Skip to main content
Log in

Polymer brush synthesis on surface modified carbon nanotubes via in situ emulsion polymerization

  • Original Contribution
  • Published:
Colloid and Polymer Science Aims and scope Submit manuscript

Abstract

In situ emulsion polymerization was employed for synthesizing carbon nanotube (CNT) composites in a colloidal system with poly(styrene) or PS to form nanostructured brush. CNTs were initially functionalized with oleic acid, followed by silanization with (3-aminopropyl) triethoxysilane to impart cross-linking properties. Styrene monomers were efficiently grafted to surface modified CNT via emulsion polymerization with variable CNT concentrations. FTIR analyses of the functionalized CNT and PS/CNT composites confirmed the bond formation and effectiveness of the developed experimental method. X-ray photoelectron spectroscopy confirmed the presence of the desired bonds and the composition of the composites. Structural properties of the composites characterized by TEM confirmed excellent deagglomeration and dispersion of CNTs in PS/CNT composite. Thermal characteristics from TGA and DSC data showed enhanced properties for the nanocomposites as a function of the CNT content. BET measurements indicated significant improvements in surface area and pore volume with enhancements in gas sorption for the polymer nanocomposites.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Ajayan PM, Linda SS, Braun PV (2003) Nanocomposite science and technology. WILEY-VCH, Weinheim, pp. 31–35

    Book  Google Scholar 

  2. Azzaroni O (2012) Polymer brushes here, there, and everywhere: recent advances in their practical applications and emerging opportunities in multiple research fields. J Polym Sci A 50:3225–3258

    Article  CAS  Google Scholar 

  3. Rastogi A, Paik MY, Tanaka M, Ober CK (2010) Direct patterning of intrinsically e-beam sensitive polymer brushes. ACS Nano 4:771–780

    Article  CAS  Google Scholar 

  4. Barbey R, Klok HA (2010) Room temperature, aqueous post-polymerization modification of glycidyl methacrylate-containing polymer brushes prepared via surface-initiated atom transfer radical polymerization. Langmuir 26:18219–18230

    Article  CAS  Google Scholar 

  5. Ayres N (2010) Polymer brushes: applications in biomaterials and nanotechnology. Polym Chem 6:769–777

    Article  Google Scholar 

  6. Yameen B, Farrukh A (2013) Polymer brushes: promises and challenges. Chem Asian J 8:1736–1753

    Article  CAS  Google Scholar 

  7. Jeon NL, Choi IS, Kim NY, Harada Y, Finnie KR, Girolami GS, Nuzzo RG, Laibinis PE, Whitesides GM (1999) The patterned polymer can be used as an etch resist to transfer the pattern into a Si substrate. Appl Phys Lett 75:4201–4203

    Article  CAS  Google Scholar 

  8. Husseman M, Malmstreom EE, McNamara M, Mate M, Mecerreyes D, Benoit DG, Hedrick JL, Mansky P, Huang E, Russell TP, Hawker CJ (1999) Controlled synthesis of polymer brushes by “living” free radical polymerization techniques. Macromolecules 32:1424–1431

    Article  CAS  Google Scholar 

  9. Matyjaszewski K (2012) Atom transfer radical polymerization (ATRP): current status and future perspectives. Macromolecules 45:4015–4039

    Article  CAS  Google Scholar 

  10. Ding S, Floyd JA, Walters KB (2009) Comparison of surface confined ATRP and SET-LRP syntheses for a series of amino (meth)acrylate polymer brushes on silicon substrates. J Polym Sci A Polym Chem 47:6552–6560

    Article  CAS  Google Scholar 

  11. Baum M, Brittain WJ (2002) Synthesis of polymer brushes on silicate substrates via reversible addition fragmentation chain transfer technique. Macromolecules 35:610–615

    Article  CAS  Google Scholar 

  12. Liu Y, Zhao Y, Sun B, Chen C (2012) Understanding the toxicity of carbon nanotubes. Acc Chem Res 46:702–713

    Article  Google Scholar 

  13. Pangilinan KD, Santos CM, Estillore NC, Rodrigues DF, Advincula RC (2013) Temperature-responsiveness and antimicrobial properties of CNT–PNIPAM hybrid brush films. Macromol Chem Phys 214:464–469

    Article  CAS  Google Scholar 

  14. Ha JU, Kim M, Lee J, Choe S, Cheong IW, Shim SE (2006) A novel synthesis of polymer brush on multiwall carbon nanotubes bearing terminal monomeric unit. J Polym Sci A Polym Chem 44:6394–6401

    Article  CAS  Google Scholar 

  15. Xu J, Xiao X, Zhang Y, Zhang W, Sun P (2013) RAFT-mediated emulsion polymerization of styrene using brush copolymer as surfactant macro-RAFT agent: effect of the brush copolymer sequence and chemical composition. J Polym Sci A Polym Chem 51:1147–1161

    Article  CAS  Google Scholar 

  16. Bech L, Elzein T, Meylheuc T, Ponche A, Brogly M, Lepoittevin B, Roger P (2009) Atom transfer radical polymerization of styrene from different poly(ethylene terephthalate) surfaces: films, fibers and fabrics. Eur Polym J 45:246–255

    Article  CAS  Google Scholar 

  17. Zou YQ, Kizhakkedathu JN, Brooks DE (2009) Surface modification of polyvinyl chloride sheets via growth of hydrophilic polymer. Macromolecules 42:3258–3268

    Article  CAS  Google Scholar 

  18. Gorman CB, Petrie RJ, Genzer J (2008) Effect of substrate geometry on polymer molecular weight and polydispersity during surface-initiated polymerization. Macromolecules 41:4856–4865

    Article  CAS  Google Scholar 

  19. Marutani E, Yamamoto S, Ninjbadgar T, Tsujii Y, Fukuda T, Takano M (2004) Surface-initiated atom transfer radical polymerization of methyl methacrylate on magnetite nanoparticles. Polymer 45:2231–2235

    Article  CAS  Google Scholar 

  20. Fan XW, Lin LJ, Dalsin JL, Messersmith PB (2005) Biomimetic anchor for surface-initiated polymerization from metal substrates. J Am Chem Soc 127:15843–15847

    Article  CAS  Google Scholar 

  21. Yang Q, Wang L, Xiang WD, Zhou JF, Tan QH (2007) Preparation of polymer-grafted carbon black nanoparticles by surface-initiated atom transfer radical polymerization. J Polym Sci A Polym Chem 45:3451–3459

    Article  CAS  Google Scholar 

  22. Thostenson E, Li C, Chou T (2005) Nanocomposites in context. Compos Sci Technol 65:491–516

    Article  CAS  Google Scholar 

  23. Vaisman L, Wagner HD, Marom G (2006) The role of surfactants in dispersion of carbon nanotubes. Adv Colloid Interf Sci 128–130:37–46

    Article  Google Scholar 

  24. Kong H, Gao C, Yan D (2004) Functionalization of multiwalled carbon nanotubes by atom transfer radical polymerization and defunctionalization of the products. Macromolecules 37:4022–4030

    Article  CAS  Google Scholar 

  25. Hilding J, Grulke EA, Zhang ZG, Lockwood FJ (2003) Dispersion of carbon nanotubes in liquids. J Dispers Sci Technol 24:1–41

    Article  CAS  Google Scholar 

  26. Khan MU, Gomes VG, Altarawneh IS (2010) Synthesizing polystyrene/carbon nanotube composites by emulsion polymerization with non-covalent and covalent functionalization. Carbon 48:2925–2933

    Article  CAS  Google Scholar 

  27. Sunkara V, Park DK, Hwang H, Chantiwas R, Soper SA, Cho YK (2011) Simple room temperature bonding of thermoplastics and poly(dimethylsiloxane). Lab Chip 11:962–965

    Article  CAS  Google Scholar 

  28. Germain J, Hradil J, Jean MJF, Svec F (2006) High surface area nanoporous polymers for reversible hydrogen storage. Chem Mater 18:4430–4435

    Article  CAS  Google Scholar 

  29. Sun YP, Fu K, Lin Y, Huang W (2002) Functionalized carbon nanotubes: properties and applications. Acc Chem Res 35:1096–1104

    Article  CAS  Google Scholar 

  30. Min Z, Zhang X, He X, Chen L, Zhang Y (2010) A facile method to coat mesoporous silica layer on carbon nanotubes by anionic surfactant. Mater Lett 64:1383–1386

    Article  Google Scholar 

  31. Bulla DAP, Morimoto NI (1998) Deposition of thick TEOS PECVD silicon oxide layers for integrated optical waveguide applications. Thin Solid Films 334:60–64

    Article  CAS  Google Scholar 

  32. McMurry J, John E (1992) Organic chemistry, 3rd edn. Wadsworth, Belmont ISBN 0-534-16218-5

    Google Scholar 

  33. March J (1992) Advanced organic chemistry: reactions, mechanisms, and structure, 4th edn. Wiley, New York ISBN 0-471-60180-2

    Google Scholar 

  34. Peng H, Alemany LB, Margrave JL, Khabashesku VN (2003) Sidewall carboxylic acid functionalization of single-walled carbon nanotubes. J Am Chem Soc 125:15174–15182

    Article  CAS  Google Scholar 

  35. Bronstein LM, Huang X, Retrum J, Schmucker A, Pink M, Stein BD (2007) Influence of iron oleate complex structure on iron oxide nanoparticle formation. Chem Mater 19:3624–3632

    Article  CAS  Google Scholar 

  36. Ding X, Zhao J, Liu Y, Zhang H, Wang Z (2004) Silica nanoparticles encapsulated by polystyrene via surface grafting and in situ emulsion polymerization. Mater Lett 58:3126–3130

    Article  CAS  Google Scholar 

  37. Lechevallier S, Hammer P, Caiut JA, Mazeres S, Mauricot R, Verelst M, Dexpert H, Sidney J, Ribeiro L (2012) Dexpert-Ghys APTES-modified RE2O3:Eu3+ luminescent beads: structure and properties. Langmuir 28:3962–3971

    Article  CAS  Google Scholar 

  38. Akiyama Y, Fujit S, Senboku H, Rayner CM, Brough SA, Arai M (2008) An in situ high pressure FTIR study on molecular interactions of ketones, esters, and amides with dense phase carbon dioxide. J Supercrit Fluids 46:197–205

    Article  CAS  Google Scholar 

  39. Briggs D, Seah MP (1990) Practical surface analysis, 2nd edn. Wiley, Chichester

    Google Scholar 

  40. Beamson G, Briggs D (1992) High resolution XPS of organic polymer, the scienta ESCA300 database. Wiley, Chichester

    Google Scholar 

  41. Emmanuel N, Lissouck O, René NNG, Hyppolite L, Christine P, Regis A, Louis-Max NM (2013) Green gluing of tropical wood part III: X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) analysis of Frake and Ayous green wood’s glue line. AFM, France

    Google Scholar 

  42. Truica-Marasescu F, Wertheimer MR (2008) Nitrogen-rich plasma-polymer films for biomedical application. Plasma Process Polym 5:44–57

    Article  CAS  Google Scholar 

  43. Briggs D, Brewis DM, Dahm RH, Fletcher IW (2003) Analysis of the surface chemistry of oxidized polyethylene: comparison of XPS and ToF-SIMS. Surf Interface Anal 35:156–167

    Article  CAS  Google Scholar 

  44. Gorham JM, Woodcock JW, Scott KC (2015) Challenges, Strategies and Opportunities for Measuring Carbon Nanotubes within a Polymer Composite by X-ray Photoelectron Spectroscopy. NIST Special Publication, 1200–10

  45. Petersen EJ, Lam T, Gorham JM, Scott KC, Long CJ, Stanley D, Sharma R, Liddle JA, Pellegrin B, Nguyen T (2014) Methods to assess the impact of UV irradiation on the surface chemistry and structure of multiwall carbon nanotube epoxy nanocomposites. Carbon 69:194–205

    Article  CAS  Google Scholar 

  46. Advincula R, Brittain WJ, Caster KC, Ruhe J (2004) Polymer brushes: synthesis, characterization, applications. VCHWiley, Weinheim

    Book  Google Scholar 

  47. Song PC, Liu CH, Fan SS (2006) Improving the thermal conductivity of nanocomposites by increasing the length efficiency of loading carbon nanotubes. Appl Phys Lett 88:153111–153113

    Article  Google Scholar 

  48. Farbod M, Mobini N (2014) Physical properties, thermal stability, and glass transition temperature of multi-walled carbon nanotube/polypyrrole nanocomposites. Compos Interfaces 21:737–747

    Article  CAS  Google Scholar 

  49. Sterzynski T, Tomaszewska J, Piszczek K, Skorczewska K (2010) The influence of carbon nanotubes on the PVC glass transition temperature. Compos Sci Technol 70:966–969

    Article  CAS  Google Scholar 

  50. Yuan S, White D, Mason A, Liu D (2013) Porous organic polymers containing carborane for hydrogen storage. Int J Energy Res 37:732–740

    Article  CAS  Google Scholar 

  51. Yang X, Yu M, Zhao Y, Zhang C, Wang X, Jiang J-X (2014) Remarkable gas adsorption by carbonized nitrogen-rich hypercrosslinked porous organic polymers. J Mater Chem A 2:15139–15145

    Article  CAS  Google Scholar 

  52. Khan MU, Darestani MT, Gomes VG (2015) Structure and electrochemical properties of polystyrene/CNT nanocomposites. J Solid State Electrochem 19:3145–3156

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Support from the University of Sydney is acknowledged for conducting part of the research. Assistance with the XPS analysis from UNSW is also acknowledged.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Vincent G. Gomes.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Miftah U. Khan, Kakarla Raghava Reddy, and Theedanai Snguanwongchai contributed equally to this work.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Khan, M.U., Reddy, K.R., Snguanwongchai, T. et al. Polymer brush synthesis on surface modified carbon nanotubes via in situ emulsion polymerization. Colloid Polym Sci 294, 1599–1610 (2016). https://doi.org/10.1007/s00396-016-3922-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00396-016-3922-7

Keywords

Navigation