Rapid chromatographic determination of flame retardants by HLPC and GC-MS [Elektronische Ressource] = Schnelle chromatographische Bestimmung von Flammschutzmitteln mit HPLC und GC-MS / vorgelegt von Manfred Pöhlein

Poehlein

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• Publié par: friedrich-alexander-universitat_erlangen-nurnberg
• Publié le: 01 janvier 2009
• Nombre de lectures: 37
• Poids de l'ouvrage: 2 Mo

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Rapid Chromatographic Determination of Flame Retardants by HPLC and GC/MS

Rapid Chromatographic Determination
of Flame Retardants by HPLC and GC/MS

Schnelle chromatographische Bestimmung
von Flammschutzmitteln mit HPLC und GC/MS


Den Naturwissenschaftlichen Fakultäten
der Friedrich'Alexander'Universität Erlangen'Nürnbe rg
zur Erlangung des Doktorgrades


vorgelegt von
Manfred Pöhlein
aus Zeil am Main
I Rapid Chromatographic Determination of Flame Retardants by HPLC and GC/MS
Als Dissertation genehmigt von den Naturwissenschaftlichen Fakultäten
der Universität Erlangen'Nürnberg.



























Tag der mündlichen Prüfung: 12. November 2009

Vorsitzender der
Promotionskommission: Prof. Dr. E. Bänsch
Erstberichterstatter: Prof. Dr. Dr. h.c. mult. Rudi van Eldik
Zweitberichterstatter: Prof. Dr. L. Dahlenburg


II Rapid Chromatographic Determination of Flame Retardants by HPLC and GC/MS
Die vorliegende Arbeit entstand zwischen November 2000 und Juli 2006 am
Lehrstuhl für Anorganische und Analytische Chemie, Department Chemie und
Pharmazie der Friedrich'Alexander'Universität Erlan gen'Nürnberg.
III Rapid Chromatographic Determination of Flame Retardants by HPLC and GC/MS
IV Rapid Chromatographic Determination of Flame Retardants by HPLC and GC/MS









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für die Geduld, das Verständnis
und die große Unterstützung
V Rapid Chromatographic Determination of Flame Retardants by HPLC and GC/MS
VI Rapid Chromatographic Determination of Flame Retardants by HPLC and GC/MS
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I’m very grateful towards Prof. Dr. Dr. h. c. mult. Rudi van Eldik, for the
competent supervision of this work, the interesting and inspiring discus'
sions, the warm and familiar environment, the financial support and, last
but not least, for always being understanding and willing to listen to my
problems. The friendly yet professional atmosphere was especially sup'
portive when discussing various topics, not only of scientific concern.
I wish to thank my working group, especially my former colleagues Dr.
Michael Rieß, Dr. Tobias Ernst, Dr. Ralf Popp, and Bernd Müller, for the
many fruitful and inspiring discussions and the scientific support.
Furthermore I greatly acknowledge my colleagues Dr. Marion Wolf, Dr.
Abdel Mnim Altwaiq, Raquel Urpi and Thomas Roth, who were especially
valuable for advancing my troubleshooting skills.
Special thanks go, of course, to the members of the technical staff, in
particular to Susanne Hoffman, Jochen Schmidt, Hans Zöbelein, Peter
Igel, Manfred Weller, and Uwe Reißer. Without their technical skills and
experience, my research would not have been possible.
Certainly many thanks go also to my dear colleagues and friends, namely
Raquel Urpi, Markus Koch, Dr. Diana Utz, Stephan Wenzel, Dr. Jürgen
Limmer, Dr. David Sarauli, Silvia Bauer and Bruce Horn, for the
efficacious and relaxingly sophisticated discussions about life, science
and, in particular, everything.
I also would like to thank the Bavarian Network for Waste Research and
Residual Re'Use (BayFORREST) for the support. Thank s are also given to
the Grundig company, to Hetzel Elektronik Recycling and to Motorola
GmbH, for supplying materials for my research.
At last, but most important, I’m deeply thankful for such a patient and
supportive family, which greatly encouraged me, motivated me and, if
necessary, pushed me to carry on, especially when I was deeply frust'
rated when my research seemed to stagnate due to equipment failures.
Finally, it worked!
VII Rapid Chromatographic Determination of Flame Retardants by HPLC and GC/MS
VIII Rapid Chromatographic Determination of Flame Retardants by HPLC and GC/MS
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Index of Tables X
Index of Figures XI
Abbreviations XII

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Flame Retardants in Styrenic Polymers 1
General Introduction 1
References 7

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Rapid Identification of RoHS''rreelleevvaan tt FFllaamee Reettaarrd aan ttss
by Ultrasonic Extraction and RP''H PPLLC/U V 9
General remark 9
1. Introduction 9
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2.1 Instrumentation 11
2.2. Chromatographic conditions 11
2.3 Materials 12
2.3.1 Reference substances 12
2.3.2 Industrial polymer reference 13
2.3.3 Special polymer reference 13
2.4 Extraction 13
3. Results and Discussion 15
3.1 Chromatographic method development 15
3.2 Extraction method advances 19
4. Conclusions 23
References 24

Chapter II:
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for the GC/MS Determination of Plastic Additives 27
General remark 27
1. Introduction 27
2. Method Development 30
2.1 Sample Preparation 30
2.1.1 Soxhlet Extraction 30
2.1.2 Thermodesorption 31
2.2 GC/MS Measurements 34
3. Results 38
4. Post'Prrocceesssiing 'Pog40
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IX Rapid Chromatographic Determination of Flame Retardants by HPLC and GC/MS
References 43

Chapter III:
Versatile and Fast Gas Chromatographic Determination
of Frequently used Brominated Flame Retardants 45
General remark 45
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2. Experimental 48
2.1 Instrumentation 48
2.2 Materials 49
2.3 Flame'retardant polymer samples 50
2.3.1 Samples for determination of the extraction performance 50
2.3.2 Samples for determination of the recovery 50
2.4 Extraction and Preparation 51
2.4.1 Extraction performance 51
2.4.2 Final preparation procedure 51
2.5 Chromatographic conditions 52
2.5.1 PTV'GC/MS conditions 52
2.5.2 PSSI'GC/ECD conditions 53
2.5.3 Thin layer chromatography 55
3. Results and Discussion 56
3.1 GC/MS separation method 56
3.2 GC/ECD separation method 62
3.3 Investigations on flame retardants 65
3.3.1 Polybrominated biphenyls 68
3.3.1.1 Hexabromobiphenyl (HBB) 68
3.3.1.2 Octabromobiphenyl (OBB) 68
3.3.1.3 Decabromobiphenyl (DBB) 68
3.3.2 Polybrominated diphenyl ethers 68
3.3.2.1 Pentabromodiphenyl ether (PENTA) 69
3.3.2.2 Octabromodiphenyl ether (OCTA) 69
3.3.2.3 Decabromodiphenyl ether (DECA) 69
3.3.3 Other brominated flame retardants 69
3.3.3.1 Tetrabromobisphenol A (TBBPA) 69
3.3.3.2 Hexabromocyclododecane (HBCD) 69
3.3.3.3 1,2'bis(tribromophenoxy)ethane (TBPE) 69
3.3.4 Standards and Quantification for BrFR 70
3.3.5 Phosphate'based flame retardants 73
3.3.6 Further identification of not clearly identified congeners 74
3.4 Detection limits 75
3.5 Extraction method and performance 77
3.6 Quantification 79
4. Conclusions 82
References 83

X