Studies Toward Highly Fluorinated Polyphenylenes by Diels-Alder Polymerization

Diels-Alder polyphenylenes (DAPPs) are chemically and thermally stable polymers, used for dielectric resins, gas separation membranes, and fuel cell proton exchange membranes. Highly fluorinated DAPPs are expected to have better thermal stability and chemical resistance, higher glass transition temperatures, improved compatibility with other fluorinated polymers (like Nafion), and better adhesion to certain surfaces such as some metals. This thesis proposes a synthesis of highly fluorinated DAPPs by reacting novel, fluorinated bis-cyclopentadienone (CPD) monomers with known aromatic dialkynes. This thesis starts with an introduction to DAPP synthesis, properties, and applications. The second chapter focuses on the synthesis of 4,4’-bis[1,2,4-tris(perfluoro-4tolyl)cyclopentadien-5-one-3-yl]octafluorobiphenyl (CPD monomer). In the first step, disodiumbis(cyclopentadieny)octafluorobiphenyl was combined with 6 equivalents of octafluorotoluene in HMPA to give 4,4’-bis[1,2,4-tris(perfluoro-4-tolyl)cyclopentadiene-3yl]octafluorobiphenyl. Oxidation to the corresponding diketone was effected using selenium dioxide. The synthesis of CPD monomer presented several unexpected challenges that were ultimately overcome. The third chapter describes a series of initial polymerization experiments as well as some model reactions that were carried out to understand monomer reactivity. Finally the future research plan of synthesizing different polymers by Diels-Alder reaction and nucleophilic substitution reaction has been discussed. Acknowledgements I wish to thank my advisor Professor Paul A. Deck for the support, guidance, and patience that he provided during my graduate studies at Virginia Tech. He is truly unique among educators and his energy/enthusiasm is unsurpassed. It has been a great opportunity to work in his vital research group. I also wish to express my sincere appreciation to my committee members, Professor David Kingston, Professor Richard Turner, Professor Timothy Long and Professor Louis Madsen who are among Virginia Tech’s finest chemistry faculty members. My fellow research group members never failed to support me in my endeavors. I would especially like to thank Mr. Brian Hickory for his generous advice and support. Finally, I am most grateful to my parents for their support and endless love over the years, they have been a source of encouragement to me. I dedicate this work to my parents, Mr Ashok Sen and Mrs Sutapa Sen. It would not been possible without their support.