Synthesis and applications of polystyrene-block-poly(N-vinyl-2-pyrrolidone) copolymers
Farias, Marcelo Alexandre de; Gonçalves, Maria do Carmo
http://dx.doi.org/10.1590/0104-1428.2066
Polímeros: Ciência e Tecnologia, vol.26, n1, p.1-10, 2016
Abstract
This work describes the synthesis and applications of amphiphilic polystyrene-block-poly(N-vinyl-2-pyrrolidone) (PS-b-PVP) copolymers as a silver and silica nanoparticle surface modification agent. The synthesis of PS-b-PVP was carried out using controlled/living radical polymerization techniques. The synthesis of the block copolymers was confirmed by gel permeation chromatography and hydrogen nuclear magnetic resonance, presenting a polydispersity index of around 1.4 and number average molecular weight ranging between 10,000-14,000 g mol-1. The PS-b-PVP copolymers were applied as a silver nanoparticle (AgNP) stabilizing agent. These nanoparticles were produced by a single step and presented an 11 ± 1 nm diameter. Furthermore, the PS-b-PVP copolymers were also applied as a silica nanoparticle (SiO2NP) surface modification agent. The SiO2NP were synthesized by the Stöber method presenting a 72 ± 9 nm diameter. The SiO2NP surface modification by adsorption of PS-b-PVP caused the formation of a 5 ± 1 nm thick polymeric layer, providing the SiO2NP with a hydrophobic surface character. The structural and chemical characteristics shown by PS-b-PVP copolymers highlights their versatility for several applications, such as: water-in-oil emulsifier, stabilizing or coupling agents between inorganic particles and polymeric matrices.
Keywords
amphiphilic block copolymers, controlled radical polymerization, silica nanoparticles, silver nanoparticles, surface modification agent
References
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7. Moad, G., Rizzardo, E., & Thang, S. H. (2005). Living radical polymerization by the RAFT process. Australian Journal of Chemistry, 58(6), 379-410. http://dx.doi.org/10.1071/CH05072.
8. Lowe, A. B., & Mccormick, C. L. (2007). Reversible addition – fragmentation chain transfer (RAFT) radical polymerization and the synthesis of water-soluble (co)polymers under homogeneous conditions in organic and aqueous media. Polymer, 32, 283-351. http://dx.doi.org/10.1016/j.progpolymsci.2006.11.003.
9. Liu, X., Wu, Z., Zhou, F., Li, D., & Chen, H. (2010). Poly(vinylpyrrolidone-b-styrene) block copolymers tethered surfaces for protein adsorption and cell adhesion regulation. Colloids and Surfaces. B, Biointerfaces, 79(2), 452-459. http://dx.doi.org/10.1016/j.colsurfb.2010.05.011. PMid:20554165.
10. Kumar, S., Changez, M., Murthy, C. N., Yamago, S., & Lee, J.-S. (2011). Synthesis of well-defined amphiphilic block copolymers by organotellurium-mediated living radical polymerization (TERP). Macromolecular Rapid Communications, 32(19), 1576-1582. http://dx.doi.org/10.1002/marc.201100277. PMid:21793088.
11. Zhang, Z., Zhao, B., & Hu, L. (1996). PVP protective mechanism of ultrafine silver powder synthesized by chemical reduction processes. Journal of Solid State Chemistry, 121(1), 105-110. http://dx.doi.org/10.1006/jssc.1996.0015.
12. Riess, G. (2003). Micellization of block copolymers. Progress in Polymer Science, 28(7), 1107-1170. http://dx.doi.org/10.1016/S0079-6700(03)00015-7.
13. Hamley, I. W. (1998). The physics of block copolymers. Oxford: Oxford University Press.
14. Xue, B., Gao, L., Hou, Y., Liu, Z., & Jiang, L. (2013). Temperature controlled water/oil wettability of a surface fabricated by a block copolymer: application as a dual water/oil on-off switch. Advanced Materials, 25(2), 273-277. http://dx.doi.org/10.1002/adma.201202799. PMid:23074035.
15. Uyen, N. T. N., Joo, S. I., Kim, W. H., Oh, M. H., Lee, J., Lim, B. S., & Hong, S. C. (2013). Application of block copolymeric surface modifier with crosslinkable units for montmorillonite nanocomposites. Journal of Applied Polymer Science, 127(1), 690-698. http://dx.doi.org/10.1002/app.37856.
16. Zhang, D., Qi, L., Ma, J., & Cheng, H. (2001). Formation of silver nanowires in aqueous solutions of a double-hydrophilic block copolymer. Chemistry of Materials, 13(9), 2753-2755. http://dx.doi.org/10.1021/cm0105007.
17. Li, N., Qi, L., Shen, Y., Li, Y., & Chen, Y. (2013). Amphiphilic block copolymer modified magnetic nanoparticles for microwave-assisted extraction of polycyclic aromatic hydrocarbons in environmental water. Journal of Chromatography. A, 1316, 1-7. http://dx.doi.org/10.1016/j.chroma.2013.09.030. PMid:24119754.
18. Shamenkova, O. A., Mokeeva, L. K., Kopylova, N. A., & Semchikov, Y. D. (2006). Synthesis of amphiphilic block copolymers polystyrene-block-polyvinylpyrrolidone from active polystyrene. Russian Journal of Applied Chemistry, 79(3), 448-452. http://dx.doi.org/10.1134/S1070427206030232.
19. Park, J. T., Koh, J. H., Lee, K. J., Seo, J. A., Min, B. R., & Kim, J. H. (2008). Formation of silver nanoparticles created in situ in an amphiphilic block copolymer film. Journal of Applied Polymer Science, 110(4), 2352-2357. http://dx.doi.org/10.1002/app.28261.
20. Hussain, H., Tan, B. H., Gudipati, C. S., Liu, Y., He, C. B., & Davis, T. P. (2008). Synthesis and self-assembly of poly(styrene)-b-poly(N-vinylpyrrolidone) amphiphilic diblock copolymers made via a combined ATRP and MADIX approach. Journal of Polymer Science. Part A, Polymer Chemistry, 46(16), 5604-5615. http://dx.doi.org/10.1002/pola.22882.
21. Hu, D., & Zheng, S. (2010). Reaction-induced microphase separation in polybenzoxazine thermosets containing poly(N-vinyl pyrrolidone)-block-polystyrene diblock copolymer. Polymer, 51(26), 6346-6354. http://dx.doi.org/10.1016/j.polymer.2010.10.047.
22. Huang, C.-F., Nicolaÿ, R., Kwak, Y., Chang, F.-C., & Matyjaszewski, K. (2009). Homopolymerization and block copolymerization of N-vinylpyrrolidone by ATRP and RAFT with haloxanthate inifers. Macromolecules, 42(21), 8198-8210. http://dx.doi.org/10.1021/ma901578z.
23. Bilalis, P., Pitsikalis, M., & Hadjichristidis, N. (2006). Controlled nitroxide-mediated and reversible addition-fragmentation chain transfer polymerization of N-vinylpyrrolidone: Synthesis of block copolymers with styrene and 2-vinylpyridine. Journal of Polymer Science. Part A, Polymer Chemistry, 44(1), 659-665. http://dx.doi.org/10.1002/pola.21198.
24. Arsalani, N., Fattahi, H., & Entezami, A. A. (2006). Synthesis of amphiphilic diblock and random copolymers of styrene and N-vinylpyrrolidone using nitroxide-mediated living free radical polymerization. Iranian Polymer Journal, 15(12), 997-1005. Retrieved in 16 January 2015, from http://www.sid.ir/en/vewssid/j_pdf/81320061207.pdf
25. Ray, B., Kotani, M., & Yamago, S. (2006). Highly controlled synthesis of poly(N-vinylpyrrolidone) and its block copolymers by organostibine-mediated living radical polymerization. Macromolecules, 39(16), 5259-5265. http://dx.doi.org/10.1021/ma060248u.
26. Zakharova, O. G., Golyagina, Y. V., & Semchikov, Y. D. (2009). Synthesis and surface properties of amphiphilic block copolymers polyvinylpyrrolidone-block-polystyrene. Russian Journal of Applied Chemistry, 82(4), 644-649. http://dx.doi.org/10.1134/S107042720904020X.
27. Wager, C. M., Haddleton, D. M., & Bon, S. A. (2004). A simple method to convert atom transfer radical polymerization (ATRP) initiators into reversible addition fragmentation chain-transfer (RAFT) mediators. European Polymer Journal, 40(3), 641-645. http://dx.doi.org/10.1016/j.eurpolymj.2003.10.025.
28. Hayes, W., & Rannard, S. (2004). Controlled/“living” polymerization methods. In F. J. Daves (Ed.). Polymer synthesis – a practical approach (pp. 99-125). New York: Oxford University Press.
29. Stöber, W., Fink, A., & Bohn, E. (1968). Controlled growth of monodisperse silica spheres in the micron size range. Journal of Colloid and Interface Science, 26(1), 62-69. http://dx.doi.org/10.1016/0021-9797(68)90272-5.
30. Costa, C. A. R., Leite, C. A. P., & Galembeck, F. (2003). Size dependence of Stöber silica nanoparticle microchemistry. The Journal of Physical Chemistry B, 107(20), 4747-4755. http://dx.doi.org/10.1021/jp027525t.
31. Mark, J. E. (1999). Polymer data handbook. New York: Oxford University Press.
32. Williams, D., & Fleming, I. (2007). Spectroscopic methods in organic chemistry (6th ed.). New York: McGraw-Hill Higher Education.
33. Wan, D., Satoh, K., Kamigaito, M., & Okamoto, Y. (2005). Xanthate-mediated radical polymerization of N-vinylpyrrolidone in fluoroalcohols for simultaneous control of molecular weight and tacticity. Macromolecules, 38(25), 10397-10405. http://dx.doi.org/10.1021/ma0515230.
34. Wang, J.-S., & Matyjaszewski, K. (1995). Controlled/“living” radical polymerization. Halogen atom transfer radical polymerization promoted by a Cu(I)/Cu(II) redox process. Macromolecules, 28(23), 7901-7910. http://dx.doi.org/10.1021/ma00127a042.
35. Matyjaszewski, K., & Xia, J. (2001). Atom transfer radical polymerization. Chemical Reviews, 101(9), 2921-2990. http://dx.doi.org/10.1021/cr940534g. PMid:11749397.
36. Perrier, S., & Takolpuckdee, P. (2005). Macromolecular design via reversible addition-fragmentation chain transfer (RAFT)/xanthates (MADIX) polymerization. Journal of Polymer Science. Part A, Polymer Chemistry, 43(22), 5347-5393. http://dx.doi.org/10.1002/pola.20986.
37. Kahveci, M. U., Acik, G., & Yagci, Y. (2012). Synthesis of block copolymers by combination of atom transfer radical polymerization and visible light-induced free radical promoted cationic polymerization. Macromolecular Rapid Communications, 33(4), 309-313. http://dx.doi.org/10.1002/marc.201100641. PMid:22253209.
38. Chavda, S., Yusa, S., Inoue, M., Abezgauz, L., Kesselman, E., Danino, D., & Bahadur, P. (2013). Synthesis of stimuli responsive PEG47–b-PAA126–b-PSt32 triblock copolymer and its self-assembly in aqueous solutions. European Polymer Journal, 49(1), 209-216. http://dx.doi.org/10.1016/j.eurpolymj.2012.09.021.
39. Wang, H., Qiao, X., Chen, J., Wang, X., & Ding, S. (2005). Mechanisms of PVP in the preparation of silver nanoparticles. Materials Chemistry and Physics, 94(2-3), 449-453. http://dx.doi.org/10.1016/j.matchemphys.2005.05.005.
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