藉由格林納反應合成硬桿-硬桿雙嵌段共聚高分子與其性質之鑑定與研究

Abstract

本實驗研究硬桿-硬桿雙嵌段共聚高分子(rod-rod diblock copolymer)的合 成，並探討其所具有的自組裝行為(self-assembling behavior)所產生的相分離現 象，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 子量分布(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 分子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 15%~70%之間。 將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， 比較熱性質、光學性質及微結構組成的差異性。包含以膠體滲透層析儀(Gel Permeation Chromatography, GPC)鑑定分子量及分子量分布情形，核磁共振氫譜 儀(1H-Nuclear Magnetic Resonance, 1H-NMR)觀察聚2,5-二己基氧對苯與聚3-己 烷噻吩的比例。透過紫外光-可見光光譜儀(UV-Vis Spectrophotometer)與光激發 螢光光譜儀(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 穿透式電子顯微鏡(Transmission Electron Microscope, TEM)，觀察PPP-b-P3HT 在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(Small Angle X-ray Scattering, SAXS)來計算PPP-b-P3HT 的分子鏈段長，以及廣角度X 光散射儀(Wide Angle X-ray Scattering, WAXS)來觀測微結構排列情形及晶體結 構。 由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 與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 基氧對苯及聚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 行為的了解。 此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 噻吩(poly(3-hexylthiophene)-b-poly(3-hexyloxythiophene), P3HT-b-P3HOT)，鑑定 其合成物，並探討熱性質、光學性質與微結構解析，並與PPP-b-P3HT 比較其 差異處。

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.