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Polyacrylonitrile–MWCNT hybrids obtained by free radical polymerization in miniemulsions

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Abstract

Polyacrylonitrile (PAN) and poly(acrylonitrile-co-vinylcarbazole) (PAN-VK) hybrids were obtained in presence of multiwalled carbon nanotubes (MWCNT) by a one-step free radical polymerization in miniemulsions. MWCNTs, in an unmodified state, as well as MWCNTs functionalized with maleic anhydride or monoethoxy dimethylvinyl silane, were used. The presence of MWCNT increased the molecular weights of the polymers and affected the polydispersity index. The polymers obtained next to the MWCNT showed a high value in their crystallinity index (33 %). The method was proven as an efficient route for dispersing nanotubes in the polymer matrix. Functionalized MWCNTs restrict the transfer reaction to areas next to the walls of the nanotubes during the polymerization and increase the dispersability in the final polymer matrix. MWCNT –polymer hybrids showed perspectives in membrane fabrication, as well as a specific profile, for carbon fibers precursors (with advantages in the three main stages: cyclization, dehydrogenation and decomposition).

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References

  1. Winey KI, Vaia RA (2007) Polymer Nanocomposites. MRS Bull 32:314–321

    Article  CAS  Google Scholar 

  2. Mittal V (2010) Polymer Nanotube, Nanocomposites Synthesis, Properties and Application. Wiley-Scrivener, New Jersey

    Book  Google Scholar 

  3. Bokobza L (2007) Multiwall carbon nanotube elastomeric composites: A review. Polymer 48:4907–4920

    Article  CAS  Google Scholar 

  4. Schaefer DW, Justice RS (2007) How Nano are Nanocomposites? Macromolecules 40:8502–8517

    Article  Google Scholar 

  5. Rana S, Alagirusamy R, Joshi M (2009) A Review on Carbon Epoxy Nanocomposites. J Reinf Plast Compos 28:461–487

    Article  CAS  Google Scholar 

  6. Bauhofer W, Kovacs JZ (2009) A review and analysis of electrical percolation in carbon nanotube polymer composites. Compos Sci Technol 69:1486–1498

    Article  CAS  Google Scholar 

  7. Hu CY, Xu YJ, Duo SW, Zhang RF, Li MS (2009) Non-Covalent Functionalization of Carbon Nanotubes with Surfactants and Polymers. J Chin Chem Soc 56:234–239

    CAS  Google Scholar 

  8. Wang T, Keddie JL (2009) Design and fabrication of colloidal polymer nanocomposites. Advances in Colloid and Interface Science 147–148:319–32

    Article  Google Scholar 

  9. Grady BP (2010) Recent Developments Concerning the Dispersion of Carbon Nanotubes in Polymers. Macromolecular Rapid Communications 31:247–257

    Article  CAS  Google Scholar 

  10. Spitalsky Z, Tasis D, Papagelis K, Galiotis C (2010) Carbonnanotube-polymercomposites: Chemistry, processing, mechanical and electrical properties. Prog Polym Sci 35:357–401

    Article  CAS  Google Scholar 

  11. Ma PC, Siddiqui NA, Marom G, Kim JK (2010) Dispersion and functionalization of carbonnanotubes for polymer-basednanocomposites: A review. Composites Part A: Applied Science and Manufacturing 41:1345–1367

    Article  Google Scholar 

  12. Martínez-Hernandez AL, Velasco-Santos C, Castano VM (2010) Carbon Nanotubes Composites: Processing, Grafting and Mechanical and Thermal Properties. Curr Nanosci 6:12–39

    Article  Google Scholar 

  13. Landfester K, Weiss CK (2010) Encapsulation by Miniemulsion Polymerization. Adv Polym Sci 229:1–49

    Article  CAS  Google Scholar 

  14. Hu J, Chen M, Wu L (2011) Organic–inorganic nanocomposites synthesized via miniemulsion polymerization. Polym Chem 2:760–772

    Article  CAS  Google Scholar 

  15. Barraza HJ, Pompeo F, O’Rear EA, Resasco DE (2002) SWNT-Filled Thermoplastic and lastomeric Composites Prepared by Mniemulsion Polymerization. Nano Letters 2:797–802

    Article  CAS  Google Scholar 

  16. Barraza HJ, Rueda O, Pompeo F, O’Rear EA, Williams RJJ., Resasco DE (2003) Utilization of SWNT-Filled Polystyrene Obtained by Miniemulsion Polymerization as a Modifier for High-Performance Epoxy Resins. In Nanotech, vol. 3, Technical Proceedings of the 2003 Nanotechnology Conference and Trade Show, Chapter 12: Physical Chemistry of Nanomaterials, 538–541

  17. Ham HT, Choi YS, Chee MG, Chung IJ (2006) Singlewall carbon nanotubes covered with polystyrene nanoparticles by in-situ miniemulsion polymerization. J Polymer Sci, Part A: Polymer Chem 44:573–584

    Article  CAS  Google Scholar 

  18. Lu HF, Fei B, Xin JH, Wang RH, Li L, Guan WC (2007) Synthesis and lubricating performance of a carbonnanotube seeded miniemulsion. Carbon 45:936–942

    Article  CAS  Google Scholar 

  19. Capek I, Kocsisova T (2011) On the preparation of composite poly(butyl acrylate)/carbon nanotube nanoparticles by miniemulsion polymerization of butyl acrylate. Polym J 43:700–707

    Article  CAS  Google Scholar 

  20. Ha MLP, Grady BP, Lolli G, Resasco DE, Ford WT (2007) Composites of single-walled carbon nanotubes and styrene-isoprene copolymer latices. Macromol Chem Phys 208:446–456

    Article  CAS  Google Scholar 

  21. Mark HF, Gaylord NG, Bikales NM (1964) Encyclopedia of Polymer. Science and Technology, vol. I. Interscience, New York

    Google Scholar 

  22. Landfester K, Antonietti M (2000) The polymerization of acrylonitrile in miniemulsions: “Crumpled latex particles” or polymer nanocrystals. Macromolecular Rapid Communications 21:820–824

    Article  CAS  Google Scholar 

  23. Reyes Y, Paulis M, Leiza JR (2010) Modeling the equilibrium morphology of nanodroplets in the presence of nanofillers. J Colloid Interface Sci 352:359–365

    Article  CAS  Google Scholar 

  24. Cheng Z, Pan Q, Rempel GL (2010) Modification of multiwall carbon nanotubes via soap-free emulsion polymerization of acrylonitrile. J Polymer Sci, Part A: Polymer Chem 48:2057–2062

    Article  CAS  Google Scholar 

  25. Zhang H, Xu L, Yang F, Geng L (2010) The synthesis of polyacrylonitrile/carbonnanotube microspheres by aqueous deposition polymerization under ultrasonication. Carbon 48:688–695

    Article  CAS  Google Scholar 

  26. Baibarac M, Baltog I, Lefrant S, Gomez-Romero P (2007) Spectroscopic evidence for the bulk polymerization of N-vinylcarbazole in the presence of single-walled carbon nanotubes. Polymer 48:5279–5288

    Article  CAS  Google Scholar 

  27. Wu GP, Lu CX, Ling LC, Lu YG (2009) Comparative investigation on the thermal degradation and stabilization of carbon fiber precursors. Polym Bull 62:667–678

    Article  CAS  Google Scholar 

  28. Liu Y, Chae HG, Kumar S (2011) Gel-spun carbonnanotubes/polyacrylonitrile composite fibers. Carbon 49:4466–4476

    Article  CAS  Google Scholar 

  29. Chae HG, Minus ML, Rasheed A, Kumar S (2007) Stabilization and carbonization of gelspun polyacrylonitrile/single wall carbon nanotube composite fibers. Polymer 48:3781–3789

    Article  CAS  Google Scholar 

  30. Sreekumar TV, Chandra L, Srivastava A, Kumar S (2007) Oxidative stabilization of polyacrylonitrile in the presence of functionalized carbon nanotubes. Carbon 45:1105–1136

    Article  Google Scholar 

  31. Chae HG, Minus ML, Kumar S (2006) Oriented and exfoliated single wallcarbonnanotubes in polyacrylonitrile. Polymer 47:3494–3504

    Article  CAS  Google Scholar 

  32. Chae HG, Sreekumar TV, Uchida T, Kumar S (2005) A comparison of reinforcement efficiency of various types of carbon nanotubes in polyacrylonitrile fiber. Polymer 46:10925–10935

    Article  CAS  Google Scholar 

  33. Min BG, Sreekumar TV, Uchida T, Kumar S (2005) Oxidativestabilization of PAN/SWNT composite fiber. Carbon 43:599–604

    Article  CAS  Google Scholar 

  34. Vaisman L, Wachtel E, Wagner HD, Marom G (2007) Polymer-nanoinclusion interactions in carbon nanotube based polyacrylonitrile extruded and electrospun fibers. Polymer 48:6843–6854

    Article  CAS  Google Scholar 

  35. Chakrabarti K, Nambissan PMG, Mukherjee CD, Bardhan KK, Kim C, Yang KS (2007) Positron annihilation spectroscopic studies of the influence of heat treatment on defect evolution in hybrid MWCNT-polyacrylonitrile-based carbon fibers. Carbon 45:2777–2782

    Article  CAS  Google Scholar 

  36. Vast L, Philippin G, Destree A, Moreau N, Fonseca A, Nagy JB, Delhalle J, Mekhalif Z (2004) Chemical functionalization by a fluorinated trichlorosilane of multi-walled carbon nanotubes. Nanotechnology 15:781–785

    Article  CAS  Google Scholar 

  37. Shanmugharaj AM, Bae JH, Lee KY, Noh WH, Lee SH, Ryu SH (2007) Physical and chemicalcharacteristics of multiwalledcarbonnanotubes functionalized with aminosilane and its influence on the properties of natural rubber composites. Compos Sci Technol 67:1813–1822

    Article  CAS  Google Scholar 

  38. Zhou Z, Wang S, Lu L, Zhang Y, Zhang Y (2008) Functionalization of multi-wall carbon nanotubes with silane and its reinforcement on polypropylene composites. Compos Sci Technol 68:1727–1733

    Article  CAS  Google Scholar 

  39. Jia Z, Wang Z, Xu C, Liang J, Wei B, Wu D, Zhu S (1999) Study on poly(methyl methacrylate)/carbon nanotube composites. Mater Sci Eng, A 271:395

    Article  Google Scholar 

  40. Kim ST, Choi HJ, Hong SM (2007) Bulk polymerized polystyrene in the presence of multiwalled carbon nanotubes. Colloid and Polymer Science 285:593–598

    Article  CAS  Google Scholar 

  41. Jin J, Dong Z, He J, Li R, Ma J (2009) Synthesis of Novel Porphyrin and its Complexes Covalently Linked to Multi-Walled Carbon Nanotubes and Study of their Spectroscopy. Nanoscale Research Letters 4:578–583

    Article  CAS  Google Scholar 

  42. Reimers JL, Schork FJ (1996) Predominant droplet nucleation in emulsion polymerization. J Appl Polym Sci 60:251–262

    Article  CAS  Google Scholar 

  43. Wu XQ, Schork FJ, Gooch JW (1999) Hybrid Miniemulsion Polymerization of Acrylic/Alkyd Systems and Characterization of the Resulting Polymers. J Polymer Sci, Part A: Polymer Chem 37:4159–4168

    Article  CAS  Google Scholar 

  44. Zetterlund PB, Nakamura T, Okubo M (2007) Mechanistic Investigation of Particle Size Effects in TEMPO- Mediated Radical Polymerization of Styrene in Aqueous Miniemulsion. Macromolecules 40:8663–8672

    Article  CAS  Google Scholar 

  45. Capek I (1994) Emulsion polymerization of butyl acrylate, 2. Effect of the initiator type and concentration. Macromol Chem Phys 195:1137–1146

    Article  CAS  Google Scholar 

  46. Liu T, Gu SJ, Zhang YH, Ren J (2012) Fabrication and characterization of carbon nanofibers with a multiple tubular porous structure via electrospinning. J Polym Res 19:9882

    Article  Google Scholar 

  47. Saeed K, Park SY (2010) Preparation and characterization of multiwalled carbon nanotubes/polyacrylonitrile nanofibers. J Polym Res 17:535–540

    Article  CAS  Google Scholar 

  48. Saligheh O, Forouharshad M, Arasteh R, Eslami-Farsani R, Khajavi R, Yadollah Roudbari B (2013) The effect of multi-walled carbon nanotubes on morphology, crystallinity and mechanical properties of PBT/MWCNT composite nanofibers. J Polym Res 20:65

    Article  Google Scholar 

  49. Shekarian E, Saljoughi E, Naderi A (2013) Polyacrylonitrile (PAN)/IGEPAL blend asymmetric membranes: preparation, morphology, and performance. J Polym Res 20:162

    Article  Google Scholar 

  50. Majeed S, Fierro D, Buhr K, Wind J, Du B, Boschetti-de-Fierro A, Abetz V (2012) Multi-walled carbon nanotubes (MWCNTs) mixed polyacrylonitrile (PAN) ultrafiltration membranes. J Membr Sci 403–404:101–109

    Article  Google Scholar 

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Acknowledgements

The authors thank Dr. Peter Simon and Maren Brinkman for GPC analysis, Sabrina Bolmer for SEM, and Clarissa Abetz for TEM investigations, respectively.

This work was financially supported by the project “High Aspect Ratio Carbon-based Nanocomposites” (HARCANA) within the European Community’s 7th Framework Programme for Research and Technological Development under the Grant Agreement number NMP3-LA-2008-213277.

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Authors and Affiliations

  1. Polymer Department, National Institute for Research & Development in Chemistry and Petrochemistry—ICECHIM Bucharest, Spl. Independentei 202, district 6, 060021, P.O. 35–174, Bucharest, Romania

    Dan Donescu, Mihai Cosmin Corobea, Cristian Petcu, Catalin Ilie Spataru & Constantin Radovici

  2. Institute of Polymer Research, Helmholtz-Zentrum Geesthacht, Max-Planck-Str. 1, 21502, Geesthacht, Germany

    Shahid Majeed & Volker Abetz

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  1. Dan Donescu
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  2. Mihai Cosmin Corobea
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Correspondence to Mihai Cosmin Corobea.

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Donescu, D., Corobea, M.C., Petcu, C. et al. Polyacrylonitrile–MWCNT hybrids obtained by free radical polymerization in miniemulsions. J Polym Res 20, 251 (2013). https://doi.org/10.1007/s10965-013-0251-0

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