一系列新型以三苯胺為主體的芳香族聚合物經由苯甲醛與不同形式的三苯胺衍生物在存在酸性催化劑條件下以縮合聚合的方式被合成。在結構的鑑定上藉由NMR的氫譜與碳譜顯示此親核性取代反應只發生在三苯胺衍生物的對位位置上。這些聚合物在甲苯溶液中的紫外光吸收帶表現在309-324 nm，最大放射波長在藍光區域大約370-417nm。由循環伏安法圖譜得知所有聚合物擁有可逆的氧化還原峰，其氧化電位 (Eonset) 大約是0.42-0. 90 V，顯示這些聚合物具有電化學活性。另外，這些芳香族聚合物溶於氯仿溶液中，在紫外光照射下會展現類似電致變色的光致變色特性，顏色由無色轉變為綠色。所有聚合物擁有高的玻璃轉換溫度 (Tg) 約 197-217 oC及好的溶解度與成模性。這些特別的光氧化形態可能可以被用作新型的光導體材料。

A series of novel triphenylamine-based aromatic polymers were synthesized by condensation polymerization of benzaldehyde with various types of triphenylamine derivatives in the presence of an acid catalyst. Structural characterization by 1H and 13C NMR spectroscopy show that the electrophilic substitution reaction occurs exclusively at the para-position of triphenylamine derivatives. These polymers exhibited UV-vis absorption bands at 309-324 nm in toluene solution. The photoluminescence spectra showed maximum bands around 370-417 nm in the blue region. Cyclic voltammograms of all polymers show reversible oxidation redox peaks and Eonset around 0.42-0.90 V, indicating that the polymers are electrochemically active. These aromatic polymers revealed photochromic characteristics in chloroform under irradiation with light conformity to their electrochromic characteristics, with color change from colorless to green. In addition to high glass transition temperatures (Tg) in the range of 197-217 oC, all the obtained polymers also possess good solubility and film formability. This special photooxidation form might be considered as a novel photoconductor.

TABLE OF CONTENTS

ABSTRACT (in Chinese)…………………...…………........................……………………I
ABSTRACT (in English)….…………………………………………………………….…II
TABLE OF CONTENTS…………….……………….…………...………………...…….III
LIST OF TABLES………………………...………………...……………………….…....VI
LIST OF FIGURES…..……………………………………………….………...……… .VII



Synthesis, Electrochromic and Photochromic Properties of Novel Aromatic Polymers from Benzaldehyde and Triphenylamine Derivatives

GRAPHICAL ABSTRACT …………….…………………..……………….……………...1
CHAPTER1 INTRODUCTION…………………………………………….………….…...2
CHAPTER 2 LITERATURE REVIEW………………………………………….…………4
2.1. Chromism..………………………………………………..................................4
2.2. Thermochromism……………………………………………….……………...5
2.3. Solvatochromism………………………………………………………….……5
2.4. Photochromism………………………………………………………………....6
2.4.1. Classes of Photochromic materials………………………………….…..8
2.4.2. Applications…………………………………………………………....10
2.5. Electrochromism……………………………………………………………...12
2.5.1. Fundamentals of Electrochromism…………….………………………14
2.5.2. Application……………………………………………........………….15
CHAPTER 3 EXPERIMENTAL SECTION...………………………….......……......……16
3.1. Materials…………………………………………………................................16
3.2. Monomer Synthesis………………………………………………..........…….16
3.2.1. 4-methoxytriphenylamine (MOTPA)…......………….………................16
3.2.2. N,N-Bis(4-methoxyphenyl)-N’,N’-diphenyl-p-phenylenediamine
(MOPD1)............................................................................................................17
3.3. Polymer synthesis via the Direct polycondensation..........................................26
3.4. Preparation of the Film…………..…………...……….............................…....28
3.5. Measurements…………………………………………………………………28
CHAPTER 4 RESULTS AND DISCUSSION………………………………….................30
4.1. Polymer Synthesis…………………………..............…………………...........30
4.2. Polymer Properties…………………..…………………………......................36
4.2.1. Basic Characterization......…………………….…………...…………....36
4.2.2. Optical and Electrochemical Properties.......................................….…...42
4.2.3. Electrochromic Characteristics.................................................................50
4.2.4. Photochromic Characteristics...................................................................53
CHAPTER 5 CONCLUSIONS……………………………................................................59
REFERENCES AND NOTES........................................................…….…….....................60


















LIST OF TABLES

1. Reaction Condition and Molecular Weights of Polymers............................................27
2. Inherent Viscosity and Solubility.................................................................................37
3. Thermal Properties.......................................................................................................41
4. Optical and Electrochemical Properties.......................................................................49



















LIST OF FIGURES

1. (a) 1H NMR and (b) 13C NMR spectra of N,N-bis(4-methoxyphenyl)- N’,N’-diphenyl-p-phenylenediamine in DMSO-d6......................................................20
2. (a) 1H NMR and (b) 13C NMR spectra of N,N’-bis(4-methoxyphenyl)- N,N’-diphenyl-p-phenylenediamine in DMSO-d6.………………………….……….21
3. H-H COSY spectrum of N,N-bis(4-methoxyphenyl)- N’,N’-diphenyl-p- phenylenediamine in DMSO-d6.……………………...………………….…….…….22
4. C-H HMQC spectrum of N,N-bis(4-methoxyphenyl)- N’,N’-diphenyl-p- phenylenediamine in DMSO-d6...……………………………………………..……..23
5. H-H COSY spectrum of N,N’-bis(4-methoxyphenyl)- N,N’-diphenyl-p- phenylenediamine in DMSO-d6..………………………………………….…………24
6. C-H HMQC spectrum of N,N’-bis(4-methoxyphenyl)- N,N’-diphenyl-p- phenylenediamine in DMSO-d6..…………………………………………..……...…25
7. The FTIR spectrum of polymer Ic which (a) have no end capped by acetic anhydride (b) have end capped by acetic anhydride.…………...……………………..…….…..32
8. (a) 1H NMR and (b) 13C NMR spectra of Ic in chloroform-d.………............….……33
9. H-H COSY spectrum of polymer Ic in chloroform-d.……………….…………........34
10. C-H HMQC spectrum of polymer Ic in chloroform-d.……………….……..……….35
11. WAXD patterns of the polymer films….…...………………………….…………….38
12. TGA and TMA curves for Ia (TGA ：at a scan rate of 20 °C /min ；TMA : heating rate = 10 °C /min; applied force = 10 mN)………………………………….……….39
13. DSC curve for detection the glass transition temperature (Tgs) of polymers Ia-Ie…………..……………………………………………………………………...40
14. Absorption (left) and normalized fluorescence intensity (right) of Ia and Ic in toluene (10-5 M) and solid thin films (thickness: 1-3 μm). a.u.: Arbitrary units…………………………………………………………………….…………….45
15. Transmission UV-visible absorption spectra of polymer films (thickness: 30-50μm)…………………………………………………...………….………….….45
16. Cyclic Voltammograms of (a) polymer Ia and (b) polymer Ic over 40 cyclic scanning in CH2Cl2 solution (10-3 M) containing 0.1M TBAP. Scan rate = 0.05 V/s………………………………………………..…………………………….…….46
17. Electorchromic behavior of Ia in CH2Cl2 solution (5×10-4 M) containing 0.1 M TBAP. Eappl. = 0.00 (■), 0.55 (●), 0.58 (▲), 0.61 (▼), and 0.64 (◆) (V vs. Ag/AgCl)………………………………………………………………………….….47
18. Cyclic Voltammograms of (a) the first oxidation redox of polymer Id (b) the first and second oxidation redox of polymer Id in CH2Cl2 solution (10-3 M) containing 0.1M TBAP. Scan rate = 0.05 V/s………………………………………………………….48
19. Electorchromic behavior of Id in CH2Cl2 solution (5×10-4 M) containing 0.1M TBAP. (A) Eappl. = 0.00 (■), 0.46 (●), 0.49 (★), 0.52 (▲), 0.55 (▼), 0.58 (□), and 0.61 (◆). (B) Eappl. = 0.91 (■), 0.94 (●), 0.97 (★), 1.00 (▲), 1.03 (▼), 1.06 (□), and 1.09 (◆), (V vs. Ag/AgCl)…………………………………………………….….….51
20. Electorchromic behavior of Ie in CH2Cl2 solution (5×10-4 M) containing 0.1M TBAP. (A) Eappl. = 0.00 (■), 0.46 (●), 0.49 (★), 0.52 (▲), 0.55 (▼), 0.58 (□), and 0.61 (◆). (B) Eappl. = 0.90 (■), 0.93 (●), 0.96 (★), 0.99 (▲), 1.02 (▼), 1.05 (□), and 1.08 (◆), (V vs. Ag/AgCl)……………………………………………….…………..52
21. (A) Electorchromic behavior of Ic in CH2Cl2 solution (5×10-4 M) containing 0.1M TBAP. Eappl. = 0.00 (■), 0.80 (●), 0.83 (★), 0.86 (▲), 0.89 (▼), and 0.92 (□), (V vs. Ag/AgCl). (B) Photochromic behavior of Ic in CHCl3 solution (10-4 M) by UV irradiation; 0 s (■), 200 s (●), 400 s (▲), 600 s (▼) and 800 s (□), (Excited 330 nm)………………………………………………………………………….………..56
22. Photochromism and electorchromism of Ic in CH2Cl2 solution containing 0.1 M TBAP, and hold at -1.0 V (V vs. Ag/AgCl) for 200 s (▲), 600 s (▼), 1600 s (◆), and 2500 s (★)……………………………………………………………………………57
23. Photochromism of PMeOTPA in CHCl3 solution (10-4 M) after UV irradiation (Excited 365 nm); irradiation time = 0 s (■), 100 s (●), 200 s (▲), 400 s (▼), 600 s (◆), 800 s (★)…………………………………………………………………….....58

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