Synthesis, characterization and properties of self-healable ionomeric carboxylated styrene–butadiene polymer

  • Shreyashi Mukhopadhyay
  • Pranabesh Sahu
  • Hiren Bhajiwala
  • Subhra Mohanty
  • Virendrakumar GuptaEmail author
  • Anil K. BhowmickEmail author
Polymers & biopolymers


The paper describes synthesis and properties of carboxylated styrene–butadiene rubber (XSBR) and its ionomer using the reaction between carboxyl groups of XSBR and zinc stearate. The self-aggregation of Zn2+ ion pairs resulted in the formation of an ionic cross-linked network, which gave excellent properties to XSBR. The transitions due to the self-association of the ionic cross-links in the ionomers in addition to the glass transition were observed in the dynamic mechanical analysis. The cross-linked XSBR with 1 and 3 wt% of zinc stearate showed a tensile strength value of 4.2 and 5.2 MPa, which were much higher than that (2.5 MPa) of pristine XSBR. Self-healing test was done for the ionomer, where a tensile strength value of 5.2 MPa (before healing) and a value of 3.5 MPa (after healing) were observed, which indicated that the ionic cross-links could heal the interphase. The ionic network polymers also displayed excellent self-healing ability, triggered by heating at 100 °C for 3 h via atomic force microscopy. The healing efficiency of the XSBR/Zn stearate compound was calculated as 68%. Thermoreversible behaviour of the polymer via ionic cross-links showed regular reversal of storage modulus (E’) with varying temperature at constant frequency and strain. This study thus opens up a route for developing the self-healable ionic cross-linked XSBR with considerable mechanical properties for various engineering applications.



The authors thank IIT Kharagpur and Reliance Industries Limited, Mumbai for providing the necessary facilities and carrying out the entire work.


The author(s) disclosed no financial support for the research, authorship and/or publication of this article.

Compliance with ethical standards

Conflict of interest

The authors declare no conflict of interest towards any individual or organization.


  1. 1.
    Kar KK, Bhowmick AK (2001) Ionomeric thermoplastic elastomer. In: Bhowmick AK, Stephens HL (eds) Handbook of elastomers. CRC Press, Taylor & Francis Group, Boca RatonGoogle Scholar
  2. 2.
    Macknight WJ, Lundberg RD (1984) Elastomeric ionomers. Rubber Chem Technol 57:652–663. CrossRefGoogle Scholar
  3. 3.
    Brown HP, Gibbs CF (1955) Ind Eng Chem 47:1006–1012CrossRefGoogle Scholar
  4. 4.
    Brown HP (1957) Carboxylic elastomers. Rubber Chem Technol 30:1347–1386. CrossRefGoogle Scholar
  5. 5.
    Brown HP (1963) Crosslinking reactions of carboxylic elastomers. Rubber Chem Technol 36:931–962. CrossRefGoogle Scholar
  6. 6.
    Fan XD, Bazuin CG (1993) Molecular orientation behavior in uniaxially stretched biphasic polystyrene-based ionomers. Macromolecules 26:2508–2513. CrossRefGoogle Scholar
  7. 7.
    Xu C, Cao L, Huang X, Chen Y, Lin B, Fu L (2017) Self-healing natural rubber with tailorable mechanical properties based on ionic supramolecular hybrid network. ACS Appl Mater Interfaces 9:29363–29373. CrossRefGoogle Scholar
  8. 8.
    Xu C, Huang X, Li C, Chen Y, Lin B, Liang X (2016) Design of “Zn2+ Salt-Bondings” cross-linked carboxylated styrene butadiene rubber with reprocessing and recycling ability via rearrangements of ionic cross-linkings. ACS Sustain Chem Eng 4:6981–6990. CrossRefGoogle Scholar
  9. 9.
    Eisenberg A (1980) Ions in polymers in ‘176th Meeting of the American Chemical Society, Miami Beach, Florida,’ Advances in Chemistry 187Google Scholar
  10. 10.
    Weiss RA, Fitzgerald JJ, Kim D (1991) Viscoelastic behavior of plasticized sulfonated polystyrene ionomers. Macromolecules 24:1064–1070CrossRefGoogle Scholar
  11. 11.
    Santana MH, Huete M, Lameda P, Araujo J, Verdejo R, López-Manchado MA (2018) Design of a new generation of sustainable SBR compounds with good trade-off between mechanical properties and self-healing ability. Eur Polym J 106:273–283. CrossRefGoogle Scholar
  12. 12.
    Kulkarni A, Pugh C, Jana SC, Wims DT, Gawad AA (2019) Crosslinking of SBR compounds for tire tread using benzocyclobutene chemistry. Rubber Chem Technol 92:25–42. CrossRefGoogle Scholar
  13. 13.
    Xu C, Nie J, Wu W, Fu L, Lin B (2019) Design of self-healable supramolecular hybrid network based on carboxylated styrene butadiene rubber and nano-chitosan. Carbohydr Polym 205:410–419. CrossRefGoogle Scholar
  14. 14.
    Xu C, Wu W, Nie J, Fu L, Lin B (2019) Preparation of carboxylic styrene butadiene rubber/chitosan composites with dense supramolecular network via solution mixing process. Compos A Appl Sci Manuf 117:116–124. CrossRefGoogle Scholar
  15. 15.
    Holliday L (1975) Ionic polymers. Applied Science Publishers, LondonGoogle Scholar
  16. 16.
    Eisenberg A, King M (1977) Ion-containing polymers: physical properties and structure. Elsevier, Amsterdam. Google Scholar
  17. 17.
    Bazuin CG, Einserberg A (1981) Ion-containing polymers: ionomers. J Chem Educ 58:938–943CrossRefGoogle Scholar
  18. 18.
    Yaruso DJ, Cooper SL (1983) Microstructure of ionomers: interpretation of small-angle X-ray scattering data. Macromolecules 16:1871–1880CrossRefGoogle Scholar
  19. 19.
    Peiffer DG, Hager BL, Weiss RA, Agarwal PK, Lundberg RD (1985) Far-infrared studies of microphase separation in sulfonated ionomers. J Polym Sci Polym Phys 23:1869–1881. CrossRefGoogle Scholar
  20. 20.
    Tant MR, Wilkes GR, Storey R, Kennedy JP (1985) Sulfonated polyisobutylene telechelic ionomers. Polym Bull 13:541–548. CrossRefGoogle Scholar
  21. 21.
    Mattera VD Jr, Risen WM Jr (1986) Composition dependence of glass transition temperature of sulfonated-polystrene ionomers. J Polym Sci Polym Phys 24:753–760. CrossRefGoogle Scholar
  22. 22.
    MacKnight WJ, Earnest TR Jr (1981) The structure and properties of ionomers. J Polym Sci Macromol Rev 16:41–122. CrossRefGoogle Scholar
  23. 23.
    Bagrodia S, Wilkes GL (1984) Comments on the effect of cation, type on ionomer properties. Polym Bull 12:389–392. CrossRefGoogle Scholar
  24. 24.
    Biswas A, Bandopadhyay A, Singha NK, Bhowmick AK (2009) Ionomeric modification of metallocene-based polyolefinic elastomers with varied pendant chain length and its influence on physico-mechanical properties. J Mater Sci 44:3125–3134. CrossRefGoogle Scholar
  25. 25.
    Biswas A, Bandopadhyay A, Singha NK, Bhowmick AK (2009) Ionomeric modification of a metallocene-based polyolefinic elastomer and its influence on the physicomechanical properties: effects of the crystallinity and pendent chain length†. J Appl Polym Sci 114:3906–3914. CrossRefGoogle Scholar
  26. 26.
    Biswas A, Bandopadhyay A, Singha NK, Bhowmick AK (2007) Chemical modification of metallocene-based polyethylene–octene elastomer through solution grafting of acrylic acid and its effect on the physico-mechanical properties. J Appl Polym Sci 105:3409–3417. CrossRefGoogle Scholar
  27. 27.
    Mattera VD Jr, Risen WM Jr (1984) A far-infrared study of ionic interactions in poly (styrene sulfonic acid) ionomers. J Appl Polym Sci Polym Phys 22:67–77. CrossRefGoogle Scholar
  28. 28.
    Ferrigno TH, Katz HS, Milewski JV (1978) Hand Book of fillers and reinforcements for plastics. Eds. Van Nostrand Reinhold, New YorkGoogle Scholar
  29. 29.
    Das A, Sallat A, Bohme F, Suckow M, Basu D, Wießner S, Stockelhuber KW, Voit B, Heinrich G (2015) Ionic modification turns commercial rubber into a self-healing material. ACS Appl Mater Interfaces 7:20623–20630. CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Rubber Technology Centre, Indian Institute of TechnologyKharagpurIndia
  2. 2.Polymer Synthesis and Catalysis DivisionReliance Industries LimitedMumbaiIndia
  3. 3.International Center for Polymers and Soft Matter, Department of Chemical and Biomolecular EngineeringThe University of HoustonHoustonUSA

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