Polímeros: Ciência e Tecnologia
Polímeros: Ciência e Tecnologia
Original Article

Influence of solvent used on oxidative polymerization of Poly(3-hexylthiophene) in their chemical properties

Fonsêca, Juliana de Castro Macêdo; Alves, Maria dos Prazeres Arruda da Silva

Downloads: 2
Views: 349


Abstract: The aim of the study is to utilize the simplicity of oxidative polymerization with ferric chloride to originates poly(3-hexylthiophene) of lower molecular weight. So, the chloroform, in general used as solvent in this synthesis, was switched by dichloromethane. The obtained polymers were characterized by infrared spectroscopy (FTIR), ultra-violet visible spectroscopy (UV-Vis), gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) were used to evaluate the structure, conjugation length, molecular weight and regioregularity with the goal of comparing these properties with those of poly (3-hexylthiophene) synthesized in chloroform. Despite large difference observed in molecular weight of polymers obtained by chloroform and dichloromethane, no significant differences were observed of these polymers in regioregularity and conjugation length.


Perepichka, I. F., & Perepichka, D. F. (2009). Handbook of thiophene-based materials: applications in organic electronics and photonics. United Kingdom: John Willey & Sons. http://dx.doi.org/10.1002/9780470745533. 

Fichou, D. (1999). Handbook of oligo- and polythiophene. United Kingdom: John Wiley & Sons. 

Lanzi, M., Salatelli, E., Benelli, T., Caretti, D., Giorgini, L., & Di-Nicola, F. P. (2015). A regioregular polythiophene-fullerene for polymeric solar cells. Journal of Applied Polymer Science, 132(25), 42121. http://dx.doi.org/10.1002/app.42121. 

Chen, T. A., & Rieke, R. D. (1992). The first regioregular head-to-tail poly(3-hexylthiophene-2,5-diyl) and a regiorandom isopolymer: nickel versus palladium catalysis of 2(5)-bromo-5(2)-(bromozincio)-3-hexylthiophene polymerization. Journal of the American Chemical Society, 114(25), 10087-10088. http://dx.doi.org/10.1021/ja00051a066. 

McCullough, R. D., Lowe, R. D., Jayaraman, M., & Anderson, D. L. (1993). Design, synthesis and control of conducting polymer architectures: structurally homogeneous poly(3-alkylthiophene)s. The Journal of Organic Chemistry, 58(4), 904-912. http://dx.doi.org/10.1021/jo00056a024. 

Jeffries-El, M., & McCullough, R. D. (2006). Regioregular polythiophenes. In T. J. Skotheim, & J. R. Reynolds (Eds.), Conjugated polymers: theory, synthesis, properties and characterization (2nd ed., pp. 9-1). Boca Raton: CRC Press.

Loewe, R., Khersonsky, S. M., & McCullough, R. D. (1999). A simple method to prepare head-to-tail coupled, regioregular poly(3-alkylthiophenes) using grignard metathesis. Advanced Materials, 11(3), 250-253. http://dx.doi.org/10.1002/(SICI)1521-4095(199903)11:3<250::AID-ADMA250>3.0.CO;2-J. 

Ballantyne, A. M., Chen, L., Dane, J., Hammant, T., Braun, F. M., Heeney, M., Duffy, W., McCulloch, I., Bradley, D. D. C., & Nelson, J. (2008). The effect of poly(3-hexylthiophene) molecular weight on charge transport and the performance of polymer:fullerene solar cells. Advanced Functional Materials, 18(16), 2373-2380. http://dx.doi.org/10.1002/adfm.200800145. 

Fumagalli, L., Binda, M., Natali, D., Sampietro, M., Salmoiraghi, E., & Di Gianvincenzo, P. (2008). Dependence of the mobility on charge carrier density and electric field in poly(3-hexylthiophene) based thin film transistors: Effect of molecular weight. Journal of Applied Physics , 104(8), 084513. http://dx.doi.org/10.1063/1.3003526. 

Kim, Y. S., Lee, Y., Lee, W., Park, H., Han, S.-H., & Lee, S.-H. (2010). Effects of molecular weight and polydispersity of poly(3-hexylthiophene) in bulk heterojunction polymer solar cells. Current Applied Physics, 10(1), 329-332. http://dx.doi.org/10.1016/j.cap.2009.06.021. 

Wang, Y., Lucht, B. L., & Euler, W. B. (2002). Investigation of the oxidative coupling polymerization of 3-alkylthiophene with iron (III) chloride. Polymer Preprints , 43(20), 1160. Retrieved in 2017, May 28, from http://copper.chm.uri.edu/weuler/wang.pdf 

Osterholm, J. E., Sunila, P., & Hjertberg, J. (1987). 13C CP-MAS NMR and FTIR studies of polythiophene. Synthetic Metals, 18(1-3), 169-176. http://dx.doi.org/10.1016/0379-6779(87)90873-3. 

Zerbi, G., Chierichetti, B., & Inganas, O. (1991). Thermochromism in polyalkylthiophenes: Molecular aspects from vibrational spectroscopy. The Journal of Chemical Physics , 94(6), 4646-4658. http://dx.doi.org/10.1063/1.460593. 

Niemi, V. M., Knuuttila, P., Osterholm, J. E., & Korvola, J. (1992). Polymerization of 3-alkylthiophenes with FeCl3. Polymer, 33(7), 1559-1562. http://dx.doi.org/10.1016/0032-3861(92)90138-M. 

McCarley, T. D., Noble, DuBois, C. J., & McCarley, R. L. (2001). MALDI-MS Evaluation of poly(3-hexylthiophene) synthesized by chemical oxidation with FeCl3. Macromolecules , 34(23), 7999-8004. http://dx.doi.org/10.1021/ma002140z. 

Zen, A., Pflaum, J., Hirschmann, S., Zhuang, W., Jaiser, F., Asawapirom, U., Rabe, J. P., Scherf, U., & Neher, D. (2004). Effect of molecular weight and anneling of poly (3-hexylthiophene)s on the performance of Organic Field Effect Transistors. Advanced Functional Materials , 14(8), 757-764. http://dx.doi.org/10.1002/adfm.200400017. 

Joshi, S., Grigorian, S., Pietsch, U., Pingel, P., Zen, A., Neher, D., & Scherf, U. (2008). Thickness dependence of the crystalline structure and hole mobility in thin films of low molecular weight poly(3-hexylthiophene). Macromolecules, 41(18), 6800-6808. http://dx.doi.org/10.1021/ma702802x. 

Maior, R. M. S., Hinkelmann, K., Eckert, H., & Wudl, F. (1990). Synthesis and characterization of two regiochemically defined poly(dialky1bithiophenes): a comparative study. Macromolecules, 23(5), 1268-1279. http://dx.doi.org/10.1021/ma00207a008. 

Barbarella, G., Bongini, A., & Zambianchi, M. (1994). Regiochemistry and conformation of poly(3-hexylthiophene) via the synthesis and the spectroscopic characterization of the model configurational triads. Macromolecules, 27(11), 3039-3045. http://dx.doi.org/10.1021/ma00089a022. 

Nicho, M. E., Hernandez, F., Hu, H., Medrano, G., Guizado, M., & Guerrero, J. A. (2009). Physicochemical and morphological properties of spin-coated poly (3-alkylthiophene) thin films. Solar Energy Materials and Solar Cells, 93(1), 37-40. http://dx.doi.org/10.1016/j.solmat.2008.02.016. 

Sivaraman, P., Mishra, S. P., Bhattacharrya, A. R., Thakur, A., Shashidhara, K., & Samui, A. B. (2012). Effect of regioregularity on specific capacitance of poly(3-hexylthiophene). Electrochimica Acta, 69, 134-138. http://dx.doi.org/10.1016/j.electacta.2012.02.085. 

Amou, S., Haba, O., Shirato, K., Hayakawa, T., Ueda, M., Takeuchi, K., & Asai, M. (1999). Head-to-tail regioregularity of poly(3-hexylthiophene) in oxidative coupling polymerization with FeCl3. Journal of Polymer Science. Part A, Polymer Chemistry, 37(13), 1943-1948. http://dx.doi.org/10.1002/(SICI)1099-0518(19990701)37:13<1943::AID-POLA7>3.0.CO;2-X. 

Urien, M., Bailly, L., Vignau, L., Cloutet, E., de Cuendias, A., Wantz, G., Cramail, H., Hirsch, L., & Parneix, J.-P. (2008). Effect of the regioregularity of poly(3-hexylthiophene) on the performances of organic photovoltaic devices. Polymer International , 57(5), 764-769. http://dx.doi.org/10.1002/pi.2407. 

McCullough, R. D., & Lowe, R. D. (1992). Enhanced electrical conductivity in regioselectively synthesized poly(3-alkylthiophenes). Journal of the Chemical Society, Chemical Communications, 0(1), 70-72. http://dx.doi.org/10.1039/c39920000070. 

5c50a9560e8825a456b25bb4 polimeros Articles
Links & Downloads

Polímeros: Ciência e Tecnologia

Share this page
Page Sections