Synthesis and Characterization of Copolycarbonates Derived from 2,2,4,4-Tetramethyl-1,3-Cyclobutanediol

Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1993 Synthesis and Characterization of Copolycarbonates Derived From 2,2,4,4-Tetramethyl-1,3-Cyclobutanediol. Carey Cecil Geiger Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Geiger, Carey Cecil, "Synthesis and Characterization of Copolycarbonates Derived From 2,2,4,4-Tetramethyl-1,3-Cyclobutanediol." (1993). LSU Historical Dissertations and Theses. 5634. https://digitalcommons.lsu.edu/gradschool_disstheses/5634 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. U M I films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UM I a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact U M I directly to order. University Microfilms International A Bell & Howell Information Company 300 North Zeeb Road. Ann Arbor, Ml 48106-1346 USA 313/761-4700 800/521-0600 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Order Number 9419888 Synthesis and characterization of copolycarbonates derived from 2,2,4,4-tetramethyl-l,3-cyclobutanediol Geiger, Carey Cecil, Ph.D. The Louisiana State University and Agricultural and Mechanical Col., 1993 UMI 300 N. Zeeb Rd. Ann Arbor, M I 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. SYNTHESIS AND CHARACTERIZATION OF COPOLYCARBONATES DERIVED FROM 2,2,4,4-TETRAMETHYL-1,3-CYCLOBUTANEDIOL A Dissertation Submitted to the Graduate Faculty of Louisiana State University Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Carey Cecil Geiger B.S., University of Southern Mississippi, 1987 December 1993 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Acknowledgments It would be a terrible error if the first paragraph of this thesis is not devoted to Dr. William H. Daly. His dedication, knowledge and inspiration have been invaluable to this research and thesis. While on sabbatical leave at IBM, Dr. Daly initialized this research and much of discussed results in this thesis are a repetition of his work. Also, his patience with the weekend golfer and fisherman are appreciated. Finally, the properties of the TMCBD homopolycarbonate and the BisTP/TMCBD copolymers are results from his research. Dr. Soo Lee and Dr. loan Negulescu need to be thanked. Both of them spent valuable time measuring the thermal properties discussed in chapter 4. The crystal structures listed in the appendix were solved by Dr. Frank Fronczek. Dr. Paul Russo loaned his lab equipment to this research. Dr. Andy Maverick, Dr. Mark McLaughlin, Dr. James Robinson and Dr. William Bernard served as committee members and gave valuable assistance. Zhaoyao Qiu, Doris Culberson, Kim Ngo, Dr. Drew Poche' and Dr. Marrietta Aniano-llao gave their time and advice to this research. Louisiana State University and IBM provided financial support. Fred Koch provided friendship and entertainment during graduate school, and had the undesirable job of editing the first draft. My father and step-father provided the occasional kick to the seat of pants that led to the completion of this work. Finally, I am dedicating this work to my mother and sisters who provided encouragement, moral support and good food. ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Table of Contents Acknowledgments ii List of Tables v List of Figures vi List of Abbreviations viii Abstract xi Chapter 1: Introduction 1 1.1 Opening Remarks 2 1.2 Review of Polycarbonates 2 1.3 Properties of an Electrical Insulator and Optical Substrate 4 1.4 Proposed Copolymers 6 1.5 Review of Previous Work 8 1.6 Objectives 10 Chapter 2: Synthesis of Monomers and Polymers 11 2.1 Introduction 12 2.2 Review of BisA/TMCBD Copolymer 14 2.3 Bis-phenols 15 2.4 2,2,4,4-Tetramethyl-1,3-cyclobutanedichloroformate 21 2.5 Copolymers 22 2.6 End Groups 25 2.7 Experimental 26 2.8 Conclusion 29 Chapter 3: Identification of Copolymers 30 3.1 Introduction 31 3.2 Molecular Weights and Viscosities 31 3.3 Infrared and NMR Spectra 34 3.4 End Groups 44 3.5 Conclusion 45 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Chapter 4: Optical Properties 47 4.1 Introduction 48 4.2 Films 48 4.3 Optical Properties 50 4.4 Conclusion 51 Chapter 5: Thermal Properties 52 5.1 Introduction 53 5.2 Transition Temperatures 53 5.3 Thermal Instability 58 5.4 Thermal Stability 60 5.5 Conclusion 63 Chapter 6: Conclusion 64 6.1 Research 65 6.2 Future Work 66 References 68 Appendix 1. Spectral Data of BisCB 74 Appendix 2. Spectral Data of BisAD 81 Appendix 3. Spectral Data of TMCBDCI 88 Appendix 4. ^ C NMR Chemical Shifts of Substituents 90 Appendix 5. Instrumentation 93 Vita 96 iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. List of Tables Table 2.1. Purchased Bis-phenols. 16 Table 2.2. Synthesized Bis-phenols. 17 Table 2.3. Experimental Conditions. 23 Table 3.1. Molecular Weights and Viscosities. 31 Table 3.2. Chemical Shifts of Backbone Hydrogens in ppm. 36 Table 3.3. Chemical Shifts of Backbone Carbons in ppm. 42 Table 4.1. Refractive Indices. 50 Table 5.1. Glass Transition Temperatures. 54 Table 5.2. Beta Transition Temperatures at 10 Hertz 56 Table 5.3. Computer Simulation of Bis-phenols. 58 v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. List of Figures Figure 1.1. Structure of Polycarbonates. 2 Figure 1.2. Poly(bisphenol A)carbonate. 3 Figure 1.3.1,1-bis(4-hydroxyphenyl)-1-phenylethane. 8 Figure 1.4. Bisphenol A and TMCBD Copolycarbonate. 9 Figure 2.1. Reaction Scheme Used to Synthesize Copolycarbonates. 13 Figure 2.2. Structure of (a) BisCB and (b) BisAD. 18 Figure 2.3. FTIR Spectrum of BisCB. 19 Figure 2.4. FTIR Spectrum of BisAD. 20 Figure 2.5.1H NMR Spectra of (a) BisA, (b) BisN and (c) BisCB. 21 Figure 2.6. 1H NMR Spectrum of TMCBDCI. 22 Figure 2.7. Structure of Copolymers. 23 Figure 2.8. Addition of Trimethylsilyl End Groups. 26 Figure 3.1. GPC Plot of BisC/TMCBD. 33 Figure 3.2. FTIR Spectrum of BisA/TMCBD. 35 Figure 3.3. Location of Backbone Hydrogens. 36 Figure 3.4.1H NMR Spectra of (a) BisA/TMCBD, (b) BisN/TMCBD 37 and (c) BisCB/TMCBD. Figure 3.5. 1H NMR Spectrum of BisA/TMCBD. 38 Figure 3.6. Rearrangement Reaction. 40 Figure 3.7. Carbon Dioxide Elimination. 40 Figure 3.8.1H NMR Spectra of (a) BisA/TMCBD and (b) BisAP/TMCBD. 41 Figure 3.9. Location of Backbone Carbons. 42 Figure 3.10. 13C NMR Spectra of (a) BisCB/TMCBD and 43 (b) BisN/TMCBD. Figure 3.11.1H NMR Spectrum of End Capped BisAP/TMCBD. 45 vi Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Figure 5.1. DSC Plot of BisA/TMCBD. 55 Figure 5.2. Dynamic Thermal Mechanical Analyzer Plot of BisCB/TMCBD. 57 Figure 5.3. Simulated Bond Angle. 57 Figure 5.4. GPC Trace of (a) BisC/TMCBD and (b) Residual. 59 Figure 5.5. 1H NMR Spectra of (a) BisAP/TMCBD and (b) Residual. 60 Figure 5.6. TGA Plot of BisA/TMCBD Precipitated from 62 (a) Tetrahydrofuran and (b) Chloroform. Figure 5.7. Reaction of Copolymer with Water. 63 vii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. List of Abbreviations A: Angstroms a\: Polarizability in the i th direction. BisA and bisphenol A: 2,2-bis(4-hydroxyphenyl)propane. BisA/TMCBD: Poly(oxy-carbonyl-oxy-1,4-phenyl-2,2-propane-1,4-phenyl-oxy- carbonyl-oxy-1,3-(2l2I4,4-tetramethyl)cyclobutane). BisAD: 9,9-bis(4-hydroxyphenyl)tricyclo[3.3.1.13>7]decane. BisAD/TMCBD: Poly(oxy-carbonyl-oxy-1,4-phenyl-2,2-tricyclo[3.3.1.1 Jdecane 1,4-phenyl-oxy-carbonyl-oxy-1,3-(2,2,4,4-tetramethyl)cyclobutane). BisAP: 1,1 -bis(4-hydroxyphenyl)-1 -phenylethane.

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