Photometric Screening of Tetrabromobisphenol A in Resin Using Iron(III) Nitrate/Hexacyanoferrate(III) Mixture as a Colorimetric Reagent.

This study aims to provide a simple way to identify the possibility of tetrabromobisphenol A (TBBPA) present in polymers without the need for complicated separation with expensive equipment. Since the presence of phenolic hydroxyl groups is known to be identifiable by the reduction of Fe3+ to Fe2+ in a ferric coloring reagent, the possibility of TBBPA being present in a polymer can be screened by a photometric measurement. A mixed solution of iron(III) nitrate and potassium hexacyanide(III) acid was used as a ferric coloring reagent. With this method, the concentration of TBBPA can be estimated from the photometric absorbance corresponding to the depth of the blue color produced by reduction of the ferric reagent in the presence of Fe(NO3)3. The limit of detection (LOD) was determined to be approximately 2 mg/kg using the Student's t-test (99% confidence), and a reproducibility of approximately 3% was determined by the relative standard deviation (RSD) from measurements of calibration samples (n = 7). Furthermore, TBBPA in actual polymer samples was screened without the need for any complex processing steps. Because this colorimetric method measures TBBPA by detecting phenolic groups, it may overestimate the TBBPA concentration in the presence of other similar phenolic substances. Nonetheless, this simple colorimetric method should help to quickly identify the presence of TBBPA in various polymers.

Development of a screening method for phthalate esters in polymers using a quantitative database in combination with pyrolyzer/thermal desorption gas chromatography mass spectrometry.

Seven phthalate esters (di-isobutyl phthalate (DIBP), di-n-butyl phthalate (DBP), benzylbutyl phthalate (BBP), di-(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DNOP), di-isononyl phthalate (DINP) and di-isodecyl phthalate (DIDP)) were analyzed by pyrolyzer/thermal desorption-gas chromatography/mass spectrometry (Py/TD-GC/MS), the retention index and relative response factor (RRF) relative to DEHP was calculated for each compound and used to construct a quantitative database (qDB). This qDB enables normalization of the retention time and response factor of each phthalate ester between any laboratory simply by analyzing an n-alkane solution and DEHP standard material. This allows for easy calculation of the phthalate ester content of samples without preparation of calibration curves. The efficacy of this qDB method was verified by performing a quantitative analysis of phthalate esters at 4 different laboratories that showed actual retention times were within ±0.012 min of the estimated retention times for all compounds at all laboratories. Similarly, the mean recovery rate (n = 6) at each laboratory was within 79-113%. Quantitative analysis was also performed on 30 real samples using both the qDB method and the Py/TD-GC/MS method set forth in IEC62321-8, which involves the preparation of 1-point calibrations to perform quantitative analysis. The difference in quantitative results between the methods was approximately within ±200 mg/kg for compounds in the concentration region of <2000 mg/kg.

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

This study describes a methodology for evaluating regulatory levels of phthalate contamination. By collecting experimental data on short-term phthalate migration using thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS), the migration of di(2-ethylhexyl) phthalate (DEHP) from polyvinyl chloride (PVC) to polyethylene (PE) was found to be expressed by the Fickian approximation model, which was originally proposed for solid (PVC)/liquid (solvent) migration of phthalates. Consequently, good data correlation was obtained using the Fickian approximation model with a diffusion coefficient of 4.2 × 10-12 cm²/s for solid (PVC)/ solid (PE) migration of DEHP at 25 °C. Results showed that temporary contact with plasticized polymers under a normal, foreseeable condition may not pose an immediate risk of being contaminated by phthalates at regulatory levels. However, as phthalates are small organic molecules designed to be dispersed in a variety of polymers as plasticizers at a high compounding ratio, the risk of migration-related contamination can be high in comparison with other additives, especially under high temperatures. With these considerations in mind, the methodology for examining regulatory levels of phthalate contamination using TD-GC-MS has been successfully demonstrated from the viewpoint of its applicability to solid (PVC)/solid (PE) migration of phthalates.

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

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.