指導教授：劉貴生臺灣大學：高分子科學與工程學研究所林璐旂Lin, Lu-ChiLu-ChiLin2014-11-282018-06-292014-11-282018-06-292014http://ntur.lib.ntu.edu.tw//handle/246246/262682本論文分為四個章節，第一章為總體序論，簡述benzoxazine、電致變色及高分子記憶體元件的發展。第二章包含了一系列新型具三苯胺結構polybenzoxazine，透過合成其前驅物再經熱交聯反應來製備，其中選用兩種二胺單體 (4,4''-diamino-4''-methoxytriphenylamine 和 N,N''-bis(4-aminophenyl)-N,N''-di(4-methoxyphenyl)-1,4-phenylenediamine)做為反應物。第三章分析了一系列新型具三苯胺結構之polybenzoxazine及其前驅物的電致變色及高分子記憶體元件特性。第四章為結論。這系列新型具三苯胺結構polybenzoxazine及其前驅物之合成與基本特性、電化學性質、電致變色及高分子記憶體元件特性已被研究與比較。與傳統不具三苯胺結構之polybenzoxazine相比，此系列之新型polybenzoxazine表現較好的熱性質(Tg, 284-312 oC)。此外，含bisphenol A 結構之polybenzoxazine及其前驅物表現特殊的電致變色特性並在可見光及紅外光光譜吸收區域表現高對比的顏色變化，相較於三苯胺對應的聚醯胺，導入三苯胺衍生物進入polybenzoxazine前驅物可有效的增加氧化的階段及呈現多段電致變色的性質。此外，在高分子記憶體元件的部分，所有含強拉電子基團 (4,4׳-sulfonyldiphenol)的polybenzoxazine及其前驅物表現出揮發性SRAM的記憶體特性。具我們所知，直至目前為止，具三苯胺結構之polybenzoxazine及其前驅物應用於電致變色及高分子記憶體元件尚未被製備並且系統化探討，故本研究開創了polybenzoxazine的新應用領域。This study has been separated into four chapters. Chapter 1 is general introduction of benzoxazine, electrochromism, and polymer memory. Chapter 2 includes a series of novel triarylamine (TPA)-based polybenzoxazines (PBs) which were prepared by the thermal-induced curing reaction of a series of novel PB precursors. Two diamines, 4,4''-diamino-4''-methoxytriphenylamine and N,N''-bis(4-aminophenyl)-N,N''-di(4-methoxyphenyl)-1,4-phenylenediamine, were used in this research, which were published by our group before. Chapter 3 includes the investigations of electrochromic and memory behaviors of novel PBs and PB precursors. Chapter 4 is conclusions. The synthesis, thermal properties, electrochemical properties, electrochromic properties, and memory behaviors of novel TPA-based PBs and PB precursors were investigated and compared. Comparing with the traditional PBs without TPA moieties, the novel TPA-based PBs exhibited more excellent thermal properties (Tg, 284-312 oC). In addition, the resulting TPA-based PBs and PB precursors containing bisphenol A (BPA) revealed interesting multi-electrochromic behavior with highly optical contrast both in visible and NIR region. Compared with their corresponding polyamides, these TPA-based PB precursors with BPA moiety not only showed lower oxidative potentials but also increased the oxidation stages due to the introduction of the TPA moieties. Besides, all the resulting polymer containing stronger electron-withdrawing group 4,4׳-sulfonyldiphenol (BPS) exhibited SRAM properties with longer retention time in terms of memory characteristics. To the best of our knowledge, this is the first time to explore and investigate the EC and memory behaviors of PB precursors and PBs with TPA moieties, and could be expected to open a new avenue of applications for PBs.ACKNOWLEGGEMENTS………………………………II ABSTRACT (in English) ……………III ABSTRACT (in Chinese) ………………IV TABLE OF CONTENTS………………………………V LIST OF TABLES………………………………………X LIST OF FIGURES…………………………………XI CHAPTER 1……………………………………………………1 CHAPTER 2…………………………………………………58 CHAPTER 3…………………………………………………81 CHAPTER 4………………………………………………113 APPENDIX…………………………………………………116 CHAPTER 1 General Introduction 1.1 BENZOXAZINE 2 1.1.1 Benzoxazine 2 1.1.2 Bifunctional Benzoxazine 3 1.1.3 Mechanism of Benzoxazine 4 1.1.4 Polybenzoxazine 5 1.1.5 Polybenzoxazine Precursor 7 1.2 INTRODUCTION OF ELECTROCHROMISM 10 1.2.1 Evolution of Electrochromism 10 1.2.2 Electrochromic Systems 13 1.2.2.1 Transition-metal Oxides 14 Tungsten Trioxide (WO3) 14 Iridium Oxide (IrO2) 15 1.2.2.2 Coordination Complexes 16 Prussian Blue (PB) 16 Phthalocyanines (Pc) 16 1.2.2.3 Organic Molecules 17 Viologens 17 1.2.2.4 Conducting Polymers 18 1.2.2.5 Arylamine-based Polymers 20 1.3 INTRODUCTION OF POLYMER MEMORY 25 1.3.1 General Concept 25 1.3.2 Types of Polymer Memory 26 1.3.3 Fundamentals and Device Architecture of Resistor-type Polymeric Memory 27 1.3.4 Mechanisms of Memory Devices 29 1.3.4.1 Filamentary Mechanism 29 1.3.4.2 Trapping-Detrapping Mechanism 31 1.3.4.3 Charge Transfer Mechanism 34 1.3.5 Evolution of Polymer Memory 37 1.3.5.1 Conjugated Polymers 37 1.3.5.2 Non-conjugated Polymers with Specific Pendent Groups 39 1.3.5.3 Polymer Composites 41 1.3.5.4 Functional High Performance Polymers 42 1.4 RESEARCH MOTIVATION 45 REFERENCES AND NOTES 48 CHAPTER 2 Flexible Polybenzoxazine Thermosets Containing Triphenylamine-based derivatives with high glass transition temperatures ABSTRACT OF CHAPTER 2 59 2.1 INTRODUCTION 60 2.2 EXPERIMENTAL SECTION 62 2.2.1 Materials 62 2.2.2 Synthesis of Polybenzoxazine Precursors 63 2.2.3 Preparation of Polybenzoxazine Thick Films 65 2.2.4 Measurements 66 2.3 RESULTS AND DISCUSSION 68 2.3.1 Synthesis of Polybenzoxazine Precursors 68 2.3.2 Basic Characterization 73 2.4 SUMMARY 78 REFERENCES AND NOTES 79 CHAPTER 3 Novel Triarylamine-based Polybenzoxazines and Polybenzoxazine Precursors for Multi-Colored Electrochromic and Memory Applications. ABSTRACT OF CHAPTER 3 82 3.1 INTRODUCTION 83 3.1.1 Part of Electrochromism 83 3.1.2 Part of Memory Device 84 3.2 EXPERIMENTAL SECTION 87 3.2.1 Preparation of Polybenzoxazine Precursor Thin Films 87 3.2.2 Preparation of Polybenzoxazine Thin Films 87 3.2.3 Fabrication of Memory Devices 88 3.2.4 Theoretical Calculation 88 3.2.5 Measurements 89 3.3 RESULTS AND DISCUSSION 90 3.3.1 Part of Electrochromism 90 3.3.1.1 Electrochemical Properties 90 3.3.1.2 Spectroelectrochemistry and Electrochromic Properties 92 3.3.2 Part of Memory Device 98 3.3.2.1 Memory Device Characteristics of Polybenzoxazine Precursors 100 3.3.2.2 Memory Device Characteristics of Polybenzoxazines 102 3.3.2.3 Switching Mechanism 105 3.4 SUMMARY 109 REFERENCES AND NOTES 1106715069 bytesapplication/pdf論文公開時間：2016/08/16論文使用權限：同意有償授權(權利金給回饋學校)三苯胺多苯胺苯並惡錯電致變色高分子記憶體元件thesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/262682/1/ntu-103-R01549004-1.pdf