supramolecular structures of amphiphilic hairy-rod conjugated copolymer

HASH(0x1ade0ee0)

廖紹憬(Liao, Shao Ching)

指導教授 ： 陳信龍

國立清華大學/工學院/化學工程學系/碩士(2008年)

https://doi.org/10.6843/NTHU.2008.00314

摘要

在這篇論文中，我們將利用小角度散射儀並輔以紫外線光譜儀與螢光光譜儀研究並分析一種兩性的共軛高分子PVEO17在塊材以及不同溶液中所顯現的結構。PVEO17是由具有半硬以及擁有疏水性質的PPV構成主鏈，柔軟以及擁有親水性質的PEO構成側鏈。在塊材中，小角度散射數據顯示PVEO17會有微相分離，分子主鏈PPV鏈段會自組裝堆疊成類似盤子的微相結構，這主鏈所構成的盤子，分散在側鏈PEO所圍繞的環境中；由於PEO是一種在常溫下會發生結晶的材料，我們也利用廣角繞射儀偵測到塊材中的EO側鏈有結晶產生。另一方面，在溶液態中，PVEO17的自組裝結構會受到溶劑與分子的交互作用力以及溶液濃度的影響。在THF溶劑的環境中，PVEO17會以單分子鏈的形式分散；在1wt% ~ 8wt%的水溶液中，PVEO17分子鏈會自組裝成圓柱形的微胞，隨著濃度的增加，形成微胞的分子鏈也增加，另外，這些圓柱微胞會在空間中產生某種程度的聚集。分子鏈所產生的聚集，會影響到PVEO17的光物理性質，當聚集行為愈趨嚴重，將會伴隨著螢光光譜的紅位移，我們能夠觀察到當PVEO17的狀態由稀薄溶液到濃溶液，進而轉換到塊材時，會有明顯的紅位移現象發生。

關鍵字

梳狀高分子 ； 共軛高分子 ； 小角度散射 ； HASH(0x1ade19c0) ； HASH(0x1ade1a60) ； HASH(0x1ade1b00)

並列摘要

The structures of an amphiphilic graft conjugated copolymer, PVEO17 ,composing of a conjugated PPV backbone and PEO side chains, in bulk and solutions with THF and water have been investigated by small-angle x-ray scattering (SAXS), UV-Vis and photoluminescence spectroscopy. In bulk state, PPV main chains in PVEO17 stacked into flat disk microdomains dispersed in the EO side-chain matrix. Wide angle x-ray scattering revealed the existence of crystallization of PEO side chain. The structure of the polymer in solution was affected by the solvent quality and the polymer concentration. PVEO17 chains were well dispersed in THF. In aqueous solutions, PVEO17 chains aggregated significantly over the concentration range of 1wt% to 8wt%, where the polymer was found to self-organize into cylindrical micelles with the length and the aggregation number increased with increasing concentration. The photophysical properties of PVEO17 were affected by the degree of aggregation, where aggregation resulted in a red-shift of the PL. A gradual red shift of PL was also observed in going from the solution state to the precipitate to the bulk.

並列關鍵字

hairy rod ； conjugated polymer ； SAXS ； PPV ； PEO ； solution

參考文獻

Stepanyan, R; Knaapila, M. Macromolecules 2003, 36, 3758.

Alexander, S. J. Phys. (Paris) 1977, 38, 983.

Schwiegk, S; Vahlenkamp, T; Xu, Y; Wegner, G. Macromolecules 1992, 25, 2513

Yingkui Yang; Xiaolin Xie. Journal of Polymer Science Part A Polymer Chemistry 2006, Vol. 44, 3869

Alan, J; Heeger, A; Hideki Shirakawa; Nobel Prize in Chemistry, 2000