藉由格林納反應合成共軛-共軛雙嵌段共聚高分子 及其自組裝行為探討和奈米混成系統之應用

Synthesis, Self-Assembly and Application of all-conjugated Block Copolymers and Their Applications in Nanohybrid System

魏凡凱(Fan-Kai Wei)

指導教授 ： 戴子安

國立臺灣大學/工學院/化學工程學研究所/碩士(2011年)

https://doi.org/10.6342/NTU.2011.10145

摘要

含有共軛鏈段之團聯共聚高分子由於本身具備的自組裝特性可進而有效藉由結構上的改變來調控其機械與光電特性，因而逐漸受到各界廣泛的注意。因此，瞭解此類含有共軛鏈段之團聯共聚高分子其自組裝特性以利後續的應用發展乃是相當重要的一環。然而目前在此研究課題上仍有許多未知的現象有待探索。
在本論文中提到利用格林納聚合法一系列的PPP-P3HT雙共軛團聯共聚高分子已被成功的合成出來。我們利用這一系列固定PPP鏈段分子量改變P3HT鏈段長度之具有不同體積分率的PPP-P3HT雙共軛團聯共聚高分子進行此一系統之自組裝行為探討。
進而利用此系列共軛團聯共聚高分子進行硫化鎘(CdS)半導體奈米微粒製備並且觀察期自組裝型態進一步去測量其光電性質，然而我們亦注意到團聯共聚合物吸附CdS奈米微粒之後對於發光有一quench效果，主因是由於高分子受到光激發後電子與電洞經由PPP-P3HT/ CdS混成系統的能階傳導造成之電荷分離效應所致。

關鍵字

團聯共聚高分子 ； 導電高分子 ； 自組裝 ； 半導體奈米微粒

並列摘要

In this study, the self-assembly behavior of all-conjugated rod-rod poly(2,5-dihexyloxy-p-phenylene)-b-poly(3-hexylthiophene) (PPP-P3HT) block copolymers was investigated. A series of monodisperse PPP-P3HT block copolymers consisting of a nearly constant molecular weight PPP block and a different molecular weight P3HT block was synthesized via a sequential Grignard metathesis method (GRIM). Small-angle x-ray scattering (SAXS), wide-angle x-ray scattering(WAXS), transmission electron microscopy (TEM) and differential scanning calorimetry(DSC) are used to map the phase diagram and molecular packing of the copolymers. On the basis of the results, the self-assembly behavior of the PPP-P3HT block copolymers show features that differ from the phase diagram of both conventional coil-coil and rod-coil block copolymers, indicating the rigid nature of PPP and P3HT chains. As a consequence, the results of this study show promises for practical uses of self-assembling block copolymers containing all-conjugated segments since the resulting phase diagram offers a level of structural control that is important for future applications.

Nanoparticles of semiconductor have many applications in areas of optoelectronic and biomedical technologies. During the past decade, many synthetic methods of nanoparticles have been developed. In this study, we fabricated organic/inorganic hybrid containing cadmium sulfide (CdS) nanoparticles using a novel conducting-conducting block copolymer as a structure template. A series of monodisperse PPP-P3HT block copolymers were synthesized via a sequential Grignard metathesis method (GRIM). Gel permeation chromatographer, NMR spectra and transmission electron microscopy were used to characterize the block copolymers. The block copolymers / CdS nanoparticles hybrid system was fabricated by adding inorganic materials in the block copolymer system. The chemical structure, morphology, thermal and optoelectronic properties of the hybrid system were studied by FTIR, UV-VIS, photoluminescence spectroscopy and transmission electron microscopy.

並列關鍵字

all-conjugated block copolymers ； Nanoparticles of semiconductor ； self-assembly behavior

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