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

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.

[1]  Jiyu He,et al.  Effect of polyphenylsilsesquioxane on the ablative and flame-retardation properties of ethylene propylene diene monomer (EPDM) composite , 2011 .

[2]  M. Loadman The analysis of rubber and rubber-like polymers , 1969 .

[3]  L. Chafetz Applied Infrared Spectroscopy , 1967 .

[4]  G. Bruni,et al.  TG/FT-IR: an analysis of the conditions affecting the combined TG/spectral response , 1995 .

[5]  J. H. van der Maas,et al.  Hyphenated On-The-Spot TG/FT-IR Technique , 1992 .

[6]  Yun-ki Kim,et al.  Formation of C7-species pyrolysis products from ethylene–propylene heterosequences of poly(ethylene-co-propylene) , 2011 .

[7]  J. Cauich‐Rodríguez,et al.  TGA/FTIR study on thermal degradation of polymethacrylates containing carboxylic groups , 2006 .

[8]  J. Coates Interpretation of Infrared Spectra, A Practical Approach , 2006 .

[9]  V. Kannappan,et al.  Molecular Modeling and Spectroscopic Studies of Benzothiazole , 2013 .

[10]  David N. Kendall,et al.  Applied Infrared Spectroscopy , 1966 .

[11]  J. Schoenung,et al.  Degassing Behavior of Nanostructured Al and Its Composites , 2010 .

[12]  R. Stephany,et al.  Some Comments on the Infrared Spectra of Vapors , 1968 .

[13]  G. W. Small Spectrometric Identification of Organic Compounds , 1992 .

[14]  Characterization of additives typically employed in EPDM formulations by using FT-IR of gaseous pyrolyzates , 2014 .

[15]  Monika Eisenhower,et al.  Encyclopedia Of Physical Science And Technology , 2016 .

[16]  M. S. Afifi,et al.  Reinvestigation of benzothiazoline-2-thione and 2-mercaptobenzothiazole tautomers: Conformational stability, barriers to internal rotation and DFT calculations , 2008 .

[17]  J. Bart Additives in Polymers: Industrial Analysis and Applications , 2005 .

[18]  T. Özdemir 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 , 2008 .

[19]  Xiao‐Hong Li,et al.  Molecular structure, IR spectra of 2-mercaptobenzothiazole and 2-mercaptobenzoxazole by density functional theory and ab initio Hartree-Fock calculations. , 2009, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[20]  W. Buchberger,et al.  Analysis of Polymer Additives and Impurities by Liquid Chromatography/Mass Spectrometry and Capillary Electrophoresis/Mass Spectrometry , 2011 .

[21]  W. Mcgill,et al.  Thiuram- and dithiocarbamate-accelerated sulfur vulcanization from the chemist's perspective; methods, materials and mechanisms reviewed , 1997 .

[22]  Yun-ki Kim,et al.  Analysis of 5-ethylidene-2-norbornene in ethylene-propylene-diene terpolymer using pyrolysis-GC/MS , 2011 .

[23]  A. Usanmaz,et al.  Comparative study on mechanical, thermal, viscoelastic and rheological properties of vulcanised EPDM rubber , 2010 .

[24]  W. Person,et al.  Absolute infrared intensifies of CS2 fundamentals in gas and liquid phases. An interpretation of the bond moments of CO2 and CS2 , 1964 .

[25]  J. Kalman,et al.  Organic Structures from Spectra , 1986 .

[26]  R. Technology Determination of Additives in Polymers and Rubbers , 2007 .

[27]  W. M. Hussein,et al.  2-Mercaptobenzothiazole and its Derivatives: Syntheses, Reactions and Applications , 2012 .

[28]  R. Richter,et al.  Gas-Phase Photoemission Study of 2-Mercaptobenzothiazole , 2000 .