Confinement effect of blocks on the morphology of composite particles in co-assembly of block copolymers/homopolymers

Document Type : Original research

Authors

1 Faculty of Polymer Engineering, Sahand University of Technology, P.O. Box 51335-1996, Tabriz, Iran

2 Institute of Polymeric Materials, Sahand University of Technology, P.O. Box 51335-1996, Tabriz, Iran

Abstract

In this study, reversible addition-fragmentation chain transfer (RAFT) polymerization was used to synthesize hydrophobic polystyrene (PS), poly(methyl acrylate) (PMA), and poly(methyl acrylate-b-styrene) (PMA-b-PS) block copolymers with three distinct molecular weights. Polyaniline (PANI) was synthesized by electrochemical method. Proton nuclear magnetic resonance (1H NMR) and gel permeation chromatography (GPC) have both been used to examine the properties of the polymers synthesized. In aqueous media at room temperature, PANI has been co-assembled with PS, PMA, and PMA-b-PS. The size and morphology of the co-assembled structures have been examined using transmission electron microscopy (TEM), dynamic light scattering (DLS), and field emission scanning electron microscopy (FE-SEM). According to the findings, polymers hydrophobicity increased with increasing molecular weight, causing faster precipitation in aqueous solution and a reduction in particle size. The results demonstrated that adding conductive polymer produced core-shell morphologies, while the core morphologies are different. Thermodynamic principles governed morphology, and the most likely morphology to develop was the one that minimized the total surface free energy. The polymers caused the surface tension between the polymers with water and the surface tension between the primary polymer and the secondary polymer to be reduced by overlapping each other and precipitation.

Graphical Abstract

Confinement effect of blocks on the morphology of composite particles in co-assembly of block copolymers/homopolymers

Keywords

References

  1. Mandal P, Patra D, Shunmugam R (2020) Hier­archical self-assembled nanostructures of lactone-derived thiobarbiturate homopolymers for stimu­li-responsive delivery applications. Polym Chem 11: 3340-3348
  2. Tanford C (1974) Thermodynamics of micelle formation: prediction of micelle size and size dis­tribution. Proc Natl Acad Sci 71: 1811-1815
  3. Muslim A, Zhao Z, Shi Y, Malik D (2017) Sec­ondary self-assembly behaviors of PEO-b-PtBA-b-PS triblock terpolymers in solution. Chem Pap 71: 1721-1729
  4. Simões FR, Pocrifka LA, Marchesi LFQP, Pereira EC (2011) Investigation of electrochemical deg­radation process in polyaniline/polystyrene sulfo­nated self-assembly films by impedance spectros­copy. J Phys Chem B 115: 11092-11097
  5. Amani F, Dehghani E, Salami-Kalajahi M (2021) Preparation and study on properties of dual re­sponsive block copolymer-grafted polypyrrole smart Janus nanoparticles. J Polym Res 28: 142
  6. Blasco E, Schmidt BV, Barner-Kowollik C, Piñol M, Oriol L (2013) Dual thermo- and photo-respon­sive micelles based on miktoarm star polymers. Polym Chem 4: 4506-4514
  7. Farbod F, Goharpey F, Salami-Kalajahi M, Khon­akdar HA (2022) Synthesis and self-assembly of polystyrene block polyacrylic acid for sub 10 nm feature size. React Funct Polym 178: 105352
  8. Feng X, Imran Q, Zhang YL, Sixdenier X, Lu X, Kaufman G, Osuji CO (2019) Precise nanofiltra­tion in a fouling-resistant self-assembled mem­brane with water-continuous transport pathways. Sci Adv 5: eaav9308
  9. Cheng CC, Chiu TW, Yang XJ, Huang SY, Fan W, Lai JY, Lee DJ (2019) Self-assembling supramo­lecular polymer membranes for highly effective filtration of water-soluble fluorescent dyes. Polym Chem 10: 827-834
  10. Liu W, Mao J, Xue Y, Zhao Z, Zhang H, Ji X (2016) Nanoparticle loading induced morphologi­cal transitions and size fractionation of coassem­blies from PS-b-PAA with quantum dots. Lang­muir 32: 7596-7605
  11. Feng X, Yang G, Xu Q, Hou W, Zhu JJ (2006) Self-assembly of polyaniline/Au composites: From nanotubes to nanofibers. Macromol Rapid Commun 27: 31-36
  12. Kumar D, Sharma RC (1998) Advances in con­ductive polymers. Eur Polym J 34: 1053-1060
  13. Khadem F, Pishvaei M, Salami-Kalajahi M, Najafi F (2017) Morphology control of conducting poly­pyrrole nanostructures via operational conditions in the emulsion polymerization. J Appl Polym Sci 134: 44697
  14. Shirakawa H, Ikeda S (1971) Infrared spectra of poly(acetylene). Polym J 2: 231-244
  15. Lahav M, Durkan C, Gabai R, Katz E, Willner I, Welland ME (2001) Redox activation of a polyan­iline-coated cantilever: An electro-driven micro­device. Angew Chem 113: 4219-4221
  16. Nakajima T, Kawagoe T (1989) Polyaniline: Structural analysis and application for battery. Synth Met 28: 629-638
  17. Li Q, Wu J, Tang Q, Lan Z, Li P, Lin J, Fan L (2008) Application of microporous polyaniline counter electrode for dye-sensitized solar cells. Electrochem Commun 10: 1299-1302
  18. Beregoi M, Evanghelidis A, Matei E, Enculescu I (2017) Polyaniline based microtubes as building-blocks for artificial muscle applications. Sens Ac­tuator B-Chem 253: 576-583
  19. Lei Y, Zhou J, Yao Z, Li L (2020) Self-assembly of porous polyaniline microspheres via template-free interfacial method for high-performance elec­tromagnetic absorption property. Mater Lett 265: 127389
  20. Mai Y, Eisenberg A (2012) Self-assembly of block copolymers. Chem Soc Rev 41: 5969-5985
  21. Liu W, Mao Y, Xue Z, Zhao H, Zhang X (2016) Nanoparticle loading induced morphological transitions and size fractionation of coassemblies from PS-b-PAA with quantum dots. Langmuir 32: 7596-7605
  22. Yu Y, Zhang L, Eisenberg A (1998) Morphogenic effect of solvent on crew-cut aggregates of am­phiphilic diblock copolymers. Macromolecules 31: 1144-1154
  23. Dehghani B, Hosseini MS, Salami-Kalajahi M (2020) Neutral pH monosaccharide receptor based on boronic acid decorated poly (2-hydroxyethyl methacrylate): Spectral methods for determina­tion of glucose-binding and ionization constants.Microchem J 157: 105112
  24. Van Hest JCM, Delnoye DAP, Baars MWPL, Van Genderen MHP, Meijer EW (1995) Polystyrene-dendrimer amphiphilic block copolymers with a generation-dependent aggregation. Science 268: 1592-1595
  25. Jung YS, Jung W, Ross CA (2008) Nanofabri­cated concentric ring structures by templated self-assembly of a diblock copolymer. Nano Lett 8: 2975-2981
  26. Dehghani E, Barzgari-Mazgar T, Salami-Kala­jahi M, Kahaie-Khosrowshahi A (2020) A pH-controlled approach to fabricate electrolyte/non-electrolyte janus particles with low cytotoxicity as carriers of DOX. Mater Chem Phys 249: 123000
  27. Skandalis A, Sentoukas T, Giaouzi D, Kafetzi M, Pispas S (2021) Latest advances on the synthesis of linear ABC-type triblock terpolymers and star-shaped polymers by RAFT polymerization. Poly­mers 13: 1698
  28. Gheitarani B, Golshan M, Safavi-Mirmahalleh S-A, Salami-Kalajahi M, Hosseini MS, Alizadeh AK (2023) Fluorescent polymeric sensors based on N-(rhodamine-6G) lactam-N'-allyl-ethylene­diamine and 7-(allyloxy)-2H-chromen-2-one for Fe3+ ion detection. Colloids Surf. A Physicochem Eng Asp 656: 130473
  29. Chong YK, Moad G, Rizzardo E, Thang SH (2007) Thiocarbonylthio end group removal from RAFT-synthesized polymers by radical-induced reduction. Macromolecules 40: 4446-4455
  30. Zheng H, Bai W, Hu K, Bai R, Pan C (2008) Fac­ile room temperature RAFT polymerization via redox initiation. J Polym Sci Polym Chem 46: 2575-2580
  31. Nikravan G, Haddadi-Asl V, Salami-Kalajahi M (2018) Synthesis of dual temperature– and pH-re­sponsive yolk-shell nanoparticles by conventional etching and new deswelling approaches: DOX release behavior. Colloids Surf B-Biointerfaces 165: 1-8
  32. Abdollahi E, Abdouss M, Salami-Kalajahi M, Mo­hammadi A (2016) Molecular recognition ability of molecularly imprinted polymer nano- and mi­cro-particles by reversible addition-fragmentation chain transfer polymerization. Polym Rev 56: 557-583
  33. Fallahi-Sambaran M, Salami-Kalajahi M, Deh­ghani E, Abbasi F (2018) Investigation of dif­ferent core-shell toward Janus morphologies by variation of surfactant and feeding composition: A study on the kinetics of DOX release. Colloids Surf B-Biointerfaces 170: 578-587
  34. Fallahi-Sambaran M, Salami-Kalajahi M, De­hghani E, Abbasi F (2019) Investigating Janus morphology development of poly (acrylic acid)/ poly(2‑(dimethylamino)ethyl methacrylate) com­posite particles: An experimental study and math­ematical modeling of DOX release. Microchem J 145: 492-500
  35. Sharifzadeh E, Salami-Kalajahi M, Hosseini MS, Aghjeh MKR (2017) Synthesis of silica Janus nanoparticles by buoyancy effect-induced desym­metrization process and their placement at the PS/ PMMA interface. Colloid Polym Sci 295: 25-36
  36. Saito N, Kagari Y, Okubo M (2006) Effect of col­loidal stabilizer on the shape of polystyrene/poly (methyl methacrylate) composite particles pre­pared in aqueous medium by the solvent evapora­tion method. Langmuir 22: 9397-9402
  37. Amirshaqaqi N, Salami-Kalajahi M, Mahdavian M (2014) Corrosion behavior of aluminum/silica/ polystyrene nanostructured hybrid fl Iran Polym J 23: 699-706
  38. Saito N, Nakatsuru R, Kagari Y, Okubo M (2007) Formation of “snowmanlike” polystyrene/poly (methyl methacrylate)/toluene droplets dispersed in an aqueous solution of a nonionic surfactant at thermodynamic equilibrium. Langmuir 23: 11506-11512
  39. Torza S, Mason SG (1970) Three-phase interac­tions in shear and electrical fields. J Colloid Inter­face Sci 33: 67-83
  40. Sakti SP, Amaliya L, Khusnah NF, Masruroh M (2017) Effect of UV radiation duration and mo­lecular weight to hydrophobicity and surface roughness of polystyrene coating on QCM sensor. J Teknol 79: 61-67

Files

History

  • Receive Date: 18 February 2023
  • Revise Date: 16 March 2023
  • Accept Date: 26 March 2023

Share

How to cite

Statistics