3-烷基噻吩之酸催化共聚合與極性溶劑對聚合之影響

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研究生：	林熹 Lin, Hsi
論文名稱：	3-烷基噻吩之酸催化共聚合與極性溶劑對聚合之影響 The Effects of Polar Solvents on Acid-Catalyzed Chain Growth Polymerization and Block Polymerization of 3-Alkylthiophenes
指導教授：	韓建中 Han, Chien-Chung
口試委員:	蔡易州 Tsai, Yi-Chou 李志聰 Lee, Jyh-Tsung
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2019
畢業學年度：	107
語文別：	中文
論文頁數：	164
中文關鍵詞：	3-烷基噻吩、酸催化聚合、酸催化聚合之溶劑效應、3-烷基噻吩之共聚和
外文關鍵詞：	3-alkylthiophenes, acid-catalyzed polymerization, solvent effects of acid-catalyzed polymerization, block polymerizations of 3-alkylthiophenes
相關次數：	點閱：3 下載：0
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傳統的天然高分子材料皆為絕緣體，但自從1976年Hideki Shirakawa、Alan J. Heeger與Alan Graham MacDiarmid三位教授以碘摻雜反式聚乙炔後，由於其導電效果幾乎與半導體相近，因此引發了學界研究導電高分子之熱潮。而本實驗室開發之以酸催化陽離子聚合法，能在沒有金屬催化劑之幫助下合成出導電高分子聚噻吩，並藉由對側鏈進行修飾大幅使聚噻吩之溶解度大幅提升。

本篇論文第一部分中，先合成出2-haloo-3-(4-(tert-butyl)benzyl)thiophene，希望透過單體側鏈設計以增加高分子產品對於不同溶劑之溶解度，並以不同的2號位取代基 (Br、Cl) 進行聚合情形的探討。接著我們嘗試提高聚合溶劑極性，並比較不同極性之溶劑對酸催化聚合系統的影響，發現提高溶劑極性能穩定陽離子活性中心，增加鏈增長速率，因此可以大幅提升聚合產物之分子量。最後我們更發現溶劑結構與單體側鏈結構有密切的關係，若是倆者結構差異過大，會導致單體分布不均且容易產生鏈轉移現象，造成產物PDI值極高。

本篇論文之第二部分中則藉由重複加入單體的實驗，證實了酸催化聚合系統確實有活性聚合之特徵。並且也利用此一特徵成功合成出由兩種不同單體組成之嵌端共聚物，最後利用MALDI-TOF與Isotope Pattern鑑定共聚物之結構。未來希望能夠由本篇論文開始，利用活性聚合之特徵合成出更多不同單體組成之嵌端共聚物，或是具有不同官能基之聚噻吩共聚物，進而提升產物的溶解度與應用性。

While natural polymers such as cotton and rubber were classified as insulating material traditionally, iodine-dopped trans-polyacetylene, was found by Hideki Shirakawa, Alan J. Heeger and Alan Graham MacDiarmid in 1976 to display the similar conductivity like semiconductor material . Since that time, many groups dedicated to the research of conducting polymer. As for our group, we engaged in acid-catalyzed chain-growth polymerization of conductive polythiophenes, which enables polymerization without transition metal catalyst.

Firstly we conducted polymerizations of 2-halo-3-(4-(tert-butyl)benzyl)thio-phene with different halogen leaving group and observe the influence of different leaving groups on the polymerization. Moreover, we found that polymer products with much higher Mn and Mw can be successfully synthesized in polar solvent, which means enhancement of polarity is capable of stabilizing cationic propagation species and increasing propagation rate. In the end of this chapter, the structural interactions between side-chain of polythiophenes and solvent were found to have strong influence on molecular weight, PDI and yield of the polymer product.

In the second part, we successfully demonstrated the characteristic of living polymerization in acid-catalyzed system by adding monomers repeatedly. Further-more, block-copolymer, composed of two different monomers, was synthesized based on the behavior of living polymerization, and the product was identified by MALDI-TOF and Isotope Pattern. We look forward to more copolymer products which comprise distinct functional groups in the future.

摘要    I
Abstract    II
謝誌    III
本文目錄    IV
圖目錄    VI
表目錄    X
附錄目錄    XII
第一章  緒論    1
1-1 前言    2
1-2 導電高分子簡介    3
1-2-1  導電高分子之原理    3
1-2-2  導電高分子之應用    5
1-3 傳統聚噻吩合成方法及其性質介紹    7
1-3-1  傳統聚噻吩合成方法    7
1-3-2  聚噻吩之側鏈結構及其影響    10
1-4 離子聚合反應    11
1-5 聚噻吩之酸催化陽離子聚合法    14
1-5-1  酸催化聚合法    14
1-5-2  酸催化聚噻吩之發展    17
1-6 研究動機    19
第二章  實驗內容    20
2-1 常用藥品列表    21
2-2 儀器設備及分析方法    23
2-3 化合物之結構與代號    29
2-4 合成噻吩單體之實驗步驟    30
2-4-1  3-(4-(tert-butyl)benzyl)thiophene合成方法    30
2-4-2  2-bromo-3-(4-(tert-butyl)benzyl)thiophene合成方法    33
2-4-3  2-chloro-3-(4-(tert-butyl)benzyl)thiophene合成方法    35
2-4-4  3-octylthiophene合成方法    37
2-4-5  2-bromo-3-octylthiophene合成方法    40
2-5 不同單體之酸催化聚合步驟    42
2-5-1  以酸催化聚合合成Poly(3-(4-(tert-butyl)benzyl)thiophene)    42
2-5-2  以酸催化聚合合成Poly(3-octylthiophene)    43
2-5-3  合成共聚物poly(3-(4-(tert-butyl)benzyl)thiophene)-block-poly(3-octylthiophene)    44
2-5-4  合成共聚物poly(3-(4-(tert-butyl)benzyl)thiophene)-block-poly(3-octylthiophene) -block- poly(3-(4-(tert-butyl)benzyl)thiophene)    45
第三章  2-halo-3-(4-(tert-butyl)benzyl)thiophene之酸催化聚合與溶劑對聚合之影響    46
3-1 前言    47
3-2  2-halo-3-(4-(tert-butyl)benzyl)thiophene 聚合條件探討    51
3-2-1  2-bromo-3-(4-(tert-butyl)benzyl)thiophene    51
3-2-2  2-chloro-3-(4-(tert-butyl)benzyl)thiophene    60
3-3 溶劑對於聚合反應之影響    65
3-3-1  高分子產物的溶解度測試    65
3-3-2  改使用極性溶劑於酸催化聚合    67
3-3-3  單體側鏈構造與溶劑結構之關聯性    75
3-4 結論    79
第四章  2-bromo-3-(4-(tert-butyl)benzyl)thiophene之酸催化共聚合    80
4-1  2-bromoo-3-(4-(tert-butyl)benzyl)thiophene 之活性聚合探討    81
4-1-1  活性聚合反應 (living polymerization)    81
4-1-2  重複在聚合反應中加入3ptBn2BT    82
4-2 在聚合反應中加入不同單體合成共聚物    87
4-2-1  共聚物簡介    87
4-2-2  Diblock Copolymer    88
4-2-3  Triblock Copolymer    94
4-3 結論    103
參考資料    104
附錄    107


                                

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