Science China Materials

, Volume 62, Issue 3, pp 437–447 | Cite as

Polyurethane networks based on disulfide bonds: from tunable multi-shape memory effects to simultaneous self-healing

  • Xiao-Ying Deng (邓小莹)
  • Hui Xie (谢辉)
  • Lan Du (杜澜)
  • Cheng-Jie Fan (范诚杰)
  • Chuan-Ying Cheng (成川颖)
  • Ke-Ke Yang (杨科珂)Email author
  • Yu-Zhong Wang (王玉忠)


With the prompt development in intellectualization nowadays, the smart materials with multi-functionality or multi-responsiveness are highly expected. But it is a big challenge to integrate the different actuating units into a single system in a synergy pattern. Herein, we put forward a new strategy to develop the polyurethane networks which can present shape-memory effect and self-healing effect in independent way as well as simultaneous acting mode. To realize this goal, poly(tetremethylene ether) glycol was chosen as the soft segment to ensure the polymer chains a good mobility, and disulfide bond as the dynamic covalent bond was embedded in the backbone of polyurethane to endow it with desirable self-healing capacity under mild condition. Moreover, a rational control of the architecture of the networks by adjusting the content of disulfide bond and the degree of cross-linking, a broad glass transition temperature (Tg) was achieved, which enabled the network a versatile shape-memory effect, covering from dual-, triple- so far as to quadruple-shape memory effect. More importantly, the shape recovery and healing process can be realized simultaneously because of the highly matched actuating condition in this system.


polyurethane network disulfide bond self-healing shape-memory 

基于二硫键的聚氨酯网络: 从可调多重形状记忆性能到同步修复


随着智能化时代的迅速发展, 具有多功能或多响应的智能材料受到高度关注. 但如何将多个智能单元以协同模式结合到单一系统中仍是研究者面临的巨大挑战. 本文设计合成了一种新型聚氨酯动态交联网络, 该材料能够以独立的方式和协同作用模式呈现形状记忆效应和自修复效应. 为了实现这一目标, 本文选择了聚四氢呋喃作为软链段以确保聚合物链具有良好的运动性, 同时将动态共价键二硫键引入聚氨酯的主链中以实现材料在温和条件下的自修复. 此外, 通过有效调节二硫键含量、 交联度和网络结构, 获得了较宽的玻璃化转变温度(Tg), 使网络具有两重、 三重甚至四重形状的记忆效应. 在此基础上, 利用该材料的形状回复和修复的外界刺激条件的高度吻合, 同时实现了材料修复和回复, 拓宽了材料的应用范围.



This work was supported financially by the National Natural Science Foundation of China (51773131 and 51721091), and the International S&T Cooperation Project of Sichuan Province (2017HH0034).

Supplementary material

40843_2018_9318_MOESM1_ESM.pdf (862 kb)
Polyurethane Networks Based On Dissulfide Bonds: Form Tunable Multi-Shape-Memory Effects Ti Simultaneous Self-Healing


  1. 1.
    Lendlein A, Kelch S. Shape-memory polymers. Angew Chem Int Ed, 2002, 41: 2034–2057Google Scholar
  2. 2.
    Behl M, Lendlein A. Shape-memory polymers. Mater Today, 2007, 10: 20–28Google Scholar
  3. 3.
    Lendlein A, Langer R. Biodegradable, elastic shape-memory polymers for potential biomedical applications. Science, 2002, 296: 1673–1676Google Scholar
  4. 4.
    Huang WM, Song CL, Fu YQ, et al. Shaping tissue with shape memory materials. Adv Drug Deliver Rev, 2013, 65: 515–535Google Scholar
  5. 5.
    Pilate F, Toncheva A, Dubois P, et al. Shape-memory polymers for multiple applications in the materials world. Eur Polymer J, 2016, 80: 268–294Google Scholar
  6. 6.
    Sun L, Huang WM, Wang CC, et al. Polymeric shape memory materials and actuators. Liquid Crysts, 2013, 41: 277–289Google Scholar
  7. 7.
    Behl M, Razzaq MY, Lendlein A. Multifunctional shape-memory polymers. Adv Mater, 2010, 22: 3388–3410Google Scholar
  8. 8.
    Yang Y, Urban MW. Self-healing polymeric materials. Chem Soc Rev, 2013, 42: 7446–7467Google Scholar
  9. 9.
    Wool RP. Self-healing materials: a review. Soft Matter, 2008, 4: 400Google Scholar
  10. 10.
    Wu DY, Meure S, Solomon D. Self-healing polymeric materials: a review of recent developments. Prog Polymer Sci, 2008, 33: 479–522Google Scholar
  11. 11.
    Mauldin TC, Kessler MR. Self-healing polymers and composites. Int Mater Rev, 2013, 55: 317–346Google Scholar
  12. 12.
    Syrett JA, Becer CR, Haddleton DM. Self-healing and self-mendable polymers. Polym Chem, 2010, 1: 978–987Google Scholar
  13. 13.
    Jia R, Li L, Ai Y, et al. Self-healable wire-shaped supercapacitors with two twisted NiCo2O4 coated polyvinyl alcohol hydrogel fibers. Sci China Mater, 2018, 61: 254–262Google Scholar
  14. 14.
    Boyer C, Hoogenboom R. Multi-responsive polymers. Eur Polymer J, 2015, 69: 438–440Google Scholar
  15. 15.
    Xie T. Recent advances in polymer shape memory. Polymer, 2011, 52: 4985–5000Google Scholar
  16. 16.
    Zhan MQ, Yang KK, Wang YZ. Shape-memory poly(p-dioxanone)–poly(-caprolactone)/sepiolite nanocomposites with enhanced recovery stress. Chin Chem Lett, 2015, 26: 1221–1224Google Scholar
  17. 17.
    Miaudet P, Derré A, Maugey M, et al. Shape and temperature memory of nanocomposites with broadened glass transition. Science, 2007, 318: 1294–1296Google Scholar
  18. 18.
    Xie T. Tunable polymer multi-shape memory effect. Nature, 2010, 464: 267–270Google Scholar
  19. 19.
    Luo Y, Guo Y, Gao X, et al. A general approach towards thermoplastic multishape-memory polymers via sequence structure design. Adv Mater, 2013, 25: 743–748Google Scholar
  20. 20.
    Wen Z, Zhang T, Hui Y, et al. Elaborate fabrication of well-defined side-chain liquid crystalline polyurethane networks with triple-shape memory capacity. J Mater Chem A, 2015, 3: 13435–13444Google Scholar
  21. 21.
    Cui J, del Campo A. Multivalent H-bonds for self-healing hydrogels. Chem Commun, 2012, 48: 9302–9304Google Scholar
  22. 22.
    Wei M, Zhan M, Yu D, et al. Novel poly(tetramethylene ether) glycol and poly(ε-caprolactone) based dynamic network via quadruple hydrogen bonding with triple-shape effect and self-healing capacity. ACS Appl Mater Interfaces, 2015, 7: 2585–2596Google Scholar
  23. 23.
    Zhu D, Ye Q, Lu X, et al. Self-healing polymers with PEG oligomer side chains based on multiple H-bonding and adhesion properties. Polym Chem, 2015, 6: 5086–5092Google Scholar
  24. 24.
    Hui Y, Wen ZB, Pilate F, et al. A facile strategy to fabricate highlystretchable self-healing poly(vinyl alcohol) hybrid hydrogels based on metal–ligand interactions and hydrogen bonding. Polym Chem, 2016, 7: 7269–7277Google Scholar
  25. 25.
    Burattini S, Colquhoun HM, Fox JD, et al. A self-repairing, supramolecular polymer system: healability as a consequence of donor–acceptor π–π stacking interactions. Chem Commun, 2009, 319: 6717–6719Google Scholar
  26. 26.
    Zhong HY, Chen L, Ding XM, et al. Physio-and chemo-dual crosslinking toward thermoand photo-response of azobenzene-containing liquid crystalline polyester. Sci China Mater, 2018, 61: 1225–1236Google Scholar
  27. 27.
    Kakuta T, Takashima Y, Nakahata M, et al. Preorganized hydrogel: self-healing properties of supramolecular hydrogels formed by polymerization of host-guest-monomers that contain cyclodextrins and hydrophobic guest groups. Adv Mater, 2013, 25: 2849–2853Google Scholar
  28. 28.
    Zhang M, Xu D, Yan X, et al. Self-healing supramolecular gels formed by crown ether based host-guest interactions. Angew Chem Int Ed, 2012, 51: 7011–7015Google Scholar
  29. 29.
    Chen X, Dam MA, Ono K, et al. A thermally re-mendable cross-linked polymeric material. Science, 2002, 295: 1698–1702Google Scholar
  30. 30.
    Li QT, Jiang MJ, Wu G, et al. Photothermal conversion triggered precisely targeted healing of epoxy resin based on thermoreversible Diels–Alder network and amino-functionalized carbon nanotubes. ACS Appl Mater Interfaces, 2017, 9: 20797–20807Google Scholar
  31. 31.
    Zhang J, Niu Y, Huang C, et al. Self-healable and recyclable triple-shape PPDO–PTMEG co-network constructed through thermoreversible Diels–Alder reaction. Polym Chem, 2012, 3: 1390–1393Google Scholar
  32. 32.
    Canadell J, Goossens H, Klumperman B. Self-healing materials based on disulfide links. Macromolecules, 2011, 44: 2536–2541Google Scholar
  33. 33.
    Lafont U, van Zeijl H, van der Zwaag S. Influence of cross-linkers on the cohesive and adhesive self-healing ability of polysulfide-based thermosets. ACS Appl Mater Interfaces, 2012, 4: 6280–6288Google Scholar
  34. 34.
    Yang WJ, Tao X, Zhao T, et al. Antifouling and antibacterial hydrogel coatings with self-healing properties based on a dynamic disulfide exchange reaction. Polym Chem, 2015, 6: 7027–7035Google Scholar
  35. 35.
    An SY, Noh SM, Nam JH, et al. Dual sulfide-disulfide cross-linked networks with rapid and room temperature self-healability. Macromol Rapid Commun, 2015, 36: 1255–1260Google Scholar
  36. 36.
    Xu Y, Chen D. A novel self-healing polyurethane based on disulfide bonds. Macromol Chem Phys, 2016, 217: 1191–1196Google Scholar
  37. 37.
    Kim SM, Jeon H, Shin SH, et al. Superior toughness and fast self-healing at room temperature engineered by transparent elastomers. Adv Mater, 2018, 30: 1705145–1705152Google Scholar
  38. 38.
    Rekondo A, Martin R, Ruiz de Luzuriaga A, et al. Catalyst-free room-temperature self-healing elastomers based on aromatic disulfide metathesis. Mater Horiz, 2014, 1: 237–240Google Scholar
  39. 39.
    Deng G, Tang C, Li F, et al. Covalent cross-linked polymer gels with reversible sol−gel transition and self-healing properties. Macromolecules, 2010, 43: 1191–1194Google Scholar
  40. 40.
    Liu F, Li F, Deng G, et al. Rheological images of dynamic covalent polymer networks and mechanisms behind mechanical and self-healing properties. Macromolecules, 2012, 45: 1636–1645Google Scholar
  41. 41.
    Roberts MC, Hanson MC, Massey AP, et al. Dynamically restructuring hydrogel networks formed with reversible covalent cross-links. Adv Mater, 2007, 19: 2503–2507Google Scholar
  42. 42.
    He L, Fullenkamp DE, Rivera JG, et al. pH responsive self-healing hydrogels formed by boronate–catechol complexation. Chem Commun, 2011, 47: 7497–7499Google Scholar
  43. 43.
    Zhang Y, Yang B, Zhang X, et al. A magnetic self-healing hydrogel. Chem Commun, 2012, 48: 9305–9307Google Scholar
  44. 44.
    Zhang Y, Tao L, Li S, et al. Synthesis of multiresponsive and dynamic chitosan-based hydrogels for controlled release of bioactive molecules. Biomacromolecules, 2011, 12: 2894–2901Google Scholar
  45. 45.
    Rodriguez ED, Ounaies Z, Luo XF, Mather PT. Shape memory miscible blends for thermal mending. Proc of SPIE, 2009, 7289: 728912Google Scholar
  46. 46.
    Luo X, Mather PT. Shape memory assisted self-healing coating. ACS Macro Lett, 2013, 2: 152–156Google Scholar
  47. 47.
    Rodriguez ED, Luo X, Mather PT. Linear/network poly(ε-caprolactone) blends exhibiting shape memory assisted self-healing (SMASH). ACS Appl Mater Interfaces, 2011, 3: 152–161Google Scholar
  48. 48.
    Du L, Xu ZY, Fan CJ, et al. A fascinating metallo-supramolecular polymer network with thermal/magnetic/light-responsive shape-memory effects anchored by Fe3O4 nanoparticles. Macromolecules, 2018, 51: 705–715Google Scholar

Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Xiao-Ying Deng (邓小莹)
    • 1
  • Hui Xie (谢辉)
    • 1
  • Lan Du (杜澜)
    • 1
  • Cheng-Jie Fan (范诚杰)
    • 1
  • Chuan-Ying Cheng (成川颖)
    • 1
  • Ke-Ke Yang (杨科珂)
    • 1
    Email author
  • Yu-Zhong Wang (王玉忠)
    • 1
  1. 1.Center for Degradable and Flame-Retardant Polymeric Materials (ERCEPM-MoE), College of Chemistry, National Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan), State Key Laboratory of Polymer Materials EngineeringSichuan UniversityChengduChina

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