Analysis of Brominated Flame Retardants and Phthalate Esters In Ploymers Under the Same Conditions Using a Pyrolysis GC-MS System (2) - Phthalate Esters -

Significance of the Topic

Modern polymer products often contain both regulated brominated flame retardants and phthalate plasticizers of concern under global directives such as RoHS and REACH. Comprehensive analytical methods capable of detecting multiple classes of additives in a single workflow are essential for compliance testing, quality control, and environmental safety assessments in manufacturing and recycling industries.

Study Objectives and Overview

This study aimed to evaluate the simultaneous analysis of seven priority phthalate esters in polymer matrices under the same pyrolysis GC-MS conditions previously established for polybrominated flame retardants. Using a combined EGA/PY-3030D Multi-Shot Pyrolyzer and GCMS-QP2020 Ultra system, the workflow integrates thermal extraction and chromatographic separation with selective mass detection for both regulated and unregulated additives.

Instrumental Setup

• Pyrolyzer: EGA/PY-3030D Multi-Shot with temperature program from 200 °C to 340 °C
• GC-MS: Shimadzu GCMS-QP2010 Ultra with Ultra ALLOY-PBDE column (15 m × 0.25 mm I.D., 0.05 µm film)
• Carrier gas: Helium, constant linear velocity at 52.1 cm/s
• Injection: Split mode, 320 °C; solvent cut 0.5 min
• Oven program: 80 °C (hold) to 300 °C at 20 °C/min, hold 5 min
• Detection: FASST simultaneous Scan (m/z 50–1000) and SIM with targeted m/z for phthalates and brominated congeners

Methodology

Standard phthalate mixtures (1–100 ng/µL) were prepared in acetone and deposited into disposable sample cups for pyrolysis. A real sample consisted of 0.5 mg shaved polyvinyl chloride (PVC) cable jacket. FASST mode enabled concurrent full-scan identification and SIM quantitation in one analysis. Calibration was performed across 5–500 ng levels for each phthalate ester.

Main Results and Discussion

• Total ion current chromatograms for 250 ng standards displayed seven distinct phthalate peaks. Although DOP, DINP, and DIDP coeluted in TIC, SIM extraction achieved clear separation.
• Calibration curves for all esters exhibited excellent linearity (R² ≥ 0.9995).
• Real PVC sample analysis confirmed DEHP, DINP, and DIDP presence. Scan spectra further identified non-regulated plasticizers: bis(2-ethylhexyl)adipate and tris(2-ethylhexyl)trimellitate.
• FASST technology provided both sensitive quantitation of target analytes and qualitative screening of unknown additives in a single run.

Practical Benefits and Applications

• Streamlined workflow reduces analysis time and sample handling.
• High sensitivity and selectivity meet regulatory detection limits for RoHS and REACH SVHC compounds.
• Simultaneous detection of regulated and emerging plasticizers aids comprehensive compliance and quality assessments.
• Applicable to diverse polymeric materials in electronics, cables, and consumer goods.

Future Trends and Potential Applications

Advancements may include integration of high-resolution mass spectrometry for non-target screening, automated data processing for rapid flagging of banned substances, and extension to volatile and semi-volatile additive classes. Miniaturized pyrolysis-GC interfaces and direct polymer sampling techniques will further increase throughput in industrial laboratories and environmental monitoring.

Conclusion

The combined pyrolysis GC-MS approach effectively quantifies multiple phthalate esters alongside brominated flame retardants under unified analytical conditions. It offers robust linearity, sensitivity, and dual scan/SIM capability, meeting stringent regulatory requirements and enabling comprehensive plasticizer profiling in polymer products.