Polímeros: Ciência e Tecnologia
https://revistapolimeros.org.br/article/doi/10.1590/0104-1428.1819
Polímeros: Ciência e Tecnologia
Scientific & Technical Article

TG/FT-IR characterization of additives typically employed in EPDM formulations

Sanches, Natália B.; Cassu, Silvana N.; Dutra, Rita C. L.

Downloads: 0
Views: 1109

Abstract

Thermogravimetric analysis coupled to Fourier transform infrared spectroscopy (TG/FT-IR) is a very popular technique for rubbers characterization. It involves analyses of the base polymer and additives. Ethylene–propylene–diene (EPDM) rubbers are frequently investigated by TG/FT-IR; however, the focus has been the degradation temperature range of the polymer. In this study, unvulcanized and vulcanized EPDM rubber and its additives were investigated by TG/FT-IR, without solvent extraction, and in a wide temperature range. Initially, the additives were individually characterized. TG/FT-IR identified the characteristic groups of all the additives analyzed and distinguished them from each other. Afterwards, unvulcanized and vulcanized EPDM rubbers were investigated without prior extraction.TG/FT-IR detected absorptions due to the additives tetramethylthiuram monosulfide and 2-mercaptobenzothiazole. Both of these sulfur-containing additives were present in the EPDM formulation at concentrations of 0.7 phr (0.63 wt %). The TG/FT-IR technique had some limitations, because not all the additives in EPDM rubber were detected. Paraffin oil, stearic acid and 2,2,4-trimethyl-1,2-dihydroquinoline functional groups were not observed in either the unvulcanized or vulcanized EPDM. Nevertheless, in addition to the ability of this method to detect sulfur-containing groups, the lack of a pre-extraction reduces the time and effort required for additive analysis in rubbers.

Keywords

EPDM, additives, characterization, TG/FT-IR, TMTM, MBT.

References

1. Bart, J. C. J. (2005). Additives in polymers: industrial analysis and applications. Chichester: John Wiley & Sons.

2. Crompton, R. (2007). Determination of additives in polymers and rubbers. United Kingdom: Rapra Technology.

3. Buchberger, W., & Stiftinger, M. (2012). Analysis of polymer additives and impurities by liquid chromatography/mass spectrometry and capillary electrophoresis/mass spectrometry. Advances in Polymer Science, 248, 39-67. http://dx.doi.org/10.1007/12_2011_147.

4. Cervantes-Uc, J. M., Cauich-Rodríguez, J. V., Vazquez-Torres, H., & Licea-Claveríe, A. (2006). TGA/FTIR study on thermal degradation of polymethacrylates containing carboxylic groups. Polymer Degradation & Stability, 91(12), 3312-3321. http://dx.doi.org/10.1016/j.polymdegradstab.2006.06.005.

5. Choi, S., & Kim, Y. (2011). Formation of C7-species pyrolysis products from ethylene-propylene heterosequences of poly(ethylene-co-propylene). Analytical and Applied Pyrolysis, 92(2), 384-391. http://dx.doi.org/10.1016/j.jaap.2011.07.014.

6. Jiang, Y., Zhang, X., He, J., Yu, L., & Yang, R. (2011). Effect of Polyphenylsilsesquioxane on the ablative and flame-retardation properties of Ethylene Propylene Diene Monomer (EPDM) composite. Polymer Degradation & Stability, 96(5), 949-954. http://dx.doi.org/10.1016/j.polymdegradstab.2011.01.034.

7. Çavdar, S., Özdemir, T., & Usanmaz, A. (2010). Comparative study on mechanical, thermal, viscoelastic and rheological properties of vulcanised EPDM rubber. Plastics. Rubber and Composites, 39(6), 277-282. http://dx.doi.org/10.1179/174328910X12647080902970.

8. Özdemir, T. (2008). Gamma irradiation degradation/modification of 5-ethylidene 2-norbornene (ENB)-based ethylene propylene diene rubber (EPDM) depending on ENB content of EPDM and type/content of peroxides used in vulcanization. Radiation Physics and Chemistry, 77(6), 787-793. http://dx.doi.org/10.1016/j.radphyschem.2007.12.010.

9. Sanches, N. B., Cassu, S. N., Diniz, M. F., & Dutra, R. C. L. (2014). Characterization of additives typically employed in EPDM formulations by using FT-IR of gaseous pyrolyzates. Polímeros: Ciência e Tecnologia, 24(3), 269-275. http://dx.doi.org/10.4322/polimeros.2014.066.

10. American Society for Testing and Materials (2011). ASTM D1566-11: Standard Terminology Relating to Rubber. West Conshohocken: ASTM.

11. Nieuwenhuizen, P. J., Reedijk, J., Van Duin, M., & McGill, W. J. (1997). Thiuram-and dithiocarbamate-accelerated sulfur vulcanization from the chemist's perspective; methods, materials and mechanisms reviewed. Rubber Chemistry and Technology, 70(3), 368-429. http://dx.doi.org/10.5254/1.3538436.

12. Contini, G., Di Castro, V., Stranges, S., Richter, R., & Alagia, M. (2002). Gas-phase photoemission study of 2-Mercaptobenzothiazole. The Journal of Physical Chemistry A, 106(12), 2833-2837. http://dx.doi.org/10.1021/jp013423b.

13. Wu, F.-L., Hussein, W. M., Ross, B. P., & McGeary, R. P. (2012). 2-Mercaptobenzothiazole and its Derivatives: Syntheses, Reactions and Applications. Current Organic Chemistry, 16(13), 1555-1580. http://dx.doi.org/10.2174/138527212800840964.

14. Mohamed, T. A., Mustafa, A. M., Zoghaib, W. M., Afifi, M. S., Farag, R. S., & Badr, Y. (2008). Reinvestigation of benzothiazoline-2-thione and 2-mercaptobenzothiazole tautomers: conformational stability, barriers to internal rotation and DFT calculations. Journal of Molecular Structure: THEOCHEM, 868(1-3), 27-36. http://dx.doi.org/10.1016/j.theochem.2008.07.037.

15. Berbenni, V., Marini, A., Bruni, G., & Zerlia, T. (1995). TG/FT-IR: an analysis of the conditions affecting the combined TG/Spectral response. Thermochimica Acta, 258, 125-133. http://dx.doi.org/10.1016/0040-6031(94)02237-I.

16. Loadman, M. J. R. (1998). Analysis of rubber and rubber-like polymers. Dordrecht: Klumer Academic Publishers.

17. Zhang, Z., Dallek, S., Vogt, R., Li, Y., Topping, T. D., Zhou, Y., Schoenung, J. M., & Lavernia, E. J. (2010). Degassing behavior of nanostructured al and its composites. Metallurgical and Materials Transactions. A, Physical Metallurgy and Materials Science, 41(2), 532-541. http://dx.doi.org/10.1007/s11661-009-0089-6.

18. Jansen, J. A. J., Van Der Maas, J. H., & Boer, A. P. (1992). Hyphenated on-the-spot TG/FT-IR technique. Applied Spectroscopy, 46(1), 88-92. http://dx.doi.org/10.1366/0003702924444452.

19. Welti, D., & Stephany, R. (1968). Some comments on the infrared spectra of vapors. Applied Spectroscopy, 22(6), 678-688. http://dx.doi.org/10.1366/000370268774384119.

20. Smith, A. L. (1979). Applied infrared spectroscopy. New York: John Wiley & Sons.

21. Silverstein, R. M., Webster, F. X., & Kiemle, D. J. (2005). Spectrometric identification of organic compounds. New York: John Wiley & Sons.

22. Meyers, R. A. (2001). Encyclopedia of physical science and technology. Oxford: Elsevier.

23. Fiels, L. D., Sternhell, S., & Kalman, J. R. (2008). Organic structures from Spectra. Chichester: John Wiley & Sons.

24. Coates, J. (2000). Interpretation of infrared Spectra, a practical approach. In R. A. Meyers (Ed.), Encyclopedia of analytical chemistry (pp. 10815-10837). Chichester: John Wiley & Sons.

25. NIST Standard Reference Database WebBook. (2013). Retrieved in 3 Mar. 2013, from http://webbook.nist.gov/cgi/cbook.cgi?ID=C75150&Units=SI&Type=IR-SPEC

26. BIO-RAD/SADTLER Reference Database. (2013). Retrieved in 3 Mar. 2013, from Retrieved from https://scifinder.cas.org/

27. Person, W. B., & Hall, L. C. (1964). Absolute infrared intensities of CS2 fundamentals in gas and liquid phases: an interpretation of the bond moments of CO2 and CS2. Spectrochimica Acta, 20(5), 771-779. http://dx.doi.org/10.1016/0371-1951(64)80076-X.

28. Hoffmann, F., Riesen, R., & Foreman, J. (2000). Characterization of thermal stability and reaction products by means of TGA-FTIR coupling. American Laboratory, 32(1), 13-17.

29. Brooks, C. T., Peacock, S. J., & Reuben, B. G. (1979). Pyrolysis of benzene. Journal of the Chemical Society, Faraday Transactions I, 75(0), 652-662. http://dx.doi.org/10.1039/f19797500652.

30. Xiao-Hong, L., Zheng-Xin, T., & Xian-Zhou, Z. (2009). Molecular structure, IR spectra of 2- mercaptobenzothiazole and 2-mercaptobenzoxazole by density funcional theory and ab initio Hartree-Fock calculations. Spectrochimica Acta. Part A: Molecular and Biomolecular Spectroscopy, 74(1), 168-173. http://dx.doi.org/10.1016/j.saa.2009.05.026.

31. Sathyanarayanmoorthi, V., Karunathan, R., & Kannappan, V. (2013). Molecular modeling and spectroscopic studies of Benzothiazole. Journal of Chemistry, 2013, 1-14. http://dx.doi.org/10.1155/2013/258519.

32. Choi, S., & Kim, Y. (2011). Analysis of 5-ethylidene-2-norbornene in ethylene-propylene-diene terpolymer using pyrolysis-GC/MS. Polymer Testing, 30(5), 509-514. http://dx.doi.org/10.1016/j.polymertesting.2011.04.005.
588371c07f8c9d0a0c8b4a4b polimeros Articles
Links & Downloads

Polímeros: Ciência e Tecnologia

Share this page
Page Sections