聚三己烷噻吩-聚三噻吩己酸乙酯嵌段式共聚物之合成、物理性質鑑定與型態學研究

劉祐誠

doi:10.6342/NTU.2011.00458

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聚三己烷噻吩-聚三噻吩己酸乙酯嵌段式共聚物之合成、物理性質鑑定與型態學研究

Synthesis, Characterization and Morphology of Block Copolymers Poly(3-hexylthiophene)-b-Poly(3-thiophene hexylacetate)

劉祐誠 , Masters　　Advisor：林唯芳　　

英文 DOI： 10.6342/NTU.2011.00458

導電共聚高分子；嵌段式共聚物；聚噻吩；聚噻吩酯；自組裝；光電性質；相圖； conjugated copolymer ； block ； polythiophene ； polythiophene ester ； self-assembly ； optical properties ； phase diagram

Abstract │ Reference (21) │ Altmetrics

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The synthesis, characterization and morphology study of copolymers of poly(3-hexylthiophene) (P3HT) and poly(3-thiophene hexylacetate) (P3THA) are performed in this thesis. By using GRIM method, polymers with high regioregularity, narrow polydispersity and controlled molecular weight can be obtained. From the optoelectronic properties characterization, the ester-functionalized P3THA shows a blue-shift UV-Vis spectrum and lower HOMO as compared to P3HT. These results are contributed to the bulky and the electron-withdrawing ester group which decrease the conjugated length. The amount of blue shift is directly proportional to the amount of P3THA in the block copolymer. From the CV measurements, each respective HOMO and LUMO is observed in each block segment of block copolymer which does not present in the random copolymers. The thermal and phase behaviors of the block copolymers were investigated by DSC, WAXS, GIWAXS and AFM. The crystalline morphology of copolymers is dependent on the block compositions of P3HT-b-P3THA. Phase separation is observed as the P3HT block higher than 50% molar ratio. When the molar ratio of P3THA is larger than 80%, the cocrystalline structure is observed. Thus, the crystalline morphology can be tuned by changing the block copolymer compositions. The results are useful for the design and fabrication of nanostructured conducting polymers.

Reference ( 21 ) 〈TOP〉

1. Chen, X. L.*, Jenekhe, S. A., Block conjugated copolymers: Toward quantum-well nanostructures for exploring spatial confinement effects on electronic, optoelectronic, and optical phenomena, Macromolecules, 1996, p. 6189-6192
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2. Cho, K., Park, Y. D., Kim, D. H., Jang, Y., Cho, J. H., Hwang, M., Lee, H. S., Lim, J. A. *, Effect of side chain length on molecular ordering and field-effect mobility in poly(3-alkylthiophene) transistors, Organic Electronics, 2006, p. 514-520
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3. Ge, J., He, M., Qiu, F., Yang, Y. L. *, Synthesis, Cocrystallization, and Microphase Separation of All-Conjugated Diblock Copoly(3-alkylthiophene)s, 2010, p. 6422-6428
連結：
4. Ho, C. C., Lee, Y. H., Dai, C. A., Segalman, R. A., Su, W. F.*, Synthesis and Self-Assembly of Poly(diethylhexyloxy-p-phenylenevinylene)-b-poly(methyl methacrylate) Rod-Coil Block Copolymers, Macromolecules, 2009, p. 4208-4219
連結：
5. Hou, J. H., Chen, T. L., Zhang, S. Q., Huo, L. J., Sista, S., Yang, Y. *, An Easy and Effective Method To Modulate Molecular Energy Level of Poly(3-alkylthiophene) for High-V-oc Polymer Solar Cells, Macromolecules, 2009, p. 9217-9219
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