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Synthesis and Characterization of Peek Analogues Utilizing 3,5 and 2,4-Difluorobenzophenone

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Synthesis and Characterization of Peek Analogues Utilizing 3,5 and 2,4-Difluorobenzophenone SYNTHESIS AND CHARACTERIZATION OF PEEK ANALOGUES UTILIZING 3,5 AND 2,4-DIFLUOROBENZOPHENONE A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science By ZACHARY EWING B.S. Northern Kentucky University, 2014 2016 Wright State University WRIGHT STATE UNIVERSITY GRADUATE SCHOOL December 14th, 2016 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Zachary Ewing ENTITLED Synthesis and Characterization of PEEK Analogues Utilizing 3,5 and 2,4-Difluorobenzophenone BE ACCEPTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science. Committee on Final Examination ___________________________ Eric Fossum, Ph.D. ___________________________ Thesis Advisor Eric Fossum, Ph.D. ___________________________ William A. Feld, Ph.D. ___________________________ David Grossie, Ph.D. ___________________________ Chair, Department of Chemistry Daniel Ketcha, Ph.D. _____________________________ Robert E. W. Fyffe, Ph.D. Vice President for Research and Dean of the Graduate School ABSTRACT Ewing, Zachary. M.S., Department of Chemistry, Wright State University, 2016. Synthesis and Characterization of PEEK Analogues Utilizing 3,5 and 2,4- Difluorobenzophenone Two routes to semi-crystalline, potentially functionalizable poly(ether ether ketone), PEEK, analogues were explored using varying percentages of 4,4’- difluorobenzophenone and either 3,5-difluorobenzophenone or 2,4- difluorobenzophenone as the electrophilic component in nucleophilic aromatic substitution polycondensation reactions with hydroquinone. PEEK analogues utilizing 3,5-difluorobenzophenone were carried out in a “one-pot” fashion and their properties were compared to the same materials prepared previously by a multi-step synthetic procedure. The use of 2,4-difluorobenzophenone led to completely new PEEK analogues. The polymers were characterized via NMR spectroscopy, Size Exclusion Chromatography, Thermogravimetic Analysis, and Differential Scanning Calorimetry. Molecular weight determinations showed the synthesized polymers to be of a variety of molecular weights, with weight averaged molecular weight (Mw) values between 7,500 and 83,000 Da and dispersity (Ð) values between 2.5 and 2.9. The polycondensation reactions were also accompanied by the formation of cyclic species that could be, and were, removed via precipitation/trituration with isopropanol or mostly avoided by a judicious choice of reaction conditions. Solubility tests showed that the 3,5- homopolymers, which were semi-crystalline, and 2,4-homopolymers, which were completely amorphous, were soluble in many common organic solvents, while the solubility of the copolymers decreased as the percentage of 4,4’-difluorobenzophenone increased. Thermal analysis of the 3,5-difluorobenzophenone polymers possessed 5 % weight loss temperature values (Td 5%) that were similar to those of the previously synthesized polymers1, with values between 330 and 500°C. For both polymer systems, iii the glass transition temperatures (Tg) were between 86 and 129°C, which is consistently lower than those of the materials previously synthesized via the multistep protocols. The 3,5 homopolymer and 75%/25% (PEEK/PAMPPO) copolymers displayed crystallization temperatures (Tc) between 156 and 210°C with melting temperatures (Tm) between 252 and 254°C. The 2,4-difluorobenzophenone polymers had Tg values ranging from 113 to 152°C with Tc and Tm values, for polymers containing 35% or less 2,4- difluorobenzophenone, ranging from 220 to 230°C, and 280 to 320°C, respectively. iv Table of Contents 1. INTRODUCTION .......................................................................................................... 1 1.1. Poly (arylene ether)s, PAEs ............................................................................ 1 1.1.1. Poly (arylene ether sulfone)s, PAES ...................................................... 2 1.1.2. Poly (phenylene oxide), PPO ................................................................... 3 1.1.3. Poly (arylene ether ketone)s, PAEKs ..................................................... 4 1.2. Synthesis of Poly (arylene ether ketone)s .................................................... 5 1.2.1. Polycondensation via Nucleophilic Aromatic Substitution (NAS) ..... 5 1.3. Isomers of Poly (ether ether ketone), PEEK ................................................. 7 1.3.1. o-PEEK ....................................................................................................... 7 1.3.2. m-PEEK ...................................................................................................... 8 1.3.3. PAMPPO ..................................................................................................... 8 1.4. Functionalization Chemistry ......................................................................... 10 1.5. Current Project ............................................................................................... 11 2. EXPERIMENTAL ........................................................................................................ 15 2.1. Materials .......................................................................................................... 15 2.2. Instrumentation .............................................................................................. 16 2.3. General Procedure for the Synthesis of PAMPPO via “Batch-wise” Approach ................................................................................................................ 17 2.4. General Procedure for the Synthesis of PAMPPO via “Step-wise” Approach ................................................................................................................ 18 2.5. Synthesis of PMPO (5a) via “Batch-wise” Approach .................................... 18 2.6. Synthesis of PMPO (5b) via “Step-wise” Approach ...................................... 19 2.7. General reaction procedure for 3,5-system (copolymers 7a, 7b, & 7c) ...... 19 3. RESULTS AND DISCUSSION ................................................................................... 23 3.1. Characterization and identification of PAMPPO ........................................ 23 3.2. Characterization and identification of PEEK/PAMPPO copolymers ........ 30 3.3. Characterization and Identification of PEEK/PAPOPO .............................. 37 4. CONCLUSIONS ......................................................................................................... 47 5. PROPOSED FUTURE WORK ................................................................................... 47 6. REFERENCES ........................................................................................................... 48 v LIST OF FIGURES Figure 1: Various PAEs, with Tg and Tm data, where applicable. .................................................................. 1 Figure 2: Various commercially available PAES with associated Tg values. .................................................. 3 Figure 3: Major PAEK's with Tg and Tm values. ............................................................................................ 4 Figure 4: Examples of isomers of traditional PEEK, with a box showing functionalization sites in each case. *PAMPPO was originally called m-PEEK by Fortney and Fossum1 .............................................................. 7 Figure 5: Visualization of the benefit of a pendent functionalization site. Red arrows show modification of the backbone, while the blue arrow shows modification that does not affect the backbone. .............................. 10 Figure 6: Representation of the main goal of this project. ........................................................................... 13 Figure 7: 2,4-difluorobenzophenone (left) and 3,5-difluorobenzophenone (right), two starting materials in this project. ...................................................................................................................................................... 14 Figure 8: Names of monomers and polymers with their names and structures for clarification .................... 16 Figure 9: Comparison of a step-wise synthesis (3e) and a batch-wise synthesis (3f) in terms of cyclic species by the peak located around 5.4 ppm ............................................................................................. 25 13 Figure 10: 75.5 MHz C CPD NMR (DMSO-d6) overlay 3f and 5a compared to Fortney’s PAMPPO. Note: The NMR sample is a mixture of the sample and NMP in DMSO-d6. .......................................................... 26 Figure 11: 300 MHz 1H NMR of 5a showing the presence of cyclic species ................................................ 27 Figure 12: (Left) TGA overlay showing similar degradation patterns for 3e, 3f, and 5a. (Right) DSC trace (second heat) for 3e (–––––––), 3f (–– –– –), 5a (––– –––) and Fortney’s PAMPPO (– – – –). ................... 28 Figure 13: Powder diffraction data for 3e, 3f, and 5a .................................................................................. 29 Figure 14: Comparison of 3f before (bottom), after 1 reprecipitation (middle), and after 2 reprecipitations in isopropanol. Note: The NMR sample is a mixture of the sample and NMP in DMSO-d6. ............................. 30 13 Figure 15: 75.5 MHz C CPD (DMSO-d6) overlay of 7a (bottom) and Fortney and Fossum's 50% copolymer. Note: The NMR sample is a mixture of the sample and NMP in DMSO-d6. ................................................. 32 13 Figure 16: 75.5 MHz C NMR (DMSO-d6)
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