Iranian Polymer Journal

, Volume 27, Issue 11, pp 889–897 | Cite as

A novel designed high strength and thermoresponsive double network hydrogels cross-linked by starch-based microspheres

  • Chang Liu
  • Ying Tan
  • Kun Xu
  • Mei Hua
  • Xiao-Hui Huo
  • Yin-Shi SunEmail author
Original Research


A new kind of nanocomposite double network (DN) hydrogels consisting of starch-based microspheres cross-linked oligo (ethylene glycol) methyl ether methacrylate) (POEGMA) as soft network and diethylene glycol dimethacrylate (DEGMA) cross-linked poly(2-(2-methoxyethoxy) ethyl methacrylate (PMEO2MA) as brittle network (named POEGMA/PMEO2MA DN hydrogels) were synthesized by a two-step free radical polymerization. The chemical structure of DN hydrogels was characterized by 1H NMR, the temperature sensitive properties were measured by the lower critical solution temperature (LCST) tested by UV-Vis spectrophotometer as a function of temperature, the mechanical properties were measured by tensile test. The LCST showed only one transition at 20.2 °C measured by the transmittance variation as a function of the ambient temperature from 5 to 70 °C. The fracture toughness and the hysteresis behaviors were also tested and showed that they were affected by the content of starch-based microspheres cross-linker in the soft POEGMA network, the content of small-molecular cross-linkers and monomer concentration in the brittle PMEO2MA network. They are related to perfect network and physical adherence and entanglements between microspheres and the networks brought by AAS microspheres, the increment of “sacrifice bond” brought by DEGMA and polymer chains entanglement brought by MEO2MA. These studies will provide theoretical support for the future research of DN hydrogel and macromolecular microspheres cross-linked hydrogel.


Hydrogel Thermosensitive Double network Microspheres cross-linked Mechanical properties 

Supplementary material

13726_2018_662_MOESM1_ESM.doc (45 kb)
Supplementary material 1 (DOC 45 KB)


  1. 1.
    Dai XY, Zhang YY, Gao LN, Bai T, Wang W, Cui YL, Liu WG (2015) A mechanically strong, highly stable, thermoplastic, and self-healable supramolecular polymer hydrogel. Adv Mater 27:3566–3571CrossRefGoogle Scholar
  2. 2.
    Seo BB, Koh JT, Song SC (2017) Tuning physical properties and BMP-2 release rates of injectable hydrogel systems for an optimal bone regeneration effect. Biomaterials 122:91–104CrossRefGoogle Scholar
  3. 3.
    Wang Q, Hou RX, Cheng YJ, Fu J (2012) Super-tough double-network hydrogels reinforced by covalently compositing with silica-nanoparticles. Soft Matter 8:6048–6056CrossRefGoogle Scholar
  4. 4.
    Gong JP, Katsuyama Y, Kurokawa T, Osada Y (2003) Double-network hydrogels with extremely high mechanical strength. Adv Mater 15:1155–1158CrossRefGoogle Scholar
  5. 5.
    Li XF, Wu C, Yang Q, Long SJ, Wu CG (2015) Low-velocity super-lubrication of sodium-alginate/polyacrylamide ionic-covalent hybrid double-network hydrogels. Soft Matter 11:3022–3033CrossRefGoogle Scholar
  6. 6.
    Okumura Y, Ito K (2001) The polyrotaxane gel: a topological gel by figure-of-eight cross-links. Adv Mater 13:485–487CrossRefGoogle Scholar
  7. 7.
    Malkoch M, Vestberg R, Gupta N, Mespouille L, Dubois P, Mason AF, Hedrick JL, Liao Q, Frank CW, Kingsbury K, Hawker CJ (2006) Synthesis of well-defined hydrogel networks using click chemistry. Chem Commun 26:2774–2776CrossRefGoogle Scholar
  8. 8.
    Sakai T, Matsunaga T, Yamamoto Y, Ito C, Yoshida R, Suzuki S, Sasaki N, Shibayama M, Chung U-I (2008) Design and fabrication of a high-strength hydrogel with ideally homogeneous network structure from tetrahedron-like macromonomers. Macromolecules 41:5379–5384CrossRefGoogle Scholar
  9. 9.
    Henderson KJ, Zhou TC, Otim KJ, Shull KR (2010) Ionically cross-linked triblock copolymer hydrogels with high strength. Macromolecules 43:6193–6201CrossRefGoogle Scholar
  10. 10.
    Zhong M, Liu Y-T, Xie X-M (2015) Self-healable, super tough graphene oxide–poly(acrylic acid) nanocomposite hydrogels facilitated by dual cross-linking effects through dynamic ionic interactions. J Mater Chem B 3:4001–4008CrossRefGoogle Scholar
  11. 11.
    Luo F, Sun TL, Nakajima T, Kurokawa T, Zhao Y, Sato K, Ihsan AB, Li X, Guo H, Gong JP (2015) Oppositely charged polyelectrolytes form tough, self-healing, and rebuildable hydrogels. Adv Mater 27:2722–2727CrossRefGoogle Scholar
  12. 12.
    Barrett DG, Fullenkamp DE, He L, Holten-Andersen N, Lee KYC, Messersmith PB (2013) pH-based regulation of hydrogel mechanical properties through mussel-inspired chemistry and processing. Adv Funct Mater 23:1111–1119CrossRefGoogle Scholar
  13. 13.
    Li C-H, Wang C, Keplinger C, Zuo J-L, Jin L, Sun Y, Zheng P, Cao Y, Lissel F, Linder C, You XZ, Bao Z (2016) A highly stretchable autonomous self-healing elastomer. Nat Chem 8:618–624CrossRefGoogle Scholar
  14. 14.
    Li WB, An HY, Tan Y, Lu CG, Liu C, Li PC, Xu K, Wang PX (2012) Hydrophobically associated hydrogels based on acrylamide and anionic surface active monomer with high mechanical strength. Soft Matter 8:5078–5086CrossRefGoogle Scholar
  15. 15.
    Jiang HY, Zhang GZ, Li FB, Zhang YQ, Lei Y, Xia YH, Jin XH, Feng XQ, Li HJ (2017) A self-healable and tough nanocomposite hydrogel cross-linked by novel ultrasmall aluminum hydroxide nanoparticles. Nanoscale 9:15470–15476CrossRefGoogle Scholar
  16. 16.
    Du ZS, Hu Y, Gu XY, Hu M, Wang CY (2016) Poly(acrylamide) microgel-reinforced poly(acrylamide)/hectorite nanocomposite hydrogels. Colloid Surf A 489:1–8CrossRefGoogle Scholar
  17. 17.
    Hu J, Hiwatashi K, Kurokawa T, Liang SM, Wu ZL, Gong JP (2011) Microgel-reinforced hydrogel films with high mechanical strength and their visible mesoscale fracture structure. Macromolecules 44:7775–7781CrossRefGoogle Scholar
  18. 18.
    Gong JP (2010) Why are double network hydrogels so tough? Soft Matter 6:2583–2590CrossRefGoogle Scholar
  19. 19.
    Tanaka Y, Gong JP, Osada Y (2005) Novel hydrogels with excellent mechanical performance. Prog Polym Sci 30:1–9CrossRefGoogle Scholar
  20. 20.
    Kurokawa T, Furukawa H, Wang W, Tanaka Y, Gong JP (2010) Formation of a strong hydrogel-porous solid interface via the double-network principle. Acta Biomater 6:1353–1359CrossRefGoogle Scholar
  21. 21.
    Brown HR (2007) A model of the fracture of double network gels. Macromolecules 40:3815–3818CrossRefGoogle Scholar
  22. 22.
    Tanaka YA (2007) local damage model for anomalous high toughness of double-network gels. Europhys Lett 78:56005CrossRefGoogle Scholar
  23. 23.
    Liang J, Shan GR, Pan PJ (2017) Double network hydrogels with highly enhanced toughness based on a modified first network. Soft Matter 13:4148–4158CrossRefGoogle Scholar
  24. 24.
    Nakajima T, Fukuda Y, Kurokawa T, Sakai T, Chung U-I, Gong JP (2013) Synthesis and fracture process analysis of double network hydrogels with a well-defined first network. ACS Macro Lett 2:518–521CrossRefGoogle Scholar
  25. 25.
    Kitiri EN, Patrickios CS, Voutouri C, Stylianopoulos T, Hoffmann I, Schweins R, Gradzielski M (2017) Double-networks based on pH-responsive, amphiphilic “core-first” star first polymer conetworks prepared by sequential RAFT polymerization. Polym Chem 8:245–259CrossRefGoogle Scholar
  26. 26.
    Rikkou-Kalourkoti M, Kitiri EN, Patrickios CS, Leontidis E, Constantinou M, Constantinides G, Zhang X, Papadakis CM (2016) Double networks based on amphiphilic cross-linked star block copolymer first conetworks and randomly cross-linked hydrophilic second networks. Macromolecules 49:1731–1742CrossRefGoogle Scholar
  27. 27.
    Zhang X, Kyriakos K, Rikkou-Kalourkoti M, Kitiri EN, Patrickios CS, Papadakis CM (2016) Amphiphilic single and double networks: a small-angle X-ray scattering investigation. Colloid Polym Sci 294:1027–1036CrossRefGoogle Scholar
  28. 28.
    Liu C, Tan Y, Xu K, Li YL, Lu CG, Wang PX (2014) Synthesis of poly(2-(2-methoxyethoxy)ethyl methacrylate) hydrogel using starch-based nanosphere cross-linkers. Carbohydr Polym 105:270–275CrossRefGoogle Scholar
  29. 29.
    Juliano BO, Perez CM, Blakeney AB, Castillo T, Kongseree N, Laignilet B, Lapis ET, Murty VVS, Paule CM, Webb BD (1981) International cooperative testing on the amylose content of milled rice. Starch 33:157–162CrossRefGoogle Scholar
  30. 30.
    Tan Y, Xu K, Li LL, Liu C, Song CL, Wang PX (2009) Fabrication of size-controlled starch-based nanospheres by nanoprecipitation. ACS Appl Mater Interfaces 1:956–959CrossRefGoogle Scholar
  31. 31.
    Tan Y, Wang PX, Xu K, Li WB, An HY, Li LL, Liu C, Dong LS (2009) Designing starch-based nanospheres to make hydrogel with high mechanical strength. Macromol Mater Eng 294:855–859Google Scholar
  32. 32.
    Gao GR, Du GL, Cheng YJ, Fu J (2014) Tough nanocomposite double network hydrogels reinforced with clay nanorods through covalent bonding and reversible chain adsorption. J Mater Chem B 2:1539–1548CrossRefGoogle Scholar
  33. 33.
    Kinloch AJ, Young RJ (1983) Fracture behaviour of polymers. Elsevier, LondonGoogle Scholar
  34. 34.
    Na Y-H, Tanaka Y, Kawauchi Y, Furukawa H, Sumiyoshi T, Gong JP, Osada Y (2006) Necking phenomenon of double-network gels. Macromolecules 39:4641–4645CrossRefGoogle Scholar
  35. 35.
    Es-haghi SS, Leonov AI, Weiss RA (2013) On the necking phenomenon in pseudo-semi-interpenetrating double-network hydrogels. Macromolecules 46:6203–6208CrossRefGoogle Scholar
  36. 36.
    Zhu MF, Liu Y, Sun B, Zhang W, Liu XL, Yu H, Zhang Y, Kuckling D, Adler HJP (2006) A novel highly resilient nanocomposite hydrogel with low hysteresis and ultrahigh elongation. Macromol Rapid Commun 27:1023–1028CrossRefGoogle Scholar

Copyright information

© Iran Polymer and Petrochemical Institute 2018

Authors and Affiliations

  • Chang Liu
    • 1
  • Ying Tan
    • 2
  • Kun Xu
    • 2
  • Mei Hua
    • 1
  • Xiao-Hui Huo
    • 1
  • Yin-Shi Sun
    • 1
    Email author
  1. 1.Institute of Special Animal and Plant ScienceChinese Academy of Agricultural SciencesChangchunPeople’s Republic of China
  2. 2.Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied ChemistryChinese Academy of ScienceChangchunPeople’s Republic of China

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