Journal of Materials Science

, Volume 53, Issue 15, pp 10798–10811 | Cite as

Preparation and mechanism of shape memory bismaleimide resins with high transition temperature, high toughness and good processability

  • Banghui Chen
  • Li Yuan
  • Qingbao Guan
  • Guozheng LiangEmail author
  • Aijuan GuEmail author
Chemical routes to materials


Developing shape memory polymers (SMPs) with high transition temperature (Ttrans), good toughness and good processability (low molding temperature and solvent-free) is still a great challenge. Herein, a new type of thermosetting shape memory resin (BDPH) is developed based on bismaleimide resin (BD), cardo-polyetherketone (PEK-C) and multi-maleimide-terminated branched polysiloxane (HSi). The effect and mechanism of the compositions on structure and key properties (heat resistance, toughness and shape memory effect) of resins were systematically investigated. Results show that BDPH system has outstanding integrated properties. Specifically, for the resin with optimal composition (BDPH10), its Ttrans is as high as 292 °C, about 30 °C higher than that of thermosetting SMPs (TS-SMPs) reported so far; meanwhile, the maximum curing temperature of BDPH10 is about 40 °C lower than those of TS-SMPs of which Ttrans values are higher than 270 °C. The shape fixed rate and shape recovery rate of BDPH10 are 97.5 and 98.7%, respectively; besides, BDPH10 has high toughness, its impact strength is 21.8 kJ m−2, about two times of that of BD resin, overcoming the drawback of traditional thermosetting SMPs. The mechanism behind those attractive performances of BDPH is proved to be attributed to the effects derived from PEK-C and HSi.



We thank the National Natural Science Foundation of China (51473107), the Priority Academic Program Development of the Jiangsu Higher Education Institution (PAPD) financially supporting this project.

Supplementary material

Supplementary material 1 (MPG 6089 kb)

10853_2018_2367_MOESM2_ESM.docx (471 kb)
Supplementary material 2 (DOCX 471 kb)


  1. 1.
    Abishera R, Velmurugan R, Gopal KVN (2017) Reversible plasticity shape memory effect in epoxy/CNT nanocomposites—a theoretical study. Compos Sci Technol 141:145–153CrossRefGoogle Scholar
  2. 2.
    Zamani Alavijeh R, Shokrollahi P, Barzin J (2017) A thermally and water activated shape memory gelatin physical hydrogel, with a gel point above the physiological temperature, for biomedical applications. J Mater Chem B 5:2302–2314CrossRefGoogle Scholar
  3. 3.
    Xiao XL, Hu JL, Gui XT, Qian K (2017) Shape memory investigation of α-keratin fibers as multi-coupled stimuli of responsive smart materials. Polymers 9(3):87CrossRefGoogle Scholar
  4. 4.
    Wu Y, Hu J, Zhang C, Han J, Wang Y, Kumar B (2015) A facile approach to fabricate a UV/heat dual-responsive triple shape memory polymer. J Mater Chem A 3:97–100CrossRefGoogle Scholar
  5. 5.
    Belmonte A, Fernández-Francos X, De la Flor S (2016) New understanding of the shape-memory response in thiol-epoxy click systems: towards controlling the recovery process. J Mater Sci 52:1625–1638. CrossRefGoogle Scholar
  6. 6.
    Fang Y, Leo SY, Ni YL et al (2017) Reconfigurable photonic crystals enabled by multistimuli-responsive shape memory polymers possessing room temperature shape processability. ACS Appl Mater Interfaces 9:5457–5467CrossRefGoogle Scholar
  7. 7.
    Kahn JS, Hu Y, Willner I (2017) Stimuli-responsive DNA-based hydrogels: from basic principles to applications. Acc Chem Res 50:680–690CrossRefGoogle Scholar
  8. 8.
    Liu YY, Zhao J, Zhao LY, Li WW, Zhang H, Yu X, Zhang Z (2016) High performance shape memory epoxy/carbon nanotube nanocomposites. ACS Appl Mater Interfaces 8:311–320CrossRefGoogle Scholar
  9. 9.
    Boothby JM, Kim H, Ware TH (2017) Shape changes in chemoresponsive liquid crystal elastomers. Sens Actuatators B 240:511–518CrossRefGoogle Scholar
  10. 10.
    Turan D, Sängerlaub S, Stramm C, Gunes G (2017) Gas permeabilities of polyurethane films for fresh produce packaging: response of O2 permeability to temperature and relative humidity. Polym Test 59:237–244CrossRefGoogle Scholar
  11. 11.
    Hu JL, Zhu Y, Huang HH, Lu J (2012) Recent advances in shape-memory polymers: structure, mechanism, functionality, modeling and applications. Prog Polym Sci 37:1720–1763CrossRefGoogle Scholar
  12. 12.
    Hearon K, Singhal P, Horn J et al (2013) Porous shape-memory polymers. Polym Rev 53:41–75CrossRefGoogle Scholar
  13. 13.
    Xiao XL, Kong DY, Qiu XY et al (2015) Shape-memory polymers with adjustable high glass transition temperatures. Macromolecules 48:3582–3589CrossRefGoogle Scholar
  14. 14.
    Yang ZH, Chen Y, Wang QH, Wang TM (2016) High performance multiple-shape memory behaviors of poly(benzoxazole-co-imide)s. Polymer 88:19–28CrossRefGoogle Scholar
  15. 15.
    Xie F, Huang LN, Liu YJ, Leng JS (2014) Synthesis and characterization of high temperature cyanate-based shape memory polymers with functional polybutadiene/acrylonitrile. Polymer 55:5873–5879CrossRefGoogle Scholar
  16. 16.
    Shi Y, Weiss RA (2014) Sulfonated poly(ether ether ketone) ionomers and their high temperature shape memory behavior. Macromolecules 47:1732–1740CrossRefGoogle Scholar
  17. 17.
    Biju R, Nair CPR (2013) High transition temperature shape memory polymer composites based on bismaleimide resin. High Perform Polym 25:464–474CrossRefGoogle Scholar
  18. 18.
    Santiago D, Fabregat-Sanjuan A, Ferrando F, De la Flor S (2017) Hyperbranched-modified epoxy thermosets: enhancement of thermomechanical and shape-memory performances. J Appl Polym Sci 134:44623CrossRefGoogle Scholar
  19. 19.
    Zhang QW, Wei HQ, Liu YY, Leng JS, Du SY (2016) Triple-shape memory effects of bismaleimide based thermosetting polymer networks prepared via heterogeneous crosslinking structures. RSC Adv 6:10233–10241CrossRefGoogle Scholar
  20. 20.
    Yang ZH, Song FZ, Wang QH, Wang TM (2016) Shape memory induced structural evolution of high performance copolyimides. J Polym Sci Part A Polym Chem 54:3858–3867CrossRefGoogle Scholar
  21. 21.
    Yang ZH, Wang QH, Bai YK, Wang TM (2015) AO-resistant shape memory polyimide/silica composites with excellent thermal stability and mechanical properties. RSC Adv 5:72971–72980CrossRefGoogle Scholar
  22. 22.
    Kong DY, Xiao XL (2016) High cycle-life shape memory polymer at high temperature. Sci Rep 6:33610CrossRefGoogle Scholar
  23. 23.
    Shi Y, Yoonessi M, Weiss RA (2013) High temperature shape memory polymers. Macromolecules 46:4160–4167CrossRefGoogle Scholar
  24. 24.
    Chandra R, Rajabi L (1997) Recent advances in bismaleimides and epoxy-lmide/bismaleimide formulations and composites. J Macromol Sci Part C 37:61–96CrossRefGoogle Scholar
  25. 25.
    Nair CPR, Mathew D, Ninan KN (2001) Cyanate ester resins, recent developments. Adv Polym Sci 155:1–99CrossRefGoogle Scholar
  26. 26.
    Takeichi T, Kawauchi T, Agag T (2008) High performance polybenzoxazines as a novel type of phenolic resin. Polym J 40:1121–1131CrossRefGoogle Scholar
  27. 27.
    Wang YK, Tian WC, Liu XH, Ye JJ (2017) Thermal sensitive shape memory behavior of epoxy composites reinforced with silicon carbide whiskers. Appl Sci 7:108CrossRefGoogle Scholar
  28. 28.
    Kumar KSS, Biju R, Nair CPR (2013) Progress in shape memory epoxy resins. React Funct Polym 73:421–430CrossRefGoogle Scholar
  29. 29.
    Jing XH, Liu YY, Liu YX, Liu ZG, Tan HF (2014) Toughening-modified epoxy-amine system: cure kinetics, mechanical behavior, and shape memory performances. J Appl Polym Sci 131:40853Google Scholar
  30. 30.
    Biju R, Gouri C, Nair CPR (2012) Shape memory polymers based on cyanate ester-epoxy-poly(tetramethyleneoxide) co-reacted system. Eur Polym J 48:499–511CrossRefGoogle Scholar
  31. 31.
    Jing XH, Liu YX, Liao R, Kang HJ, Tan HF, Liu YY (2016) Synthesis, characterization, and shape-memory performances of monoamine-toughened epoxy resin. High Perform Polym 28:1082–1089CrossRefGoogle Scholar
  32. 32.
    Jiang ZJ, Yuan L, Liang GZ, Gu AJ (2015) Unique liquid multi-maleimide terminated branched polysiloxane and its flame retarding bismaleimide resin with outstanding thermal and mechanical properties. Polym Degrad Stab 121:30–41CrossRefGoogle Scholar
  33. 33.
    Hong X, Jean YC, Yang HJ, Jordan SS, Koros WJ (1996) Free-volume hole properties of gas-exposed polycarbonate studied by positron annihilation lifetime spectroscopy. Macromolecules 29:7859–7864CrossRefGoogle Scholar
  34. 34.
    Dong YB, Ni QQ (2015) Effect of vapor-grown carbon nanofibers and in situ hydrolyzed silica on the mechanical and shape memory properties of water-borne epoxy composites. Polym Compos 36:1712–1720CrossRefGoogle Scholar
  35. 35.
    Chen YF, Dai QW, Zhang XW, Feng T (2014) Microstructure and properties of SCE-Al2O3/PES-MBAE composite. J Nanomater 2014:356273Google Scholar
  36. 36.
    Phelan JC, Sung CSP (1997) Cure characterization in bis(maleimide)/diallylbisphenol a resin by fluorescence, FT-IR, and UV-reflection spectroscopy. Macromolecules 30:6845–6851CrossRefGoogle Scholar
  37. 37.
    Shibata M, Teramoto N, Shimasaki T, Ogihara M (2011) High-performance bio-based bismaleimide resins using succinic acid and eugenol. Polym J 43:916–922CrossRefGoogle Scholar
  38. 38.
    Hu X, Meng JR (2005) Effect of organoclay on the curing reactions in bismaleimide/diallyl bisphenol a resin. J Polym Sci Part A Polym Chem 43:994–1006CrossRefGoogle Scholar
  39. 39.
    Zhao L, Yuan L, Liang GZ, Gu AJ (2015) Novel tough and thermally stable cyanate ester resins with high flame retardancy, low dielectric loss and constant based on a phenolphthalein type polyarylether sulfone. RSC Adv 5:58989–59002CrossRefGoogle Scholar
  40. 40.
    Sekkar V (2010) Comparison between crosslink densities derived from stress-strain data and theoretically data evaluated through the alpha-model approach for a polyurethane network system based on hydroxyl terminated polybutadiene and isophorone-diisocyanate. J Appl Polym Sci 117:920–925CrossRefGoogle Scholar
  41. 41.
    Jain SR, Sekkar V, Krishnamurthy VN (1993) Mechanical and swelling properties of HTPB-based copolyurethane networks. J Appl Polym Sci 48:1515–1523CrossRefGoogle Scholar
  42. 42.
    Luo LJ, Meng Y, Qiu T, Li XY (2013) An epoxy-ended hyperbranched polymer as a new modifier for toughening and reinforcing in epoxy resin. J Appl Polym Sci 130:1064–1073CrossRefGoogle Scholar
  43. 43.
    Li TT, Liu XQ, Jiang YH, Ma SQ, Zhu J (2016) Bio-based shape memory epoxy resin synthesized from rosin acid. Iran Polym J 25:957–965CrossRefGoogle Scholar
  44. 44.
    Zhuo DX, Gu AJ, Liang GZ, Hu JT, Cao L, Yuan L (2011) Flame retardancy and flame retarding mechanism of high performance hyperbranched polysiloxane modified bismaleimide/cyanate ester resin. Polym Degrad Stab 96:505–514CrossRefGoogle Scholar
  45. 45.
    Hu JT, Gu AJ, Liang GZ, Zhuo DX, Yuan L (2011) Preparation and properties of high-performance polysilsesquioxanes/bismaleimide-triazine hybrids. J Appl Polym Sci 120:360–367CrossRefGoogle Scholar
  46. 46.
    Santiago D, De la Flor S, Ferrando F, Ramis X, Sangermano M (2016) Thermomechanical properties and shape-memory behavior of bisphenol a diacrylate-based shape-memory polymers. Macromol Chem Phys 217:39–50CrossRefGoogle Scholar
  47. 47.
    Santiago D, Fabregat-Sanjuan A, Ferrando F, De la Flor S (2016) Recovery stress and work output in hyperbranched poly(ethyleneimine)-modified shape-memory epoxy polymers. J Polym Sci Part B Polym Phys 54:1002–1013CrossRefGoogle Scholar
  48. 48.
    Wang WX, Liu DY, Liu YJ, Leng JS, Bhattacharyya DB (2015) Electrical actuation properties of reduced graphene oxide paper/epoxy-based shape memory composites. Compos Sci Technol 106:20–24CrossRefGoogle Scholar
  49. 49.
    Li H, Sivasankarapillai G, McDonald AG (2015) Highly biobased thermally-stimulated shape memory copolymeric elastomers derived from lignin and glycerol-adipic acid based hyperbranched prepolymer. Ind Crops Prod 67:143–154CrossRefGoogle Scholar
  50. 50.
    Rimdusit S, Lohwerathama M, Hemvichian K, Kasemsiri P, Dueramae I (2013) Shape memory polymers from benzoxazine-modified epoxy. Smart Mater Struct 22:075033CrossRefGoogle Scholar
  51. 51.
    Biju R, Nair CPR (2014) Effect of phenol end functional switching segments on the shape memory properties of epoxy-cyanate ester system. J Appl Polym Sci 131:41196CrossRefGoogle Scholar
  52. 52.
    Perkins WG (1999) Polymer toughness and impact resistance. Polym Eng Sci 39:2445–2460CrossRefGoogle Scholar
  53. 53.
    Gu HB, Ma C, Liang CB, Meng XD, Gu JW, Guo ZH (2017) A low loading of grafted thermoplastic polystyrene strengthens and toughens transparent epoxy composites. J Mater Chem C 5:4275–4285CrossRefGoogle Scholar
  54. 54.
    Zhuo DX, Gu AJ, Liang GZ, Hu JT, Yuan L, Ji L (2011) Novel hyperbranched polyphenylsilsesquioxane-modified cyanate ester resins with improved toughness and stiffness. Polym Int 60:1277–1286CrossRefGoogle Scholar
  55. 55.
    Zhang JN, Deng SQ, Wang YL, Ye L (2016) Role of rigid nanoparticles and CTBN rubber in the toughening of epoxies with different crosslinking densities. Compos Part A Appl Sci Manuf 80:82–94CrossRefGoogle Scholar
  56. 56.
    Zhang JH, Jia ZX, Jia DM, Zhang DH, Zhang AQ (2014) Chemical functionalization for improving dispersion and interfacial bonding of halloysite nanotubes in epoxy nanocomposites. High Perform Polym 26:734–743CrossRefGoogle Scholar
  57. 57.
    Zhang ZY, Gu AJ, Liang GZ, Yuan L, Zhuo DX (2013) A novel hyperbranched polysiloxane containing epoxy and phosphaphenanthrene groups and its multi-functional modification of cyanate ester resin. Soft Mater 11:346–352CrossRefGoogle Scholar
  58. 58.
    Feldkamp DM, Rousseau IA (2010) Effect of the deformation temperature on the shape-memory behavior of epoxy networks. Macromol Mater Eng 295:726–734CrossRefGoogle Scholar
  59. 59.
    Wu X, Yang X, Zhang Y, Huang W (2016) A new shape memory epoxy resin with excellent comprehensive properties. J Mater Sci 51:3231–3240. CrossRefGoogle Scholar
  60. 60.
    Wei K, Zhu GM, Tang YS, Liu TT, Xie JQ (2013) The effects of crosslink density on thermo-mechanical properties of shape-memory hydro-epoxy resin. J Mater Res 28:2903–2910CrossRefGoogle Scholar
  61. 61.
    Santiago D, Fernández-Francos X, Ferrando F, De la Flor S (2015) Shape-memory effect in hyperbranched poly(ethyleneimine)-modified epoxy thermosets. J Polym Sci Part B Polym Phys 53:924–933CrossRefGoogle Scholar
  62. 62.
    Yao YT, Wang JJ, Lu HB, Xu B, Fu YQ, Liu YJ, Leng JS (2016) Thermosetting epoxy resin/thermoplastic system with combined shape memory and self-healing properties. Smart Mater Struct 25:015021CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Materials Science and Engineering, College of Chemistry, Chemical Engineering and Materials ScienceSoochow UniversitySuzhouChina

Personalised recommendations