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Metal Catalyzed Formation of Aliphatic Polycarbonates

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Metal Catalyzed Formation of Aliphatic Polycarbonates METAL CATALYZED FORMATION OF ALIPHATIC POLYCARBONATES INVOLVING OXETANES AND CARBON DIOXIDE AS MONOMERS A Dissertation by ADRIANA INEZ MONCADA Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY May 2010 Major Subject: Chemistry METAL CATALYZED FORMATION OF ALIPHATIC POLYCARBONATES INVOLVING OXETANES AND CARBON DIOXIDE AS MONOMERS A Dissertation by ADRIANA INEZ MONCADA Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Approved by: Chair of Committee, Donald J. Darensbourg Committee Members, Michael B. Hall Timothy R. Hughbanks Hong Liang Head of Department, David H. Russell May 2010 Major Subject: Chemistry iii ABSTRACT Metal Catalyzed Formation of Aliphatic Polycarbonates Involving Oxetanes and Carbon Dioxide as Monomers. (May 2010) Adriana Inez Moncada, B.S., La Universidad del Zulia; M.S., Oklahoma State University Chair of Advisory Committee: Dr. Donald J. Darensbourg Biodegradable aliphatic polycarbonates are important components of non-toxic thermoplastic elastomers, which have a variety of medical applications. Industrially, aliphatic polycarbonates derived from six-membered cyclic carbonates such as trimethylene carbonate (TMC or 1,3-dioxan-2-one) are produced via ring-opening polymerization (ROP) processes in the presence of a tin catalyst. It is worth mentioning that TMC is readily obtained by transesterification of 1,3-propanediol with various reagents including phosgene and its derivatives. Therefore, it has been of great interest to investigate greener routes for the production of this important class of polymers. Toward this goal, the synthesis of aliphatic polycarbonates via the metal catalyzed alternative coupling of oxetanes and carbon dioxide represents an attractive alternative. The use of an abundant, inexpensive, non-toxic, and biorenewable resource, carbon dioxide, makes this method very valuable. Furthermore, in this reaction, the six- membered cyclic carbonate byproduct, TMC, can also be ring-opened and transformed into the same polycarbonate. For over a decade, the Darensbourg research group has iv successfully utilized metal salen complexes as catalysts for the epoxide/CO2 copolymerization process. Hence, this dissertation focuses on the examination of these complexes as catalysts for the oxetane/CO2 copolymerization reaction and the further elucidation of its mechanism. Chromium(III) salen derivatives in the presence of an azide ion initiator were determined to be very effective catalysts for the coupling of oxetanes and carbon dioxide providing polycarbonates with minimal amounts of ether linkages. Kinetic and mechanistic investigations performed on this process suggested that copolymer formation proceeded by two routes. These are the direct enchainment of oxetane and CO2, and the intermediacy of trimethylene carbonate, which was observed as a minor product of the coupling reaction. Anion initiators which are good leaving groups, e.g. bromide and iodide, are effective at affording TMC, and hence, more polycarbonate can be formed by the ROP of preformed trimethylene carbonate. Research efforts at tuning the selectivity of the oxetane/CO2 coupling process for TMC and/or polycarbonate produced from the homopolymerization of preformed TMC have been performed using cobalt(II) salen derivatives along with anion initiators. Lastly, investigations of this process involving 3-methoxy-methyl-3-methyloxetane will be presented. v DEDICATION I dedicate this dissertation to my mother and father, Emelida and Diego, and to my husband, Manuel. Mom and Dad, your love, guidance, unconditional support in everything I do, and your prayers have given me the strength needed to be where I am today reaching my goals and dreams. Manuel, you are an essential ingredient of my life. You are my love, my support, and my encouragement always. I love you all very much. I also dedicate this dissertation to my Lord Jesus Christ for always being by my side, giving me so much love, the strength, directions, and spiritual peace to accomplish what I have thus far in my life. vi ACKNOWLEDGEMENTS I first would like to thank my research advisor, Prof. Donald J. Darensbourg, for giving me the great opportunity and pleasure to work in his research laboratory. He is an excellent scientist, a great advisor and person. His guidance, support, and encouragement were very valuable during my graduate studies at Texas A&M University. He has contributed in many ways to my science career. More importantly, I have learned how to independently conduct scientific research and how to write up my research results and present them to other people. I would like to thank Professors Timothy R. Hughbanks, Michael B. Hall, Hong Liang, and Marcetta Y. Darensbourg for also being involved in my education, for their guidance and assistance when needed, and for serving on my dissertation committee. The Women in Science and Engineering and the Society of Plastics Engineers Organizations student chapters at Texas A&M University have influenced me in many ways to further develop my leadership and organizational skills. My sincere thanks also go to my undergraduate advisor Prof. Dora M. Finol who let me experience for the first time the conduction of scientific research. This knowledge was very precious and inspired me to look forward to a career in science. I also must thank my M.S advisor, Prof. Legrande M. Slaughter, who introduced me to the theory of organometallic chemistry of the transition metals and who has always supported and mentored me throughout the years. I gratefully acknowledge the financial support of the research presented in this dissertation from the National Science Foundation (CHE-0543133) and the Robert A. vii Welch Foundation (A-0923). I also would like to thank Dr. Joseph H. Reibenspies and Dr. Nattamai Bhuvanesh for their invaluable teachings on X-ray Crystallography and for their assistance in solving very complicated X-ray crystal structures. Thanks to Dr. Joseph H. Reibenspies who solved and finished material for publication for the crystal structures of complexes II-5, II-6, III-7, VI-1, and trimethylene carbonate presented in this dissertation. My most sincere and special thanks should go to my friends Dr. Wonsook Choi, Osit “Pop” Karroonnirun, Roxanne Jenkins, and Dr. Elky Almaraz for the beautiful friendship that we have had and, I hope, will always keep through the years and for the countless times that we had discussions about our research. I want to also thank you all for celebrating many special occasions with me and my family and for letting me take part in many of yours with your families. I must also thank my other fellow members of the DJD and MJD research groups for their friendship and assistance in the lab: Dr. Eric Frantz, Dr. Shawn Fitch, Dr. Jeremy Andreatta, Dr. Liu Tianbiao, Dr. Kayla Green, Dr. Christine Thomas, Dr. Chung-Hung Hsieh, Susan Winters, Ethel Mejías, Ross Poland, Sheng Hsuan Wei, Stephanie Wilson, Bin Li, Scott Brothers, Mike Singleton, Tiffany Pinder, Jennifer Hess, William Foley, Jason Denny, and Ryan Bethel. Special thanks also go to three undergraduate students who worked with me at different stages of this journey: Curtis Boyd, Leah Salganik, and Viviana Salon. With my Venezuelan background I have always been interested in diversity, and what I mean by that is meeting people from other countries and learning about their different cultures. This is something that I had the pleasure to experience in the DJD viii group. I am so thankful to have met and worked with many Postdoctoral Fellows and visiting scholars from Brazil, Turkey, Hungary, China, and Italy: Dr. Carla Rodarte de Maura, Dr. Adolfo Horn Jr, Dr. Mamut Ulusoy, Dr. Attila, Dr. Xiao-Bing Lu, and Paolo Bottarelli. Finally, I would like to thank my family: my Mom and Dad, Emelida and Diego, for their love, unconditional support, encouragement, and for their direction and teachings throughout my life; my sister and brother in law, Gloria and Dale, for their love, support, and for helping me proofread a lot of my letters, resumes, and CVs; my brother, Alejandro, for his love and unconditional support; my nephew, Lucas Daniel, for bringing so much happiness to my life and to all my family. From the bottom of my heart I want to thank my husband, Manuel, for being my strongest support, my love, my encouragement in many difficult and stressful times, for always being there for me, for believing in me, and for giving me the biggest happiness anyone could ever imagine. Thank you very much for being the most important part of my life; I love you so much. I also want to thank my political family for their support, love, and encouragement during this journey: my parents-in-law, Jose Prado “Chalo” and Nelly Prado; my brothers-in-law; Jose Prado “Chalingo,” Chris Cooper, Rafael Suárez, and Carlos Luis Sánchez; my sisters-in-law; Mónica Prado, Diana Prado, Alicia Prado, and Mónica Carbonell; and my nephews and niece, José Rafael Suárez, José Miguel Prado, José Alonso Suárez, Victor Gonzalo Cooper, Luis Alejandro Sánchez, and Stephanie Prado. ix TABLE OF CONTENTS Page ABSTRACT .............................................................................................................. iii DEDICATION .......................................................................................................... v ACKNOWLEDGEMENTS .....................................................................................
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