利用陰離子聚合反應法合成硬桿-柔曲-硬桿嵌段共聚物及其自組裝特性研究

Anionic Synthesis and Self-Assembly Behavior of π-Conjugated Rod-Coil-Rod Block Copolymers

張俊安(Jun-An Chang)

指導教授 ： 程耀毅

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.2011.00420

摘要

本實驗研究是利用陰離子聚合反應合成出poly-(diethylhexyloxy-p-phenylenevinylene)-b-poly(2-vinylpyridine)-b-poly(3-hexyl thiophene)(PPV-P2VP-P3HT)硬桿-柔曲-硬桿三團聯共聚高分子(rod-coil-rod triblock copolymer)，首先先合成均一高分子聚3-己烷噻吩(P3HT)且α和ω位置具有乙烯和苯環基團再以巨起始劑法起始，之後加入2-乙烯吡啶(2VP)單體聚合，最後再以尾端具有醛基的共軛高分子-聚對苯乙烯(DEH-PPV)進行尾端偶合反應，終止活性的P3HT-P2VP陰離子鏈段而合成出PPV-P2VP-P3HT三團聯共聚高分子。將合成得到的三團聯共聚高分子，進行合成鑑定以及基本性質量測。包含以膠體滲透層析儀(Gel Permeation Chromatography, GPC)測量其分子量與分子量分布情形，核磁共振氫譜儀(1H-Nuclear Magnetic Resonance, 1H-NMR)鑑定比例，以及用紫外光-可見光光譜儀(UV-Vis Spectrophotometer)和螢光光譜儀(Photoluminescence, PL)量測其光學性質。之後藉由穿透式電子顯微鏡(Transmission Electron Microscope, TEM)的觀察，發現柱狀的微結構。最後經由小角度X光散射儀(Small Angle X-ray Scattering, SAXS)更進一步確定其奈米結構。

關鍵字

三團聯共聚高分子 ； 硬桿-柔曲-硬桿 ； 陰離子聚合 ； 巨起始劑法 ； 巨終止劑法 ； 自組裝行為

並列摘要

In this thesis, we studied the synthesis of poly-(diethylhexyloxy-p-phenylenevinylene)-b-poly(2-vinylpyridine)-b-poly(3-hexyl thiophene)(PPV-P2VP-P3HT) rod-coil-rod triblock copolymer via anionic polymerization. We synthesized the triblock copolymer by first synthesizing homopolymer P3HT, with a α-vinyl-ω-(phenyl) end functional P3HT using sec-butyllithium as macroinitiator at -78℃ in THF. 2-vinylpyridine(2VP) monomers were then added into P3HT macroinitiator solution for initiation and polymerization. Finally the PPV-P2VP-P3HT triblock copolymer was synthesized by using aldehyde end functionalized PPV rods as a macroterminator to quench the living P3HT-P2VP anionic chains.
The synthesized PPV-P2VP-P3HT was characterized by using various techniques including Gel Permeation Chromatography(GPC) to ensure molecular weight and PDI of triblock copolymer, 1H-Nuclear Magnetic Resonance(1H-NMR) to ensure each of the fractions of PPV, P2VP and P3HT in triblock copolymer, UV-VIS and Photoluminescence(PL) to examine optical properties. Furthermore, the self-assembling behavior of triblock copolymer was investigated by using Transmission Electron Microscope(TEM). Cylinder microphase structures of the triblock copolymer. In the end, can be observed the small angle X-ray scattering(SAXS) technique was used to study of PPV-P2VP-P3HT nanostructure.

並列關鍵字

triblock copolymer ； rod-coil-rod ； anionic polymerization ； macroinitiator ； macroterminator ； self-assembling behavior

參考文獻

[1] Yingdong Xia; Jizhong Chen; Zhaoyan Sun; Tongfei Shi; Lijia An; Yuxi Jia, Self-assembly of linear ABC coil-coil-rod triblock copolymers. E.L. Polymer 2010, 51, 3315.

[2] Sariciftci, N. S.; Heeger, A. J. Int. J. Modern Phys. B 1994, 8, 237.

[3] Sariciftci, N. S.; Prog. Quantum Electron. 1995, 19, 131.

[4] Yingdong Xia; Jizhong Chen; Zhaoyan Sun; Tongfei Shi; Lijia An; Yuxi Jia, Self-assembly of linear ABC coil-coil-rod triblock copolymers. E.L. Polymer 2010, 51, 3317.

[10] D. Marsitzky, M. K., and K. Mullen. Macromolecules 1999, 32, (25), 8685-8688.