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Thermal and crystallization behaviour of epoxidized high cis-polybutadiene rubber

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Abstract

High cis-polybutadiene (HCBR) was epoxidized by using in situ formed formic acid and hydrogen peroxide in the absence and presence of Tween 20 at 50 °C at different reaction times. Epoxidized HCBR (EHCBR) with degree of epoxidation from 3.7 to 38.8% was obtained. Low degree epoxidation EHCBR are semi-crystalline rubbers presenting lower crystallization temperatures than the non-epoxidized rubber on cooling and a cold crystallization and melting temperature on heating, differently from high epoxidation content rubbers (over 10%) which are amorphous materials. Epoxidation increases the glass transition temperature and decreases the melting temperature and the degree of crystallinity of the polybutadiene. The increase of epoxidation also decreases its thermal stability, which drops about 28 °C when the content of epoxidation is increased about 30%. Non-isothermal crystallization experiments of HCBR and EHCBR were systematically carried out at cooling rates of 5, 10, 20, and 30 °C/min to evaluate the crystallinity developed upon cooling. By increasing the cooling rate, the crystallization enthalpy increases for HCBR while it decreases for EHCBR.

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References

  1. Saijo K, Zhu YP, Hashimoto T, Wasiak A, Brzostowski N (2007) Oriented crystallization of crosslinked cis-1,4-polybutadiene rubber. Appl Polym Sci 105:137–157. https://doi.org/10.1002/app.26019

    Article  CAS  Google Scholar 

  2. Chiu HT, Li WC, Tsai PA (2006) A Study of rheological behavior and compatibility of NR/BR blends. Polym Plast Technol Eng 45:845–855. https://doi.org/10.1080/03602550600614069

    Article  CAS  Google Scholar 

  3. Bucknall CB (1977) Toughened plastics. Applied Science Publishers, London

    Book  Google Scholar 

  4. Candia FD, Romano G, Russo R (1987) Stress and thermally induced crystallization in crosslinked cis-polybutadiene. Appl Polym Sci. 34:211–221. https://doi.org/10.1002/app.1987.070340118

    Article  Google Scholar 

  5. Cheng TL, Su AC (1993) Spherulites of long-chain branched cis-1,4-polybutadiene. Macromolecules 26:7161–7166. https://doi.org/10.1021/ma00078a008

    Article  CAS  Google Scholar 

  6. Cheng TL, Su AC (1995) Spherulites of cis-1,4-polybutadiene: molecular weight effects. Polymer 36:73–80. https://doi.org/10.1016/0032-3861(95)90677-T

    Article  CAS  Google Scholar 

  7. Di Lorenzo ML (2010) Crystallization kinetics of cis-1,4-polybutadiene. J Appl Polym Sci 116:1408–1413. https://doi.org/10.1002/app.30681

    Article  CAS  Google Scholar 

  8. Di Lorenzo ML (2010) Thermal properties and three-phase structure of cis-1,4-polybutadiene. Open Macromol J 4:15–21

    Article  Google Scholar 

  9. Rajabi FHP, Nikje MMA, Farahani BV, Sabouri N (2011) Kinetic study of cis-polybutadiene epoxidation by using 1HNMR spectroscopy in buffered Oxone® solution with tetra-n-butyl ammonium bromide as phase transfer catalyst (PTC). J Iran Chem Res 4:1–8

    Google Scholar 

  10. Jacobi MM, Santin CK, Vigânico ME (2004) Study of the epoxidation of polydiene rubbers II. Influence of the microstructure on the epoxidation of BR with performic acid. Kautsch Gummi Kunstst 57:82–89

    CAS  Google Scholar 

  11. Zuchowska D (1980) Polybutadiene modified by epoxidation. I. Effect of polybutadiene microstructure on the reactivity of double bonds. Polymer 21:514–520. https://doi.org/10.1016/0032-3861(80)90217-7

    Article  CAS  Google Scholar 

  12. Baker CSL, Gelling IR, Newell R (1985) Epoxidized natural rubber. Rubber Chem Techn 58:67–85. https://doi.org/10.5254/1.3536059

    Article  CAS  Google Scholar 

  13. Margaritis G, Kalfoglou NK (1988) Compatibility of poly(vinyl chloride) with epoxidized polybutadiene. Eur Polym. J 24:1043–1047

    Article  CAS  Google Scholar 

  14. Roy S, Gupta BR, De SK (1993) Elastomer technology handbook. CRC Press, Boca Raton

    Google Scholar 

  15. Wang SM, Tsiang RCC (1996) Epoxidation of partially hydrogenated styrene-butadiene block-copolymers using peracetic-acid in a cyclohexane water heterogeneous system. J Polym Sci 34:1483–1491. https://doi.org/10.1002/(SICI)1099-0518(199606)34:8%3c1483:AID-POLA12%3e3.0.CO;2-4

    Article  CAS  Google Scholar 

  16. Gemmer RV, Golub MA (1978) 13C NMR spectroscopic study of epoxidized 1,4-polyisoprene and 1,4-polybutadiene. J Polym Sci Polym Chem 16:2985–2990. https://doi.org/10.1002/pol.1978.170161123

    Article  CAS  Google Scholar 

  17. Perera MCS, Elix JA, Bradbury JH (1988) Furanized rubber studied by NMR spectroscopy. J Polym Sci Polym Chem 26:637–651. https://doi.org/10.1002/pola.1988.080260227

    Article  CAS  Google Scholar 

  18. Lin JP, Chang CY, Wu CH, Shih SM (1996) Thermal degradation kinetics of polybutadiene rubber. Polym Degrad Stab 53:295–300. https://doi.org/10.1016/0141-3910(96)00098-5

    Article  CAS  Google Scholar 

  19. Silva GM, Ferreira ILM, Costa MPM, Pires NMT, Costa MAS (2014) Copolymerization of 1-hexene and 1-dodecene with 1,3-butadiene by a versatate/diisobutylaluminum hydride/t-butyl chloride catalyst system. Polímeros 24:153–161. https://doi.org/10.4322/polimeros.2014.040

    Article  CAS  Google Scholar 

  20. Di Lorenzo ML, Silvestre C (1999) Non-isothermal crystallization of polymers. Prog Polym Sci 24:917–950. https://doi.org/10.1016/S0079-6700(99)00019-2

    Article  Google Scholar 

  21. Bianchi O, Martins JN, Luvison C, Echeverrigaray SG (2014) Melt crystallization kinetics of polyhedral oligomeric silsesquioxane under non-isothermal conditions. J Non-Cryst Solids 394–395:29–35. https://doi.org/10.1016/j.jnoncrysol.2014.04.008

    Article  CAS  Google Scholar 

  22. Mashak A, Ghaee A, Ravari F (2016) Effect of poly (n- vinypyrrolidone) on the non-isothermal crystallization kinetics and viscoelastic properties of PVDF films. Braz J Chem Eng 33(4):945–956. https://doi.org/10.1590/0104-6632.20160334s20150172

    Article  CAS  Google Scholar 

  23. Piccarolo S, Brucato V, Kiflie Z (2000) Non-Isothermal crystallization kinetics of PET. Polym Eng Sci 40:1263–1272. https://doi.org/10.1002/pen.11254

    Article  CAS  Google Scholar 

  24. Seo Y (2000) Non-isothermal crystallization kinetics of polytetrafiuoroethylene. Polym Eng Sci 40(6):1293–1297. https://doi.org/10.1002/pen.11257

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors are grateful to CNPq (310917/2014-0), CNPq-PIBIC, CAPES, and FAPERJ (E-26/201.304/2014) for the financial support.

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Authors and Affiliations

  1. Universidade Federal do Rio de Janeiro (UFRJ), Instituto de Macromoléculas Professora Eloisa Mano (IMA), Av. Horácio Macedo, 2.030. Centro de Tecnologia. B. J., Rio de Janeiro, 21941-598, Brazil

    Marcos L. Dias, Frederico A. P. Schoene, Camila Ramirez, Isabela A. Graciano, Lys Sirelli & Raquel P. Gonçalves

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  1. Marcos L. Dias
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  2. Frederico A. P. Schoene
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Correspondence to Marcos L. Dias.

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Dias, M.L., Schoene, F.A.P., Ramirez, C. et al. Thermal and crystallization behaviour of epoxidized high cis-polybutadiene rubber. J Rubber Res 22, 195–201 (2019). https://doi.org/10.1007/s42464-019-00028-5

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  • DOI: https://doi.org/10.1007/s42464-019-00028-5

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