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pH-responsive amphiphilic copolymers based on N-vinylpyrrolidone and fluoroacrylates with different structures: synthesis via RAFT process and surface properties

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Abstract

The copolymerization of 1,1,1,3,3,3-hexafluoroisopropylacrylate (HFIPA) and 2,2,3,3,4,4,5,5-octafluoropentyl acrylate (OFPA) with N-vinylpyrrolidone (NVP) in the presence of S,S’-dibenzyl trithiocarbonate (BTC) and polymeric RAFT agents based on fluoroacrylates were investigated. The copolymerization process proceeds in a control mode at any conditions investigated that was confirmed by the first order of reaction by monomer and SEC curves. Reactivity ratios of monomers were determined by the Fineman-Ross and Kelen-Tudos models. Aggregation behavior of copolymers at the air/water interface was studied by the Langmuir film balance technique. The influence of the composition and pH of the subphase on the surface properties of copolymers is considered. With the rise of subphase pH, as well as an increase in the mole fraction of NVP in the copolymer, the pressure of the plateau formation process increases. The morphology of LB films of various compositions was studied by atomic force microscopy. With the elevation in the proportion of NVP, a change in the size of micelles is traced.

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References

  1. Li Z, Wang S, Yang X, Liu H, Shan Y, Xu X, Shang S, Song Z (2020) Antimicrobial and antifouling coating constructed using rosin acid-based quaternary ammonium salt and N-vinylpyrrolidone via RAFT polymerization. Appl Surf Sci 530:147193. https://doi.org/10.1016/j.apsusc.2020.147193

    Article  CAS  Google Scholar 

  2. Mishra AK, Lim J, Lee J, Park S, Seo Y, Hwang H, Kim JK (2021) Control drug release behavior by highly stable and pH sensitive poly(N-vinylpyrrolidone)-block-poly(4-vinylpyridine) copolymer micelles. Polymer 213:123329. https://doi.org/10.1016/j.polymer.2020.123329

    Article  CAS  Google Scholar 

  3. Zamyshlyayeva OG, Lapteva OS, Baten´kin MA, Semchikov YD, Mel´nikova NB (2014) Self-organization and aggregation of amphiphilic block copolymers of N-vinylpyrrolidone-block-2,2,3,3-tetrafluoropropylmethacrylate at interfaces. Rus Chem Bullet 63:1823–1836. https://doi.org/10.1007/s11172-014-0672-x

    Article  CAS  Google Scholar 

  4. Zaitsev SD, Semchikov YD, Chernikova EV (2009) Controlled radical copolymerization of N-vinylpyrrolidone with 1,1,1,3,3,3-hexafluoroisopropyl-α-fluoroacrylate. Polym Sci Ser B 51:84–88. https://doi.org/10.1134/S1560090409030026

    Article  Google Scholar 

  5. Zaitsev SD, Semchikov YD, Vasil’eva EV, Kurushina LV (2012) Controlled radical (co)polymerization of (meth)acrylic esters via the reversible addition-fragmentation chain-transfer mechanism. Polym Sci Ser B 54:205–214. https://doi.org/10.1134/S1560090412040070

    Article  CAS  Google Scholar 

  6. Grigoreva A, Tarankova K, Zamyshlyayeva O, Zaitsev S (2021) Aggregation behaviour of poly(fluoro(meth)acrylate)-block-poly(acrylic acid) copolymers at the air/water interface. J Polym Res 28:267. https://doi.org/10.1007/s10965-021-02629-4

    Article  CAS  Google Scholar 

  7. Grigoreva AO, Polozov EY, Zaitsev SD (2019) Effect of chain microstructure and subphase pH on the surface properties and aggregation behavior of amphiphilic copolymers based on fluoroacrylates, Key Engineering materials. Trans Tech Publications Ltd 816:312–317. https://doi.org/10.4028/www.scientific.net/KEM.816.312

    Article  Google Scholar 

  8. Chen H, Wen G, Chrysostomou V, Pispas S, Pan W, Zuo J, Li M, Li H, Sun Z (2020) Effects of Copolymer Composition and Subphase pH/Temperature on the Interfacial Aggregation Behavior of Poly(2-(dimethylamino)ethyl methacrylate)- block-poly(lauryl methacrylate). J Phys Chem C 124:4563–4570. https://doi.org/10.1021/acs.jpcc.9b10673

    Article  CAS  Google Scholar 

  9. You K, Wen G, Skandalis A, Pispas S, Yang S, Li H, Sun Z (2019) Effects of Subphase pH and temperature on the aggregation behavior of poly(lauryl acrylate)-block-poly(N-isopropylacrylamide) at the Air/Water interface. J Phys Chem C 123:10435–10442. https://doi.org/10.1021/acs.jpcc.9b01320

    Article  CAS  Google Scholar 

  10. dos Santos Claro PC, Coustet ME, Diaz C, Maza E, Cortizo MS, Requejo FG, Pietrasanta LI, Ceolín M, Azzaroni O (2013) Self-assembly of PBzMA-b-PDMAEMA diblock copolymer films at the air-water interface and deposition on solid substrates via Langmuir-Blodgett transfer. Soft Matter 9:10899–10912. https://doi.org/10.1039/c3sm52336e

    Article  CAS  Google Scholar 

  11. Chernikova EV, Terpugova PS, Garina ES, Golubev VB (2007) Controlled radical polymerization of styrene and n-butyl acrylate mediated by trithiocarbonates. Polym Sci Ser A 49:108–119. https://doi.org/10.1134/S0965545X07020022

    Article  Google Scholar 

  12. Wang Y, Wen G, Pispas S, Yang S, You K (2018) Effects of subphase pH, temperature and ionic strength on the aggregation behavior of PnBA-b-PAA at the air/water interface. J Colloid Interface Sci 512:862–870. https://doi.org/10.1016/j.jcis.2017.11.002

    Article  CAS  PubMed  Google Scholar 

  13. Nuhn L, Overhoff I, Sperner M, Kaltenberg K, Zentel R (2014) RAFT-polymerized poly(hexafluoroisopropyl methacrylate)s as precursors for functional water-soluble polymers. Polym Chem 5:2484–2495. https://doi.org/10.1039/c3py01630g

    Article  CAS  Google Scholar 

  14. Zhu J, Eisenberg A, Lennox RB (1992) Interfacial behavior of Block Polyelectrolytes. 5. Effect of varying Block Lengths on the Properties of Surface Micelles. Macromolecules 25:6547–6555. https://doi.org/10.1021/ma00050a025

    Article  CAS  Google Scholar 

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Funding

The work was supported by the Ministry of Science and Higher Education of the Russian Federation (the basic part of the state order, project №FSWR-2023-0025).

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Authors and Affiliations

  1. Lobachevsky State University of Nizhny Novgorod, Nizhny Novgorod, Russia

    Oleg Lebedev, Alexandra Grigoreva, Aleksandr Chicharov, Alexey Markin & Sergey Zaitsev

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  1. Oleg Lebedev
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  2. Alexandra Grigoreva
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  3. Aleksandr Chicharov
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  4. Alexey Markin
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  5. Sergey Zaitsev
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Correspondence to Alexandra Grigoreva.

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Lebedev, O., Grigoreva, A., Chicharov, A. et al. pH-responsive amphiphilic copolymers based on N-vinylpyrrolidone and fluoroacrylates with different structures: synthesis via RAFT process and surface properties. J Polym Res 30, 304 (2023). https://doi.org/10.1007/s10965-023-03683-w

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  • DOI: https://doi.org/10.1007/s10965-023-03683-w

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