Simultaneous Screening of Major Flame Retardants and Plasticizers in Polymer Materials Using Pyrolyzer/Thermal Desorption Gas Chromatography Mass Spectrometry (Py/TD–GC–MS)

Abstract

This study was conducted with the aim of achieving the simultaneous screening of various additives in polymer materials by utilizing a solvent-free pyrolyzer/thermal desorption gas chromatography mass spectrometry (Py/TD-GC–MS) method. As a first step to achieve this goal, simultaneous screening has been examined by selecting major substances representing plasticizers and flame retardants, such as short chain chlorinated paraffins (SCCPs), decabromodiphenyl ether (DecaBDE), hexabromocyclododecane (HBCDD), and di(2-ethylhexyl) phthalate (DEHP). A quantitative MS analysis was performed to check for the peak areas and sensitivities. Since Py/TD-GC–MS is fraught with the risk of thermal degradation of the sample, temperatures during the analytical process were finely tuned for securing reliable results. The instrumental sensitivity was confirmed by the S/N ratio on each component. The detection limits of all components were less than 50 mg/kg, which are sufficiently lower than the regulatory criteria. With regard to reproducibility, a relative standard deviation (RSD) of about 5% was confirmed by employing a spike recovery test on a polystyrene polymer solution containing mixed standard solution (ca. 1000 mg/kg). In conclusion, the results obtained in this study indicate that Py/TD-GC–MS is applicable for the screening of major flame retardants and plasticizers in real samples with sufficient reproducibility at regulatory levels.

Evaluating Phthalate Contaminant Migration Using Thermal Desorption–Gas Chromatography–Mass Spectrometry (TD–GC–MS)

“…An additional experiment was performed to verify the migration of DEHP from PVC to different contact media. As shown in Figure 4a, the difference in DEHP’s migration from PVC to solvent (ethanol) and solid (PE sheet) was confirmed to be similar to that predicted from past literature [11]. Figure 4b provides extrapolated results by applying the migration model [13].…”

“…A blank PE sheet was placed as a sample between two PVC sheets (containing phthalates at 7.4% (w/w)) to form a sandwich configuration. The migration test was performed in reference to the ISO 177, which provides a standardized method for evaluating the tendency of plasticizers to migrate from plastic materials to other materials placed in close contact by monitoring the weight increase of the sample [11]. However, the gravimetric measurement set out in ISO 177 was not sensitive enough to incrementally evaluate time-sequential migration.…”

Simple Colorimetric Determination of Phthalates in Polymers by Dye Formation

“…The instrument settings were the same as those used in previous studies. 6,7 Synthesis of fluorescein from phthalates The phthalates were hydrolyzed to phthalic acid with sodium hydroxide and dehydrated using the dry thermo unit. After dehydration, fluorescein was synthesized by the selective reaction between phthalic anhydride and resorcinol with concentrated sulfuric acid as the catalyst.…”

“…5 The Py/TD-GC-MS method enables solvent-free direct sample injection without the need for complicated pretreatment procedures. [6][7][8] However, in an actual business scenario, a simple screening method that enables manufacturers to verify the ingredients of various materials on a daily basis is needed. For example, Fourier transform infrared (FTIR) spectroscopy enables the nondestructive analysis of phthalates, 9,10 but the detection limits are usually considerably higher than the regulatory criteria and FTIR spectroscopy cannot be used for performing compliance assessment.…”

Small polymeric toys placed in child-dedicated chocolate food products - do they contain harmful chemicals? Examination of quality by example of selected VOCs and SVOCs

“…The presence of VOCs and SVOCs in polymeric materials mainly occurs by the following routes: (i) residues from the polymer synthesis process (residues of polymerisation, or traces of the initiators, catalysts, or solvents that were used therein); and (ii) substances introduced in the manufacturing process of plastic materials (antioxidants, plasticisers, UV stabilisers, as well as ame retardants) (Hankett et al2013;Pei et al 2017;Azwa et al 2013;; Kozai et al 2018;Yanagisawa et al 2018). In addition, various compounds can be formed and released due to structural degradation of the polymeric material, for example, after exposure to high temperatures and/or UV light (Royaux et al 2017;Formela et al 2017;Yu et al 2016;Bhaskar et al 2007).…”