.6.1 PMMA-b-P1 41
3.6.2 PMMA-b-P2 41
3.7 Self-Assembly of PMMA-b-P1 43
3.7.1 PMMA-b-P1 in Solution 44
3.7.2 Thermal Annealing 45
3.7.3 Solvent Annealing 46
Chapter 4 Results and Discussion 47
4.1 Synthesis of Novel Monomers 47
4.2 Synthesis of Homopolymer 51
4.3 Synthesis of Diblock Copolymer 58
4.4 Self-Assembly of PMMA-b-P1 Diblock Copolymer 62
4.4.1 Phase Separated Nano-particles in THF/H2O 63
4.4.2 Thermal Annealing 68
3.3.1 Solvent Annealing 77
Chapter 5 Conclusions 80
Chapter 6 References 81
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