Iranian Polymer Journal

, Volume 27, Issue 6, pp 371–379 | Cite as

Preparation of multi-responsive amphiphilic particles by one-step soapless emulsion polymerization

  • Bin Wang
  • Wenzhong Zhai
  • Rong-Min Wang
  • Xuling Wei
  • Pengfei Song
  • Yufeng He
Original Research


A novel multi-responsive amphiphilic copolymer (mRAP) particles with tunable emulsifiability was successfully prepared via one-step soapless emulsion polymerization using common monomers, such as methyl methacrylate, methacrylic acid (MAA), butyl acrylate (BA) and N,N-diethylacrylamide (DEAA). The obtained monodisperse spherical mRAP particles were characterized by dynamic light scattering, Fourier transform infrared spectroscopy, scanning electron microscope and transmission electron microscope, which provided the information of particle size, components and anisotropic structure. Its multiple responsivities were investigated under the condition of diversified pH values, salinity and temperature. The results showed that the mRAP particles exhibited good dispersivity based on uniform particle size, as well as tunable emulsifiability and anticipated multiple responsiveness. Furthermore, the tunable emulsifiability of oil–water mixtures could be easily achieved by adjusting the mass ratios of MAA to DEAA. Meanwhile, the obtained multi-responsive polymers relying on simple and effective copolymerization can be used in fundamental research and industrial production.


Multi-responsive particles Amphiphilic acrylate copolymer Good dispersivity Tunable emulsifiabilities Soapless emulsion polymerization 



This work was financially supported by the National Natural Science Foundation of China (NSFC) (21364012, 21263024).

Supplementary material

13726_2018_608_MOESM1_ESM.docx (5.6 mb)
Supplementary material 1 (DOCX 5785 kb)


  1. 1.
    Bajpai AK, Shukla SK, Bhanu S, Kankane S (2008) Responsive polymers in controlled drug delivery. Prog Polym Sci 33:1088–1118CrossRefGoogle Scholar
  2. 2.
    Schattling P, Jochum FD, Theato P (2014) Multi-stimuli responsive polymers—the all-in-one talents. Polym Chem 5:25–36CrossRefGoogle Scholar
  3. 3.
    Bajpai AK, Bajpai J, Saini R, Gupta R (2011) Responsive polymers in biology and technology. Polym Rev 51:53–97CrossRefGoogle Scholar
  4. 4.
    Mura S, Nicolas J, Couvreur P (2013) Stimuli-responsive nanocarriers for drug delivery. Nat Mater 12:991–1003CrossRefPubMedGoogle Scholar
  5. 5.
    Kesharwani P, Jain K, Jain NK (2014) Dendrimer as nanocarrier for drug delivery. Prog Polym Sci 39:268–307CrossRefGoogle Scholar
  6. 6.
    Chen C-J, Jin Q, Liu G-Y, Li D-D, Wang J-L, Ji J (2012) Reversibly light-responsive micelles constructed via a simple modification of hyperbranched polymers with chromophores. Polymer 53:3695–3703CrossRefGoogle Scholar
  7. 7.
    Stuart MAC, Huck WTS, Genzer J, Müller M, Ober C, Stamm M, Sukhorukov GB, Szleifer I, Tsukruk VV, Urban M, Winnik F, Zauscher S, Luzinov I, Minko S (2010) Emerging applications of stimuli-responsive polymer materials. Nat Mater 9:101–113CrossRefPubMedGoogle Scholar
  8. 8.
    Tanaka T, Okayama M, Minami H, Okubo M (2010) Dual stimuli-responsive “mushroom-like” Janus polymer particles as particulate surfactants. Langmuir 26:11732–11736CrossRefPubMedGoogle Scholar
  9. 9.
    Feng C, Lü S, Gao C, Wang X, Xu X, Bai X, Gao N, Liu M, Wu L (2015) “Smart” fertilizer with temperature-and pH-responsive behavior via surface-Initiated polymerization for controlled release of nutrients. ACS Sustain Chem Eng 3:3157–3166CrossRefGoogle Scholar
  10. 10.
    Dan M, Su Y, Xiao X, Li S, Zhang W (2013) A new family of thermo-responsive polymers based on poly[N-(4-vinylbenzyl)-N,N-dialkylamine. Macromolecules 46:3137–3146CrossRefGoogle Scholar
  11. 11.
    de Jongh PA, Mortiboy A, Sulley GS, Bennett MR, Anastasaki A, Wilson P, Haddleton DM, Kempe K (2016) Dual stimuli-responsive comb polymers from modular N-acylated poly(aminoester)-based macromonomers. ACS Macro Lett 5:321–325CrossRefGoogle Scholar
  12. 12.
    Zhang X, Lü S, Gao C, Chen C, Zhang X, Liu M (2013) Highly stable and degradable multifunctional microgel for self-regulated insulin delivery under physiological conditions. Nanoscale 5:6498–6506CrossRefPubMedGoogle Scholar
  13. 13.
    Lu C, Urban MW (2014) Tri-phasic size-and janus balance-tunable colloidal nanoparticles (JNPs). ACS Macro Lett 3:346–352CrossRefGoogle Scholar
  14. 14.
    Tu F, Lee D (2014) Shape-changing and amphiphilicity-reversing Janus particles with pH-responsive surfactant properties. J Am Chem Soc 136:9999–10006CrossRefPubMedGoogle Scholar
  15. 15.
    Wu G, Chen S-C, Liu C-L, Wang Y-Z (2015) Direct aqueous self-assembly of an amphiphilic diblock copolymer toward multistimuli-responsive fluorescent anisotropic micelles. ACS Nano 9:4649–4659CrossRefPubMedGoogle Scholar
  16. 16.
    Liu X, Hu D, Jiang Z, Zhuang J, Xu Y, Guo X, Thayumanavan S (2016) Multi-stimuli-responsive amphiphilic assemblies through simple postpolymerization modifications. Macromolecules 49:6186–6192CrossRefPubMedPubMedCentralGoogle Scholar
  17. 17.
    Cao Z, Zhou X, Wang G (2016) Selective release of hydrophobic and hydrophilic cargos from multi-stimuli-responsive nanogels. ACS Appl Mater Interfaces 8:28888–28896CrossRefPubMedGoogle Scholar
  18. 18.
    Xiong Y, Liu J, Wang Y, Wang H, Wang RM (2012) One-step synthesis of thermosensitive nanogels based on highly cross-linked poly(ionic liquid)s. Angew Chem Int Ed 51:9114–9118CrossRefGoogle Scholar
  19. 19.
    Li C, Wu Z, He YF, Song PF, Zhai W, Wang RM (2014) A facile fabrication of amphiphilic Janus and hollow latex particles by controlling multistage emulsion polymerization. J Colloid Interface Sci 426:39–43CrossRefPubMedGoogle Scholar
  20. 20.
    Zhai W, Li T, He Y-F, Xiong Y, Wang R-M (2015) One-pot facile synthesis of half-cauliflower amphiphilic Janus particles with pH-switchable emulsifiabilities. RSC Adv 5:76211–76215CrossRefGoogle Scholar
  21. 21.
    Zhai W, Wang B, Wang Y, He YF, Song P, Wang RM (2016) An efficient strategy for preparation of polymeric Janus particles with controllable morphologies and emulsifiabilities. Colloid Surf A Physicochem Eng Aspects 503:94–100CrossRefGoogle Scholar
  22. 22.
    Yang F, Cao Z, Wang G (2015) Micellar assembly of a photo- and temperature-responsive amphiphilic block copolymer for controlled release. Polym Chem 6:7995–8002CrossRefGoogle Scholar
  23. 23.
    Wu W-C, Chen C-Y, Lee W-Y, Chen W-C (2015) Stimuli-responsive conjugated rod-coil block copolymers: synthesis, morphology, and applications. Polymer 65:A1–A16CrossRefGoogle Scholar
  24. 24.
    Topuzogullari M, Bulmus V, Dalgakiran E, Dincer S (2014) pH- and temperature-responsive amphiphilic diblock copolymers of 4-vinylpyridine and oligoethyleneglycol methacrylate synthesized by RAFT polymerization. Polymer 55:525–534CrossRefGoogle Scholar
  25. 25.
    Ercole F, Davis TP, Evans RA (2010) Photo-responsive systems and biomaterials: photochromic polymers, light-triggered self-assembly, surface modification, fluorescence modulation and beyond. Polym Chem 1:37–54CrossRefGoogle Scholar
  26. 26.
    Wang Z, Rutjes FPJT, van Hest JCM (2014) pH responsive polymersome Pickering emulsion for simple and efficient Janus polymersome fabrication. Chem Commun 50:14550–14553CrossRefGoogle Scholar
  27. 27.
    Binks BP, Murakami R, Armes SP, Fujii S (2005) Temperature-induced inversion of nanoparticle-stabilized emulsions. Angew Chem 117:4873–4876CrossRefGoogle Scholar
  28. 28.
    Guragain S, Bastakoti BP, Malgras V, Nakashima K, Yamauchi Y (2015) Multi-stimuli-responsive polymeric materials. Chem Eur J 21:13164–13174CrossRefPubMedGoogle Scholar
  29. 29.
    Wang XH, Jiang GH, Li X, Tang BL, Wei Z, Mai CY (2013) Synthesis of multi-responsive polymeric nanocarriers for controlled release of bioactive agents. Polym Chem 4:4574–4577CrossRefGoogle Scholar
  30. 30.
    Fan X, Liu Y, Jia X, Wang S, Li C, Zhang B, Zhang H, Zhang Q (2015) Regulating the size and molecular weight of polymeric particles by 1,1-diphenylethene controlled soap-free emulsion polymerization. RSC Adv 5:95183–95190CrossRefGoogle Scholar
  31. 31.
    Guimaraes TR, Chaparro TDC, D’Agosto F, Lansalot M, Dos Santos AM, Bourgeat-Lami E (2014) Synthesis of multi-hollow clay-armored latexes by surfactant-free emulsion polymerization of styrene mediated by poly(ethylene oxide)-based macroRAFT/laponite complexes. Polym Chem 5:6611–6622CrossRefGoogle Scholar
  32. 32.
    Ren C, Liu X, Jiang X, Sun G, Huang X (2015) Polyisobutylene-b-poly(N,N-diethylacrylamide) well-defined amphiphilic diblock copolymer: synthesis and thermo-responsive phase behavior. J Polym Sci Polym Chem 53:1143–1150CrossRefGoogle Scholar
  33. 33.
    Binks BP, Rodrigues JA (2005) Inversion of emulsions stabilized solely by ionizable nanoparticles. Angew Chem Int Ed 44:441–444CrossRefGoogle Scholar

Copyright information

© Iran Polymer and Petrochemical Institute 2018

Authors and Affiliations

  1. 1.Key Lab Eco-Environment-Related Polymer Materials of Ministry of Education, Institute of Polymer, College of Chemistry and Chemical EngineeringNorthwest Normal UniversityLanzhouChina

Personalised recommendations