SpringerLink
Log in

Grafting isocyanate onto graphene oxide for polyurethane composites to improve their thermal stability and mechanical properties

  • Original Research
  • Published:
Iranian Polymer Journal Aims and scope Submit manuscript

Abstract

Modification of graphene oxide (GO) to apply to polymer composites has important potential for improving the mechanical properties and thermal stability of polymers. In this work, isophorone diisocyanate (IPDI) was used to chemically modify GO, and isocyanate-functionalized GO (IPDI-GO) was successfully synthesized at different reaction times and compounded with aqueous polyurethane (WPU) to prepare IPDI-GO/WPU composites. The test results indicated that the interlayer spacing of the prepared IPDI-GO has increased by 2.36 Å. Covalent bonds had been formed between isocyanate groups of IPDI and hydroxyl and carboxyl groups on the surface of GO. The atomic ratio of carbon to oxygen in IPDI-GO had increased from 2.79 to 4.05, and a characteristic peak of nitrogen (N) appeared. Moreover, the obtained IPDI-GO was insoluble in water, and hydrophobicity of the IPDI-GO/WPU composites was enhanced, and the contact angle increased from 63.8 to 92.6. The stability of IPDI-GO had been improved, it could stably disperse in the polar aprotic solvent DMF for 14 days without sedimentation. When modification time was 48 h and loading amount of the IPDI-GO in composites was 0.5 wt%, tensile strength of the IPDI-GO/WPU composite films increased by 33.1%. Additionally, thermal stability of the composite films improved compared to pure WPU. This work simulated the reinforcement mechanism of the composite films, as well.

Graphical Abstract

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

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price includes VAT (France)

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

Data availability

Not applicable.

Code availability

Not applicable.

References

  1. Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, Grigorieva IV, Firsov AA (2004) Electric field effect in atomically thin carbon films. Science 306:666–669

    Article  CAS  PubMed  Google Scholar 

  2. Tang Z, Kang H, Shen Z, Guo B, Zhang L, Jia D (2012) Grafting of polyester onto graphene for electrically and thermally conductive composites. Macromolecules 45:3444–3451

    Article  CAS  Google Scholar 

  3. Lee C, Wei X, Kysar J, Hone J (2008) Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321:385–388

    Article  CAS  PubMed  Google Scholar 

  4. Dikin DA, Stankovich S, Zimney EJ, Piner R, Dommett GHB, Evmenenko G, Nguyen ST, Ruoff RS (2007) Preparation and characterization of graphene oxide paper. Nature 448:457–460

    Article  CAS  PubMed  Google Scholar 

  5. Stankovich S, Dikin DA, Dommett GHB, Kohlhaas KM, Zimney EJ, Stach EA, Piner RD, Nguyen ST, Ruoff RS (2006) Graphene-based composite materials. Nature 442:282–286

    Article  CAS  PubMed  Google Scholar 

  6. Balandin AA, Ghosh S, Bao W, Calizo I, Teweldebrhan D, Miao F, Lau CN (2008) Superior thermal conductivity of single-layer graphene. Nano Lett 8:902–907

    Article  CAS  PubMed  Google Scholar 

  7. Hou S, He S, Zhu T, Li J, Ma L, Du H, Shen W, Kang F, Huang Z-H (2021) Environment-friendly preparation of exfoliated graphite and functional graphite sheets. J Materiomics 7:136–145

    Article  Google Scholar 

  8. Stankovich S, Dikin DA, Piner RD, Kohlhaas K, Kleinhammes A, Jia Y, Wu Y, Nguyen S, Ruoff RS (2007) Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon 45:1558–1565

    Article  CAS  Google Scholar 

  9. Wang Y, Huang K, Derré A, Puech P, Rouzière S, Launois P, Castro C, Monthioux M, Pénicaud A (2017) Conductive graphene coatings synthesized from graphenide solutions. Carbon 121:217–225

    Article  Google Scholar 

  10. Teng C, **e D, Wang J, Yang Z, Ren G, Zhu Y (2017) Ultrahigh conductive graphene paper based on ball-milling exfoliated graphene. Adv Funct Mater 27:1700240

    Article  Google Scholar 

  11. (2019) The graphene times. Nat Nanotechnol 14:903

  12. Zaman I, Phan TT, Kuan H-C, Meng Q, La Bao LT, Luong L, Youssf O, Ma J (2011) Epoxy/graphene platelets nanocomposites with two levels of interface strength. Polymer 52:1603–1611

    Article  CAS  Google Scholar 

  13. McAllister MJ, Li J-L, Adamson DH, Adamson DH, Schniepp HC, Abdala AA, Liu J, Herrera-Alonso M, Milius DL, Car R, Prudhomme RK, Aksay IA (2007) Single sheet functionalized graphene by oxidation and thermal expansion of graphite. Chem Mater 19:4396–4404

    Article  CAS  Google Scholar 

  14. Zhu C, Xu JG, Momina A, Bushra ZK, Hao YY, Ma HR, Zarak M (2023) Facile approach for nanoconfinement of multilayer graphene oxide with polyether polyurethane sponge as biological carrier for the establishment of microalgal-bacterial bioreactor. Bioresource Technol 387:128997

    Google Scholar 

  15. Kim H, Lee J, Shim SB, Kim MS, Shrimant B, Lee JH, Nam SY, Kwon D-J, Park JH (2023) Influence of milled and acid-treated graphene oxide on the self-healing properties of graphene oxide reinforced polyurethane. Compos Part B Eng 259:110702

    Article  CAS  Google Scholar 

  16. Nilawar S, Bs M, Chatterjee K (2023) Nanoceria-decorated graphene nanosheets enhance mechanical properties and bioactivity of a degradable polyurethane for biomedical applications. J Polym Environ 31:2941–2955

    Article  CAS  Google Scholar 

  17. Liang GT, Yao FB, Qi YR, Gong RZ, Li R, Liu BX, Zhao Y, Lian CL, Li LM, Dong XY, Li YF (2023) Improvement of mechanical properties and solvent resistance of polyurethane coating by chemical grafting of graphene oxide. Polymers 15:882

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  18. Luo D, Zhang X (2018) The effect of oxygen–containing functional groups on the H2 adsorption of graphene–based nanomaterials: experiment and theory. Internat J Hydrogen Energ 43:5668–5679

    Article  CAS  Google Scholar 

  19. Guo S, Nishina Y, Bianco A, Menard-Moyon C (2020) A flexible method for covalent double functionalization of graphene oxide. Angew Chem Internat Edit 59:1542–1547

    Article  CAS  Google Scholar 

  20. Yu H, He Y, **ao G, Fan Y, Ma J, Gao YX, Hou RT, Yin XY, Wang YQ, Mei X (2020) The roles of oxygen-containing functional groups in modulating water purification performance of graphene oxide-based membrane. Chem Eng, J 389:124375

    Article  CAS  Google Scholar 

  21. Luceño-Sánchez JA, Maties G, Gonzalez-Arellano C, Díez-Pascual AM (2018) Synthesis and characterization of graphene oxide derivatives via functionalization reaction with hexamethylene diisocyanate. Nanomaterials 8:870

    Article  PubMed  PubMed Central  Google Scholar 

  22. Stankovich S, Piner RD, Nguyen ST, Ruoff RS (2006) Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets. Carbon 44:3342–3347

    Article  CAS  Google Scholar 

  23. Yong Q, Liao B, Huang J, Guo Y, Liang CZ, Pang H (2018) Preparation and characterization of a novel low gloss waterborne polyurethane resin. Surf Coat Technol 341:78–85

    Article  CAS  Google Scholar 

  24. Zhang J, Wu Y, Zhang H, Yan T, Huang Y, Jiang J, Tang J (2021) Castor oil-glycerol-based waterborne polyurethane dispersions. Prog Org Coat 157:106333

    Article  CAS  Google Scholar 

  25. Wan T, Chen D (2018) Mechanical enhancement of self-healing waterborne polyurethane by graphene oxide. Prog Org Coat 121:73–79

    Article  CAS  Google Scholar 

  26. Ramezanzadeh B, Ghasemi E, Mahdavian M, Changizi E, Mohamadzadeh Moghadam MH (2015) Characterization of covalently-grafted polyisocyanate chains onto graphene oxide for polyurethane composites with improved mechanical properties. Chem Eng J 281:869–883

    Article  CAS  Google Scholar 

  27. Ha H, Shanmuganathan K, Ellison CJ (2015) Mechanically stable thermally crosslinked poly(acrylic acid)/reduced graphene oxide aerogels. ACS Appl Mater Interfaces 7:6220–6229

    Article  CAS  PubMed  Google Scholar 

  28. Yuan H, Ye J, Ye C, Yin SS, Li JY, Su K, Fang G, Wu YH, Zheng YX, Ge M, Tang RL, Feng GP, Qu Y, Zhu YW (2021) Highly efficient preparation of graphite oxide without water enhanced oxidation. Chem Mater 33:1731–1739

    Article  CAS  Google Scholar 

  29. Zhang S, **ong P, Yang X, Wang X (2011) Novel PEG functionalized graphene nanosheets: enhancement of dispersibility and thermal stability. Nanoscale 3:2169–2174

    Article  CAS  PubMed  Google Scholar 

  30. Ye W, Chen Y, Zhou Y, Fu JJ, Wu WC, Gao DQ, Zhou F, Wang CM, Xue DH (2014) Enhancing the catalytic activity of flowerike Pt nanocrystals using polydopamine functionalized graphene supports for methanol electrooxidation. Electrochim Acta 142:18–24

    Article  CAS  Google Scholar 

  31. Ramanathan T, Fisher FT, Ruoff RS, Brinson LC (2005) Amino-functionalized carbon nanotubes for binding to polymers and biological systems. Chem Mater 17:1290–1295

    Article  CAS  Google Scholar 

  32. Tang X-Z, Mu C, Zhu W, Yan XL, Hu X, Yang JL (2016) Flexible polyurethane composites prepared by incorporation of polyethylenimine-modified slightly reduced graphene oxide. Carbon 98:432–440

    Article  CAS  Google Scholar 

  33. Chen WY, Qiao HB, Zhang DW, Tian XM, ** L (2023) Silane coupling agent γ-aminopropyltriethoxysilane-modified nanoparticles/polyurethan elastomer nanocomposites. Iran Polym J 32:715–727

    Article  CAS  Google Scholar 

  34. Yin YH, Muhammad Y, Zeng X, Yang J, Li J, Yang S, Zhao ZX, Subhan S (2018) Synthesis and properties of octadecylamine-graphene oxide modified highly hydrophobic waterborne polyurethane emulsion. Prog Org Coat 125:234–241

    Article  CAS  Google Scholar 

  35. Li J, Yin YH, Muhammad Y, Yang J, Yang S, Yang HQ, Sahibzada M (2019) Preparation and properties of modified graphene oxide incorporated waterborne polyurethane acrylate. Polym Int 68:1091–1101

    Article  CAS  Google Scholar 

  36. Lei L, **a ZB, Zhang L, Zhang YH, Zhong L (2016) Preparation and properties of amino-functional reduced graphene oxide/waterborne polyurethane hybrid emulsions. Prog Org Coat 97:19–27

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the project of Natural Science Foundation of China (NO. 51903129), China postdoctoral Science Foundation (No. 2017M612196), Natural Science Foundation of Shandong Province (No. 2014ZRB01840, 201807070028), and Qingdao Postdoctoral Scientific Research Foundation.

Funding

Not applicable.

Author information

Authors and Affiliations

  1. School of Material Science and Engineering, Institute of Polymer Materials, Qingdao University, No. 308 Ningxia Road, Qingdao, 266071, Shandong, People’s Republic of China

    Yinghu Song, Jialiang Li, **aoran Wang, Guojun Song, **aoru Li, Yuxin Cui, Zhiyong Feng, Yuankun Ning & Yangming Wu

Authors
  1. Yinghu Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jialiang Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. **aoran Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Guojun Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. **aoru Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yuxin Cui
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zhiyong Feng
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Yuankun Ning
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Yangming Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

All authors contributed equally.

Corresponding authors

Correspondence to Guojun Song or **aoru Li.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Ethics approval

Not applicable.

Consent to participate

Not applicable.

Consent for publication

All authors have read and agreed to publish the manuscript.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Song, Y., Li, J., Wang, X. et al. Grafting isocyanate onto graphene oxide for polyurethane composites to improve their thermal stability and mechanical properties. Iran Polym J 33, 45–55 (2024). https://doi.org/10.1007/s13726-023-01233-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13726-023-01233-1

Keywords

Search

Navigation