Processable High Performance Polymers: Synthesis, Characterization and Application Thesis submitted to the UNIVERSITY OF PUNE For the degree of DOCTOR OF PHILOSOPHY In CHEMISTRY By Snehalata P. Bapat Research Guide Dr. P. P. Wadgaonkar Polymer Science and Engineering Division National Chemical Laboratory Pune-411008 December 2007 1 Dedicated To My Parents and Parents-in-law 2 Certificate of the Guide Certified that the work incorporated in the thesis entitled “Processable High Performance Polymers: Synthesis, Characterization and Application” submitted by Snehalata P. Bapat was carried out under my supervision. Such material as has been obtained from other sources has been duly acknowledged in this thesis. December, 2007 P. P. Wadgaonkar Pune (Research Guide) 3 Declaration by the Candidate I declare that the thesis entitled “Processable High Performance Polymers: Synthesis, Characterization and Application” is my own work conducted under the supervision of Dr. P. P. Wadgaonkar, at Polymer Science and Engineering Division, National Chemical Laboratory, Pune. I further declare that to the best of my knowledge, this thesis does not contain any part of work, which has been submitted for the award of any degree either of this University or any other University without proper citation. (Snehalata P. Bapat) Research student (P. P. Wadgaonkar) Research Guide 4 Acknowledgement First and foremost, I take this opportunity to express my gratitude to my guide, Dr.P.P.Wadgaonkar for his valuable and inspiring guidance and constant support throughout my pursuance of this work. I wish to place on record my sincere thanks to Dr. S. Sivaram, Director, National Chemical Laboratory, for his inspiring guidance and for giving me the opportunity to work in this esteemed Institute. I am grateful to Dr. Ulhas Kharul, Dr. S. Radhakrishnan, Dr.Ashish Lele Mr. H.Pol, Dr.J.P.Jog, Dr.P.R.Rajamohanan, Mrs.Usha Phalgune, Mr.V.T.Sathe, Dr.C.Ramesh, Dr. Mohan Bhadbhade, Dr.(Mrs.)V.G. Puranik, Dr.N.P.Argade and Dr.N.Swamy (CLRI, Chennai) for valuable discussions. I express my sincere thanks to Mrs.D.A.Dhoble, Mr.S.K.Menon, Dr.A.S.Jadhav Dr.N.N.Chavan, Dr.C.V.Avadhani, Dr.T.P.Mohandas, Dr.(Ms.)R.S.Khisti, Dr.R.A.Kulkarni, Mr.K.G.Raut, Dr.B.D.Sarwade, Dr. B.B.Idage, Dr.(Mrs.) S.B. Idage, Dr.(Mrs.) A.N.Bote, Dr. R.P.Singh, Dr.S.S.Mahajan, Dr.(Mrs.) B.Garnaik., Dr. S.P.Vernekar, Mr.A.S.Patil and Dr. P.G.Shukla for their timely help. I take this opportunity to express my deep sense of gratitude to my labmates Anjana, Sony, Arun , Arvind, Nana, Prakash , Anil, Pandu , Vijay, Divya, Vidya Mahadev, Neelakshi, Poorvi, Rahul, Susheel, Rahul Jadhav, Smitha, Smita, Bhoje, Malli, Dilip, Pradip, Yogesh, Harshada, Santosh Kumbharkar, Santosh Mhaske, Santosh Wanjale, Shailesh Vidhate, Ramanujam, K. Santosh, Raju, Radhika, Punjab, Sanket, and my erstwhile colleague Jinu, Nirmala, Srilatha, Sulatha, R.Gnaneshwar, Vaibhav, Lav, Anjali Shah, Sunita, Rupali Bhagwat, L.S.Ramanathan, Sachin and Ranjit for their support and co- operation. Many thanks go to the members of central NMR facility, members of SMIS and DIRC, glassblowing, stores, workshop and administrative section and divisional office staff for their help. 5 I am blessed with a very caring and loving family. My special gratitude goes to my parents and my parents-in-law who taught me the value of hard work and the value of time. My thanks are due to my loving sisters, sisters-in-law and brothers-in-law. I am indebted to my husband Sachin for his patience beyond limits and for giving encouragement, full freedom and for being my true friend during moments of both success and despair. The presence of my loving daughter Srushti has helped in a long way during critical times. Finally, my thanks are due to the Council of Scientific and Industrial Research, New Delhi for the award of a research fellowship. Snehalata Bapat 6 CONTENTS Description Page No. * Abstract i * List of Tables v * List of Schemes viii * List of Figures x * Glossary xvii CHAPTER 1 Introduction and Literature Survey 1.1 Introduction 1 1.2 Polyimides 3 1.2.1 Synthesis of polyimides 3 1.2.1.1 Classical two step methods via poly(amic acid)s 3 1.2.1.2 One-step high temperature solution polycondensation of polyimides 12 1.2.1.3 Other synthetic routes to polyimides 13 1.2.1.3.1 Polyimides via derivatized poly (amic acid) precursors 13 1.2.1.3.2 Polyimides via polyisoimide precursors 15 1.2.1.3.3 Polyimides from diester-acids and diamines (Ester-acid 15 route) 1.2.1.3.4 Polyimides from tetracarboxylic acids and diamines 16 1.2.1.3.5 Polyimides from dianhydrides and diisocyanates. 16 1.2.1.3.6 Polyimides via nucleophilic aromatic substitution reactions 17 1.2.1.3.7 Other routes to polyimide formation 18 1.2.2 Structure-property relationship in aromatic polyimides 19 1.2.2.1 Glass transition and solubility 19 1.2.2.2 Optical properties 20 1.2.2.3 Dielectric properties 21 1.2.2.4 Applications of polyimides in microelectronics 23 1.2.2.5 Gas separation 28 1.2.2.5.1 Aromatic polyimides as gas separation membranes 31 7 1.3 Polyamides 34 1.3.1 Synthesis of polyamides 34 1.3.1.1 Low temperature polycondensation of diamines and diacid chlorides 34 1.3.1.1.1 Solution polycondensation of diamines and diacid chlorides 34 1.3.1.1.2 Interfacial polycondensation of diamines and diacid chlorides 35 1.3.1.2 High temperature solution polycondensation of dicarboxylic acids and 36 diamines 1.3.1.3 Polycondensation of N-silylated diamines and diacid chlorides 37 1.3.1.4 Polycondensation of diisocyanates and dicarboxylic acids 37 1.3.1.5 Transition metal-catalyzed polycondensation of aromatic diamines, 38 dihalides and carbon monoxide 1.3.2 Effect of structure on properties of polyamides 38 1.3.2.1 Solubility and thermal stability 38 1.3.2.1.1 Halogen substituents 38 1.3.2.1.2 Other substituents 39 1.3.2.2 Pendent alkyl/aryl group containing polyamides 39 1.3.2.3 Polyamides containing flexible linkages 40 1.3.3 Applications of polyamides 42 1.4 Polyesters 42 1.4.1 Synthesis of Polyesters 43 1.4.1.1 Acid chloride route 43 1.4.1.1.1 Interfacial polycondensation 43 1.4.1.1.2 Low temperature solution polycondensation 45 1.4.1.1.3 High temperature solution polycondensation 45 1.4.1.2 Transesterification route 46 1.4.1.2.1 Phenyl ester route 46 1.4.1.2.2 Phenol acetate route 46 1.4.1.2.3 Phenyl ester and phenol acetate route 47 1.4.1.3 Other routes for polyester synthesis 47 1.4.1.3.1 Phenol silyl ether route 47 1.4.1.3.2 Direct esterification route 48 8 1.4.1.3.3 Palladium-catalyzed carbonylation of aromatic dibromides 49 and bisphenols 1.4.2 Structure-property relationship in aromatic polyesters 50 1.4.3 Applications of polyarylates 52 References 53 CHAPTER 2 Scope and Objective 71 CHAPTER 3 Synthesis and Characterization of Difunctional Monomers 3.1 Introduction 76 3.2 Experimental 84 3.2.1 Materials 84 3.2.2 Measurements 84 3.3 Synthesis 85 3.3.1 Synthesis of Bisphenols and Diamines containing bulky pendent groups 85 3.3.1.1 Synthesis of 1,1-bis –[ 4hydroxyphenyl-1-(2-naphthyl) ]ethane (NABP) 85 3.3.1.2 Synthesis of 1,1-bis-[(4-hydroxyphenyl)-1-(4-phenylsulfonylphenyl)] ethane (DPSBP) 85 3.3.1.2.1 : Synthesis of 4 acetyl diphenyl sulphide 85 3.3.1.2.2 : Synthesis of 4-(phenyl sulfonyl) acetophenone 86 3.3.1.2.3: Synthesis of 1,1-bis[4-hydroxyphenyl-(4-phenyl 86 sulphonyl phenyl) ]ethane (DPSBP) 3.3.1.3 Synthesis of 1,1-bis–[(4-hydroxyphenyl)-1-biphenyl] ethane (BBHPE) 87 3.3.1.3.1 Synthesis of 4 -acetylbiphenyl 87 3.3.1.3.2 Synthesis of 1,1-bis–[(4-hydroxyphenyl)-1-biphenyl] ethane (BBHPE) 87 3.3.1.4 Synthesis of 1,1- bis-[4-(4-aminophenoxy) phenyl-1-(2- naphthyl)]ethane 88 (NABPDA) 3.3.1.4.1 Synthesis of 1,1-bis-[4-(4-nitrophenoxy) phenyl-1-(2- 88 naphthyl)] ethane (DNNABP) 3.3.1.4.2. Synthesis of 1,1-bis-[4-(4-aminophenoxy)phenyl-1- 88 (2-naphthyl)] ethane (NABPDA) 9 3.3.1.5 Synthesis of 1,1-bis-[4-(4-aminophenoxy) phenyl]-1-biphenyl 88 ethane (BBHPDA) 3.3.1.5.1 Synthesis of 1,1-bis-[4-(4-nitrophenoxy) phenyl]-1- 88 biphenylethane(DNBBHPE) 3.3.1.5.2 Synthesis of 1,1- bis-[4-(4-aminophenoxy) phenyl]-1- 89 biphenylethane (BBHPDA) 3.3.2 Synthesis of bisphenols and diamines containing cardo groups 89 3.3.2.1. Synthesis of 1,1-bis(4-hydroxyphenyl) -4-perhydrocumyl 89 cyclohexane (PCPBP) 3.3.2.1.1 Synthesis of 4-(1-cyclohexyl-1-methyl ethyl) cyclohexanol 89 (HPCP) 3.3.2.1.2 Synthesis of 4-(1-cyclohexyl-1-methyl ethyl) 90 cyclohexanone (HPCP-K) 3.3.2.1.3 Synthesis of 1,1-bis-(4-hydroxyphenyl)-4-perhydrocumyl 90 cyclohexane (PCPBP) 3.3.2.2. Synthesis of 1,1-bis-(4-hydroxy-3,5-dimethylphenyl)-4- 91 perhydrocumyl cyclohexane (TMPCPBP) 3.3.2.3. Synthesis of 1,1-bis-(4-hydroxy phenyl)-octahydro-2(1H)- 91 naphthalene (DCHBP) 3.3.2.3.1 Synthesis of 2-decalone 91 3.3.2.3.2 Synthesis of 1,1-bis-(4-hydroxyphenyl)-octahydro-2(1H)- 91 naphthalene (DCHBP) 3.3.2.4.