含蒽基團之聚噻吩的合成與性質研究

Synthesis and Characterization of Anthracene-Containing Polythiophenes

何漪彤(Yi-Tung Ho)

指導教授 ： 芮祥鵬 ； 王立義

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2011年)

https://doi.org/10.6841/NTUT.2011.00190

摘要

近年來，共軛高分子已成功地被應用於製備有機太陽能電池，而且其效率年年皆有提升，最高已可達約8%。使用具有寬廣的吸收光譜之高分子作為吸光材料係為進一步提高電池效率的重要途徑之一。由於，anthracene為共平面性良好的共軛基團，並具有高載子遷移率，因此本研究中，將anthracene以側鏈及主鏈的方式導入至聚噻吩系統而合成兩種系列的anthracene-containing polythiophene。
在合成上，分為兩系列：(1) 含anthracene之官能基鏈結在聚噻吩的側鏈上：單體2,5-dibromo-3-dodecylthiophene、3-(2-(anthracen-9-yl)vinyl)-2,5-dibromo-thiophene以及2,5-bis(trimethylstannyl)thiophene以不同的比例做Stille偶合反應 [形成random排列的聚合物]；另外將2,5”-bis(trimethylstannyl)-3’-dodecyl-2,2’:5’,2”-terthiophene與等當量
2,5-dibromo-3-dodecylthiophene做Stille偶合反應[成為兩種單體交互連接的聚合物]。(2) 含anthracene之官能基鑲入至聚噻吩的主鏈上：將2,5-dibromo-3-dodecylthiophene、9,10-dibromoanthracene、2,5-bis(trimethylstannyl)-thiophene以不同的比例做Stille偶合反應[形成random排列的聚合物]；另外將2,5”-bis(trimethylstannyl)-3’-dodecyl-2,2’:5’,2”-terthiophene與等當量9,10-dibromo-anthracene做Stille偶合反應[成為兩種單體交互連接的聚合物]。
我們將合成完的聚合物以1H NMR做結構分析，並以凝膠滲透層析(Gel-Permeation Chromatography)測量其分子量。再以紫外-可見光分光光譜儀(UV-vis)觀察這兩系列的吸光範圍有何不同，結果發現將anthracene接在側鏈端，並以alternative的方式讓其有規則性的排列之聚合物，在吸收光譜有較寬廣且紅位移的表現。最後用電化學分析儀(Electrospray analyzer)觀測其能階電位，結果顯示以有規則的alternative方式排列，不管是anthracene接在主鏈或側鏈的位置，其HOMO值都相對的來得低。

關鍵字

共軛高分子 ； 蒽噻吩 ； Stille偶合反應

並列摘要

In recent years, the conjugated polymer has been successfully applied to organic polymer solar cells, and its power conversion efficiency ( PCE ) is increasing in every year. Using the materials with extersive absorption is the way to improve the PCE of polymer solar cells. Basically, anthracene is a conjugated functional group with good coplanarity and high hole mobility. Therefor, in our study, we use this properties to develop two series of anthracene –containing polythiophenes.
There are two seriers of polymers：[1] one is anthracene linking to the side chain ：2,5-dibromo-3-dodecylthiophene、3-(2-(anthracen-9-yl)vinyl)-2,5-dibromo-thiophene and 2,5-bis(trimethylstannyl) thiophene react by Stille coupling reaction with different ratio ( random copolymer)；2,5”-bis(trimethylstannyl)-3’-dodecyl-2,2’:5’,2”-terthiophene and 2,5-dibromo-3-dodecylthiophene react by Stille coupling reaction(alternative copolymer). [2] another one is anthracene linking to the main chain：2,5-dibromo-3-dodecylthiophene、9,10-dibromoanthracene、2,5-bis(trimethyl-stannyl)-thiophene react by Stille coupling reaction with different ratio ( random copolymer)；2,5”-bis(trimethylstannyl)-3’-dodecyl-2,2’:5’,2”-terthiophene and 9,10
-dibromoanthracene react by Stille coupling reaction(alternative copolymer).
We distinguish these structures by 1H NMR, and decided the molecular weight by GPC( Gel Permeation Chromatography ). Using UV- Vis spectrophotometer( UV-vis spectrum )to observe the absorption of them,we find that the alternative polymer of anthracene linking to the side chain has the red shift and board absorption . Finally, we use electrospray analyzer to observe the energy level,the alternative polymers have lower HOMO level.

並列關鍵字

Organic polymer solar cells ； Anthracene ； Thiophene ； Stille coupling reaction

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