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Synthesis and Characterization of Functionalized Poly(Arylene Ether Sulfone)S Using Click Chemistry

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Synthesis and Characterization of Functionalized Poly(Arylene Ether Sulfone)S Using Click Chemistry Wright State University CORE Scholar Browse all Theses and Dissertations Theses and Dissertations 2016 Synthesis and Characterization of Functionalized Poly(arylene ether sulfone)s using Click Chemistry Kavitha Neithikunta Wright State University Follow this and additional works at: https://corescholar.libraries.wright.edu/etd_all Part of the Chemistry Commons Repository Citation Neithikunta, Kavitha, "Synthesis and Characterization of Functionalized Poly(arylene ether sulfone)s using Click Chemistry" (2016). Browse all Theses and Dissertations. 1650. https://corescholar.libraries.wright.edu/etd_all/1650 This Thesis is brought to you for free and open access by the Theses and Dissertations at CORE Scholar. It has been accepted for inclusion in Browse all Theses and Dissertations by an authorized administrator of CORE Scholar. For more information, please contact [email protected]. SYNTHESIS AND CHARACTERIZATION OF FUNCTIONALIZED POLY (ARYLENE ETHER SULFONE)S USING CLICK CHEMSITRY A thesis submitted in partial fulfilment of the requirements for the degree of Master of Science By Kavitha Neithikunta B.sc Osmania University, 2010 2016 Wright State University WRIGHT STATE UNIVERSITY GRADUATE SCHOOL August 26, 2016 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MYSUPERVISION BY Kavitha Neithikunta ENTITLED Synthesis and Characterization of Functionalized Poly(arylene ether sulfone)s using Click chemistry BE ACCEPTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science __________________________ Eric Fossum, Ph.D. Thesis Advisor ___________________________ David Grossie, Ph.D. Chair, Department of Chemistry Committee on Final Examination ____________________________ Eric Fossum, Ph.D. _____________________________ Daniel M. Ketcha, Ph.D. _____________________________ William A. Feld, Ph.D. _______________________________ Robert E. W. Fyffe, Ph.D Vice President for Research and Dean of the Graduate School ABSTRACT Neithikunta, Kavitha M.S., Department of Chemistry, Wright State University, 2016. Synthesis and Characterization of Functionalized Poly(arylene ether sulfone)s using Click Chemistry Poly(arylene ether sulfone)s with pendent aryl iodide group was successfully synthesized via Nucleophilic aromatic polycondensation of 1-(3,5-difluorophenyl sulfonyl)-4-iodobenzene using 4,4’-difluorodiphenylsulfone (DFDPS) and Bisphenol A in the ratio 25:75:100. Iodo monomer was prepared by reacting 3,5-difluorodiphenyl sulfone with N-iodo succinimide (NIS). Using GC/MS and NMR spectroscopy, the quantitative analysis was done to this monomer. Modification was done to iodo copolymer using sodium azide and copper sulfate as catalyst to form azide copolymer. Further modification of the azide copolymer to triazole copolymers via Click Chemistry using different alkynes such as 1-octyne, phenyl acetylene, propargyl alcohol and acetylenedicarboxylic acid. Polymers characterization was done using 1H, 13C NMR, IR spectroscopy and SEC. The highest molecular weight (Mw) was found to be 19,033 Da with a PDI 3.0 for iodo copolymer and the least was found to be 6,888 with a PDI 2.5 for acetylenedicarboxylic acid derivative copolymer. Thermal analysis of polymers was done o o using TGA and DSC. The Td5% values were ranging from 260 to 476 . The highest Tg was 191o for phenyl derivative copolymer and the least was 174o for alkyl derivative copolymer. TGA was not ran on azide copolymer as it may contain explosive copper azide traces. IR spectroscopy was used to confirm the structures of azide copolymer, propargyl alcohol derivative and acetylenedicarboxylic acid derivative copolymers. iii TABLE OF CONTENTS 1. INTRODUCTION……………………………………………………………… 1 1.1 Poly (arylene ether)s(PAE)………………………………………………….... 1 1.1.1. Poly (phenylene oxide) PPO…………………………………………. 2 1.1.2. Poly (ether ether ketone) PEEK……………………………………… 3 1.1.3. Poly (arylene ether sulfones) PAES………………………………….. 7 1.2 Synthesis of PAEs by Nucleophilic Aromatic Substitution (NAS)..................... 10 1.3 “Pre” and “Post” modification chemistry………………………………………. 12 1.4 Functionalization of Poly (arylene ether)s, PAEs……………………………... 14 1.4.1. Sulfonated PAE……………………………………………………….. 16 1.4.2. Halogenated PAE……………………………………………………... 18 1.4.3. Click Chemistry……………………………………………………….. 22 1.5 Current work…………………………………………………………………… 24 2. EXPERIMENTAL……………………………................................................. 27 2.1 Instrumentation………………………………………………………………... 27 2.2 Materials………………………………………………………………………. 27 2.3 Synthesis of 1-(3, 5-Difluorophenyl sulfonyl)-4-iodobenzene 2……………... 28 2.4 Polymerization of Iodo monomer 2 to Iodo copolymer (25%) 3…………….. 29 2.5 Synthesis of Azide copolymer 4 ……………………………………………... 30 2.6 Synthesis of Triazole copolymers 5a-d ………………………………………. 30 2.7 CHARACTERIZATION……………………………………………………… 32 2.7.1. Thermogravimetric Analysis (TGA)…………………………………. 32 2.7.2. Differential Scanning Calorimetry (DSC)……………………………. 32 2.7.3. Size Exclusion Chromatography (SEC)………………………………. 33 iv 3. RESULT AND DISCUSSION………………….............................................. 34 3.1 Synthesis of 1-(3, 5-Difluorophenyl sulfonyl)-4-iodobenzene 2….................... 34 3.2 Polymerization of Iodo monomer 2 to Iodo copolymer (25%) 3………............ 36 3.3 Synthesis of Azide Copolymer 4……………………………………................ 39 3.4 “Post Click” Modification of Azide Copolymer 4 to Triazole copolymers 5a-d 42 3.5 Polymer Characterization ……………………………………………………... 49 3.5.1 Thermal analysis………………………………………………………… 51 4. CONCLUSION.................................................................................................. 55 5. FUTURE WORK…………………………………………………………….. 56 6. REFERENCES……………………………………………………………….. 57 v LIST OF FIGURES Figure 1. General representation of poly(arylene ether) backbone structure ……… 1 Figure 2. General structures, trade names and thermal properties of some commercial PAEs………………………………………………………………………………… 2 Figure 3. Structures of PEK, PEKK, PEEK……………………………………….. 4 Figure 4. General structure of PAES………………………………………………. 7 Figure 5. Commercially available PAES…………………………………………... 8 Figure 6. Routes to “pre” and “post” chemistry……………………………………. 15 1 Figure 7. 300 MHz H NMR spectrum (CDCl3) of Iodo monomer 2……………… 35 13 Figure 8. 75.5 MHz C NMR spectrum (CDCl3) of Iodo monomer 2……………. 36 13 Figure 9. 75.5 MHz C NMR spectrum (CDCl3) of Iodo copolymer 3…………… 38 13 Figure 10. 75.5 MHz C overlay spectra (CDCl3) of Iodo monomer 2 (bottom) and Iodo copolymer 3 (top)…………………………………………………………………… 39 13 Figure 11. 75.5 MHz C overlay spectra (CDCl3) of Iodo copolymer 3 (bottom) and Azide copolymer 4 (top) …………………………………………………………… 41 Figure 12. IR Spectroscopy of Azide copolymer 4………………………………… 42 1 Figure 13. 300 MHZ H NMR spectrum (CDCl3) of 5a …………………………... 44 1 Figure 14. 300 MHz H NMR spectrum (CDCl3) of 5b …………………………… 45 1 Figure 15. 300 MHz H NMR spectrum (CDCl3) of 5c …………………………… 46 Figure 16. IR spectrum of 5c……………………………………………………….. 47 1 Figure 17. 300 MHZ H NMR spectrum (CDCl3) of 5d …………………………… 48 Figure 18. IR spectrum of 5d……………………………………………………….. 49 vi Figure 19. TGA traces of polymers 3, 5a, 5b, 5c, and 5d………………………….. 52 Figure 20. DSC traces of polymers 3, 4, 5a, 5b, 5c, and 5d……………………….. 54 vii LIST OF SCHEMES Scheme 1. Oxidative coupling of 2,6-dimethylphenol to form poly(phenylene oxide), PPO…….................................................................................................................... 3 Scheme 2. Synthesis of poly (ether ketone ketone) by EAS………………………. 5 Scheme 3. Synthesis of PEEK and PEEKEK by EAS…………………………….. 6 Scheme 4. Synthesis of poly(ether ether ketone) via NAS………………………… 7 Scheme 5. Synthesis of poly (arylene ether sulfone), PAES by NAS…................... 9 Scheme 6. Synthesis of PAES by EAS…………………………………………….. 9 Scheme 7. EAS of a single AB monomer route for PAES………………………… 10 Scheme 8. Typical NAS mechanism for a para activated system…………………. 11 Scheme 9. Synthesis of PAE via meta-activated NAS polycondensation reactions.. 12 Scheme 10. Introducing functionality via pre and post modification chemistry …... 13 Scheme 11. Post modification of aryl iodides……………………………………… 14 Scheme12.Sulfonation of PAES via “post” modification chemistry…..................... 16 Scheme 13. Synthesis of sulfonated PAES via “pre” modification........................... 17 Scheme 14. Bromination via NBS…………………………………………………. 19 Scheme 15. Synthesis of halogen-rich PAEK and PAES…………………………. 20 Scheme 16. Bromination and Lithiation of poly (sulfone)………………………… 21 Scheme 17. Example of post modification of aryl iodides………………………….. 22 Scheme 18. Synthesis of sulfonated poly(sulfone) copolymer via crosslinking …... 24 Scheme 19. Synthetic route for triazoles via click chemistry……………………..... 26 Scheme 20. Synthesis of 2 via Electrophilic Aromatic substitution……………....... 34 Scheme 21. Polymerization of Iodo monomer 2 to Iodo copolymer 3………............ 37 viii Scheme 22. Synthesis procedure for Azide copolymer 4…………………………… 40 Scheme 23. Synthesis procedure for Triazole copolymer 5(a-d)……………………. 43 ix LIST OF TABLES Table 1. Polymer Characterization Data of Copolymers 3-5(a-d) using SEC……….. 50 Table 2. Thermal analysis data of the polymers of Copolymers 3-5(a-d) using TGA and DSC…………………………………………………………………………………… 51 x ACKNOWLEDGEMENTS I would like to thank my advisor, Dr. Eric Fossum for his patience and guidance in my academic life. I am very thankful to the committee members, Dr. William Feld and Dr. Daniel Ketcha. I would also like to thank the present and past members of Fossum research
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