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| 研究生： |
張維倫 Jhang, Wei-Lun |
|---|---|
| 論文名稱： |
3-芐基-2-溴噻吩之酸催化聚合及共聚合之研究 The Study of Acid-catalyzed Polymerization and Copolymerization of 3-Benzyl-2-bromothiophene |
| 指導教授： |
韓建中
Han, Chien-Chung |
| 口試委員: |
彭之皓
Peng, Chi-How 白孟宜 Bai, Meng-Yi |
| 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： | 2018 |
| 畢業學年度： | 106 |
| 語文別： | 中文 |
| 論文頁數： | 192 |
| 中文關鍵詞： | 導電高分子 、酸催化聚合法 、烷基聚噻吩 、鏈式聚合 、嵌段共聚物 、位向選擇性 |
| 外文關鍵詞： | Conduction Ploymers, Acid-catalyzed Polymerization, Poly(alkylthiophene)s, Chain Growth Polymerization, Block Copolymer, Regioselectivity |
| 相關次數： | 點閱：3 下載：0 |
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本篇論文針對長碳鏈噻吩進行酸催化聚合時，在反應過程中為了提升產率而增加單體濃度或提高溫度皆可能會出現不溶之凝膠的現象進行改良，藉由在噻吩3號位上做側鏈修飾，引入立體障礙稍大的官能基，來避免其交聯化而產
生網狀結構。基於以上動機，我們合成了3-苄基-2-溴噻吩做一系列的酸催化聚合實驗探討。
首先，為了找出3-苄基-2-溴噻吩最佳化聚合條件，我們透過改變反應濃度、反應溫度、酸催化當量數等條件，觀察其聚合情形並透過UV-Vis、GPC、NMR、MALDI-TOF等儀器的輔助進行分析，探討其聚合行為。同時也嘗試不同的質子酸，了解質子酸的作用及其對酸聚合反應的影響。
接著我們在3-苄基-2-溴噻吩的聚合情形中，觀察到其具有活性聚合的特性:「只要反應溶液中還有單體或存在聚合鏈，高分子鏈就會不斷地持續增長。」藉由此特性可以合成出材料性能較單一均聚物多元的嵌段共聚物 (block copolymer)。
之後我們使用不同溶劑將poly(3-benzylthiophene)進行一系列的溶解度測試，發現使用poly(3-benzylthiophene)對其微溶的溶劑進行沉澱析出時，可以使寡聚物溶於該溶劑，因此收集到的高分子鏈鏈較長，分子量較平均，PDI較為集中。最後利用本實驗的酸聚合法成功將3-苄基-2-溴噻吩及2-溴-3-戊基噻吩進行共聚，合成出poly(3-benzylthiophene-co-3-pentylthiophene)。
In this thesis, when the acid-catalyzed polymerization of alkyl group on third position of thiophene is carried out, an insoluble gel will occur. By modifying a side chain on third position of thiophene and introducing a functional group having a slightly larger steric hindrance in order to avoid cross-linking and a network structure happening. In view of above mentioned reasons, we synthesized 3-benzyl-2-bromothiophene to observe an unusual acid-catalyzed polymerization appearance.
With a view to finding out the optimized polymerization conditions for 3-benzyl-2-bromothiophene, we focus on changing monomer concentrations, reaction temperature, equivalents of acid and using different protic acids to understand the effects of them on polymerization. By doing so, we can observe its polymerization behavior and realize how the reaction going.
For the polymerization part, we found the property of living polymerization: "As long as there are monomers or polymer chains in the solution, the polymer chains can continue to grow gradually. " With this property, we can make a novel block copolymer which is multi-functioning material.
We run the solubility test of poly(3-benzylthiophene) with series of different organic solvents. With some specific solvents that the oligomer could be dissolved in, on the other hand, the polymer could not. Then the polymer having longer chain could be collected by the difference in sloubility. If so then we can get higher conjugation, Mn, Mw, and lower PDI.
Finally, we synthesized poly(3-benzylthiophene-co-3-pentylthiophene) successfully via acid-catalyzed polymerization technique, this method can be potential and developmental in the future.
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