SOLID-STATE OLEFIN METATHESIS by GARRETT W. OAKLEY A
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SOLID-STATE OLEFIN METATHESIS By GARRETT W. OAKLEY A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2004 Copyright 2004 by Garrett W. Oakley This dissertation is dedicated to my family. ACKNOWLEDGMENTS First and foremost, I thank Jennifer Sippel/Oakley, the girl who became my wife on October 2, 2004. I met her when I visited the University of Florida on my recruiting trip, we started dating the day I moved to Florida, and we are getting married the same semester that I plan to graduate. She has been there throughout my entire graduate career, and the motivation, understanding, and love she has given me during the completion of this work is irreplaceable. I would like to thank my family, both immediate and extended, past and present, to whom this document is dedicated, for being an endless source of support in my education and life. Without this, I would have been lost. In particular, I want to thank my father, David Oakley, for all his help and advice. Even after eight years of schooling and going into debt, my father has encouraged me to get the best education I could. I thank my mother, Jeanne Qualey, for the time in recent years that we were able to spend together since she moved to Florida. This time has given me a renewed appreciation for the love a mother can give. I also need to thank my mother for all the time she spent in raising me. She, above all others, was the most instrumental in my development and the way I think on a daily basis. I want to thank my brother, Brenton, and sister, Loren, for being my family in the most loving sense of the word. I cannot imagine my life without them in it. I thank my stepparents, Beverly Oakley and Thomas Qualey, for their love and support, and for treating me like a son. I likewise thank my stepsister, Jackie, for treating me like a brother, and for playing checkers every time I had a chance to visit. I would also like to iv thank my grandparents, Wilmot and Ann Oakley and Cathy Garrett, as well as my late grandfather, Roger Garrett, for the encouragement and love they have given me over the years. Additionally, several aunts, uncles, and cousins deserve my thanks for their advice and support. I would like to acknowledge the people who helped mold my career choice of chemistry, and then later the choice to specialize in polymer chemistry. I was first exposed to chemistry in my sophomore year in high school by Mrs. Merle Cohen, who I thank for being a wonderful teacher. The following year, I took AP chemistry from Mr. Bruce Dinsmore. By the end of his class, I had decided that I wanted a career in chemistry. I thank him for his logical teaching style, for preparing the class well for the AP exam, and for telling us more than we needed to know, as I was more than ready to take on sophomore organic chemistry as a freshman in college. At Rensselaer Polytechnic Institute (RPI), I met Dr. Brian Benicewicz, whom I thank for being the person most responsible for focusing my interest in chemistry towards polymers. He was also the person who first suggested the University of Florida to me as a place for graduate study. His enthusiasm for polymer chemistry truly inspired me, and I thank him for being a very approachable research advisor and a friend. Other professors at RPI that I would like to thank for their help and guidance include Dr. R. A. Bailey, Dr. Tom Apple, Dr. Charles Gillies, Dr. Sonja Krause, Dr. Leonard Interrante, Dr. Wilfredo Colon, and Dr. Kim Fortun. During my junior year at Rensselaer, I was fortunate to be able to spend eight months on a co-op with the Bayer Corporation. I would like to thank Dr. Ray Burk, Dr. Wan Wu, David Jenney, Dr. Inny Kim, Dr. Laura Spangler, and Tim Rappl for a wonderful experience, which piqued my appetite for the polymer industry. v Ray and Laura deserve extra thanks for their encouragement in applying to graduate schools. At the University of Florida, I would like to thank all my coworkers on the George and Josephine Butler Polymer Floor. Special thanks needs to be given to Stephen “Ed” Lehman, Jr.; Barry C. Thompson; and Ben Reeves. Ed was a fellow RPI alumni and my mentor in the laboratory, and I thank him for all the advice he has given me over the years. Barry, my best friend and best man, has also been an invaluable resource of knowledge in the lab, and has been a huge source of encouragement at every milestone in achieving my degree. Barry, Ben, and I started graduate school together and supported each other through classes, T-Hud, cumes, oral exams, and dissertation research, and I thank them both for their help and support in all these obstacles. Other floor members to whom I owe extra thanks for their help along the way are Jason Smith, Carl Gaupp, Jim Pawlow, John Schwendeman, Pat O’Donnell, Tim Hopkins, John Sworen, Shane Waybright, Avni Argun, Stephen Carino, Andrew Skolnik, Travis Baughman, Florence Courchay, Piotr Matloka, Genay Jones, Christophe Grenier, Aubry Dyer, Emine Boz, and Bob Brookins. Enough thanks cannot be expressed to Lorraine Williams and Sara Klosser in the polymer office. Without them, the little things that make everything run smoothly, but no one wants to think about, would never get done. I also extend my thanks to Lori Clark and Dr. Jim Deyrup for their help in the graduate office. I am extremely grateful to Dr. George B. Butler and his wife Josephine for establishing the Butler Polymer Laboratory. It has truly been a unique and wonderful place to work and study. vi Many thanks are extended to my committee members, Dr. John R. Reynolds, Dr. J. Eric Enholm, Dr. Danial R. Talham, and Dr. Anthony B. Brennan. Their efforts in reading and discussing the material presented in this dissertation have been instrumental in making it a stronger document. Finally, I must express my sincerest appreciation to my research director and supervisory committee chair, Dr. Kenneth B. Wagener. His door was always open and whenever I talked with him, I always felt encouraged, with my motivation to work hard revitalized. “Don’t give up!” he would say, when things seemed the most bleak. Never once have I seen him appear angry, as he always deals with situations in a calm and collected manner. Dr. Wagener has given me a wealth of advice and guidance for things both inside and outside the laboratory. I will forever be thankful for his presence in my life. vii TABLE OF CONTENTS page ACKNOWLEDGMENTS ................................................................................................. iv LIST OF TABLES............................................................................................................. xi LIST OF FIGURES .......................................................................................................... xii ABSTRACT.......................................................................................................................xv CHAPTER 1 INTRODUCTION TO SOLID-STATE POLYMERIZATION AND OLEFIN METATHESIS ..............................................................................................1 1.1 Solid-State Reactions vs. Liquid-State Reactions ..................................................1 1.2 Crystal-to-Crystal Solid-State Polymerization .......................................................4 1.3 Solid-State Polycondensation of Semicrystalline Polymers.................................12 1.3.1 Monomer-to-Polymer Condensation SSP ..................................................13 1.3.2 Prepolymer-to-Polymer Condensation SSP ...............................................15 1.4 Olefin Metathesis..................................................................................................23 1.4.1 Historical Overview of the Mechanism......................................................26 1.4.2 Development of Well-Defined Catalysts....................................................31 1.5 Opportunities of Olefin Metathesis in the Solid State..........................................44 2 EXPERIMENTAL METHODS.................................................................................47 2.1 The Solid-State Apparatus....................................................................................47 2.2 Making a Solid Mixture of Reactants...................................................................48 2.2.1 Melt Polymerization ...................................................................................49 2.2.2 Freeze-Drying.............................................................................................50 2.2.3 Grinding Together Diene and Catalyst.......................................................51 2.2.4 Regrinding Clean Polymer with Fresh Catalyst .........................................52 2.3 Sampling of the Solid Mixtures............................................................................52 2.4 Characterization Techniques Used on the Samples..............................................55 2.4.1 Gel Permeation Chromatography (GPC)....................................................55 2.4.2 Nuclear Magnetic Resonance (NMR) Spectroscopy..................................56 viii 3 SOLID-STATE ADMET OF SEMICRYSTALLINE POLYMERS .........................58 3.1 Introduction...........................................................................................................58 3.2 Experimental.........................................................................................................62 3.2.1