Skip to main content
SpringerLink
Log in

Radical Degradation Processes Initiated by Catalytic Nanoparticles of CoFe2O4 Towards Polymer Waste Application

  • Original Paper
  • Published:
Journal of Polymers and the Environment Aims and scope Submit manuscript

Abstract

Polymer waste presents a modern environmental challenge due to the long-term stability of these materials. Elastomer-based polymers (e.g., tires, pipelines and shoes) are unique in comprising numerous double bonds, which are typically sensitive to radical-initiated oxidative degradation leading to the scission of polymer chains. In this paper, we propose a new approach for radical-initiated oxidative degradation of polymers using cobalt ferrite (CoFe2O4) nanoparticles (NPs). We show that magnetic CoFe2O4 NPs can effectively catalyze the oxidative degradation of polybutadiene (PB), offering easy magnetic recycling and reuse without affecting their catalytic efficiency. The CoFe2O4 NPs were synthesized via a facile surfactant-free method based on a sonochemical reaction. We used methyl ethyl ketone peroxide (MEKP), a model system, to study the rate of radical decomposition catalyzed by the NPs. The radical decomposition rates were determined by following the discoloration of methylene blue (MB) using ultraviolet–visible (UV/Vis) spectroscopy; electron paramagnetic resonance (EPR) measurements were used to study radical formation. The radical-initiated oxidative degradation of PB was studied by thermogravimetric analysis with mass spectrometry detection (TGA–MS). Our results show that cobalt ferrite NPs lead to formation of polymers with low molecular weight fragments and crosslinking, indicating that these NPs are very effective catalysts for the radical degradation of PB. CoFe2O4 NPs are potentially suitable for other polymers, hence this approach may provide a novel route for the chemical (tertiary) recycling of polymers.

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

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Al-Salem SM, Lettieri P, Baeyens J (2009) Recycling and recovery routes of plastic solid waste (PSW): a review. Waste Manag 29.10:2625–2643

    Article  CAS  PubMed  Google Scholar 

  2. Adhikari B, De D, Maiti S (2000) Reclamation and recycling of waste rubber. Progr Polym Sci 25.7:909–948.

    Article  CAS  Google Scholar 

  3. Khan M, Sohail M, Khattak NS(2016) Conversion of mixed low-density polyethylene wastes into liquid fuel by novel CaO/SiO2 catalyst. J Polym Environ 24.3:255–263

    Article  CAS  Google Scholar 

  4. Shah J, Jan MR, Mabood F (2007) Catalytic conversion of waste tyres into valuable hydrocarbons. J Polym Environ 15.3:207–211.‏

    Article  CAS  Google Scholar 

  5. Li H (2010) Metal-catalyzed oxidation of polybutadiene in oxygen scavenging packaging applications. Dissertation

  6. Wise J, Gillen KT, Clough RL (1997) Quantitative model for the time development of diffusion-limited oxidation profiles. Polymer 38(8):1929–1944.

    Article  CAS  Google Scholar 

  7. Sheldon RA, Kochi JK (1981) Metal-catalyzed oxidations of organic compounds: mechanistic principles. Academic Press, New York

    Google Scholar 

  8. Panda AK, Singh RK, Mishra DK (2010) Thermolysis of waste plastics to liquid fuel: a suitable method for plastic waste management and manufacture of value added products—a world prospective. Renew Sustain Energy Rev 14(1):233–248.

    Article  CAS  Google Scholar 

  9. Chaturvedi S, Dave PN, Shah NK (2012) Applications of nano-catalyst in new era. J Saudi Chem Soc 16.3:307–325.

    Article  CAS  Google Scholar 

  10. Serrano DP, Aguado J, Rodríguez JM (2002) Nanocrystalline ZSM-5: a highly active catalyst for polyolefin feedstock recycling. Stud Surf Sci Catal 142:77–84.‏

    Article  Google Scholar 

  11. Aguado J et al (2001) Influence of the operating variables on the catalytic conversion of a polyolefin mixture over HMCM-41 and nanosized HZSM-5. Ind Eng Chem Res 40:5696–5704.‏‏ 24)

    Article  CAS  Google Scholar 

  12. Mastral JF et al (2006) Catalytic degradation of high density polyethylene over nanocrystalline HZSM-5 zeolite. Polym Degrad Stab 91(12):3330–3338.

    Article  CAS  Google Scholar 

  13. Marczewski M et al (2013) Catalytic decomposition of polystyrene. The role of acid and basic active centers. Appl Catal B 129:236–246.

    Article  CAS  Google Scholar 

  14. Xie C et al (2008) Study on catalytic pyrolysis of polystyrene over base modified silicon mesoporous molecular sieve. Catal Commun 9(6):1132–1136.

    Article  CAS  Google Scholar 

  15. Ramli A, Abu Bakar DR(2011) Effect of calcination method on the catalytic degradation of polystyrene using Al2O3 supported Sn and Cd catalysts. J Appl Sci 11:1346–1350.‏

    Article  CAS  Google Scholar 

  16. Thomas RT, Sandhyarani N (2013) Enhancement in the photocatalytic degradation of low density polyethylene–TiO2 nanocomposite films under solar irradiation. RSC Adv 3(33):14080–14087.‏

    Article  CAS  Google Scholar 

  17. Bhatia M et al (2013) Implicating nanoparticles as potential biodegradation enhancers: a review. J Nanomed Nanotechol 4(175):2

    Google Scholar 

  18. Kooti M, Afshari M (2012) Magnetic cobalt ferrite nanoparticles as an efficient catalyst for oxidation of alkenes. Sci Iran 19(6):1991–1995.

    Article  Google Scholar 

  19. Turtelli RS et al (2008) Magnetic properties of nanocrystalline CoFe2O4 synthesized by modified citrate-gel method. J Magn Magn Mater 320:e339–e342

    Google Scholar 

  20. Senapati K, Kamal C, Borgohain, Phukan P (2011) Synthesis of highly stable CoFe2O4 nanoparticles and their use as magnetically separable catalyst for Knoevenagel reaction in aqueous medium. J Mol Catal A: Chem 339(1–2):24–31.

    Article  CAS  Google Scholar 

  21. Güven O (2012) Crosslinking and scission in polymers, vol 292. Springer, New York

    Google Scholar 

  22. Janowska G, Janczak T (1990) Effect of metal with variable valence on the thermal properties of polybutadiene. J Therm Anal Calorim 36(3):901–914.

    Article  CAS  Google Scholar 

  23. Chodak I, Rado R (1975) Polymer crosslinking by a bimolecular peroxide decomposition. J Polym Sci: Polym Symp 53(1):133–140‏

    Google Scholar 

  24. Goswami PP et al (2013) Sonochemical synthesis of cobalt ferrite nanoparticles. Int J Chem Eng. https://doi.org/10.1155/2013/934234

    Article  Google Scholar 

  25. Vijayakumar R et al (2000) Sonochemical synthesis and characterization of pure nanometer-sized Fe3O4 particles. Mater Sci Eng A 286(1):101–105.

    Article  Google Scholar 

  26. Chithambararaj A et al (2013) Flower-like hierarchical h-MoO3: new findings of efficient visible light driven nano photocatalyst for methylene blue degradation. Catal Sci Technol 3(5):1405–1414.‏‏

    Article  CAS  Google Scholar 

  27. Lee J-E et al (2015) Fabrication of Au/GO/ZnO composite nanostructures with excellent photocatalytic performance. Mater Chem Phys 164:29–35.

    Article  CAS  Google Scholar 

  28. Buettner GR (1987) Spin trapping: ESR parameters of spin adduct 1474 1528V. Free Radic Biol Med 3(4):259–303.

    Article  CAS  PubMed  Google Scholar 

  29. Maaz K et al (2007) Synthesis and magnetic properties of cobalt ferrite (CoFe2O4) nanoparticles prepared by wet chemical route. J Magn Magn Mater 308(2):289–295‏‏

    Article  CAS  Google Scholar 

  30. El-Okr MM et al (2011) Synthesis of cobalt ferrite nano-particles and their magnetic characterization. J Magn Magn Mater 323(7):920–926

    Article  CAS  Google Scholar 

  31. Abadie MJM, Mekhissi K, Burchill PJ (2002) Effects of processing conditions on the curing of a vinyl ester resin. J Appl Polym Sci 84(6):1146–1154

    Article  CAS  Google Scholar 

  32. Beyler CL, Hirschler MM (2002) Thermal decomposition of polymers. SFPE Handb Fire Prot Eng 2:111–131

    Google Scholar 

  33. Golub MA, Gargiulo RJ (1972) Thermal degradation of 1, 4-polyisoprene and 1, 4-polybutadiene. J Polym Sci Part C: Polym Lett 10(1):41–49

    CAS  Google Scholar 

  34. Chen F, Qian J (2003) Studies of the thermal degradation of waste rubber. Waste Manag 23(6):463–467

    Article  CAS  PubMed  Google Scholar 

  35. Cullis CF, Laver HS (1978) The thermal degradation and oxidation of polybutadiene. Eur Polym J 14(8):571–573

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We would like to acknowledge Dr. Ronit Lavi for her help and guidance in EPR measurements, Dr. Michal Weitman for assistance with the TGA–MS measurements, and our research group for their support in this work.

Author information

Authors and Affiliations

  1. Department of Chemistry and Bar-Ilan Institute for Nanotechnology and Advanced Materials (BINA), Bar Ilan University, 5290002, Ramat Gan, Israel

    Dario Espino & Yitzhak Mastai

  2. Soreq Nuclear Research Center (SNRC), 81800, Yavne, Israel

    Yaara Haruvy-Manor & Yossef Bar

Authors
  1. Dario Espino
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yaara Haruvy-Manor
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yossef Bar
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yitzhak Mastai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yitzhak Mastai.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 258 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Espino, D., Haruvy-Manor, Y., Bar, Y. et al. Radical Degradation Processes Initiated by Catalytic Nanoparticles of CoFe2O4 Towards Polymer Waste Application. J Polym Environ 26, 3389–3396 (2018). https://doi.org/10.1007/s10924-018-1222-7

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10924-018-1222-7

Keywords

Search

Navigation