臺灣博碩士論文加值系統

現今大多數的材料都需要經過額外化學的處理或改質才能使材料更適合用在各領域中，然而經過分子設計過後的團聯式共聚高分子，可以利用許多方法使其自組裝行程某特殊型態結構，而可應用於特殊功能、材料之上，可省去許多繁雜的改質步驟或費時的額外處理功夫。因此運用分子設計，而具有自組裝特性的團聯式共聚高分子已受到許多的矚目與探討。
本論文主要研究在不同溶劑下(THF and DMF)，溶劑性質對非共價鍵鍵結的微胞型態所造成的影響。以甲基丙烯酸甲酯(methyl methacrylate) 及4-乙烯吡啶(4-vinyl pyridine)為單體，用陰離子聚合反應合成出Poly(methyl methacrylate-b-4-vinyl pyridine)團聯式共聚高分子，再以苯乙烯(styrene) 及 第三丁基氧苯乙烯(4-tert-Butoxystyrene)為單體，用自由基聚合反應及一水解反應去除保護基，合成出Poly(styrene-r-vinylphenol) 無規式共聚高分子。
將合成出的團聯式及無規式共聚高分子分別溶於同一種溶劑中，在溶液中慢慢滴加混摻成不同比例，使其藉由氫鍵自組裝成不同型態的微胞，並以傅立葉轉換紅外線光譜(FTIR) 分析其氫鍵作用力、穿透式電子顯微鏡(TEM) 觀察其微胞型態、動態光散射儀(DLS) 測量其粒徑分布。

Most of today’s materials require additional processing or modification steps in order to obtain the properties that make them suitable for a particular application. As an alternative to these traditional fabrication pathways, routes that use the self-assembly of polymeric building blocks are attracting increasing attention.
We have synthesized poly(methyl methacrylate-b-4-vinylpyridine) (PMMA- b-P4VP) and poly(styrene-r-vinylphenol) (PS-r-PVPh) copolymers by using the anionic polymerization and the free radical polymerization, respectively. Well defined micelles through hydrogen bond have been prepared by mixing PMMA-b-P4VP diblock copolymer and PS-r-PVPh random copolymer in single solvent. The block copolymers were mixed with random copolymers, with the various B/R ratio (4/1, 2/1, 1/1, and 1/4) in which “B” and “R” represents block copolymers and random copolymers, respectively. The presence distribution of PVPh/P4VP and PVPh/PMMA hydrogen bonding depends on the feeding ratio of PVPh to P4VP. When the PVPh content lower than P4VP, hydrogen bonding occurs only between PVPh and P4VP; with excess PVPh, additional hydrogen bonding between PVPh and PMMA could occur.
Furthermore, the effect of the solvent quality on the self-assembly behavior of PMMA-b-P4VP/PS-r-PVPh blends is investigated by considering THF and DMF as common solvent.

Outline of Contents I
List of Tables IV
List of Schemes V
List of Figures VI
Abstract(in Chinese) IX
Abstract(in English) X

Chapter1 Introduction 1
1-1 An Over of Self-organization of Block Copolymers 1
1-2 Micellization of Block Copolymers 3
1-2.1 Preparation of Amphiphilic Block Copolymer Aggregates 3
1-2.2 Factors Affecting the Morphology 4
1-3 Nonconvalently Connected Micelles (NCCM) 5
1-3.1 A-B/C Type Complex System 6
1-3.2 A-B/C-D Type Complex system 6
1-4 Motivation 9
References 10

Chapter 2 Theory 17
2-1 Theories of Polymerization 17
2-1.1 Anionic Polymerization 17
2-1.2 Free Radical Polymerization 19
2-2 Theories of Micellization 21
2-2.1 Block Copolymer Micelle Free Energies 22
2-2.2 Estimation of Micelle Free Energies 24
2-2.3 Geometrical Theories 25
References 28

Chapter 3 Expermental Section 33
3-1 Materials 33
3-2 Synthesis of PMMA-b-P4VP by Anionic Polymerization 35
3-3 Synthesis of PS-r-PVPh by Free Radical Polymerization 36
3-4 Copolymer Characterization 37
3-5 Preparation of PS-r-PVPh/PMMA-b-P4VP Micelle Solutions 39
3-6 Characterizations 40
3-6.1 Gel Permeation Chromatography 40
3-6.2 Infrared Spectroscopy 40
3-6.3 Transmission Electron Microscopy 40
3-6.4 Dynamic Light Scattering 41

Chapter 4 Results and Discussion 50
4-1 Infrared Analyses 51
4-2 Differential Scanning Calorimetry Analyses 55
4-3 Transmission Electro Microscopy Analyses 57
4-3.1 Structures of PMMA-b-P4VP/ PS-r-PVPh Micelles in
THF solution 58
4-3.2 Structures of PMMA-b-P4VP/ PS-r-PVPh Micelles in
DMF solution 59
4-4 Dynamic Light Scattering Analyses 61
4-4.1 Hydrodynamic Diameter Distribution of PMMA-b-P4VP
/ PS-r-PVPh Micelles in THF solution 61
4-4.2 Hydrodynamic Diameter Distribution of PMMA-b-P4VP
/ PS-r-PVPh Micelles in DMF solution 62
References 64

Chapter 5 Conclusions 80
Introduction to Author 82

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