Cyclodextrins-Based Shape Memory Polymers and Self-Healing Polymers

Living reference work entry


Shape memory polymers (SMPs) and self-healing polymers (SHPs) are two representative examples of biomimetic smart materials. SMPs have the ability to change from one or more temporary shapes to a predetermined shape in response to external stimulus. SHPs can repair cracks or fracture by themselves after being damaged. When introducing CDs-guest interactions that have been featured as dynamic and reversible into the design of novel SMPs and SHPs, intriguing and unique functionalities have been engendered and thereby broaden their potential applications. In this chapter, we summarize recent progress made in SMPs and SHPs based on CDs-guest interactions, provide insight into their design and mechanism, elucidate and evaluate their properties and performance, and point out possible future developments.


  1. 1.
    Serrano MC, Ameer GA (2012) Recent insights into the biomedical applications of shape-memory polymers. Macromol Biosci 12:1156–1171PubMedCrossRefPubMedCentralGoogle Scholar
  2. 2.
    Mather PT, Luo XF, Rousseau IA (2009) Shape memory polymer research. Annu Rev Mater Res 39:445–471CrossRefGoogle Scholar
  3. 3.
    Leng J, Lan X, Liu Y, Du S (2011) Shape-memory polymers and their composites: stimulus methods and applications. Prog Mater Sci 56:1077–1135CrossRefGoogle Scholar
  4. 4.
    Davies DJ, Vaccaro AR, Morris SM, Herzer N, Schenning AP, Bastiaansen CW (2013) A printable optical time-temperature integrator based on shape memory in a chiral nematic polymer network. Adv Funct Mater 23:2723–2727CrossRefGoogle Scholar
  5. 5.
    Behl M, Razzaq MY, Lendlein A (2010) Multifunctional shape-memory polymers. Adv Mater 22:3388–3410PubMedCrossRefPubMedCentralGoogle Scholar
  6. 6.
    Wang L, Yang X, Chen H, Yang G, Gong T, Li W, Zhou S (2013) Multi-stimuli sensitive shape memory poly (vinyl alcohol)-graft-polyurethane. Polym Chem 4:4461–4468CrossRefGoogle Scholar
  7. 7.
    Luo Y, Guo Y, Gao X, Li BG, Xie T (2013) A general approach towards thermoplastic multishape-memory polymers via sequence structure design. Adv Mater 25:743–748PubMedCrossRefPubMedCentralGoogle Scholar
  8. 8.
    Calvo-Correas T, Santamaria-Echart A, Saralegi A, Martin L, Valea Á, Corcuera MA, Eceiza A (2015) Thermally-responsive biopolyurethanes from a biobased diisocyanate. Eur Polym J 70:173–185CrossRefGoogle Scholar
  9. 9.
    Lendlein A, Kelch S (2002) Shape-memory polymers. Angew Chem Int Ed 41:2034–2057CrossRefGoogle Scholar
  10. 10.
    He Z, Satarkar N, Xie T, Cheng YT, Hilt JZ (2011) Remote controlled multishape polymer nanocomposites with selective radiofrequency actuations. Adv Mater 23:3192–3196PubMedCrossRefPubMedCentralGoogle Scholar
  11. 11.
    Agarwal P, Chopra M, Archer LA (2011) Nanoparticle netpoints for shape-memory polymers. Angew Chem Int Ed 50:8670–8673CrossRefGoogle Scholar
  12. 12.
    Rousseau IA (2008) Challenges of shape memory polymers: a review of the progress toward overcoming SMP’s limitations. Polym Eng Sci 48:2075–2089CrossRefGoogle Scholar
  13. 13.
    Harada A, Hashidzume A, Yamaguchi H, Takashima Y (2009) Polymeric rotaxanes. Chem Rev 109:5974–6023PubMedCrossRefPubMedCentralGoogle Scholar
  14. 14.
    Li J, Ni X, Zhou Z, Leong KW (2003) Preparation and characterization of polypseudorotaxanes based on block-selected inclusion complexation between poly (propylene oxide)-poly (ethylene oxide)-poly (propylene oxide) triblock copolymers and α-cyclodextrin. J Am Chem Soc 125:1788–1795PubMedCrossRefPubMedCentralGoogle Scholar
  15. 15.
    Zhang S, Yu ZJ, Govender T, Luo H, Li BJ (2008) A novel supramolecular shape memory material based on partial α-CD–PEG inclusion complex. Polymer 49:3205–3210CrossRefGoogle Scholar
  16. 16.
    Luo H, Fan M, Yu ZJ, Meng X, Li BJ, Zhang S (2009) Preparation and properties of degradable shape memory material based on partial α-Cyclodextrin–poly (ε-caprolactone) inclusion complex. Macromol Chem Phys 210:669–676CrossRefGoogle Scholar
  17. 17.
    Luo H, Liu Y, Yu ZJ, Zhang S, Li BJ (2008) Novel biodegradable shape memory material based on partial inclusion complex formation between α-Cyclodextrin and poly (ϵ-caprolactone). Biomacromolecules 9:2573–2577PubMedCrossRefPubMedCentralGoogle Scholar
  18. 18.
    Fan MM, Yu ZJ, Luo HY, Zhang S, Li BJ (2009) Supramolecular network based on the self-assembly of γ-Cyclodextrin with poly (ethylene glycol) and its shape memory effect. Macromol Rapid Commun 30:897–903PubMedCrossRefPubMedCentralGoogle Scholar
  19. 19.
    Yasin A, Zhou W, Yang H, Li H, Chen Y, Zhang X (2015) Shape memory hydrogel based on a hydrophobically-modified polyacrylamide (HMPAM)/α-CD mixture via a host-guest approach. Macromol Rapid Commun 36:845–851PubMedCrossRefPubMedCentralGoogle Scholar
  20. 20.
    Xiao YY, Gong XL, Kang Y, Jiang ZC, Zhang S, Li BJ (2016) Light-, pH-and thermal-responsive hydrogels with the triple-shape memory effect. Chem Commun 52:10609–10612CrossRefGoogle Scholar
  21. 21.
    Harada A, Takashima Y, Nakahata M (2014) Supramolecular polymeric materials via cyclodextrin–guest interactions. Acc Chem Res 47:2128–2140PubMedCrossRefPubMedCentralGoogle Scholar
  22. 22.
    Han XJ, Dong ZQ, Fan MM, Liu Y, li JH, Wang YF, Yuan QJ, Li BJ, Zhang S (2012) pH-induced shape-memory polymers. Macromol Rapid Commun 33:1055–1060PubMedCrossRefPubMedCentralGoogle Scholar
  23. 23.
    Dong ZQ, Cao Y, Yuan QJ, Wang YF, Li JH, Li BJ, Zhang S (2013) Redox-and glucose-induced shape-memory polymers. Macromol Rapid Commun 34:867–872PubMedCrossRefPubMedCentralGoogle Scholar
  24. 24.
    Pan M, Yuan QJ, Gong XL, Zhang S, Li BJ (2016) A tri-stimuli-responsive shape-memory material using host–guest interactions as molecular switches. Macromol Rapid Commun 37:433–438PubMedCrossRefPubMedCentralGoogle Scholar
  25. 25.
    Peters O, Ritter H (2013) Supramolecular controlled water uptake of macroscopic materials by a Cyclodextrin-induced hydrophobic-to-hydrophilic transition. Angew Chem Int Ed 52:8961–8963CrossRefGoogle Scholar
  26. 26.
    Yuan C, Guo J, Yan F (2014) Shape memory poly (ionic liquid) gels controlled by host–guest interaction with β-cyclodextrin. Polymer 55:3431–3435CrossRefGoogle Scholar
  27. 27.
    Kretschmann O, Steffens C, Ritter H (2007) Cyclodextrin complexes of polymers bearing adamantyl groups: host–guest interactions and the effect of spacers on water solubility. Angew Chem Int Ed 46:2708–2711CrossRefGoogle Scholar
  28. 28.
    Nakahata M, Takashima Y, Yamaguchi H, Harada A (2011) Redox-responsive self-healing materials formed from host–guest polymers. Nat Commun 2:511–516PubMedPubMedCentralCrossRefGoogle Scholar
  29. 29.
    Kakuta T, Takashima Y, Nakahata M, Otsubo M, Yamaguchi H, Harada A (2013) Preorganized hydrogel: self-healing properties of supramolecular hydrogels formed by polymerization of host–guest-monomers that contain cyclodextrins and hydrophobic guest groups. Adv Mater 25:2849–2853PubMedCrossRefPubMedCentralGoogle Scholar
  30. 30.
    Rodell CB, Highley CB, Chen MH, Dusaj NN, Wang C, Han L, Burdick JA (2016) Evolution of hierarchical porous structures in supramolecular guest–host hydrogels. Soft Matter 12:7839–7847PubMedPubMedCentralCrossRefGoogle Scholar
  31. 31.
    Jia YG, Zhu XX (2014) Self-healing supramolecular hydrogel made of polymers bearing cholic acid and β-cyclodextrin pendants. Chem Mater 27:387–393CrossRefGoogle Scholar
  32. 32.
    Rodell CB, Kaminske AL, Burdick A (2013) Rational design of network properties in guest-host assembled and shear-thinning hyaluronic acid hydrogel. Biomacromolecules 14:4125–4134PubMedCrossRefPubMedCentralGoogle Scholar
  33. 33.
    Li G, Wu J, Wang B, Yan S, Zhang K, Ding J, Yin J (2015) Self-healing supramolecular self-assembled hydrogels based on poly(L-glutamic acid). Biomacromolecules 16:3508–3518PubMedCrossRefPubMedCentralGoogle Scholar
  34. 34.
    Takashima Y, Yonekura K, Koyanagi K, Iwaso K, Nakahata M, Yamaguchi H, Harada A (2017) Multifunctional stimuli-responsive supramolecular materials with stretching, coloring, and self-healing properties functionalized via host–guest interactions. Macromolecules 50:4144–4150CrossRefGoogle Scholar
  35. 35.
    Zhang H, Zhang X, Bao C, Li X, Sun D, Duan F, Yang J (2018) Direct microencapsulation of pure polyamine by integrating microfluidic emulsion and interfacial polymerization for practical self-healing materials. J Mater Chem A 6:24092–24099CrossRefGoogle Scholar
  36. 36.
    Kang J, Son D, Wang GJN, Liu Y, Lopez J, Kim Y, Jin L (2018) Tough and water-insensitive self-healing elastomer for robust electronic skin. Adv Mater 30:1706846CrossRefGoogle Scholar
  37. 37.
    Chandler DL (2018) Biomedical materials learn to heal themselves: self-healing polymers, hydrogels, and artificial muscles are mimicking Nature’s repair mechanisms. IEEE Pulse 9:10–14PubMedCrossRefGoogle Scholar
  38. 38.
    Xu T, Chu M, Wu Y, Liu J, Chi B, Xu H, Mao C (2018) Safer cables based on advanced materials with a self-healing technique that can be directly powered off and restored easily at any time. New J Chem 42:4803–4806CrossRefGoogle Scholar
  39. 39.
    Suleiman AR, Nehdi ML (2018) Effect of environmental exposure on autogenous self-healing of cracked cement-based materials. Cem Concr Res 111:197–208CrossRefGoogle Scholar
  40. 40.
    Zhang DL, Ju X, Li LH, Kang Y, Gong XL, Li BJ, Zhang S (2015) An efficient multiple healing conductive composite via host–guest inclusion. Chem Commun 51:6377–6380CrossRefGoogle Scholar
  41. 41.
    Guo K, Zhang DL, Zhang XM, Zhang J, Ding LS, Li BJ, Zhang S (2015) Conductive elastomers with autonomic self-healing properties. Angew Chem Int Ed 54:12127–12133CrossRefGoogle Scholar
  42. 42.
    Wang YM, Pan M, Liang XY, Li BJ, Zhang S (2017) Electromagnetic wave absorption coating material with self-healing properties. Macromol Rapid Commun 38:1700447CrossRefGoogle Scholar
  43. 43.
    Liang XY, Wang L, Wang YM, Ding LS, Li BJ, Zhang S (2017) UV-blocking coating with self-healing capacity. Macromol Chem Phys 218:1700213CrossRefGoogle Scholar
  44. 44.
    Liang XY, Wang L, Chang ZY, Ding LS, Li BJ, Zhang S (2017) Reusable xergel containg quantum dots with high fluorescence retention. Polymers 10:310–315CrossRefGoogle Scholar
  45. 45.
    Guo K, Lin MS, Feng JF, Pan M, Ding LS, Li BJ, Zhang S (2017) The deeply understanding of the self-healing mechanism for self-healing behavior of supramolecular materials based on Cyclodextrin–guest interactions. Macromol Chem Phys 218:1600593CrossRefGoogle Scholar
  46. 46.
    Kirkby EL, Rule JD, Michaud VJ, Sottos NR, White SR, Månson JAE (2008) Embedded shape-memory alloy wires for improved performance of self-healing polymers. Adv Funct Mater 18:2253–2260CrossRefGoogle Scholar
  47. 47.
    Li G, Shojaei A (2012) A viscoplastic theory of shape memory polymer fibres with application to self-healing materials. Proc R Soc A 468:2319–2346CrossRefGoogle Scholar
  48. 48.
    Meng H, Xiao P, Gu J, Wen X, Xu J, Zhao C, Chen T (2014) Self-healable macro−/microscopic shape memory hydrogels based on supramolecular interactions. Chem Commun 50:12277–12280CrossRefGoogle Scholar
  49. 49.
    Miyamae K, Nakahata M, Takashima Y, Harada A (2015) Self-healing, expansion–contraction, and shape-memory properties of a preorganized supramolecular hydrogel through host–guest interactions. Angew Chem Int Ed 54:8984–8987CrossRefGoogle Scholar
  50. 50.
    Li G, Zhang H, Fortin D, Xia H, Zhao Y (2015) Poly (vinyl alcohol)–poly (ethylene glycol) double-network hydrogel: a general approach to shape memory and self-healing functionalities. Langmuir 31:11709–11716PubMedCrossRefPubMedCentralGoogle Scholar
  51. 51.
    Jiang ZC, Xiao YY, Kang Y, Li BJ, Zhang S (2017) Semi-IPNs with moisture-triggered shape memory and self-healing properties. Macromol Rapid Commun 38:1700149CrossRefGoogle Scholar
  52. 52.
    Kuang Q, Lao C, Wang ZL, Xie Z, Zheng L (2007) High-sensitivity humidity sensor based on a single SnO2 nanowire. J Am Chem Soc 129:6070–6071PubMedCrossRefPubMedCentralGoogle Scholar

Authors and Affiliations

  1. 1.Sichuan UniversityChengduChina
  2. 2.Chengdu Institute of Biology, Chinese Academy of SciencesChengduChina

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