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Environmental Fate of Fluorotelomer-Based Acrylate Polymers

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Environmental Fate of Fluorotelomer-Based Acrylate Polymers Environmental Fate of Fluorotelomer-based Acrylate Polymers by Pablo Jorge Z.Y. Tseng A thesis submitted in conformity with the requirements for the degree Master of Science Department of Chemistry University of Toronto © Copyright by Pablo Jorge Z.Y. Tseng (2009) Library and Archives Bibliotheque et 1*1 Canada Archives Canada Published Heritage Direction du Branch Patrimoine de I'edition 395 Wellington Street 395, rue Wellington Ottawa ON K1A 0N4 OttawaONK1A0N4 Canada Canada Your file Votre reference ISBN: 978-0-494-81225-9 Our file Notre reference ISBN: 978-0-494-81225-9 NOTICE: AVIS: The author has granted a non­ L'auteur a accorde une licence non exclusive exclusive license allowing Library and permettant a la Bibliotheque et Archives Archives Canada to reproduce, Canada de reproduire, publier, archiver, publish, archive, preserve, conserve, sauvegarder, conserver, transmettre au public communicate to the public by par telecommunication ou par I'lnternet, prefer, telecommunication or on the Internet, distribuer et vendre des theses partout dans le loan, distribute and sell theses monde, a des fins commerciales ou autres, sur worldwide, for commercial or non­ support microforme, papier, electronique et/ou commercial purposes, in microform, autres formats. paper, electronic and/or any other formats. The author retains copyright L'auteur conserve la propriete du droit d'auteur ownership and moral rights in this et des droits moraux qui protege cette these. Ni thesis. Neither the thesis nor la these ni des extraits substantias de celle-ci substantial extracts from it may be ne doivent etre imprimes ou autrement printed or otherwise reproduced reproduits sans son autorisation. without the author's permission. In compliance with the Canadian Conformement a la loi canadienne sur la Privacy Act some supporting forms protection de la vie privee, quelques may have been removed from this formulaires secondaires ont ete enleves de thesis. cette these. While these forms may be included Bien que ces formulaires aient inclus dans in the document page count, their la pagination, il n'y aura aucun contenu removal does not represent any loss manquant. of content from the thesis. 1+1 Canada Environmental Fate of Fluorotelomer-based Acrylate Polymers Pablo Jorge Zhi Yong Tseng Master of Science Department of Chemistry University of Toronto 2009 Abstract Fluorotelomer (FT)-based acrylate polymers have applications in textile, upholstery, carpet, and apparel and leather industries as components of surface protecting coatings. Currently, there is concern that these polymers may be a potential indirect source of perfluoro-carboxylic acids (PFCAs) in the environment. To address this concern, the current thesis investigated the lability of the ester linkages of a model FT-based acrylate polymer in two potential environmental compartments: sewage wastewater, and surface waters. The in-house synthesized model FT-based acrylate polymer was characterized by ]H and 19F NMR spectroscopy and MALDl-ToF. Potential degradation products including FT alcohols and PFCAs were analyzed by GC-MS and LC-MS/MS respectively. Also, polymer degradation was monitored by lyF NMR spectroscopy and MALDI- ToF. Evidence of FT polymer degradation was observed in the hydrolysis and wastewater studies, suggesting that FT-polymer degradation potentially contributes to the PFCA burden in the environment. ii Acknowledgements This thesis was made possible by those whom 1 have had the good fortune to cross paths with. To all the members and support staff of the chemistry department at the University, your tireless efforts have made this Department a success, and my thesis a possibility. To my colleagues on the 2nd and 3rd floors of LM, and at UTSc, your inspiration and the friendly hallway banter have made my stay at LM memorable and enjoyable. To CB, JC, ADS, DJ, HL, EM, AM, AR, and CY, my time at the Mabury lab has been rewarding academically and socially. Since my starting at the lab as a summer student in 2006. you have become more than colleagues, and though time parts us now, we need not despair; the foundations to our lasting friendships have been lain already. To CQ. thank you. To my committee members Professors Jennifer Murphy and Douglas Stephan, your availability and insight into my research have been a great help to my graduate work. 1 would like to especially thank Professor Scott A. Mabury for unparalleled research guidance, professional support, and camaraderie. This thesis is dedicated to Science. As a tree in the passage of time, so shall you remain. iii iv Table of Contents Abstract ii Acknowledgements iii Table of Contents v List of Figures viii List of tables x 1 Introduction to Perfluorinated Chemicals 2 1.1 Perfluorinated Carboxylic Acids 2 1.2 Fluorotelomer Alcohols 3 1.3 Fluorotelomer-based polymers 5 1.4 Research Objectives 8 1.5 Literature Cited 10 2 Degradation of Fluorotelomer based Polymers in Wastewaters 14 2.1 Abstract 14 2.2 Introduction 15 2.3 Experimental Section 17 2.3.1 Chemicals 17 2.3.2 Polymer Synthesis , 17 2.3.3 Polymer Characterization 18 2.3.4 Polymer Solubility and Residual Removal 22 2.3.5 Experimental Set-up 24 2.3.6 Vessel Headspace Analysis 27 2.3.7 Vessel Aqueous Medium Analysis , 28 v 2.3.8 Data Analysis 29 2.3.9 Quality Assurance and Control 29 2.4 Results and Discussion 30 2.4.1 Hydrolysis Study 30 2.4.2 Wastewater Study 38 2.5 Environmental Implications 46 2.6 Acknowledgements 46 2.7 Literature Cited 47 Research Directions and Future Considerations 52 3.1 Polymer Synthesis and Characterization 52 3.2 The Degradation of Ruorotelomer Acrylate Polymers in Soils 57 3.2.1 Residual Removal and Polymer Solubility 58 3.2.2 Experimental Set-Up 59 3.3 Thermal and Mechanical Degradation 60 3.4 Future Considerations 63 3.5 Literature Cited 65 Appendix 67 4.1 Section 2.3.4 - Polymer Solubility and Residual Removal 67 4.2 Section 2.3.7 - Vessel Aqueous Medium Analysis 70 4.3 Section 2.4.1 - 8:2 FTOH Evolution 71 4.4 Section 2.4.1 - 19F NMR Spectroscopy Analysis 77 4.5 Section 2.4.1 - MALDI-ToF Analysis 81 4.6 Section 2.4.1 - Hydrolytic Degradation Rates 89 4.7 Section 2.4.2 - Wastewater Sludge Viability Test 90 4.8 Section 2.4.2 - Headspace Analysis 91 4.9 Section 2.4.2 - Aqueous Analysis 92 4.10 Section 3.1 - Polymer Synthesis and Characterization 97 VII List of Figures Figure 1-1. (a) atmospheric degradation pathway; (b) biodegradation pathway 4 Figure 1-2. (a) 8:2 FT acrylate; (b) 8:2 FT methacrylate 5 Figure 1-3. Ruorotelomer-based polymer synthesis 6 Figure 2-1. Fluorotelomer-based acrylate polymer synthesis 18 Figure 2-2. (a) Schematic of Model Polymer (b) 19F NMR spectrum of polymer 19 Figure 2-3. MALDI Spectrum of synthesized fluorotelomer acrylate based polymer 21 Figure 2-4. GC chromatogram of polymer solution after 30 days of residual purging, immediately prior to the start of the experiment 23 Figure 2-5. Schematic Diagram of Experimental Set-up for Hydrolysis/Wastewater Studies. 25 Figure 2-6. Evolution of 8:2 FTOH at pHs 4, 6, 8 and 10 31 Figure 2-7. Hydrolytic degradation rates of FT polymer at various pH conditions 37 Figure 2-8. Transformation of 6:2 FTUCA to PFHxA - Viability Test 38 Figure 2-9. 8:2 FTOH evolution in Control Set 2 and Experimental Vessels 39 Figure 2-10. Amounts of 8:2 FTOH metabolites detected in Sample Vessels (a) PFHxA; (b) PFHpA: (c) PFOA: td) 8:2 FTUCA 41 Figure 3-1. Schematic of New Model Polymer 53 Figure 3-2. MALDI Spectrum of New Model Ruorotelomer acrylate based Polymer 55 Figure 3-3. Summary of the identity of FT acrylate polymer signals 56 Figure 3-4. Proposed mechanism of thermal degradation of 8:2 FT acrylate polymers 61 Figure 3-5. atmospheric oxidation pathway of ethylene thermal degradation product 61 Figure 3-6. Proposed mechanism of FTOH evolution from polymeric thermal degradation... 62 Figure 4-1. Concentration of Polymer in the prepared polymer solution 67 Figure 4-2. I9F NMR spectrum of the lOOppm polymer calibration standard 69 viii Figure 4-3. Comparison of the Hansen and Higgin methods of PFCA extraction 70 Figure 4-4.19F NMR spectrum of hydrolysis Sample Experimental Vessel at Day 0 78 Figure 4-5. 19F NMR spectrum of hydrolysis pH = 4 Experimental Vessel at Day 80 79 Figure 4-6. 19F NMR spectrum of hydrolysis pH = 10 Experimental Vessel at Day 80 80 Figure 4-7. MALDI Spectrum of Polymer in Sample Experimental Vessel at day 0 (I) 81 Figure 4-8. MALDI Spectrum of Polymer in pH =4 Experimental Vessel at day 80 (I) 82 Figure 4-9. MALDI Spectrum of Polymer in pH =6 Experimental Vessel at day 80 (I) 83 Figure 4-10. MALDI Spectrum of Polymer in pH =10 Experimental Vessel at day 80 (I) 84 Figure 4-11. MALDI Spectrum of Polymer in Sample Experimental Vessel at day 0 (II) 85 Figure 4-12. MALDI Spectrum of Polymer in pH = 4 Experimental Vessel at day 80 ill) 86 Figure 4-13. MALDI Spectmm of Polymer in pH = 6 Experimental Vessel at day 80 (II) 87 Figure 4-14. MALDI Spectrum of Polymer in pH = 10 Experimental Vessel at day 80 (II)... 88 Figure 4-15.DSC - Melting and Crystallization Points of newly synthesized polymer 97 Figure 4-16. Repeating Polymeric Units in the Polymer Distribution 98 Figure 4-17. Determination of FT acrylate polymer signal (1) 99 Figure 4-18. Determination of FT acrylate polymer signals (2) 100 IX List of tables Table 2-1.
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