Skip to main content
SpringerLink
Log in

Fabrication of macroporous foam and microspheres of polystyrene by Pickering emulsion polymerization

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

Abstract

Poly(styrene-co-methacrylic acid) (PS-co-MAA) particles were synthesized via surfactant-free emulsion polymerization and then used as particulate emulsifiers for preparation of Pickering emulsions. Our results showed that adjusting the solution pH can tune the wettability of PS-co-MAA particles to stabilize either water-in-oil (W/O) or oil-in-water (O/W) Pickering emulsions. Stable W/O emulsions were obtained with PS-co-MAA particles at low pH values due to their better affinity to the dispersed oil phase. In contrast, increasing the pH value significantly changed the stabilizing behavior of the PS-co-MAA particles, leading to the phase inversion and formation of stable O/W emulsions. We found that the oil/water ratio had a significant influence on pH value of the phase inversion. It decreased with decreasing the oil/water ratio, and no phase inversion occurred when the styrene volume fraction reduced to 10 %. Additionally, macroporous polystyrene (PS) foam and PS microspheres were obtained via polymerization of Pickering high internal phase emulsion (Pickering HIPE) and O/W Pickering emulsion, respectively.

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

Access this article

Log in via an institution

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

Similar content being viewed by others

References

  1. Ramsden W (1903) Separation of solids in the surface-layers of solutions and 'Suspensions' (Observations on surface-membranes, bubbles, emulsions, and mechanical coagulation). Preliminary Account. Proc R Soc London 72:156–164

    Google Scholar 

  2. Pickering SU (1907) Emulsions. J Chem Soc 91:2001–2021

  3. Aveyard R, Binks BP, Clint JH (2003) Emulsions stabilised solely by colloidal particles. Adv Colloid Interface Sci 100:503–546

    Article  Google Scholar 

  4. Gu ZZ, Wang D, Möhwald DH (2006) Self-assembly of microspheres at the air/water/air interface into free-standing colloidal crystal films. Soft Matter 3:68–70

    Article  Google Scholar 

  5. Binks BP (2002) Particles as surfactants—similarities and differences. Curr Opin Colloid Interface Sci 7:21–41

    Article  CAS  Google Scholar 

  6. Levine S, Bowen BD, Partridge SJ (1989) Stabilization of emulsions by fine particles: I Partitioning of particles between continuous phase and oil/water interface. Colloids Surf 38:325–343

    Article  CAS  Google Scholar 

  7. Liu Y, Chen X, Wang R (2006) Polymer microspheres stabilized by titania nanoparticles. Mater Lett 60:3731–3734

    Article  CAS  Google Scholar 

  8. Amalvy JI, Armes SP, Binks BP (2003) Use of sterically-stabilised polystyrene latex particles as a pH-responsive particulate emulsifier to prepare surfactant-free oil-in-water emulsions. Chem Commun 15:1826–1827

    Article  Google Scholar 

  9. Amalvy JI, Unali GF, Li Y (2004) Synthesis of sterically stabilized polystyrene latex particles using cationic block copolymers and macromonomers and their application as stimulus-responsive particulate emulsifiers for oil-in-water emulsions. Langmuir 20:4345–4354

    Article  CAS  Google Scholar 

  10. Read ES, Fujii S, Amalvy JI, Randall DP, Armes SP (2004) Effect of varying the oil phase on the behavior of pH-responsive latex-based emulsifiers: demulsification versus transitional phase inversion. Langmuir 20:7422–7429

    Article  CAS  Google Scholar 

  11. Fujii S, Randall DP, Armes SP (2004) Synthesis of polystyrene/poly[2-(dimethylamino) ethyl methacrylate-stat-ethylene glycol dimethacrylate] core–shell latex particles by seeded emulsion polymerization and their application as stimulus-responsive particulate Emulsifiers for oil-in-water Emulsions. Langmuir 20:11329–11335

    Article  CAS  Google Scholar 

  12. Fujii S, Cai Y, Weaver JVM, Armes SP (2005) Syntheses of shell cross-linked micelles using acidic ABC triblock copolymers and their application as pH-responsive particulate emulsifiers. J Am Chem Soc 127:7304–7305

    Article  CAS  Google Scholar 

  13. Fujii S, Read ES, Binks BP, Armes SP (2005) Stimulus-responsive emulsifiers based on Nanocomposite microgel particles. Adv Mater 17:1014–1018

    Article  CAS  Google Scholar 

  14. Binks BP, Rodrigues JA (2005) Inversion of emulsions stabilized solely by ionizable nanoparticles. Angew Chem Int Edit 44:441–444

    Article  CAS  Google Scholar 

  15. Fujii S, Armes SP (2006) Stimulus-responsive particulate emulsifiers based on lightly cross-linked poly(4-vinylpyridine)-silica nanocomposite microgels. Langmuir 22:6818–6825

    Article  CAS  Google Scholar 

  16. Ngai T, Auweter H, Behrens SH (2006) Environmental responsiveness of microgel particles and particle-stabilized emulsions. Macromolecules 39:8171–8177

    Article  CAS  Google Scholar 

  17. Li J, Stöver HD (2008) Doubly pH-responsive Pickering emulsion. Langmuir 24:13237–13240

    Article  CAS  Google Scholar 

  18. Tsyalkovsky V, Burtovyy R, Klep V, Lupitskyy R, Motornov M, Minko S, Luzinov I (2010) Fluorescent nanoparticles stabilized by poly(ethylene glycol) containing shell for pH-triggered tunable aggregation in aqueous environment. Langmuir 26:10684–10692

    Article  CAS  Google Scholar 

  19. Richtering W (2012) Responsive emulsions stabilized by stimuli-sensitive microgels: emulsions with special non-Pickering properties. Langmuir 28:17218–17229

    Article  CAS  Google Scholar 

  20. Morse AJ, Dupin D, Thompson KL, Armes SP, Ouzineb K, Mills P, Swart R (2012) Novel Pickering Emulsifiers based on pH-responsive poly(tert-butylaminoethyl methacrylate) Latexes. J Am Chem Soc 28:1733–11744

    Google Scholar 

  21. Mironov MA, Shulepov ID, Ponomarev VS, Bakulev VA (2013) Synthesis of polyampholyte microgels from colloidal salts of pectinic acid and their application as pH-responsive emulsifiers. Colloid Polym Sci 291:1683–1691

    Article  CAS  Google Scholar 

  22. Binks BP, Murakami R, Armes SP, Fujii S (2005) Temperature-induced inversion of nanoparticle-stabilized emulsions. Angew Chem Int Edit 117:4873–4876

    Google Scholar 

  23. Tsuji S, Kawaguchi H (2008) Thermosensitive Pickering emulsion stabilized by poly (N-isopropylacrylamide)-carrying particles. Langmuir 24:3300–3305

    Article  CAS  Google Scholar 

  24. Ngai T, Behrens SH, Auweter H (2005) Novel emulsions stabilized by pH and temperature sensitive microgels. Chem Comm 3:331–333

    Article  Google Scholar 

  25. Binks BP, Murakami R, Armes SP, Fujii S (2006) Effects of pH and salt concentration on oil-in-water emulsions stabilized solely by nanocomposite microgel particles. Langmuir 22:2050–2057

    Article  CAS  Google Scholar 

  26. Liu X, Yi C, Zhu Y, Yang Y, Jiang J, Cui Z, Jiang M (2010) Pickering emulsions stabilized by self-assembled colloidal particles of copolymers of P(St-alt-MAn)-co-P(VM-alt-MAn). J Colloid Interf Sci 351:315–322

    Article  CAS  Google Scholar 

  27. Yang F, Liu S, Xu J, Sun D (2006) Pickering emulsions stabilized solely by layered double hydroxides particles: the effect of salt on emulsion formation and stability. J Colloid Interf Sci 302:159–169

    Article  CAS  Google Scholar 

  28. Melle S, Lask M, Fuller GG (2005) Pickering emulsions with controllable stability. Langmuir 21:2158–2162

    Article  CAS  Google Scholar 

  29. Velev OD, Furusawa K, Nagayama K (1996) Assembly of latex particles by using emulsion droplets as templates: 1 Microstructured hollow spheres. Langmuir 12:2374–2384

    Article  CAS  Google Scholar 

  30. He Y (2004) Preparation of polyaniline/nano-ZnO composites via a novel Pickering emulsion route. Powder Technol 147:59–63

    Article  CAS  Google Scholar 

  31. Chen M, Zhou S, You B, Wu L (2005) A novel preparation method of raspberry-like PMMA/SiO2 hybrid microspheres. Macromolecules 38:6411–6417

    Article  CAS  Google Scholar 

  32. Zhang K, Wu W, Meng H, Chen JF (2009) Pickering emulsion polymerization: preparation of polystyrene/nano-SiO2 composite microspheres with core–shell structure. Powder Technol 190:393–400

    Article  CAS  Google Scholar 

  33. Dyab AKF, Al-LohedanHA, Essawy HA, Abd El-Mageed HIA,Taha F (2011) Fabrication of core/shell hybrid organic–inorganic polymer microspheres via Pickering emulsion polymerization using laponite nanoparticles. J Saudi Chem Soc doi:10.1016/j.jscs.2011.12.008

  34. Yin DZ, Du X, Zhang QY, Liu H (2013) Covalently bonded polystyrene/SiO2 microspheres via emulsion polymerisation stabilised solely by surface active Pickering stabiliser. Mater Tech: Adv Perform Mater 28:138–144

    CAS  Google Scholar 

  35. Dinsmore AD, Hsu MF, Nikolaides MG, Marquez M, Bausch AR, Weitz DA (2002) Colloidosomes: selectively permeable capsules composed of colloidal particles. Science 298:1006–1009

    Article  CAS  Google Scholar 

  36. Bon SAF, Chen T (2007) Pickering stabilization as a tool in the fabrication of complex nanopatterned silica microcapsules. Langmuir 23:9527–9530

    Article  CAS  Google Scholar 

  37. Chen W, Liu X, Liu Y, Kim H (2010) Synthesis of microcapsules with polystyrene/ZnO hybrid shell by Pickering emulsion polymerization. Colloid Polym Sci 288:1393–1399

    Article  CAS  Google Scholar 

  38. Wu CH, Chiu WY, Don TM (2012) Conductive composite particles synthesized via Pickering emulsion polymerization using conductive latex of poly(3,4-ethylenedioxythiophene) (PEDOT) as stabilizer. Polymer 53:1086–1092

    Article  CAS  Google Scholar 

  39. Vílchez A, Rodríguez-Abreu C, Esquena J, Menner BA (2011) Macroporous polymers obtained in highly concentrated emulsions stabilized solely with magnetic nanoparticles. Langmuir 27:13342–13352

    Article  Google Scholar 

  40. Mao D, Li T, Liu H, Shao H, Li M (2013) Preparation of macroporous polyHIPE foams via radiation-induced polymerization at room temperature. Colloid Polym Sci 291:1649–1656

    Article  CAS  Google Scholar 

  41. Li Z, Ngai T (2009) Macroporous polymer from core–shell particle-stabilized Pickering emulsions. Langmuir 26:5088–5092

    Article  Google Scholar 

  42. Ikem VO, Menner A, Bismarck A (2008) High internal phase emulsions stabilized solely by functionalized silica particles. Angew Chem Int Ed 47:8277–8279

    Article  CAS  Google Scholar 

  43. Ikem VO, Menner A, Horozov TS, Bismarck A (2010) Highly permeable macroporous polymers synthesized from Pickering medium and high internal phase emulsion templates. Adv Mater 22:3588–3592

    Article  CAS  Google Scholar 

  44. Capron I, Cathala B (2013) Surfactant-free high internal phase emulsions stabilized by cellulose nanocrystals. Biomacromolecules 14:291–296

    Article  CAS  Google Scholar 

  45. Cauvin S, Colver PJ, Bon SAF (2005) Pickering stabilized miniemulsion polymerization: preparation of clay armored latexes. Macromolecules 38:7887–7889

    Article  CAS  Google Scholar 

  46. Voorn DJ, Ming W, Van Herk AM (2006) Polymer–clay nanocomposite latex particles by inverse pickering emulsion polymerization stabilized with hydrophobic montmorillonite platelets. Macromolecules 39:2137–2143

    Article  CAS  Google Scholar 

  47. Fujii S, Okada M, Sawa H, Furuzono T, Nakamura Y (2009) Hydroxyapatite nanoparticles as particulate emulsifier: fabrication of hydroxyapatite-coated biodegradable microspheres. Langmuir 25:9759–9766

    Article  CAS  Google Scholar 

  48. Duan L, Chen M, Zhou S, Wu L (2009) Synthesis and characterization of poly(N-isopropylacrylamide)/silica composite microspheres via inverse Pickering suspension polymerization. Langmuir 25:3467–3472

    Article  CAS  Google Scholar 

  49. Yin D, Zhang Q, Yin C, Jia Y, Zhang H (2010) Effect of particle coverage on morphology of SiO2-covered polymer microspheres by Pickering emulsion polymerization. Colloid Surface A 367:70–75

    Article  CAS  Google Scholar 

  50. Song X, Zhao Y, Wang H, Du Q (2009) Fabrication of polymer microspheres using titania as a photocatalyst and Pickering stabilizer. Langmuir 25:4443–4449

    Article  CAS  Google Scholar 

  51. Yin G, Zheng Z, Wang H, Du Q (2011) Slightly surface-functionalized polystyrene microspheres prepared via Pickering emulsion polymerization using for electrophoretic displays. J Colloid Interf Sci 361:456–464

    Article  CAS  Google Scholar 

  52. Kim YJ, Liu YD, Seo Y, Choi HJ (2013) Pickering-emulsion-polymerized polystyrene/Fe2O3 composite particles and their magnetoresponsive characteristics. Langmuir 29:4959–4965

    Article  CAS  Google Scholar 

  53. Ferchichi K, Hbaieb S, Amdouni N, Pralong V, Chevalier Y (2013) Structural and electrochemical characterization of polyaniline/LiCoO2 nanocomposites prepared via a Pickering emulsion. J Solid State Electr 17:1435–1447

    Article  CAS  Google Scholar 

  54. Chen JH, Cheng CY, Chiu WY, Lee CF, Liang NY (2008) Synthesis of ZnO/polystyrene composites particles by Pickering emulsion polymerization. Eur Polym J 44:3271–3279

    Article  CAS  Google Scholar 

  55. Liu H, Wang C, Zou S, Wei Z, Tong Z (2012) Facile fabrication of polystyrene/halloysite nanotube microspheres with core–shell structure via Pickering suspension polymerization. Polym Bull 69:765–777

    Article  CAS  Google Scholar 

  56. Song X, Yang Y, Liu J, Zhao H (2010) PS colloidal particles stabilized by graphene oxide. Langmuir 27:1186–1191

    Article  Google Scholar 

  57. Yin G, Zheng Z, Wang H, Du Q, Zhang H (2013) Preparation of graphene oxide coated polystyrene microspheres by Pickering emulsion polymerization. J Colloid Interf Sci 394:192–198

    Google Scholar 

  58. Menner A, Powell R, Bismarck A (2006) Open porous polymer foams via inverse emulsion polymerization: should the definition of high internal phase (ratio) emulsions be extended? Macromolecules 39:2034–2035

    Article  CAS  Google Scholar 

  59. Yuan Q, Yang L, Wang M, Wang H, Ge X, Ge X (2009) The mechanism of the formation of multihollow polymer spheres through sulfonated polystyrene particles. Langmuir 25:2729–2735

    Article  CAS  Google Scholar 

  60. Li T, Liu H, Zeng L, Miao W, Wu Y (2011) Study of emulsion polymerization stabilized by amphiphilic polymer nanoparticles. Colloid Polym Sci 289:1543–1551

    Article  CAS  Google Scholar 

  61. Binks BP, Rodrigues (2005) Inversion of emulsions stabilized solely by ionizable nanoparticles. Angew Chem Int Edit 44:441–444

    Article  CAS  Google Scholar 

  62. Sun GQ, Li ZF, Ngai T (2010) Inversion of particle-stabilized emulsions to form high-internal-phase emulsions. Angew Chem Int Edit 49:2163–2166

    Article  CAS  Google Scholar 

  63. Colver PJ, Bon SAF (2007) Cellular polymer monoliths made via Pickering high internal phase emulsions. Chem Mater 19:1537–1539

    Article  CAS  Google Scholar 

  64. Whitby CP, Lotte L, Lang C (2012) Structure of concentrated oil-in-water Pickering emulsions. Soft Matter 8:7784–7789

    Article  CAS  Google Scholar 

Download references

Acknowledgment

We gratefully acknowledge financial supports from Natural Science Foundation (21074067).

Author information

Authors and Affiliations

  1. Key Laboratory for Special Functional Aggregated Materials of Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, China

    Xiaona Li, Chunli Zhu, Yanze Wei & Zaijun Lu

Authors
  1. Xiaona Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chunli Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yanze Wei
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Zaijun Lu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Zaijun Lu.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Li, X., Zhu, C., Wei, Y. et al. Fabrication of macroporous foam and microspheres of polystyrene by Pickering emulsion polymerization. Colloid Polym Sci 292, 115–122 (2014). https://doi.org/10.1007/s00396-013-3058-y

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00396-013-3058-y

Keywords

Search

Navigation