CoFe2O4 Nano-particles for Radical Oxidative Degradation of High Molecular Weight Polybutadiene

  • Dario Espino
  • Yaara Haruvy-Manor
  • Yitzhak MastaiEmail author
Original paper


Polymer waste production increased dramatically in the last decades, and has reached to 380 million tons (Mt.) in 2015. Due to their long-term stability, these materials impose a serious environmental challenge. Currently, recycling of polymer waste focuses on re-use of actual products, mechanical processing, chemical recycling, and bio-degradation into environmentally friendly materials. In our previous work, we proposed a new approach for radical-initiated oxidative degradation of polymers using cobalt ferrite (CoFe2O4) nanoparticles. In our current work, we focus on the use of CoFe2O4 nanoparticles as catalysts for radical degradation of high molecular weight polybutadiene. Cobalt ferrite nanoparticles were embedded into the polybutadiene polymeric matrix, with the aim of studying degradation in polymeric products that can be manufactured with catalytic nanoparticles. The polymer degradation process was characterized using gel permeation and size exclusion chromatography measurements, thermogravimetric analysis, FTIR, NMR, and mass spectroscopy. Based on the results from these diverse measurements, we propose a mechanism for the degradation process. Overall, our results show that the radical processes within the polybutadiene polymer lead to two parallel processes: polymer crosslinking and polymer scission. Moreover, we show that the ratio between crosslinking and degradation can be controlled by the reaction duration and catalyst concentration.


Sonochemistry Radical degradation Magnetic CoFe2O4 nanoparticles Elastomer based polymers Polymers recycling 



We would like to acknowledge Mr. Mochalov Alexander for assistance with GPC measurements, Dr. Michal Weitman for assistance with APCI-MS measurements, Dr. Michal Afri for assistance with NMR measurements, and our research group for their support throughout this work.

Supplementary material

10924_2019_1399_MOESM1_ESM.docx (1023 kb)
Supplementary material 1 (DOCX 1022 KB)


  1. 1.
    Geyer R, Jambeck JR, Law KL (2017) Production, use, and fate of all plastics ever made. Sci Adv 3:e1700782CrossRefGoogle Scholar
  2. 2.
    Hamad K, Kaseem M, Deri F (2013) Recycling of waste from polymer materials: an overview of the recent works. Polym Degrad Stab 98:2801–2812CrossRefGoogle Scholar
  3. 3.
    Ali Shah A, Hasan F, Shah Z, Kanwal N, Zeb S (2013) Biodegradation of natural and synthetic rubbers: a review. Int Biodeterior Biodegrad 83:145–157CrossRefGoogle Scholar
  4. 4.
    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 14:233–248CrossRefGoogle Scholar
  5. 5.
    Garforth AA, Lin YH, Sharratt PN, Dwyer J (1998) Production of hydrocarbons by catalytic degradation of high density polyethylene in a laboratory fluidised-bed reactor. Appl Catal A 169:331–342CrossRefGoogle Scholar
  6. 6.
    Shah J, Jan ÆMR, Mabood ÆF (2007) Catalytic conversion of waste tyres into valuable hydrocarbons. J Polym Environ 15:207–211CrossRefGoogle Scholar
  7. 7.
    Pickering SJ (2006) Recycling technologies for thermoset composite materials—current status. Composites A 37:1206–1215CrossRefGoogle Scholar
  8. 8.
    La Mantia FP et al (2017) Degradation of polymer blends: a brief review. Polym Degrad Stab 145:79–92CrossRefGoogle Scholar
  9. 9.
    Tsuchii A, Suzuki T, Fukuoka S (1984) Bacterial degradation of 1,4-type polybutadiene. Agric Biol Chem 48:621–625Google Scholar
  10. 10.
    Adam C, Lacoste J, Lemaire J (1989) Photo-oxidation of elastomeric materials. 1. Photooxidation of polybutadienes. Polym Degrad Stab 24:185–200CrossRefGoogle Scholar
  11. 11.
    Jiang DD, Levchik GF, Levchik SV, Wilkie CA (1999) Thermal decomposition of cross-linked polybutadiene and its copolymers. Polym Degrad Stab 65:387–394CrossRefGoogle Scholar
  12. 12.
    Liu FS, Li Z, Yu S et al (2009) Methanolysis and hydrolysis of polycarbonate under moderate conditions. J Polym Environ 17:208–211CrossRefGoogle Scholar
  13. 13.
    Kaczmarek H (1995) Polymer bulletin accelerated photodegradation of cis 1,4-polybutadiene in the presence of hydrogen peroxide. Polym Bull 34:211–218CrossRefGoogle Scholar
  14. 14.
    Zheng J et al (2013) Controlled chain-scission of polybutadiene by the schwartz hydrozirconation. Chem: Eur J 19:541–548CrossRefGoogle Scholar
  15. 15.
    Gupte SL, Madras G (2004) Catalytic degradation of polybutadiene. Polym Degrad Stab 86:529–533CrossRefGoogle Scholar
  16. 16.
    Espino D, Haruvy Y, Yossef B, Yitzhak M (2018) Radical degradation processes initiated by catalytic nanoparticles of CoFe2O4 towards polymer waste application. J Polym Environ 8:3389–3396CrossRefGoogle Scholar
  17. 17.
    Saleem M, Inamullah K, Sohail M, Saeed N (2016) Conversion of mixed low-density polyethylene wastes into liquid fuel by novel CaO/SiO2 catalyst. J Polym Environ 24:255–263CrossRefGoogle Scholar
  18. 18.
    Aguado J, Serrano DP, Sotelo JL, Van Grieken R, Escola JM (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 40:5696–5704CrossRefGoogle Scholar
  19. 19.
    Serrano DP, Aguado J, Escola JM, Rodríguez JM (2002) Studies in surface science and catalysis, vol 142A. Elsevier, Amsterdam, pp 77–84Google Scholar
  20. 20.
    Marczewski M et al (2013) Catalytic decomposition of polystyrene. The role of acid and basic active centers. Appl Catal B 129:236–246CrossRefGoogle Scholar
  21. 21.
    Xie C et al (2008) Study on catalytic pyrolysis of polystyrene over base modified silicon mesoporous molecular sieve. Catal Commun 9:1132–1136CrossRefGoogle Scholar
  22. 22.
    Ramli A, Bakar A, Ratnasari D (2011) Effect of calcination method on the catalytic degradation of polystyrene using Al2O3 supported Sn and Cd catalysts. J Appl Sci 11:1346–1350CrossRefGoogle Scholar
  23. 23.
    Thomas RT, Sandhyarani N (2013) Enhancement in the photocatalytic degradation of low density polyethylene–TiO2 nanocomposite films under solar irradiation. RSC Adv 3:14080–14087CrossRefGoogle Scholar
  24. 24.
    Bhatia M, Girdhar A, Chandrakar B, Tiwari A (2013) Implicating nanoparticles as potential biodegradation enhancers: a review. J Nanomed Nanotechnol 4:2CrossRefGoogle Scholar
  25. 25.
    Enoki M, Kaita S, Wakatsuki Y, Doi Y, Iwata T (2004) Oxidative degradation of cis- and trans-1,4-polybutadienes by horseradish peroxidase/1-hydroxybenzotriazole. Polym Degrad Stab 84:321–326CrossRefGoogle Scholar
  26. 26.
    Lefebure S, Dubois E, Cabuil V, Neveu S, Massart R (1998) Monodisperse magnetic nanoparticles: preparation and dispersion in water and oils. J Mater Res 13:2975–2981CrossRefGoogle Scholar
  27. 27.
    Ayyappan S, Panneerselvam G, Antony MP, Philip J (2011) High temperature stability of surfactant capped CoFe2O4 nanoparticles. Mater Chem Phys 130:1300–1306CrossRefGoogle Scholar
  28. 28.
    Beißmann S et al (2013) Monitoring the degradation of stabilization systems in polypropylene during accelerated aging tests by liquid chromatography combined with atmospheric pressure chemical ionization mass spectrometry. Polym Degrad Stab 98:1655–1661CrossRefGoogle Scholar
  29. 29.
    McNeill IC, Stevenson WTK (1985) The structure and stability of oxidised polybutadiene. Polym Degrad Stab 11:123–143CrossRefGoogle Scholar
  30. 30.
    Binder JL (1963) The infrared spectra and structures of polybutadienes. J Polym Sci A 1:47–58Google Scholar
  31. 31.
    Vollhardt KPC, Shore N (2007) Organic chemistry. W. H. Freeman, New YorkGoogle Scholar
  32. 32.
    Badertscher M, Bischofberger K, Munk ME, Pretsch E (2001) A novel formalism to characterize the degree of unsaturation of organic molecules. J Chem Inf Comput Sci 41:889–893CrossRefGoogle Scholar
  33. 33.
    Black JF (1978) Metal-catalyzed autoxidation. The unrecognized consequences of metal-hydroperoxide complex formation. J Am Chem Soc 100:527–535CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Chemistry and Bar-Ilan Institute for Nanotechnology and Advanced Materials (BINA)Bar-Ilan UniversityRamat GanIsrael
  2. 2.Soreq Nuclear Research Center (SNRC)YavneIsrael

Personalised recommendations