Skip to main content
SpringerLink
Log in

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

  • Chemical routes to materials
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11

Similar content being viewed by others

References

  1. Abishera R, Velmurugan R, Gopal KVN (2017) Reversible plasticity shape memory effect in epoxy/CNT nanocomposites—a theoretical study. Compos Sci Technol 141:145–153

    Article  Google Scholar 

  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 5:2302–2314

    Article  Google Scholar 

  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):87

    Article  Google Scholar 

  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 3:97–100

    Article  Google Scholar 

  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. https://doi.org/10.1007/s10853-016-0456-9

    Article  Google Scholar 

  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 9:5457–5467

    Article  Google Scholar 

  7. Kahn JS, Hu Y, Willner I (2017) Stimuli-responsive DNA-based hydrogels: from basic principles to applications. Acc Chem Res 50:680–690

    Article  Google Scholar 

  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 8:311–320

    Article  Google Scholar 

  9. Boothby JM, Kim H, Ware TH (2017) Shape changes in chemoresponsive liquid crystal elastomers. Sens Actuatators B 240:511–518

    Article  Google Scholar 

  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 59:237–244

    Article  Google Scholar 

  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 37:1720–1763

    Article  Google Scholar 

  12. Hearon K, Singhal P, Horn J et al (2013) Porous shape-memory polymers. Polym Rev 53:41–75

    Article  Google Scholar 

  13. Xiao XL, Kong DY, Qiu XY et al (2015) Shape-memory polymers with adjustable high glass transition temperatures. Macromolecules 48:3582–3589

    Article  Google Scholar 

  14. Yang ZH, Chen Y, Wang QH, Wang TM (2016) High performance multiple-shape memory behaviors of poly(benzoxazole-co-imide)s. Polymer 88:19–28

    Article  Google Scholar 

  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 55:5873–5879

    Article  Google Scholar 

  16. Shi Y, Weiss RA (2014) Sulfonated poly(ether ether ketone) ionomers and their high temperature shape memory behavior. Macromolecules 47:1732–1740

    Article  Google Scholar 

  17. Biju R, Nair CPR (2013) High transition temperature shape memory polymer composites based on bismaleimide resin. High Perform Polym 25:464–474

    Article  Google Scholar 

  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 134:44623

    Article  Google Scholar 

  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 6:10233–10241

    Article  Google Scholar 

  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 54:3858–3867

    Article  Google Scholar 

  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 5:72971–72980

    Article  Google Scholar 

  22. Kong DY, Xiao XL (2016) High cycle-life shape memory polymer at high temperature. Sci Rep 6:33610

    Article  Google Scholar 

  23. Shi Y, Yoonessi M, Weiss RA (2013) High temperature shape memory polymers. Macromolecules 46:4160–4167

    Article  Google Scholar 

  24. Chandra R, Rajabi L (1997) Recent advances in bismaleimides and epoxy-lmide/bismaleimide formulations and composites. J Macromol Sci Part C 37:61–96

    Article  Google Scholar 

  25. Nair CPR, Mathew D, Ninan KN (2001) Cyanate ester resins, recent developments. Adv Polym Sci 155:1–99

    Article  Google Scholar 

  26. Takeichi T, Kawauchi T, Agag T (2008) High performance polybenzoxazines as a novel type of phenolic resin. Polym J 40:1121–1131

    Article  Google Scholar 

  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 7:108

    Article  Google Scholar 

  28. Kumar KSS, Biju R, Nair CPR (2013) Progress in shape memory epoxy resins. React Funct Polym 73:421–430

    Article  Google Scholar 

  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 131:40853

    Google Scholar 

  30. Biju R, Gouri C, Nair CPR (2012) Shape memory polymers based on cyanate ester-epoxy-poly(tetramethyleneoxide) co-reacted system. Eur Polym J 48:499–511

    Article  Google Scholar 

  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 28:1082–1089

    Article  Google Scholar 

  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 121:30–41

    Article  Google Scholar 

  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 29:7859–7864

    Article  Google Scholar 

  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 36:1712–1720

    Article  Google Scholar 

  35. Chen YF, Dai QW, Zhang XW, Feng T (2014) Microstructure and properties of SCE-Al2O3/PES-MBAE composite. J Nanomater 2014:356273

    Google Scholar 

  36. Phelan JC, Sung CSP (1997) Cure characterization in bis(maleimide)/diallylbisphenol a resin by fluorescence, FT-IR, and UV-reflection spectroscopy. Macromolecules 30:6845–6851

    Article  Google Scholar 

  37. Shibata M, Teramoto N, Shimasaki T, Ogihara M (2011) High-performance bio-based bismaleimide resins using succinic acid and eugenol. Polym J 43:916–922

    Article  Google Scholar 

  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 43:994–1006

    Article  Google Scholar 

  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 5:58989–59002

    Article  Google Scholar 

  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 117:920–925

    Article  Google Scholar 

  41. Jain SR, Sekkar V, Krishnamurthy VN (1993) Mechanical and swelling properties of HTPB-based copolyurethane networks. J Appl Polym Sci 48:1515–1523

    Article  Google Scholar 

  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 130:1064–1073

    Article  Google Scholar 

  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 25:957–965

    Article  Google Scholar 

  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 96:505–514

    Article  Google Scholar 

  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 120:360–367

    Article  Google Scholar 

  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 217:39–50

    Article  Google Scholar 

  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 54:1002–1013

    Article  Google Scholar 

  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 106:20–24

    Article  Google Scholar 

  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 67:143–154

    Article  Google Scholar 

  50. Rimdusit S, Lohwerathama M, Hemvichian K, Kasemsiri P, Dueramae I (2013) Shape memory polymers from benzoxazine-modified epoxy. Smart Mater Struct 22:075033

    Article  Google Scholar 

  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 131:41196

    Article  Google Scholar 

  52. Perkins WG (1999) Polymer toughness and impact resistance. Polym Eng Sci 39:2445–2460

    Article  Google Scholar 

  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 5:4275–4285

    Article  Google Scholar 

  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 60:1277–1286

    Article  Google Scholar 

  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 80:82–94

    Article  Google Scholar 

  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 26:734–743

    Article  Google Scholar 

  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 11:346–352

    Article  Google Scholar 

  58. Feldkamp DM, Rousseau IA (2010) Effect of the deformation temperature on the shape-memory behavior of epoxy networks. Macromol Mater Eng 295:726–734

    Article  Google Scholar 

  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. https://doi.org/10.1007/s10853-015-9634-4

    Article  Google Scholar 

  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 28:2903–2910

    Article  Google Scholar 

  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 53:924–933

    Article  Google Scholar 

  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 25:015021

    Article  Google Scholar 

Download references

Acknowledgements

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.

Author information

Authors and Affiliations

  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 Science, Soochow University, Suzhou, 215123, China

    Banghui Chen, Li Yuan, Qingbao Guan, Guozheng Liang & Aijuan Gu

Authors
  1. Banghui Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Li Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Qingbao Guan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Guozheng Liang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Aijuan Gu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Guozheng Liang or Aijuan Gu.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (MPG 6089 kb)

Supplementary material 2 (DOCX 471 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, B., Yuan, L., Guan, Q. et al. Preparation and mechanism of shape memory bismaleimide resins with high transition temperature, high toughness and good processability. J Mater Sci 53, 10798–10811 (2018). https://doi.org/10.1007/s10853-018-2367-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-018-2367-4

Keywords

Search

Navigation