Synthesis of Polyfluorene-Polytriarylamine Block Copolymer with Emitting Part at Junction Point for Light Emitting Applications


A block copolymer consisting of polyfluorene (PF) and polytriarylamine (PTAA) functionalized with green emitting phenoxazine moiety at the junction point of two blocks was designed and prepared for electroluminescent application. PF homopolymer was synthesized by Suzuki coupling polymerization, and was reacted with brominated phenoxazine. In the presence of the resulting PF functionalized with phenoxazine, C-N coupling polymerization of 4-(4’-bromophenyl)-4’’-butyldiphenylamine was carried out to afford a triblock copolymer, PTAA-phenoxazine-PF-phenoxazine-PTAA (PF-Ph-PTAA). Two types of random copolymers were also synthesized with fluorene and phenoxazine (PF2) by Suzuki coupling polymerization for comparison. All the polymers were soluble in common organic solvents and readily formed thin films by a solution processing. Prepared polymers exhibited similar UV absorption and PL emission in chloroform solutions. In a film state, the existence of phenoxazine unit drastically changed PL spectra. Although the content of phenoxazine unit in PF-Ph-PTAA was relatively high (13 mol%), it showed similar PL spectrum to that of PF2(phenoxazine content, 0.2 mol%) indicating that phenoxazine unit is isolated in single polymer chain nevertheless the high content. EL device based on PF-Ph-PTAA showed green-emission, suggesting that emission sites predominantly located in the vicinity of phenoxazine moiety because of its shallow HOMO level.

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M. Jahanfar, K. Suwa, K. Tsuchiya and K. Ogino, "Synthesis of Polyfluorene-Polytriarylamine Block Copolymer with Emitting Part at Junction Point for Light Emitting Applications," Open Journal of Organic Polymer Materials, Vol. 3 No. 2, 2013, pp. 46-52. doi: 10.4236/ojopm.2013.32008.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns and A. B. Holmes, “Light-Emitting Diodes Based on Conjugated Polymers,” Nature, Vol. 347, No. 6293, 1990, pp. 539-541. doi:10.1038/347539a0
[2] L. Akcelrud, “Electroluminescent Polymers,” Progress in Polymer Science, Vol. 18, No. 6, 2003, pp. 875-962. doi:10.1016/S0079-6700(02)00140-5
[3] K. Tsuchiya, K. Sakaguchi, H. Kasuga, A. Kawakami, H. Taka, H. Kita and K. Ogino, “Synthesis of Charge Transporting Block Copolymers Containing 2,7-Dimethoxycarbazole Units for Light Emitting Device,” Polymer, Vol. 50, No. 3, 2010, pp. 616-622. doi:10.1016/j.polymer.2009.12.024
[4] K. Tsuchiya, H. Kasuga, A. Kawakami, H. Taka, H. Kita and K. Ogino, “Synthesis of Bipolar Charge Transporting Block Copolymers and Characterization for Organic Light-Emitting Diode,” Journal of Polymer Science Part A: Polymer Chemistry, Vol. 48, No. 7, 2010, pp. 1461-1468. doi:10.1002/pola.23853
[5] K. Tsuchiya, K. Sakaguchi, A. Kawakami, H. Taka, H. Kita, T. Shimomura and K. Ogino, “Charge Transporting Block Copolymer for Morphological Control in Light Emitting Device Based on Polymer Blends,” Synthetic Metals, Vol. 160, No. 15-16, 2010, pp. 1679-1682. doi:10.1016/j.synthmet.2010.05.040
[6] J. K. Kim, S. Y. Yang, Y. Lee and Y. Kim, “Functional Nanomaterials Based on Block Copolymer Self-Assembly,” Progress in Polymer Science, Vol. 35, No. 11, 2010, pp. 1325-1349. doi:10.1016/j.progpolymsci.2010.06.002
[7] L. Deng, P. T. Furuta, S. Garon, J. Li, D. Kavulak, M. E. Thompson and J. M. J. Fréchet, “Living Radical Polymerization of Bipolar Transport Materials for Highly Efficient Light Emitting Diodes,” Chemistry of Materials, Vol. 18, No. 2, 2006, pp. 386-395. doi:10.1021/cm051922+
[8] B. Ma, B. J. Kim, L. Deng, D. A. Poulsen, M. E. Thompson and J. M. J. Fréchet, “Bipolar Copolymers as Host for Electroluminescent Devices: Effects of Molecular Structure on Film Morphology and Device Performance,” Macromolecules, Vol. 40, No. 23, 2007, pp. 8156-8161. doi:10.1021/ma0715526
[9] Y. Tan, Z. Gu, K. Tsuchiya and K. Ogino, “Synthesis and Luminescent Properties of Block copolymers Based on Polyfluorene and Polytriphenylamine,” Polymer, Vol. 53, No. 7, 2012, pp. 1444-1452. doi:10.1016/j.polymer.2012.02.021
[10] Y. Tan, K. Tsuchiya and K. Ogino, “Synthesis of Polyfluorene Block Copolymers and Effect of Side Chain Group on Electroluminescent Device Performance,” Chemistry Letters, Vol. 41, No. 3, 2012, pp. 257-259. doi:10.1246/cl.2012.257
[11] A. Nowakowska-Oleksy, J. Sooducho and J. Cabaj, “Phenoxazine Based Units-Synthesis, Photophysics and Electrochemistry,” Journal of Fluorescence, Vol. 21, No. 1, 2011, pp. 169-178. doi:10.1007/s10895-010-0701-6
[12] H. Tanaka, K. Shizu, H. Miyazaki and C. Adachi, “Efficient Green Thermally Activated Delayed Fluorescence (TADF) from a Phenoxazine-Triphenyltriazine (PXZ-TRZ) Derivative,” Chemical Communications, Vol. 48, No. 93, 2012, pp. 11392-11394. doi:10.1039/c2cc36237f
[13] J.-H Park, N. S. Cho, Y. K. Jung, H.-J. Cho, H.-K. Shim, H. Kim and Y. S. Lee, “Polymeric Light Emitting Properties and Structural Relationships of Fluorene-Based Conjugated Copolymers Containing Various Hole Transporting Derivatives,” Organic Electronics, Vol. 8, No. 2-3, 2007, pp. 272-285. doi:10.1016/j.orgel.2006.08.002
[14] Y. Pei, M. Otake, M. Vacha and H. Sato, “Synthesis and Characterization of a Novel Electroluminescent Polymer Based on Phenoxazine and Fluorene Derivatives,” React. Funct. Polym., Vol. 67, No. 11, 2007, pp. 1211-1217. doi:10.1016/j.reactfunctpolym.2007.07.011
[15] K. Tsuchiya, T. Shimomura and K. Ogino, “Preparation of Diblock Copolymer Based on Poly(4-n-butyltriphenyl amine) via Palladium Coupling Polymerization,” Polymer, Vol. 50, No. 1, 2009, pp. 95-101. doi:10.1016/j.polymer.2008.10.057

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