SYNTHESIS, FABRICATION, CHARACTERIZATION, PROPERTIES AND THERMAL DEGRADATION KINETICS STUDY OF LOW-K POLY(ETHER IMIDE)S AND CO-POLY(ETHER IMIDE)S, AND POLY(ETHER IMIDE)/MMT CLAY NANOCOMPOSITES. ROHITKUMAR H. VORA [M.S. (Polym. Sci. & Eng.), Polytechnic Institute of New York, USA (1980)] A DISSERTATION SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMISTRY FACULTY OF SCIENCE NATIONAL UNIVERSITY OF SINGAPORE 2003 i ROHIT KUMAR H. VORA Degree: Doctor of Philosophy (PhD), 1998-2003. Department: Chemistry PhD Thesis Title: Synthesis, Fabrication, Characterization, Properties, and Thermal Degradation Kinetics Study of Low-K Poly(ether imide)s, Copoly(ether imide)s, and Poly(ether imide)/MMT Clay Nanocomposites. ABSTRACT The objective of the PhD thesis research was the synthesis, film fabrication, characterization, and structure properties study of series of partially fluorinated poly(ether imide) (6F-PEI), copoly(ether imide)s (6F-CoPEI) and (6F-PEI)/organosoluble MMT clay nanocomposite from commercially available monomers and materials. The approach involved the polymerization of 2,2’-bis(3,4-dicarboxyphenyl) hexafluropropane dianhydride (6FDA) with a variety of di-ethercontaining (non-fluorinated) diamines: 4,4-bis(3-aminophenoxy)diphenyl sulfone (m-SED), 4,4bis(4-aminophenoxy)diphenyl sulfone (p-SED), and 4,4-bis(4-aminophenoxy)diphenyl propane (BPADE). The films of these melt processable (6F-PEI) and (6F-CoPEI) polymers from p-SED and BPADE having trifluoromethyl groups showed excellent electrical properties. Fluoropoly(ether imide)s [6FDA + p-SED] and [6FDA + BPADE] had dielectric constants (ε’) of 2.74 and 2.65 at 10MHz respectively. Mathematical model equations were developed to estimate the dielectric constant (ε’co) of copolyimides. For the copoly(ether imide)s, the dielectric constant values were in the range between 3.05 to 3.10 at kHz. These values are lower than the commercially available poly(ether imide) ULTEM1000 (ε’=3.15), and polyimide KaptonH films (ε’=3.5) at kHz. In addition, (6F-PEI)s, (6F-CoPEI)s, and nanocomposite films not only showed extraordinary long-term thermo-oxidative stability (TOS), but also exhibited excellent reduced water absorption relative to commercial polyimides. The transparencies of polymer films were in the range between 80-90% at 500nm solar wavelength. The nanocomposites showed excellent solvent resistance, increased glass transition (Tg) values with increasing clay content, a sharp lowering of the coefficient of thermal expansion (CTE), and improved surface energy. Keywords: Fluoro-poly(ether imide), Fluoro-copoly(ether imide), Fluoro-poly(ether imide)/MMT clay nanocomposites, Low-dielectric, Estimation of dielectric constant, Thermal degradation kinetics, Thermooxidative stability, Surface properties. ii DEDICATION “We measure ourselves by many standards. Our strengths and our intelligence, our wealth and even our good luck, are things which warm our heart and make us feel ourselves a match for life. But deeper than all such things and able to suffice unto itself without them is the sense of the amount of effort we can put forth…. He who can make none is but a shadow; he who can make much is a hero.” -Prof. William James [A prominent American psychologist of the 19th century (1898).] I would like to dedicate this dissertation to my beautiful wife, Neela R. Vora, who is my better half and a very good friend, and to my two extraordinarily special teenage children, son Ashish and daughter Amee, for their all-out encouragement, support, and unconditional love during the course of this long research. They are my heroes, who patiently and lovingly accepted my long and late hours at work at the Institute of Materials Research and Engineering (IMRE)’s laboratory during those years, at which time, I almost became a weekend husband and father, but never did they ever fail to let me know that they loved me. I owe them my deepest gratitude and thanks from the bottom of my heart. I love you, guys. ii ACKNOWLEDGEMENTS “Mind is a terrible thing to waste” -Rev. Martin Luther King, Jr. “Poverty is the greatest form of ‘Violence and Sin’ of mankind” -Mahatma Gandhi I would like to express my sincere appreciation and profound gratitude to my doctoral thesis advisor, distinguished Professor Suat Hong Goh at the Dept. of Chemistry for his time, resources support, valuable guidance and mentorship throughout my graduate studies, and also to my coadvisor Prof. Tai-Shung (Neal) Chung, for allowing me a complete creative freedom in deciding my thesis research topic and objectives, and for his continuing encouragement. I would like to express my heartfelt thanks to the President of the National University of Singapore, Prof. Fong Choon Shih, then the founding director of the Institute of Materials Research and Engineering (IMRE) for giving me his permission in 1998 to enroll for PhD studies at the Dept. of Chemistry at NUS, and for also allowing me to carry out a simultaneous PhD research work at IMRE in the Advanced Polymers Group’s lab while working at IMRE. I would also like to thank distinguished professor emeritus Prof. Huang Hsing Hua for his willingness to accept me as his PhD student and, also to allow me to use his laboratory at S9-0303 at the Dept. of Chemistry during the early years (1997-1999) of IMRE. With the blessings of these wonderful teachers and mentors, I initiated my PhD thesis research work in November 1998 at IMRE. During the last five years, their patience and helpful suggestions have kept me going in carrying out sustained vigorous research work, because of which I was successfully able to meet the objectives of my thesis. I would like to acknowledge and sincerely thank Dr. Motonori Takeda, Senior Managing Director and Chief Technical Officer of Wakayama Seika Kogyo Co. Ltd., Japan for his friendship, and for providing various diether-containing diamine monomers free of charge for my research work. I also would like to thank the wonderful staff of the Advanced Polymers and Chemicals Cluster at IMRE for many meaningful discussions on analytical techniques. I must not forget to thank Prof. Syamal K. Lahiri of IMRE, Assoc. Prof. B. V. R. Chowdari of the Dept. of Physics, Assoc. Prof. Jagdese J. Vittal of the Dept. of Chemistry, Assoc. Prof. Madapusi P. Srinivasan and Assoc. Prof. Ajay Kumar Ray from the Dept of Chemical & Environmental Engineering and Assoc. Prof. L. C. Lim from Dept. of Mechanical Engineering. for their friendship and intellectually stimulating discussions and moral support. I would also like to thank Prof. Neal Chung and Prof. En-Tang Kang of the Dept of Chemical & Environmental Engineering for the research collaborations and allowing me to co-supervise their PhD students, who used my fluoro-polyimides in their research work. Similarly, I would also like to thank Prof. Michael Philpott, the Head of Dept. Materials Science for inviting me last iii year to teach a 2nd year undergraduate level module ‘Polymeric Engineering Materials’ in his department, thus giving me a unique opportunity to provide manpower training, and have real experience and feel for an academic teaching, which I enjoyed very much, and at the same time I was able concentrate on writing this thesis. In addition, I would like to take this opportunity to thank several of my colleagues and wonderful friends at IMRE: Dr. Ramam Akkipeddi, Dr. Wang Huimin, Mr. Subramanian Veeramani, Dr. P. Santhana Gopala Krishnan, Dr. Pramoda Kumari Pallathadka, Dr. Liu Song Lin, Mr. Sunil Bhangale, Mr. Suresh Kumar Donthu, Mr. Mithilesh Shah, and also to Mr. Rajamani Lakshminarayanan, Mr. Chinnappan Baskar, Mr. Vetrichelvan Muthalagu, Mr. Venkataramanan Balasubramaniam, Mr. Goh Ho Wee, Mr. Li Xuedong from the Dept. of Chemistry; Dr Prashant D. Sawant and Mr. Siddharth Joshi from the Dept. of Physics; Dr. Igor Goliney, Dr. Rengaswamy Jayaganthan, Dr. Santhiagu Ezhilvalavn from the Dept. of Materials Science, for sharing their ideas and for their valuable friendship. Working and/or socializing with all of them has always been a special privilege for me for all these years. I would like to acknowledge the National University of Singapore for sponsoring my trip to attend and present an invited technical paper, and to chair a session at the 6th European Technical Symposium on Polyimides and High Performance Functional Polymers (STEPI-6), held in Montpellier (FRANCE), during May 13-15, 2002. Last, but not least, I would like to thank my dear and loving mother Mrs. Hiralaxmi H. Vora, who taught me how to read, and to my 77 year old dear father, Mr. Harkisondas A. Vora, a Chemical Engineer (from the UDCT-Bombay University, INDIA) and a very successful technopreneur and businessman, who got me interested in the subject of science at an early age. I also thank my dear brother Mayur H. Vora, and sisters Mrs. Chhaya Acharya, Late Mrs. Maya Parikh, and Mrs. Jayshree Doshi. Also thank my respected parent-in-laws: Late Mrs. Ramabahen B. Kanakia and Mr. Babubhai M. Kanakia, brother-in-laws: Rashesh B. Kanakia and his wife Mrs. Rupal Kanakia, and Himanshu B. Kanakia and his wife Mrs. Hiral Kanakia, sister-in-laws: Mrs. Meena Muni, Mrs. Asha Shah and Mrs. Manisha Vora, and my family for their continual loving support, and understanding and prayers. Finally, remembering last three lines from the last stanza of the all-time masterpiece poem ‘Stopping by the woods on a snowy evening’ by the great American poet: “ But I have promises to keep, And miles to go before I sleep, And miles to go before I sleep.” -Robert Frost I am happy to state that my journey for higher learning will not end with getting a PhD degree, as I truly believe that learning is a life long process. May Lord Shree Krishna, the merciful, bless and guide my wisdom in the pursuit of knowledge and happiness in this journey iv CONTENTS DEDICATION ii ACKNOWLEDGEMENTS iii CONTENTS v SUMMARY xx LIST OF PUBLICATIONS xxv CHAPTER - 1. INTRODUCTION 1. INTRODUCTION 1.1. Research background polyimides 1.1.1. High performance polymeric materials 1.1.1.1. Thermosets resins 1.1.1.2. Manufacturing process technology for thermosetting polymers 1.1.1.3. Trends in R&D of high performance polymers 1.1.2. Polyimides 1.1.2.1 History of commercial development of polyimides 10 1.1.2.2. Brief history on polyimide R&D and worldwide major 11 commercial product introduction 1.1.2.3. Brief summary of polyimide market size and growth 20 projection (year 2000 to 2010) 1.1.2.4. Brief summary of literature survey on worldwide 21 polyimide R&D activities 1.1.2.5. Types of polyimides 25 1.1.3. Synthesis of polyimides 27 on polyimides and fluoro- v 1.1.3.1. Monomers 28 1.1.3.2. Polyimides by polycondensation 29 1.1.3.2.1. Polyimides from dianhydrides and diamines 31 1.1.3.2.2. Chemical mechanism of polymerization reaction 32 1.1.3.2.3. Chemical imidization reaction 35 1.1.3.2.3.1. Mechanism of chemical imidization 35 1.1.4. Fluoro-polyimides 38 1.1.5. Characterization techniques of polyimides 48 1.1.5.1. Characterization of polyimide’s chemical characteristics 48 1.1.5.2. Characterization for polyimide’s physical characteristics 48 1.1.5.2.1. Glass transition 49 1.1.5.2.2. Glass transition in copolymers and miscible polymer 52 blends 1.1.6. Processes and properties 53 1.1.6.1. Processing of polyimides 53 1.1.6.2. Mechanical, thermal, and thermo-oxidative stability 54 properties 1.1.6.2.2. Mechanical properties 54 1.1.6.2.3. Thermal properties 55 1.1.6.2.4. Thermo-oxidative stability (TOS) of polyimides 57 1.1.6.3. Electrical and optical properties, dimensional stability 58 and coefficient of thermal expansion (CTE) 1.1.6.3.1. Electrical properties 58 1.1.6.4. Optical properties 60 1.1.6.5. Dimensional stability and CTE 61 1.1.6.6. Other properties 62 vi 1.1.7. Applications of polyimides 63 1.1.7.1. Films 64 1.1.7.2. Molded plastics 64 1.1.7.3. Fibers 65 1.1.7.4. Adhesives and varnishes 66 1.1.7.5. Printed circuit board and packaging materials 66 1.1.7.6. Photo-sensitive polyimides 68 1.1.7.7. Membrane separation 69 1.2. FUTURE OF POLYIMIDES R&D 70 1.3. SCOPE OF RESEARCH ON FLUORO-POLY(ETHER 75 IMIDE)S (6F-PEI) PROJECT 1.4. REFERENCES 80 CHAPTER - 2. SYNTHESIS AND PROPERTIES OF FLUORO 94 -POLY(ETHER IMIDE)S 2.1. INTRODUCTION 95 2.1.1. Research background 95 2.1.2. Research objectives 96 2.2. EXPERIMENTAL 97 2.2.1. Materials 97 2.2.2. Polymerization 98 2.2.2.1. Synthesis of poly(ether imide) (PEI) 98 2.2.2.1.A. Synthesis of fluoro-poly(ether imide) polymers 100 2.2.2.1.A.1. Synthesis of [6FDA + m-SED] fluoro-poly(ether imide) 100 polymer 2.2.2.1.A.1.a. Synthesis procedure 100 vii 2.2.2.1.A.1.a.1. Step-1: Condensation polymerization procedure 100 2.2.2.1.A.1.a.2. Step-2: Chemical imidization procedure 101 2.2.2.1.B. Synthesis of non-fluorinated poly(ether imide) polymers 104 2.2.2.1.B.1. Synthesis of [PMDA + p-SED] poly(ether imide) polymer 104 2.3. FABRICATION 105 2.3.1. Polymer film preparation 105 2.3.2. Poly(amic acid) film preparation for FT-IR analysis 106 2.3.3. Thin polymer plates by compression molding 107 2.4. CHARACTERIZATION 107 2.4.1. Solubility of solid polymers 107 2.4.2. Viscosity of polymers 107 2.4.3. Fourier transform-IR (FT-IR) spectroscopy 109 2.4.4. Gel permeation chromatography (GPC) [a.k.a. Size 110 exclusion chromatography (SEC)] 2.4.5. Density of polymer films 112 2.4.6. Hydrolytic stability 112 2.4.7. UV-VIS spectroscopy 113 2.4.8. Differential scanning calorimetry (DSC) 113 2.4.9. Thermogravimetric analysis (TGA) 114 2.4.10. Thermo-oxidative stability (TOS) 114 2.4.11. Dynamic mechanical analysis (DMA) 115 2.4.12. Thermal mechanical analysis (TMA) 115 2.4.13. Coefficient of thermal expansion (CTE) 116 2.4.14. X-ray diffraction (XRD) 116 2.4.15. Mechanical properties 117 viii 2.4.16. Dielectric analysis (DEA) 117 2.4.17. Rheology 120 2.5. RESULTS AND DISCUSSION 122 2.5.1. Properties 122 2.5.1.1. Poly(ether imide)’s chemical structural characteristics 122 2.5.1.2. Solubility 123 2.5.1.3. Viscosity and molecular weights 124 2.5.1.4. Glass transition temperature (Tg) 125 2.5.1.5. Thermal stability and degradation 130 2.5.1.6. Thermo-oxidative stability (TOS) 135 2.5.1.7. Thermo-mechanical properties 136 2.5.1.8. Coefficient of thermal expansion (CTE) 137 2.5.1.9. Transparency and color 137 2.5.1.10. Hydrolytic stability 139 2.5.1.11. Morphology 140 2.5.1.12. Mechanical properties 141 2.5.1.13. Electrical properties 142 2.5.1.14. Polymer melt flow viscosity stability 143 2.6. CONCLUSION 144 2.7. REFERENCES 145 CHAPTER - 3. SYNTHESIS AND PROPERTIES OF DESIGNED LOW-K FLUOROCOPOLY(ETHER IMIDE)S 152 3.1. INTRODUCTION 153 3.1.1. Research background 153 ix B-2.2. Estimation of dielectric constant of [6FDA + p-PDA] fluoro-polyimide O O CF3 C C C N N CF3 C n C O O [6FDA + p-PDA] Fluoro-polyimide (6F-PI) Group Contribution of Molar Polarization No. of GROUP PLL V Groups O 2x 51.28 2x 108.50 C PV M 2x 276.59 2x 145.10 N C O 1x 25.00 1x 65.50 1x 128.60 1x 76.10 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 –C– –CF3 ∑ 146.16 355.94 888.18 516.30 Now using Lorentz and Lorenz’s and Vogel’s equations (10) and (11) respectively 2P + V ε ' = LL V − PLL (10) We get values of dielectric constant P  ε'=  V  M  (11) for [6FDA + p-PDA] at kHz = (2x146.16 + 355.94) ÷ 355.94-146.16) = (888.18 ÷ 516.30)2 = 3.09 = 2.96 by eq. (10) by eq. (11) LITERATURE Value : = 2.90 (at MHz)*, EXPERIMENTAL Value : = 3.036 (at kHz), 3.016 (at 10 MHz) * : Chapter 3, References # [33] 323 B-2.3. Estimation of dielectric constant of [6FDA + 1,4-Dimino Durene] fluoropolyimide O O CF3 H3C CH3 C C C N N CF3 C n C O H3C O CH3 6FDA + 1,4-Diamino Durene] Fluoro-polyimide (6F-PI) Group Contribution of Molar Polarization No. of GROUP PLL V Groups O 2x 51.28 2x 108.50 C PV M 2x 276.59 2x 145.10 N C O H3C CH3 H3C CH3 1x 47.56 1x 151.5 1x 199.24 1x 134.20 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 –C– –CF3 ∑ 168.74 441.94 958.76 574.40 Now using Lorentz and Lorenz’s and Vogel’s equations (10) and (11) respectively 2P + V ε ' = LL V − PLL (11) We get values of dielectric constant P  ε'=  V  M  (10) for [6FDA + Durene Diamine] at kHz = (2x168.74 + 441.94) ÷ 441.94-168.74) = 2.85 = (958.76. ÷ 574.40)2 = 2.79 LITERATURE Value : EXPERIMENTAL Value by eq. (10) by eq. (11) = 2.87 (at MHz)*, : = 2.90 (at kHz), * : Chapter 3, References # [48] 324 B-2.4. Estimation of dielectric constant of [6FDA + 4,4-6F-Diamine] fluoropolyimide O O CF3 C C CF3 C N N CF3 C C C O n CF3 O [6FDA + 4,4-6F-Diamine] Fluoro-polyimide (6F-PI) Group Contribution of Molar Polarization No. of GROUP PLL V Groups O 2x 51.28 2x 108.50 C PV M 2x 276.59 2x 145.10 N C O 2x 25.00 2x 65.50 2x 128.60 2x 76.10 2x 2.60 2x 5.28 2x 26.40 2x 12.00 4x 8.00 4x 34.08 4x 90.00 4x 69.00 –C– –CF3 ∑ 189.76 491.88 1223.18 742.40 Now using Lorentz and Lorenz’s and Vogel’s equations (10) and (11) respectively 2P + V ε ' = LL V − PLL (10) We get values of dielectric constant P  ε'=  V  M  (11) for [6FDA + 4,4-6F-Diamine] at KHz = (2x189.76 + 491.88) ÷ 491.88-189.76) = 2.88 by eq. (10) = (1223.18 ÷ 742.40)2 = 2.72 by eq. (11) LITERATURE Value : EXPERIMENTAL Value = 2.78 (at MHz)*, 2.58 (at 10 MHz)*, : = 2.87 (at kHz), * : Chapter 3, References # [32] 325 B-2.5. Estimation of dielectric constant of [6FDA + 4,4-ODA] fluoro-polyimide O O CF3 C C C N N CF3 C O n C O O [6FDA + 4,4-ODA] Fluoro-polyimide (6F-PI) Group Contribution of Molar Polarization No. of GROUP PLL V Groups O 2x 51.28 2x 108.50 C PV M 2x 276.59 2x 145.10 N C O 2x 25.00 2x 65.50 2x 128.60 2x 76.10 1x 5.20 1x 8.5 1x 30.00 1x 16.00 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 -O- –C– – CF3 ∑ 176.36 429.94 1046.78 608.40 Now using Lorentz and Lorenz’s and Vogel’s equations (10) and (11) respectively 2P + V ε ' = LL V − PLL (10) We get values of dielectric constant P  ε'=  V  M  (11) for [6FDA + 4,4-ODA] at kHz = (2x176.36 + 429.94) ÷ 429.94-176.36) = 3.09 by eq. (10) = (1046.78 ÷ 608.40)2 = 2.96 by eq. (11) LITERATURE Value : EXPERIMENTAL Value = 2.90 (at MHz)*, : = 3.01 (at kHz), * : Chapter 3, References # [33] 326 B-3. Fluoro-copolyimides B-3.1. Estimation of dielectric constant of [6FDA + (50%) m-PDA + (50%) p-PDA] fluoro-copolyimide O O O CF3 C C C C N N C O C C N CF3 C O CF3 50 O N CF3 C 50 C O O [6FDA +(50%) p-PDA + (50%) m-PDA] Fluoro-copolyimide (6F-CoPI) Group Contribution of Molar Polarization No. of GROUP PLL V PV M Groups O 2x 51.28 2x 108.50 2x 276.59 2x 145.10 C N C O 0.5 0.5x25.00 0.5x 65.50 0.5x 128.60 0.5x 76.10 0.5 0.5x25.00 0.5x 69.00 0.5x 128.60 0.5x 76.10 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 –C– –CF3 ∑ 146.16 357.69 888.18 516.30 Now using Vora-Wang’s equations (13) and (14) respectively ε ' CO = ε ' CO PLLCO + VCO n( PLL1 + V1 ) + m( PLL + V2 ) = VCO − PLLCO n(V1 − PLL1 ) + m(V2 − PLL ) P =  VCO  M CO   nP + mPV   =  V  nM mM +    We get values of dielectric constant at kHz (13) (14) for [6FDA + (50%) m-PDA + (50%) p-PDA] = (2x146.16 + 357.69) ÷ 357.69 - 146.16) = 3.07 by eq. (13) = (888.18 ÷ 516.30)2 = 2.96 by eq. (14) EXPERIMENTAL Value : = 3.05 (at kHz) 327 B-3.2. Estimation of dielectric constant of [6FDA + (50%) m-PDA + (50%) Durene Diamine] fluoro-copolyimide O O CF3 C CF3 C N H3C N N C O O CF3 C CF3 C C C O O CH3 n CH3 H3C C N C C O O m [6FDA + (50%) 1,4 Diamino Durene + (50%) m-PDA] Fluoro-copolyimide (6F-CoPI) Group Contribution of Molar Polarization No. of GROUP PLL V PV M Groups O 2x 51.28 2x 108.50 2x 276.59 2x 145.10 C N C O 0.5 0.5x 25.00 0.5x 69.00 0.5x 128.60 0.5x 76.10 0.5 H3C CH3 H3C CH3 0.5x 47.56 0.5x 151.5 0.5x 199.24 1x 134.20 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 –C– –CF3 ∑ 157.44 400.69 923.50 545.35 Now using Vora-Wang’s equations (13) and (14) respectively ε ' CO = ε ' CO PLLCO + VCO n( PLL1 + V1 ) + m( PLL + V2 ) = VCO − PLLCO n(V1 − PLL1 ) + m(V2 − PLL ) P =  VCO  M CO   nP + mPV   =  V  + nM mM    We get values of dielectric constant Diamine] at kHz (13) (14) for [6FDA + (50%) m-PDA + (50%) Durene = (2x157.44 + 400.69) ÷ 400.69 - 157.44) = 2.94 by eq. (13) = (923.5 ÷ 545.35)2 = 2.87 by eq. (14) EXPERIMENTAL Value : = 3.00 (at kHz) 328 B-3.3. Estimation of dielectric constant of [6FDA + (50%) p-PDA + (50%) Durene Diamine] fluoro-copolyimide O O CF3 C O H3C C C C C C N N CF3 C O CF3 CH3 N 50 C O O H3C CH3 N CF3 C C O 50 O [6FDA + (50%) 1,4-Diamino Durene + (50%) p-PDA] Fluro-copolyimide (6F-CoPI) Group Contribution of Molar Polarization No. of GROUP PLL V PV M Groups O 2x 51.28 2x 108.50 2x 276.59 2x 145.10 C N C O 0.5 0.5x 25.00 0.5x 65.50 0.5x128.60 0.5 H3C CH3 H3C CH3 0.5x 76.10 0.5x 47.56 0.5x 151.5 0.5x 199.24 1x 134.20 1x 2.60 1x 5.28 1x 2x 8.00 2x 34.08 2x 26.40 1x 12.00 90.00 69.00 –C– 2x –CF3 ∑ 157.44 398.94 923.50 545.35 Now using Vora-Wang’s equations (13) and (14) respectively ε ' CO = ε ' CO PLLCO + VCO n( PLL1 + V1 ) + m( PLL + V2 ) = VCO − PLLCO n(V1 − PLL1 ) + m(V2 − PLL ) P =  VCO  M CO   nP + mPV   =  V  + nM mM    We get values of dielectric constant Diamine] at kHz (13) (14) for [6FDA + (50%) p-PDA + (50%) Durene = (2x157.44 + 398.94) ÷ 398.94 - 157.44) = 2.96 by eq. (13) = (923.5.83 ÷ 545.35)2 = 2.87 by eq. (14) EXPERIMENTAL Value : = 2.98 (at kHz) 329 B-4. Fluoro-poly(ether imide)s B-4.1. Estimation of dielectric constant of [6FDA + p-SED] fluoro-poly(ether imide) O O CF3 C N N CF3 C O C C S O C O O O n O [6FDA + p-SED] Fluoro-poly(ether imide) (6F-PEI) Group Contribution of Molar Polarization GROUP PLL V PV No. of Groups O M 2x 51.28 2x 108.50 2x 276.59 2x 145.10 4x 25.00 4x 65.50 4x 128.60 4x 76.10 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 2x 5.20 2x 2x 30.00 2x 16.00 C N C O –C– –CF3 8.50 –O– 1x 18.40 1x 32.50 249.96 608.94 1x 120.00 1x 64.06 – SO2– ∑ 1453.18 840.06 Now using Lorentz and Lorenz’s and Vogel’s equations (10) and (11) respectively 2P + V ε ' = LL V − PLL (10) We get values of dielectric constant P  ε'=  V  M  (11) for [6FDA + p-SED] at kHz = (2x249.66 + 608.94) ÷ 608.94 - 249.66) = 3.09 by eq. (10) = (1453.18 ÷ 840.66)2 = 2.99 by eq. (11) LITERATURE Value : EXPERIMENTAL Value = 2.87 (at MHz)*, : = 2.74 (at 10 MHz)* = 3.10 (at kHz) * : Chapter 3, References # [80] 330 B-4.2. Estimation of dielectric constant of [6FDA + BPADE] fluoro-poly(ether imide) O O CF3 C C N C O N CF3 C CH3 C C O O CH3 n O [6FDA + BPADE] Fluoro-poly(ether imide) (6F-PEI) Group Contribution of Molar Polarization No. of GROUP PLL V Groups O 2x 51.28 2x 108.50 C PV M 2x 276.59 2x 145.10 N C O 4x 25.00 4x 65.50 4x 128.60 4x 76.10 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 2x 5.20 2x 8.50 2x 30.00 2x 16.00 1x 13.90 1x 49.00 1x 61.00 1x 42.00 245.46 618.44 –C– –CF3 –O– CH3-C-CH3– ∑ 1395.68 818.60 Now using Lorentz and Lorenz’s and Vogel’s equations (10) and (11) respectively 2P + V ε ' = LL V − PLL (10) We get values of dielectric constant P  ε'=  V  M  (11) for [6FDA + BPADE] at kHz = (2x245.46 + 618.44) ÷ 618.44 - 245.46) = 2.97 by eq. (10) = (1395.68 ÷ 818.60)2 = 2.907 by eq. (11) LITERATURE Value : = 2.65 (at 10 MHz)* EXPERIMENTAL Value : = 3.04 (at kHz)*, * : Chapter 3, References # [80] 331 B-4.3. Estimation of dielectric constant of [6FDA + BDAF] fluoro-poly(ether imide_ O O CF3 C CF3 C C N N CF3 C C O C O O CF3 n O [6FDA + BDAF] Fluoro-poly(ether imide) (6F-PEI) Group Contribution of Molar Polarization No. of GROUP PLL V Groups O 2x 51.28 2x 108.50 C PV M 2x 276.59 2x 145.10 N C O 4x 25.00 4x 65.50 4x 128.60 4x 76.10 2x 2.60 2x 5.28 2x 26.40 2x 12.00 4x 8.00 4x 34.08 4x 90.00 4x 69.00 2x 5.20 2x 2x 30.00 2x 16.00 –C– –CF3 8.50 –O– ∑ 250.16 642.88 1540.38 926.60 Now using Lorentz and Lorenz’s and Vogel’s equations (10) and (11) respectively 2P + V ε ' = LL V − PLL (10) We get values of dielectric constant P  ε'=  V  M  (11) for [6FDA + BDAF] at kHz = (2x250.16 + 642.88) ÷ 642.88 - 250.16) = 2.92 by eq. (10) = (1540.38 ÷ 926.60)2 = 2.77 by eq. (11) LITERATURE Value : = 2.99 (at 100 kHz)* EXPERIMENTAL Value : = 3.00 (at kHz) * : Chapter 3, References # [80] 332 B-5. Fluoro-copoly(ether imide)s B-5.1. Estimation of dielectric constant of [6FDA + (75%) p-SED + (25%) BPADE] fluoro-copoly(ether imide) O CF3 C C N CF3 C O O C O N O S O O C O CF3 C O C N 0.75 CH3 N CF3 C O C O C O C O O 0.25 CH3 Fluoro-copoly(ether imide): [ 6FDA +(75%) p-SED + (25%) BPADE ] (6F-CoPEI) Group Contribution of Molar Polarization No. of GROUP PLL V PV M Groups O 2x 51.28 2x 108.50 2x 276.59 2x 145.10 C N C O 4x 25.00 4x 65.50 4x 128.60 4x 76.10 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 2x 5.20 2x 8.50 2x 30.00 2x 16.00 –C– –CF3 –O– 0.75 0.75x18.40 0.75x32.50 0.75x120.00 0.75x64.06 – SO2– 0.25 0.25x13.90 0.25x49.00 0.25x 61.70 0.25x42.00 H3C– C –CH3 ∑ 248.835 606.065 1439.365 835.145 Now using Vora-Wang’s equations (13) and (14) respectively ε ' CO = ε ' CO PLLCO + VCO n( PLL1 + V1 ) + m( PLL + V2 ) = VCO − PLLCO n(V1 − PLL1 ) + m(V2 − PLL ) P =  VCO  M CO   nP + mPV   =  V  + nM mM    We get values of dielectric constant at kHz (13) (14) for [6FDA + (75%) p-SED + (25%) BPADE] = (2x248.835 + 606.065) ÷ 606.065 - 248.835) = 3.09 by eq. (13) = (1439.365 ÷ 835.1445)2 by eq. (14) EXPERIMENTAL Value = 2.97 : = 3.09 (at kHz) 333 B-5.2. Estimation of dielectric constant of [6FDA + (50%) p-SED + (50%) BPADE] fluoro-copoly(ether imide) O CF3 C C N CF3 C O O O O S O C N O C O CF3 C O C N 0.50 CH3 C N CF3 C O O O C O C O 0.50 CH3 Fluoro-copoly(ether imide): [ 6FDA +(50%) p-SED + (50%) BPADE ] (6F-CoPEI) Group Contribution of Molar Polarization V PV M No. of GROUP PLL Groups O 2x 51.28 2x 108.50 2x 276.59 2x 145.10 C N C O 4x 25.00 4x 65.50 4x 128.60 4x 76.10 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 2x 5.20 2x 8.50 2x 30.00 2x 16.00 –C– –CF3 –O– 0.50 0.50x18.40 0.50x32.50 0.50x120.00 0.50x64.06 – SO2– 0.50x13.90 0.50x 49.0 0.50x 61.70 0.50x 42.0 0.50 H3C– C –CH3 ∑ 247.71 610.19 1424.83 830.63 Now using Vora-Wang’s equations (13) and (14) respectively ε ' CO = ε ' CO PLLCO + VCO n( PLL1 + V1 ) + m( PLL + V2 ) = VCO − PLLCO n(V1 − PLL1 ) + m(V2 − PLL ) P =  VCO  M CO   nP + mPV   =  V  + nM mM    We get values of dielectric constant at kHz (13) (14) for [6FDA + (50%) p-SED + (50%) BPADE] = (2x247.71 + 610.19) ÷ 610.19 - 247.71) = 3.05 by eq. (13) = (1424.83 ÷ 830.63)2 = 2.94 by eq. (14) EXPERIMENTAL Value : = 3.10 (at kHz) 334 B-5.3. Estimation of dielectric constant of 6FDA + (25%) p-SED + (75%) BPADE] fluoro-copoly(ether imide) O O C CF3 C C N N CF3 C O O O S O O C O C O N C 0.25 O C CF3 C CH3 N CF3 O C O O O C 0.75 CH3 Fluoro-copoly(ether imide): [ 6FDA + (25%) p-SED + (75%) BPADE ] (6F-CoPEI) Group Contribution of Molar Polarization GROUP PLL V PV No. of Groups O C M 2x 51.28 2x 108.50 2x 276.59 2x 145.10 4x 25.00 4x 65.50 4x 128.60 4x 76.10 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 2x 5.20 2x 8.50 30.00 2x 16.00 N C O –C– –CF3 2x –O– 0.25 0.25x18.40 0.25x32.50 0.25x120.00 0.25x64.06 – SO2– 0.75x13.90 0.75x49.00 0.75x 61.70 0.75x42.00 0.75 H3C– C –CH3 ∑ 246.585 614.315 1410.215 824.115 Now using Vora-Wang’s equations (13) and (14) respectively ε ' CO = ε ' CO PLLCO + VCO n( PLL1 + V1 ) + m( PLL + V2 ) = VCO − PLLCO n(V1 − PLL1 ) + m(V2 − PLL ) P =  VCO  M CO   nP + mPV   =  V  + nM mM    We get values of dielectric constant at kHz (13) (14) for [6FDA + (25%) p-SED + (75%) BPADE] = (2x246.585 + 614.315) ÷ 614.315 - 246.585) = 3.01 by eq. (18) = (1410.215 ÷ 824.115)2 (19) EXPERIMENTAL Value = 2.93 by eq. : = 3.05 (at kHz) 335 B-5.4. Estimation of dielectric constant of [6FDA + (75%) p-SED + (25%) BDAF] fluoro-copoly(ether imide) O O C CF3 C C N N CF3 C O O S O O C O O O C N CF3 N CF3 C 0.75 O C CF3 C O C O O O C 0.25 CF3 Fluoro-copoly(ether imide): [ 6FDA +(75%) p-SED + (25%) BDAF ] (6F-CoPEI) Group Contribution of Molar Polarization No. of GROUP PLL V Groups 2x 51.28 2x 108.50 PV 2x M 276.59 2x 145.10 O C N C O 4x 25.00 4x 65.50 4x 128.60 4x 76.10 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 2x 5.20 2x 8.50 2x 30.00 2x 16.00 –C– –CF3 –O– 0.75 0.75x18.40 0.75x32.50 0.75x120.00 0.75x64.06 – SO2– 0.25 0.25x18.60 0.25x72.24 0.25x206.00 0.25x42.00 F3C– C –CF3 ∑ 250.01 611.875 1475.54 862.15 Now using Vora-Wang’s equations (13) and (14) respectively ε ' CO = ε ' CO PLLCO + VCO n( PLL1 + V1 ) + m( PLL + V2 ) = VCO − PLLCO n(V1 − PLL1 ) + m(V2 − PLL ) P =  VCO  M CO   nP + mPV   =  V  + nM mM    We get values of dielectric constant at kHz (13) (14) for [6FDA + (75%) p-SED + (25%) BDAF] = (2x250.01 + 611.875) ÷ 611.875 - 250.01) = 3.07 by eq. (13) = (1475.54 ÷ 862.15)2 = 2.93 by eq. (14) EXPERIMENTAL Value : = 3.10 (at kHz) 336 B-5.5. Estimation of dielectric constant of [6FDA + (50%) p-SED + (50%) BDAF] fluoro-copoly(ether imide) O CF3 C C N O N CF3 C O O O S O C O C O O N CF3 C CF3 C C N 0.50 O CF3 C C O O O C O 0.50 CF3 Fluoro-copoly(ether imide): [ 6FDA + (50%) p-SED + (50%) BDAF ] (6F-PEI) Group Contribution of Molar Polarization No. of GROUP PLL V PV Groups O 2x 51.28 2x 108.50 2x 276.59 2x C M 145.10 N C O 4x 25.00 4x 65.50 4x 128.60 4x 76.10 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 2x 5.20 2x 8.50 2x 30.00 2x 16.00 –C– –CF3 –O– 0.50 0.50x18.40 0.50x32.50 0.50x120.00 0.50x 64.06 – SO2– 0.50x18.60 0.50x72.24 0.50x206.40 0.50x150.02. 0.50 F3C– C –CF3 ∑ 250.06 621.81 1497.18 883.63 Now using Vora-Wang’s equations (13) and (14) respectively ε ' CO = ε ' CO PLLCO + VCO n( PLL1 + V1 ) + m( PLL + V2 ) = VCO − PLLCO n(V1 − PLL1 ) + m(V2 − PLL ) P =  VCO  M CO   nP + mPV   =  V  + nM mM    We get values of dielectric constant at kHz (13) (14) for [6FDA + (50%) p-SED + (50%) BDAF] = (2x250.06 + 621.81) ÷ 621.81 - 250.06) = 3.02 by eq. (13) = (1424.83 ÷ 830.63)2 = 2.87 by eq. (14) EXPERIMENTAL Value : = 2.99 (at kHz) 337 B-5.6. Estimation of dielectric constant of [6FDA + (25%) p-SED + (75%) BDAF] fluoro-copoly(ether imide) O O CF3 C N N CF3 C O O O S O C C O C O C O N C 0.25 CF3 C O C CF3 N CF3 O C O O O C 0.75 CF3 Fluoro-copoly(ether imide): [ 6FDA + (25%) p-SED + (75%) BDAF ] (6F-CoPEI) Group Contribution of Molar Polarization No. of GROUP PLL V PV Groups O 2x 51.28 2x 108.50 2x 276.59 2x C M 145.10 N C O 4x 25.00 4x 65.50 4x 128.60 4x 76.10 1x 2.60 1x 5.28 1x 26.40 1x 12.00 2x 8.00 2x 34.08 2x 90.00 2x 69.00 2x 5.20 2x 8.50 2x 30.00 2x 16.00 –C– –CF3 –O– 0.25 0.25x18.40 0.25x32.50 0.25x120.00 0.25x 64.06 – SO2– 0.75 0.75x18.60 0.75x72.24 0.75x206.40 0.75x150.02 F3C– C –CF3 ∑ 250.11 631.745 1518.74 905.13 Now using Vora-Wang’s equations (13) and (14) respectively ε ' CO = ε ' CO PLLCO + VCO n( PLL1 + V1 ) + m( PLL + V2 ) = VCO − PLLCO n(V1 − PLL1 ) + m(V2 − PLL ) P =  VCO  M CO   nP + mPV   =  V  + nM mM    We get values of dielectric constant at kHz (13) (14) for [6FDA + (25%) p-SED + (75%) BDAF] = (2x250.11 + 631.745) ÷ 631.745 - 250.11) = 2.97 by eq. (13) = (1518.74 ÷ 905.13)2 (14) EXPERIMENTAL Value = 2.82 by eq. : = 3.05 (at kHz) 338 [...]... objective of the present research work was to synthesize, fabricate, characterize, and to study the properties and thermal degradation kinetics of low- K poly(ether imide)s and copoly(ether imide)s, and poly(ether imide)/ organo-soluble MMT clay nanocomposites film The effort for the thesis research work as reported in Chapter 2 was focused on the synthesis, characterization, and study of a series of high-performance... (6F-PI) 3.5.12.2.2 Estimation of dielectric constant of copolyimides (Co- PI) 3.5.12.2.2.1 Dielectric constant of fluorine-containing copolyimides 219 (6F-CoPI) 3.5.12.2.2.2 Dielectric constant of fluoro -poly(ether imide)s (6F-PEI) 219 and fluoro-copoly(ether imide)s (6F-CoPEI) 204 207 217 xii 3.5.12.2.2.2.A Dielectric constant as a function of fluorine content in 222 copoly(ether imide) polymers 3.5.12.2.2.3... imide) B-4.3 Estimation of dielectric constant of [6FDA + BDAF] fluoro- 332 poly(ether imide) B-5 Fluoro-copoly(ether imide)s B-5.1 Estimation of dielectric constant of [6FDA + (75%) p-SED 333 + (25%) BPADE] fluoro-copoly(ether imide) B-5.2 Estimation of dielectric constant of [6FDA + (50%) p-SED 334 + (50%) BPADE] fluoro-copoly(ether imide) B-5.3 Estimation of dielectric constant of [6FDA + (25%) p-SED... BPADE] fluoro-copoly(ether imide) B-5.4 Estimation of dielectric constant of [6FDA + (75%) p-SED 336 + (25%) BDAF] fluoro-copoly(ether imide) B-5.5 Estimation of dielectric constant of [6FDA + (50%) p-SED 337 + (50%) BDAF] fluoro-copoly(ether imide) B-5.6 Estimation of dielectric constant of [6FDA + (25%) p-SED 338 + (75%) BDAF] fluoro-copoly(ether imide) 330 333 xix SUMMARY Polyimides are one of the important... Chung, “Synthesis and Properties of Designed Low K FluoroCopoly(ether -imide)s -Part 1.”, Advanced Functional Materials, 11(5) (2001), 361-373 3 P Santhana Gopala Krishnan, Rohit H Vora*, S Veeramani, Suat Hong Goh, Tai-Shung Chung, Kinetics of Thermal Degradation of 6FDA Based Copolyimides-I”, Polymer Degradation and Stability, 75(2) (2002), 273-285 4 Rohitkumar H Vora*, Pramoda K Pallathadka, Suat Hong... A-2.2.16 Synthesis of [ODPA + BPADE] poly(ether imide) polymer 303 A-2.2.16 Synthesis of [ODPA + BDAF] poly(ether imide) polymer 304 A-2.3 Synthesis of fluorinated copoly(ether imide) (6F-CoPEI) 304 polymers xvi A-3.1 Reaction scheme for synthesis of fluoro-copoly(ether imide) 305 (6F-CoPEI) A-3.2.1 Series-1: Synthesis of [6FDA + (n Mole%) p-SED + (m 305 Mole%) BPADE] fluoro-copoly(ether imide) polymer... dielectric constant of [6FDA + (50%) m- 328 PDA + (50%) 1,4-Diamino Durene] fluoro-copolyimide B-3.3 Estimation of dielectric constant of [6FDA + (50%) p- PDA 329 + (50%) 1,4-Diamino Durene] fluoro-copolyimide B-4 Fluoro -poly(ether imide)s B-4.1 Estimation of dielectric constant of [6FDA + p-SED] 330 fluoro -poly(ether imide) B-4.2 Estimation of dielectric constant of [6FDA + BPADE] 331 fluoro -poly(ether imide). .. Preparation of p-SED treated MMT clay suspensions in 245 NMP xiii 4.2.2.1.4 Preparation of fluoro -poly(ether amic acid) /MMT clay 245 nanocomposites pre-formulations 4.3 FABRICATION 4.3.1 [6FDA + p-SED] Fluoro -poly(ether imide), and [6FDA + 246 p- SED] /MMT clay nanocomposite film preparation 4.4 CHARACTERIZATION 248 4.4.1 Viscosity of polymer 248 4.4.1.1 Inherent viscosity 248 4.4.1.2 Bulk viscosity 249... Synthesis of fluorinated poly(ether imide)s 162 3.2.2.1.1 Synthesis of fluoro -poly(ether imide) (6F-PEI) polymers 162 3.2.2.1.1.A Synthesis of [6FDA + p-SED] fluoro -poly(ether imide) 162 polymer 3.2.2.1.1.A.1 Synthesis procedure 163 3.2.2.1.1 A.2 Chemical imidization procedure 163 3.2.2.2 Synthesis of fluorinated copoly(ether imide) polymers 164 3.2.2.2.1 Synthesis of fluoro-copoly(ether imide) (6F-CoPEI)... fluoro -poly(ether imide) 292 (6F-PEI) A-2.1.2 Synthesis of [6FDA + p-SED] fluoro -poly(ether imide) 292 polymer A-2.1.3 Synthesis of [6FDA + BPADE] fluoro -poly(ether imide) 293 polymer A-2.1.4 Synthesis of [6FDA + BDAF] fluoro -poly(ether imide) 294 polymer A-2.2 Synthesis of non-fluorinated poly(ether imide)s 294 A-2.2.1 Reaction scheme for synthesis of poly(ether imide) (PEI) 295 A-2.2.2 Synthesis of [PMDA . i SYNTHESIS, FABRICATION, CHARACTERIZATION, PROPERTIES AND THERMAL DEGRADATION KINETICS STUDY OF LOW- K POLY(ETHER IMIDE)S AND CO -POLY(ETHER IMIDE)S, AND POLY(ETHER IMIDE)/ MMT CLAY NANOCOMPOSITES. . Title: Synthesis, Fabrication, Characterization, Properties, and Thermal Degradation Kinetics Study of Low- K Poly(ether imide)s, Copoly(ether imide)s, and Poly(ether imide)/ MMT Clay Nanocomposites. . Mrs. Ramabahen B. Kanakia and Mr. Babubhai M. Kanakia, brother-in-laws: Rashesh B. Kanakia and his wife Mrs. Rupal Kanakia, and Himanshu B. Kanakia and his wife Mrs. Hiral Kanakia, sister-in-laws: