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研究生： 林芝因
Lin, Chih-Yin
論文名稱： 利用可逆加成-斷裂鏈轉移聚合法合成聚乙酸乙烯酯-聚苯乙烯區段共聚高分子
Straightforward Synthesis of Poly(vinyl acetate)-block-polystyrene Copolymers through Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization
指導教授： 劉英麟
Liu, Ying-Ling
口試委員: 趙基揚
Chao, Chi-Yang
邱昱誠
Chiu, Yu-Cheng
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2021
畢業學年度： 109
語文別： 英文
論文頁數： 105
中文關鍵詞： 高分子合成 、區段共聚高分子 、電引發聚合 、可逆加成-斷裂鏈轉移聚合法 、聚乙酸乙烯酯-聚苯乙烯
外文關鍵詞： eRAFT, PVAc-b-PS
相關次數： 點閱：3  下載：0 
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    • 區段共聚高分子已被廣泛運用在許多領域，如奈米科技、奈米光刻、控制藥物傳遞等。而可逆-去活化自由基聚合法為合成區段共聚高分子之方法之一，其中，可逆加成-斷裂鏈轉移聚合法可簡單地藉由依序加入單體之方式，合成出區段共聚高分子，為一具有高度潛力的區段共聚物合成方法。
    然而，由於MAM (more-activated monomer)及LAM (less-activated monomer)兩種種類之單體性質差異甚大，而不同種類之單體須以特定之鏈轉移劑進行控制。因此，以可逆加成-斷裂鏈轉移聚合法合成poly(LAM)-block-poly(MAM)區段共聚高分子相對複雜。而欲在良好控制之情況下，合成出含MAM及LAM兩種單體之區段共聚物更為一大挑戰。
    許多新穎的合成反應被開發用以解決上述之問題，但是這些設計往往都包含了兩種以上的合成步驟，才得以控制兩種差異極大的單體。相對複雜且困難的操作也帶給這些設計相當大的不便利性。因此，考量實用性及需求性，僅使用單一鏈轉移劑控制合成poly(LAM)-block-poly(MAM)之聚合法有其被開發之必要。
    本研究以商用之鏈轉移劑BM1481進行單一鏈轉移劑之可逆加成-斷裂鏈轉移聚合。藉由調控反應物濃度比及反應時間等參數，可成功合成出具良好控制性之poly(LAM)-block-poly(MAM)。另外，為了增加此反應系統在低溫下之應用性，將電致引發之起始劑BrPhN2+引入上述反應系統，取代熱起始劑AIBN。接著，改以電致引發可逆加成-斷裂鏈轉移聚合法合成出區段共聚物，並期望達到與熱致引發系統相同之效果。
    在產物性質鑑定中，本研究以傅立葉轉換紅外線光譜儀及核磁共振儀進行高分子化學結構之確認。並以差式掃描量熱儀及熱重分析儀對其進行熱性質分析。另外，也以奈米粒徑量測儀及穿透式電子顯微鏡進行兩性性質的觀察。最後，以凝膠滲透層析儀進行產物分子量及聚合物分散性指數之量測。而可由這些分析數據結果顯示，具良好控制性之區段共聚高分子之成功合成。亦顯示在適當之反應參數下，單一鏈轉移劑之可逆加成-斷裂鏈轉移聚合法可藉由熱致引發及電致引發，控制合成出目標高分子產物。

    Block copolymers have been widely applied in various fields, including nanotechnology, nanolithography, controlled drug delivery, etc. Meanwhile, RAFT polymerization, one of the most commonly used RDRP methods, holds high potential in synthesis of block copolymers simply via sequential addition of monomers.
    However, due to the opposite properties of two different monomers, there are still challenges in the synthesis of well-controlled poly(LAM)-block-poly(MAM), where LAM and MAM are two categories of monomers represent less activated monomers and more activated monomers respectively. Certain RAFT agents are required in polymerization of different monomers for good control. The limitation of selection of RAFT agents results in the difficulty for a single RAFT agent controlling two different kinds of monomers.
    Some polymerization strategies were designed to solve the issue, yet they involved two or more synthetic methods to control the two dissimilar monomers, leading to considerably complex polymerization procedure. Thus, an uncomplicated RAFT polymerization using a universal RAFT agent to produce poly(LAM)-b-poly(MAM) was more attractive.
    In the first part of this work, a straightforward synthesis of block copolymers mediated by a commercially available RAFT agent, BM1481, was proposed. Through adjusting the concentration ratio of reactants and reaction conditions, well-defined poly(LAM)-b-poly(MAM) were synthesized. In the second part, aiming to broaden the range of application of this RAFT polymerization system under low temperature, the electrochemically-induced initiator, BrPhN2+, was introduced to replace the thermally-induced one, AIBN.
    For the characterization of the products, the chemical structures were confirmed by FTIR and 1H NMR and the thermal properties were analyzed by DSC and TGA. The amphiphilic property was determined by DLS and TEM as well. Most importantly, the molecular weight and low polydispersity values determined by GPC indicated the good controllability the RAFT polymerization system provided. The results of these instrumental analyses implied the successful synthesis of the polymers.

    摘要 I ABSTRACT III TABLE OF CONTENT V LIST OF FIGURES X LIST OF TABLES XV CHAPTER 1 INTRODUCTION 1 1.1 Reversible Deactivation Radical Polymerization Methods 1 1.2 Reversible Addition-fragmentation Chain Transfer (RAFT) Radical Polymerization 4 1.3 External Stimuli-regulated RAFT Polymerization 7 1.4 Block Copolymer 9 1.4.1 Introduction to Block Copolymer 9 1.4.2 Synthesis of Block Copolymers by RAFT Polymerization 10 CHAPTER 2 LITERATURE REVIEW 13 2.1 Guidelines for Selection of RAFT Agent 13 2.1.1 Monomer Classes 13 2.1.2 RAFT Agents 15 2.2 Strategies of Synthesis of Poly(LAM)-block-poly(MAM) 19 2.3 Straightforward Synthesis of Poly(LAM)-b-poly(MAM), PVAc Containing Block Copolymers 21 2.4 Electrochemically Mediated RAFT Polymerization 23 2.5 Motivation and Objective 26 2.5.1 Synthesis of Block Copolymers with a Single RAFT CTA Using RAFT Polymerization 27 2.5.2 Synthesis of Block Copolymers by eRAFT Polymerization 28 CHAPTER 3 MATERIAL AND METHODS 29 3.1 Framework 29 3.2 Chemicals 30 3.3 Instrumental Analysis 33 3.4 Synthesis of Polymers 36 3.4.1 Removal of Monomer Inhibitor 36 3.4.2 Thermally-Initiated RAFT Polymerization 36 3.4.2.1 Synthesis of Polystyrene 37 3.4.2.2 Synthesis of Poly(vinyl acetate) 37 3.4.2.3 Synthesis of Polystyrene-block-poly(vinyl acetate) 38 3.4.2.4 Synthesis of Poly(vinyl acetate)-block-polystyrene 39 3.4.3 eRAFT Polymerization 40 3.4.3.1 Synthesis of Poly(methyl methacrylate) by Electrochemically-induced Free Radical Polymerization (eFRP) 40 3.4.3.2 Synthesis of Poly(methyl methacrylate) by eRAFT 41 3.4.3.3 Synthesis of Polystyrene by eFRP 41 3.4.3.4 Synthesis of Polystyrene by eRAFT 42 3.4.3.5 Synthesis of Poly(Vinyl Acetate) by eFRP 42 3.4.3.6 Synthesis of Poly(Vinyl Acetate) by eRAFT 43 3.5 Surfactant Performance Test 44 3.5.1 PS/PVAc Blend Solution 44 3.5.2 PS/PVAc Film 44 CHAPTER 4 RESULTS AND DISCUSSION 46 4.1 Thermally-Initiated RAFT Polymerization 46 4.1.1 Characterization of Homopolymers, PS-CTA and PVAc-CTA 46 4.1.1.1 GPC Traces and Living Characteristic 46 4.1.1.2 Chemical Structure 50 4.1.1.3 Thermal Properties 53 4.1.2 Characterization of Block Copolymers, PS-b-PVAc and PVAc-b-PS 55 4.1.2.1 Chemical Structure 55 4.1.2.2 GPC Traces and Living Characteristic 58 4.1.2.3 Thermal Properties 67 4.1.2.4 Amphiphilic Properties 70 4.1.3 Surfactant Performance 73 4.1.3.1 PS/PVAc Blend Solution 73 4.1.3.2 PS/PVAc Film 74 4.2 eRAFT Polymerization 75 4.2.1 Characterization of Polymers, PMMA-eFRP and PMMA-eRAFT 76 4.2.1.1 Cyclic Voltammetry of Reactants 77 4.2.1.2 Chemical Structure 78 4.2.1.3 Current (I) versus Time (t) 79 4.2.1.4 GPC Traces 81 4.2.1.5 Thermal Properties 82 4.2.2 Synthesis and Characterization of PS-eRAFT and PVAc-eRAFT 85 4.2.2.1 Cyclic Voltammetry of Reactants 85 4.2.2.2 GPC Traces 87 4.2.2.3 Chemical Structure 89 4.2.2.4 Current (I) versus Time (t) 90 CHAPTER 5 CONCLUSION 92 5.1 Synthesis of Block Copolymers with a Single RAFT Chain Transfer Agent Using RAFT Polymerization 92 5.2 Development of eRAFT Polymerization System 93 CHAPTER 6 REFERENCE 95

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