謝國煌臺灣大學：高分子科學與工程學研究所洪欣怡Hung, Shin-YiShin-YiHung2007-11-292018-06-292007-11-292018-06-292007http://ntur.lib.ntu.edu.tw//handle/246246/62879導電高分子由於溶解性差，常使其在加工或分析的過程中受到限制，因此本研究之主要目標即為合成有機可溶解之導電高分子。本研究之導電高分子可大致分為三個系統，第一個系統是可溶於有機溶劑之Polydihexyloxythiophene (PDHOT)，第二個系統是具有水溶解性之poly(3-thienyl)ethoxybutanesulfonate (PTEBS)，第三個系統則是合併前兩系統之單體所形成的有機可溶解性共聚合物。 在第一個系統中，由於引進了柔軟的長碳烷基側鏈，使得所形成之高分子可溶於有機溶劑。此系統以DBSA為摻雜劑，實驗中所得之最適化的條件為以二氯甲烷為溶劑，固定DSBA/DHOT比例為0.5:1時。將此條件下的PDHOT溶液製膜量測後可得知其導電度為1.58*10-3 S/cm。在第二個系統中，側鏈上共價鍵結磺酸根基團的PTEBS是可溶於水的。它擁有自摻雜的效果且其導電度為2.64*10-3 S/cm。而在第三個系統中，共聚合物可溶於有機溶劑中，而其導電度會隨著兩單體的比例越接近50:50就越差，不過共聚合物可藉由暴露在酸環境中使其本身所連接之磺酸根基團轉為酸型式達到自摻雜的效果。 在測試方面，以傅立葉紅外光譜儀、微差掃瞄卡計、熱重損失分析儀、紫外光-可見光譜儀、四點量測裝置來分析聚合物的結構、熱性質、導電度跟摻雜狀態。Characterization and processing of the conducting polymer have been limited by the inherent insolubility of these compounds. The main target of this study is the synthesis of organic soluble conducting polymer. In this study the studied conducting polymer are separated into three systems：(1) Polydihexyloxythiophene (PDHOT) which is soluble in organic solvents. (2) The water soluble poly(3-thienyl) ethoxybutanesulfonate (PTEBS). (3)The organic soluble copolymers incorporating DHOT and TEBSTBA. In series (1), the conducting polymer which is soluble in organic solvents is obtained by incorporation of relatively long and flexible side chains. The optimum condition of the system is PDHOT dissolved in dichloromethane while fixing the ratio of dopant to monomer at 0.5. In this condition, the conductivity of PDHOT film is 1.58*10-3 S/cm. In series (2), the PTEBS with sulfonate group in the side chain was soluble in water. PTEBS is doped by itself and the conductivity of it is 2.64*10-3 S/cm. In series (3), the conductivity of the copolymers is getting lower and lower as the ratio of the two monomers is getting close to 50:50. The self-doping copolymer is obtained by exposing copolymers to acid condition which lead to the formation of the acid form of the polymer. The polymers were analyzed by Fourier transform infrared spectroscopy, Differential scanning calorimetry, Thermogravimetric analysis, UV-Visible spectroscopy, a four-point probe device to correlate the characterization, thermal properties, doping state, and conductivity.Table of Contents……………………………………………….I List of Figures……………………………………………V List of Tables...............................VII List of Schemes…………………………………………VIII Abstract (in Chinese)……………………………………………IX Abstract (in English) ……………………………………X Chapter 1 Introduction …………………………………………1 Chapter 2 Background and Significance…………………………3 2-1 A brief history of conducting polymer ………………3 2-2 Types of conducting polymer……………7 2-3 The concept of doping…………………………………9 2-4 The concept of self-doping………………………………13 2-5 Application of conducting polymer……………………14 2-6 Polythiophene……………………………………………15 Chapter 3 Experimants……………………………………………………………19 3-1 Materials……………………………………………………19 3-2 Instruments………………………………………………22 3-3 Experimental method………………………………………24 3-3-1 Flow chart of the synthesis of 3,4-dihexyloxythiophene………24 3-3-2 Flow chart of the synthesis of tetrabutylammonium (3-thienyl) ethoxybutanesolfonate……………………………………………25 3-3-3 Flow chart of the synthesis of PDHOT which is soluble in organic solvents.………………………………25 3-3-4 Flow chart of the synthesis of PTEBS which is soluble in water……26 3-3-5 Flow chart of the synthesis of copolymers which are soluble in organic solvents……………………………………26 3-4 Experimental steps………………………………………27 3-4-1 Synthesis of monomer……………………………………….27 3-4-2 PDHOT which is soluble in organic solvents…………33 3-4-2-1 Polymerization of DHOT…………………33 3-4-2-2 Doped with different ratio of DBSA…33 3-4-2-3 Doped in the different solvent………34 3-4-3 The water soluble PTEBS .....35 3-4-4 Copolymers incorporating DHOT and TEBSTBA…36 3-4-4-1 Copolymerization of the copolymers…..36 3-3-4-2 Copolymers doped by DBSA……………37 3-3-4-3 Self-doped copolymers…………37 3-5Characterization……………………………………38 3-5-1 Gel-permeation chromatography(GPC) ………38 3-5-2 Thermal Gravimetric Analysis (TGA) ………38 3-5-3 Differential Scanning Calorimetry (DSC) …38 3-5-4 UV-Visible spectra………………………39 3-5-5 Conductivity……………………………………39 Chapter 4 Results and and discussion………………………40 4-1 Monomer synthesis.…………………………………………40 4-2 PDHOT which is soluble in organic solvents…………42 4-2-1 Polymerization of polydihexyloxythiophene…42 4-2-2 Thermal properties of PDHOT……………………43 4-2-3 PDHOT doped by DBSA…………………………45 4-3 Water soluble poly(3-thienyl)ethoxybutanesulfonate………………53 4-3-1 Polymerization of PTEBS………………………53 4-3-2 Thermal properties of PTEBS……………………54 4-3-3 Self-doping of PTEBS……………………………56 4-4 The series of copolymers incorporating the DHOT and TEBSTBA………58 4-4-1 Copolymerization of the monomers………………58 4-4-2 Doped by DBSA……………………………………61 4-4-3 Self-doping of copolymer………………………63 Chapter 5 Conclusion……………………………………………………………65 Reference …………………………………………………………67 Appendix……………………………………………………………70 1. NMR Spectra..…………………………………………………71 2. IR Spectra……..………………………………………………782403641 bytesapplication/pdfen-US導電高分子聚噻吩衍生物自摻雜有機可溶解性Conducting polymerpolythiopheneself-dopingorganic solublethesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/62879/1/ntu-96-R94549019-1.pdf