戴子安Dai, Chi-An臺灣大學:化學工程學研究所吳佳鴻Wu, Chia-HungChia-HungWu2010-06-302018-06-282010-06-302018-06-282009U0001-2507200923595800http://ntur.lib.ntu.edu.tw//handle/246246/187016本實驗研究硬桿-硬桿雙嵌段共聚高分子(rod-rod diblock copolymer)的合，並探討其所具有的自組裝行為(self-assembling behavior)所產生的相分離現，利用格林納聚合反應法(Grignard Metathesis)合成五組分子量約為4.0k 且分量分布(polydispersity index, PDI)均在1.2 以內的聚2,5-二己基氧對苯poly(2,5-dihexyloxy-p-phenylene), PPP)後，再以相同方法接上聚3-己烷噻吩poly(3-hexylthiophene), P3HT)，得到五組不同分子量的硬桿-硬桿雙嵌段共聚高子PPP-b-P3HT。其中聚對-二己基氧苯在雙嵌段共聚高分子所佔的比例約在5%~70%之間。合成得到的五組雙嵌段共聚高分子，進行合成鑑定以及基本性質量測，較熱性質、光學性質及微結構組成的差異性。包含以膠體滲透層析儀(Gelermeation Chromatography, GPC)鑑定分子量及分子量分布情形，核磁共振氫譜(1H-Nuclear Magnetic Resonance, 1H-NMR)觀察聚2,5-二己基氧對苯與聚3-己噻吩的比例。透過紫外光-可見光光譜儀(UV-Vis Spectrophotometer)與光激發光光譜儀(Photoluminescence, PL)量測光學性質並比較其差異，及熱重分析儀Thermogravimetric Analyzer, TGA)比較五組塊狀共聚高分子熱性質差異。藉由透式電子顯微鏡(Transmission Electron Microscope, TEM)，觀察PPP-b-P3HT微觀下產生相分離的自組裝行為及排列情形，再以小角度X 光散射儀(Smallngle X-ray Scattering, SAXS)來計算PPP-b-P3HT 的分子鏈段長，以及廣角度X散射儀(Wide Angle X-ray Scattering, WAXS)來觀測微結構排列情形及晶體結。上述的儀器分析結果得知雙嵌段共聚高分子具有奈米等級的微結構，且二種均聚物的性質有些許差異，由以上數據整理比較後，得到以聚2,5-二己氧對苯及聚3-己噻吩所組成的雙嵌段共聚高分子之基本特性及在微觀自組裝amp;#64008;為的了解。外在附錄中亦以格林納聚合反應法合成了聚3-己烷噻吩-b-聚3-己烷氧amp;#22139;吩(poly(3-hexylthiophene)-b-poly(3-hexyloxythiophene), P3HT-b-P3HOT)，鑑定合成物，並探討熱性質、光學性質與微結構解析，並與PPP-b-P3HT 比較其異處。In this thesis, we studied the synthesis of rod-rod diblock copolymers via Grignard Metathesis chain-growth polymerization, and the self-assembling behavior lead to phase separation. The rod-rod diblock copolymer which was composed by poly(2,5-dihexyloxy-p-phenylene (PPP) and poly(3-hexylthiophene) (P3HT), and we synthesized five different composition which all of the PPP molecular weight is about 4000, the polydispersity index (PDI) of PPP is lower than 1.2, and then polymerized to various molecular weight of PPP-b-P3HT. The fraction of PPP in the PPP-b-P3HT diblock copolymer is about 15%~70%. The synthesized PPP-b-P3HTs were characterized by using various techniques including gel permeation chromatography (GPC) to ensure molecular weight and PDI of diblock copolymer, 1H-Nuclear Magnetic Resonance (1H-NMR) to ensure each of the fractions of PPP and P3HT in diblock copolymer, UV-VIS and photoluminescence (PL) to analysis photo characterization and compare which of the difference, thermogravimetric analysis (TGA) to compare the difference between thermoresistivity of various composition of the diblock copolymers. Furthermore, the self-assembling behavior of block copolymer was investigated by TEM. We observed lamellae and fiber, which has different microphase structures for different compositions of the diblock copolymers. In the end, we used the small angle X-ray scattering technique to calculate the length of diblock copolymer, and the wide angle X-ray scattering technique to study the crystalline of PPP-b-P3HT nanostructure. We could observe that PPP-b-P3HT diblock copolymers which microphase structures within nanometer, and with difference between each of homopolymers. We could recognize the basic property and microscopic self-assembling behavior of PPP-b-P3HT by the techniques. We also synthesized poly(3-hexylthiophene)-b-poly(3-hexyloxythiophene) (P3HT-b-P3HOT) by Grignard Metathesis and characterized by using various techniques to compare the difference between PPP-b-P3HT in appendix.誌謝………………………………………………………………...……I要……………………………………………………………………IIIBSTRACT……………………………………………………….…V錄…….……………………………………….…………………….VII目錄………………………………………………………………..XI目錄………………………………………………………………XVII一章 緒論………………………….………………………………1二章 文獻回顧………………………………………….………....4.1 嵌段共聚物(Block copolymer)…………………………….....….……..4.1.1 介紹……………………….……………….………….…………….4.1.2 微觀相分離型態……………….……….…………..……...……….5.2 聚3-己烷噻吩(poly(3-hexylthiophene), P3HT)..………….…….………...7.3 聚2,5-二己烷氧對苯(poly(2,5-dihexyloxy-p-phenylene), PPP)………..14.3.1 聚2,5-己烷氧對苯-b-聚3-己烷噻吩之雙嵌段共聚物poly(2,5-dihexyoxy-p-phenylene)-b-poly(3-hexylthiophene), PPP-b-P3HT)….16.4 聚3-己烷氧噻吩(poly(3-(hexyloxythiophene), P3HOT)……………….20.4.1 聚3-己烷噻吩-b-聚3-己烷氧噻吩之雙嵌段共聚物poly(3-hexylthiophene)-b-poly(3-hexyloxythiophene), P3HT-b-P3HOT)………..21.5 研究硬桿-硬桿雙嵌段共聚物(Rod-Rod diblock copolymer)之目的….24三章 實驗…………………………………….…………………..25.1 實驗藥品…………………………………………….…………………...25.2 儀器設備…………………………………………….…………………...27.3 單體製備………………………………………………………………...28.3.1 合成3-己烷噻吩(3-hexylthiophene)..……………………………28.3.2 合成2,5-二溴-3-己烷噻吩(2,5-dibromo-3-hexylthiophene)……29.3.3 合成1,4-二己基氧苯(1,4-dihexyloxybenzene)………….………30.3.4 合成1,4-二溴-2,5-二己基氧苯1,4-dibromo-2,5-dihexyloxybenzene)……………………….….………………....31.4 格林納聚合反應(Grignard Metathesis)………………………………...32.4.1 無水溶劑的製備……………………………..……………………32.4.2 合成聚2,5-二己烷氧對苯poly(2,5-dihexyloxy-p-phenylene), PPP)………………………………………...32.4.3 合成2-溴-5-氯鎂-3-己烷噻吩2-bromo-5-chloromagnesium-3-hexylthiophene).…………………….…………..34.4.4 合成聚2,5-己烷氧對苯-b-聚3-己烷噻吩之雙嵌段共聚物poly(2,5-dihexyoxy-p-phenylene)-b-poly(3-hexylthiophene), PPP-b-P3HT)….....35.4.5 合成不同比例的PPP-b-P3HT……………….…………………..36四章 結果與討論………………………………..………………..37.1 單體合成之鑑定…………………………………..……………………...37.1.1 3-己烷噻吩(3-hexylthiophene)...…………………..………..…….37.1.2 2,5-二溴-3-己烷噻吩(2,5-dibromo-3-hexylthiophene)…………..37.1.3 1,4-二己基氧苯(1,4-dihexyloxybenzene)..……………………….38.1.4 1,4-二溴-2,5-二己基氧苯(1,4-dibromo-2,5-dihexyloxybenzene)..38.2 PPP 合成之鑑定…………………………………………………………..39.3 PPP-b-P3HT 合成之鑑定………………………………...……………….41.3.1 由GPC 鑑定PPP-b-P3HT 合成結果………….………………....41.3.2 由1H-NMR 鑑定PPP-b-P3HT 合成結果…….……………….....44.4 PPP-b-P3HT 之熱性質分析…………………….…..…...……………….46.4.1 TGA 熱性質分析……………………..…..………………………46.4.2 DSC 熱性質分析………………………………………………...47.5 PPP-b-P3HT 之光學性質分析……………….…..………………………49.5.1 UV/Vis 光譜分析……………….………...………………………49.5.2 PL 光譜分析……………….………...……………………………51.6 PPP-b-P3HT 之微結構分析…………….………...…………………...…53.6.1 TEM 影像分析……….........….………...………………………....53.6.2 SAXS 圖譜分析………….…….………...………………………..54.6.3 WAXS 圖譜分析…………...…….………...……………...……….56五章 結論………………………………..………………………..59amp;#63851;考文獻…………………………………..…………………………..61錄……………………………………………..……………………..64.合成P3HT-b-P3HOT………………...………...…………….....…………....64.1 實驗目的……………...………...…………….....…………….................64.2 實驗步驟……………...………...…………….....…………….................64.2.1 單體製備……………...………...…………….....……....……....…...64.2.1.1 無水溶劑的製備…...………...….....………….....……..…........64.2.1.2 合成3-己烷氧噻吩(3-hexyloxythiophene)…......…......….......65.2.1.3 合成2,5-二溴-3-己烷氧噻吩,5-dibromo-3-hexyloxythiophene)……………………………...…...……………66.2.2 格林納聚合反應(Grignard Metathesis)....…………….…………..67.2.2.1 合成聚3-己烷噻吩(poly(3-hexylthiophene))..….……...….…..67.2.2.2 合成2-溴-5-氯鎂-3-己烷氧噻吩-bromo-5-chloromagnesium-3-hexyloxythiophene)…………...…………..…….68.2.2.3 合成聚3-己烷噻吩-b-聚3-己烷氧噻吩之塊狀共聚物poly(3-hexylthiophene)-b-poly(3-hexyloxythiophene))…………………..…..69.3 實驗結果與討論.....……………………………………...........................70.3.1 以NMR鑑定合成單體.....……………………………………..........70.3.1.1 3-己烷氧噻吩(3-hexyloxythiophene)…....…………...…….…...70.3.1.2 2,5-二溴-3-己烷氧噻吩(2,5-dibromo-3-hexyloxythiophene)…..70.3.2 以GPC 鑑定合成P3HT-b-P3HOT 之雙嵌段共聚物……………..71.3.3 TGA 熱性質分析...……………………………………......................71.3.4 UV/Vis 光譜分析...……………………………………......................72.3.5 PL 光譜分析...…………………………………….............................72.3.6 MALDI-TOF 質譜分析…………………………...............................73.4 比較PPP-b-P3HT 及P3HT-b-P3HOT……...............................................746850017 bytesapplication/pdfen-US硬桿-硬桿團聯共聚高分子聚2,5-二己基氧對苯聚3-己烷噻吩格林納聚合反應法自組裝行為rod-rod diblock copolymerpoly(2,5-dihexyloxy-p-phenylene)poly(3-hexylthiophene)Grignard Metathesisself-assembling behaviorthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/187016/1/ntu-98-R96524025-1.pdf