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Synthesis of associative block copolymers electrolytes via RAFT polymerization

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Abstract

In this work, the synthesis of associative electrolyte copolymers via the RAFT polymerization technique in solution media is reported. Well-defined polyelectrolytes as multiblock copolymers or multistickers were prepared. Previously, an hydrophilic macroRAFT agent of a statistic copolymer P(MAA-co-EA) was prepared using methacrylic acid (MAA) and ethyl acrylate (EA). Afterwards, chain extensions of the macroagent were carried out by further polymerization of stearyl methacrylate (SMA). At the end, multiblock copolymers (heptablock) were obtained by insertion of three blocks of SMA. All the polymerizations showed a living behavior with the resulting polymers exhibiting a narrow dispersity (Đ ≤ 1.5). The synthesized polymers were characterized by nuclear magnetic resonance (NMR), size exclusion chromatography (SEC) and rheological measurements. Furthermore, it was demonstrated that the insertion of hydrophobic segments into the multiblock copolymers increases considerably the viscosity of the associative electrolyte polymers.

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References

  1. Shaw KG, Leipold DPJ (1985) New cellulosic polymers for rheology control of latex paints. J Coat Technol 57:63–72

    CAS  Google Scholar 

  2. Evani S, Rose GD (1987) Water soluble hydrophobe association polymers. Polym Mater Sci Eng 57:477–481

    CAS  Google Scholar 

  3. Byham DE, Sheppard EW, Chen CSH (1980) Oil recovery process involving the injection of thickened wáter. US Patent 4 222 881

  4. Stratton CA (1971) Oil recovery process using ethoxylated phenol-formaldehyde product. US Patent 3 583 486

  5. Marquis D M, Kuehne L (1994) Enhanced oil recovery technique employing nonionic surfactants. US Patent 5 363 915

  6. Schulz DN, Glass JE (1991) Polymers as rheology modifiers. ACS Symp Ser Am Chem Soc. doi:10.1021/bk-1991-0462

    Google Scholar 

  7. Pabon M, Corpart J (2004) Synthesis in inverse emulsion and associating behavior of hydrophobically modified polyacrylamides. J Appl Polym Sci 91:916–924. doi:10.1002/app.13227

    Article  CAS  Google Scholar 

  8. Volpert E, Selb J, Candau F, Green N (1998) Adsorption of hydrophobically associating polyacrylamides on clay. Langmuir 14:1870–1879. doi:10.1021/la970358h

    Article  CAS  Google Scholar 

  9. Abdala AA, Tonelli AE, Khan SA (2003) Modulation of hydrophobic interactions in associative polymers using inclusion compounds and surfactants. Macromolecules 36:7833–7841. doi:10.1021/ma034173v

    Article  CAS  Google Scholar 

  10. Jiménez-Regalado E, Selb J, Candau F (2000) Phase behavior and rheological properties of aqueous solutions containing mixtures of associating polymers. Macromolecules 33:8720–8730. doi:10.1021/ma000579l

    Article  Google Scholar 

  11. Li Y, Kwak JCT (2003) Rheology and binding studies in aqueous systems of hydrophobically modified acrylamide and acrylic acid copolymers and surfactants. Colloids Surf A physicochem Eng Asp 225:169–180. doi:10.1016/S0927-7757(03)00353-4

    Article  CAS  Google Scholar 

  12. Ma J, Cui P, Zhao L, Huang R (2002) Synthesis and solution behavior of hydrophobic association water-soluble polymers containing arylalkyl group. Eur Polym J 38:1627–1633. doi:10.1016/S0014-3057(02)00034-4

    Article  CAS  Google Scholar 

  13. Hourdet D, L’Alloret F, Audebert R (1994) Reversible thermothickening of aqueous polymer solutions. Polymer 35:2624–2630. doi:10.1016/0032-3861(94)90390-5

    Article  CAS  Google Scholar 

  14. Matyjaszewski K (2009) Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP and OMRP. ACS Symp Ser Am Chem Soc. doi:10.1021/bk-2009-1024.fw001

    Google Scholar 

  15. Chassenieux C, Nicolai T, Benyahia L (2011) Rheology of associative polymer solutions. Curr Opin Colloid Interface Sci 16:18–26. doi:10.1016/j.cocis.2010.07.007

    Article  CAS  Google Scholar 

  16. English RJ, Gulati HS, Jenkins RD, Khan SA (1997) Solution rheology of a hydrophobically modified alkali-soluble associative polymer. J Rheol 41:427–444. doi:10.1122/1.550807

    Article  CAS  Google Scholar 

  17. Dai S, Tam KC, Jenkins RD, Bassett DR (2000) Light scattering of dilute hydrophobically modified alkali-soluble emulsion solutions: effects of hydrophobicity and spacer length of macromonomer. Macromolecules 33:7021–7028. doi:10.1021/ma000528o

    Article  CAS  Google Scholar 

  18. Yao J, Ravi P, Tam KC, Gan LH (2004) Association behavior of poly(methyl methacrylate-block-methacrylic acid) in aqueous medium. Langmuir 20:2157–2163. doi:10.1021/la0355343

    Article  CAS  Google Scholar 

  19. Tsitsilianis C, Gotzamanis G, Iatridi Z (2012) Design of “smart” segmented polymers by incorporating random copolymers as building blocks. Eur Polymer J 47:497–510. doi:10.1016/j.eurpolymj.2010.10.005

    Article  Google Scholar 

  20. Popescu MT, Athanasoulias I, Tsitsilianis C, Hadjiantoniou NA, Patrickios CS (2010) Reversible hydrogels from amphiphilic polyelectrolyte model multiblock copolymers: the importance of macromolecular topology. Soft Matter 6:5417–5424. doi:10.1039/C0SM00489H

    Article  CAS  Google Scholar 

  21. Jenkins AD, Jones RG, Moad G (2010) Terminology for reversible-deactivation radical polymerization previously called “controlled” radical or “living” radical polymerization (IUPAC Recommendations 2010). Pure Appl Chem 82:483–491. doi:10.1351/PAC-REP-08-04-03

    CAS  Google Scholar 

  22. Hawker CJ (1994) Molecular weight control by a “living” free-radical polymerization process. J Am Chem Soc 116:11185–11186. doi:10.1021/ja00103a055

    Article  CAS  Google Scholar 

  23. Tebben L, Studer A (2011) Nitroxides: applications in synthesis and in polymer chemistry. Angew Chem Int Ed 50:5034–5068. doi:10.1002/anie.201002547

    Article  CAS  Google Scholar 

  24. Lessard BH, Marić M (2008) Nitroxide-mediated synthesis of poly(poly(ethylene glycol) acrylate) (PPEGA) comb-like homopolymers and block copolymers. Macromolecules 41:7870–7880. doi:10.1021/ma800603a

    Article  CAS  Google Scholar 

  25. Payne KA, Nesvadba P, Debling J, Cunningham MF, Hutchinson RA (2015) Nitroxide-mediated polymerization at elevated temperatures. ACS Macro Lett 4:280–283. doi:10.1021/acsmacrolett.5b00054

    Article  CAS  Google Scholar 

  26. Burguiere C, Chassenieux C, Charleux B (2003) Characterization of aqueous micellar solutions of amphiphilic block copolymers of poly(acrylic acid) and polystyrene prepared via ATRP. Toward the control of the number of particles in emulsion polymerization. Polymer 44:509–518. doi:10.1016/S0032-3861(02)00811-X

    Article  CAS  Google Scholar 

  27. Matyjaszewski K (2012) Atom transfer radical polymerization (ATRP): current status and future perspectives. Macromolecules 45:4015–4039. doi:10.1021/ma3001719

    Article  CAS  Google Scholar 

  28. Burdyńska J, Cho HY, Mueller L, Matyjaszewski K (2010) Synthesis of star polymers using ARGET ATRP. Macromolecules 43:9227–9229. doi:10.1021/ma101971z

    Article  Google Scholar 

  29. Moad G, Chong YK, Postma A, Rizzardo E, Thang SH (2005) Advances in RAFT polymerization: the synthesis of polymers with defined end-groups. Polymer 46:8458–8468. doi:10.1016/j.polymer.2004.12.061

    Article  CAS  Google Scholar 

  30. Lowe AB, McCormick CL (2007) Reversible addition–fragmentation chain transfer (RAFT) radical polymerization and the synthesis of water-soluble (co)polymers under homogeneous conditions in organic and aqueous media. Prog Polym Sci 32:283–351. doi:10.1016/j.progpolymsci.2006.11.003

    Article  CAS  Google Scholar 

  31. Zhang W, D’Agosto F, Dugas P, Rieger J, Charleux B (2013) RAFT-mediated one-pot aqueous emulsion polymerization of methyl methacrylate in presence of poly(methacrylic acid-co-poly(ethylene oxide) methacrylate) trithiocarbonate macromolecular chain transfer agent. Polymer 54:2011–2019. doi:10.1016/j.polymer.2012.12.028

    Article  CAS  Google Scholar 

  32. Derry MJ, Fielding LA, Armes SP (2016) Polymerization-induced self-assembly of block copolymer nanoparticles via RAFT non-aqueous dispersion polymerization. Prog Polym Sci 52:1–18. doi:10.1016/j.progpolymsci.2015.10.002

    Article  CAS  Google Scholar 

  33. Sigma-Aldrich, Materials, Science (2012) Controlled Radical Polymerization Guide: ATRP, RAFT, NMP https://www.sigmaaldrich.com/content/dam/sigma-aldrich/docs/Aldrich/Brochure/1/controlled-radical-polymerization-guide.pdf. Accesed 28 Feb 2017

  34. Moad G, Rizardo E, Thang SH (2008) Toward living radical polymerization. Acc Chem Res 41:1133–1142. doi:10.1021/ar800075n

    Article  CAS  Google Scholar 

  35. Chaduc I, Girod M, Antoine R, Charleux B, D’Agosto F, Lansalot M (2012) Batch emulsion polymerization mediated by poly(methacrylic acid) MacroRAFT agents: one-pot synthesis of self-stabilized particles. Macromolecules 45:5881–5893. doi:10.1021/ma300875y

    Article  CAS  Google Scholar 

  36. Pelet JM, Putnam D (2009) High molecular weight poly(methacrylic acid) with narrow polydispersity by RAFT polymerization. Macromolecules 42:1494–1499. doi:10.1021/ma801433g

    Article  CAS  Google Scholar 

  37. Relógio P, Charreyre M, Farinha JPS, Martinho JMG, Pichot C (2004) Well-defined polymer precursors synthesized by RAFT polymerization of N,N-dimethylacrylamide/N-acryloxysuccinimide: random and block copolymers. Polymer 45:8639–8649. doi:10.1016/j.polymer.2004.10.056

    Article  Google Scholar 

  38. Lai JT, Filla D, Shea R (2002) Functional polymers from novel carboxyl-terminated trithiocarbonates as highly efficient RAFT agents. Macromolecules 35:6754–6756. doi:10.1021/ma020362m

    Article  CAS  Google Scholar 

  39. Chaduc I, Lansalot M, D’Agosto F, Charleux B (2012) RAFT polymerization of methacrylic acid in water. Macromolecules 45:1241–1247. doi:10.1021/ma2023815

    Article  CAS  Google Scholar 

  40. Couvreur L, Lefay C, Belleney J, Charleux B, Guerret O, Magnet S (2003) First nitroxide-mediated controlled free-radical polymerization of acrylic acid. Macromolecules 36:8260–8267. doi:10.1021/ma035043p

    Article  CAS  Google Scholar 

  41. Odian G (2004) Principles of polymerization, 4th edn. Wiley, New York

    Book  Google Scholar 

  42. Graessley WW (1980) Polymer chain dimensions and the dependence of viscoelastic properties on concentration, molecular weight and solvent power. Polymer 21:258–262. doi:10.1016/0032-3861(80)90266-9

    Article  CAS  Google Scholar 

  43. De Gennes PG (1978) Scaling laws for incompatible polymer solutions. J Polym Sci Part B Polym Phys Ed 16:1883–1885. doi:10.1002/pol.1978.180161016

    Article  Google Scholar 

  44. Jiménez Regalado E, Selb J, Candau F (1999) Viscoelastic behavior of semidilute solutions of multisticker polymer chains. Macromolecules 32:8580–8588. doi:10.1021/ma990999e

    Article  Google Scholar 

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Acknowledgements

Special thanks are expressed to M. C. Ricardo Mendoza-Carrizales, José G. Telles-Padilla and Dr. Tania Segura-Moctezuma for all their support in the fulfillment of the GPC trials. Also to Dr. Luis Ernesto Elizalde-Herrera for all his support provided on the NMR tests.

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Authors and Affiliations

  1. Centro de Investigación en Química Aplicada (CIQA), Blvd Enrique Reyna Hermosillo # 140, Saltillo, Coahuila, 25294, Mexico

    Sergio Díaz-Silvestre, Enrique Saldívar-Guerra, Claudia Rivera-Vallejo, Judith Cabello-Romero, Ramiro Guerrero-Santos & Enrique Jiménez-Regalado

  2. CONACYT-Centro de Investigación en Química Aplicada (CIQA), Blvd Enrique Reyna Hermosillo # 140, Saltillo, Coahuila, 25294, Mexico

    Claude St Thomas

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  1. Sergio Díaz-Silvestre
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  2. Enrique Saldívar-Guerra
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Correspondence to Enrique Jiménez-Regalado.

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Díaz-Silvestre, S., Saldívar-Guerra, E., Rivera-Vallejo, C. et al. Synthesis of associative block copolymers electrolytes via RAFT polymerization. Polym. Bull. 75, 891–907 (2018). https://doi.org/10.1007/s00289-017-2071-6

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