CHEMICAL MODIFICATIONS TO PRODUCE SOY-BASED POLYOLS __________________________________________________________ A Dissertation presented to the Faculty of the Graduate School University of Missouri- Columbia __________________________________________________________ In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy __________________________________________________________ by ZULEICA LOZADA-RODRÍGUEZ Dr. GALEN J. SUPPES, Dissertation Supervisor JULY 2009. © Copyright by Zuleica Lozada-Rodriguez 2009. All Right Reserved The undersigned, appointed by the Dean of the Graduate School, have examined the dissertation entitled CHEMICAL MODIFICATIONS TO PRODUCE SOY-BASED POLYOLS presented by Zuleica Lozada-Rodríguez a candidate for the degree of Doctor of Philosophy and hereby certify that in their opinion it is worthy of acceptance. ___________________________________ Dr. Galen J. Suppes ___________________________________ Dr. Thomas R. Marrero ___________________________________ Dr. Truman Storvick ___________________________________ Dr. Fu-Hung Hsieh ACKNOWLEDGEMENTS I would like to take this opportunity to express my sincere gratitude to Dr. Galen J. Suppes, for his unfailing support, guidance and patience. I will never forget the great opportunity that he gives me by accepting me to his research group. All his help made it possible for me to complete this research project. I also wish to express my sincere appreciation and thanks to my committee members Drs. Fu-Hung Hsieh, Thomas R. Marrero and Truman Storvick for their valuable time, suggestions and critical reviews on the dissertation. I gratefully acknowledge the financial support from Missouri Soybean Merchandising Council, United Soybean Board and the Consortium for Plant Biotechnology Research. I am grateful to Arnold, Pimphan, Yuan-Chan and Hongyu for being excellent co- workers in the polyol group, advising and helping me in crucial moments at all stages on my research. Moreover, their ideas and arguments added immeasurably to this work. I owe a deep gratitude to Mohan, Roger, Parag, Kiran, Shailesh, Liza and Wei for his invaluable help to get used to the equipments in our laboratory on my starting years of PhD research. I greatly appreciate the technical support and advice on analytical methods provided by Ali Teekei. I owe my love and respect to my mother Elba, father Pedro, sister Linnette and brothers Pedro and Enrique, for always being on my side throughout my life and career. Their love, encouragement and support made possible this success in my life. In special ii dedication to my brother and my grandmother, Enrique and Carmen, I know that you are always with me somehow helping, supporting and protecting me from heaven. I will love you and I know that my success is your happiness. Finally, I would like to thank to all my “Boricuas” friends for making my stay at Columbia a pleasant and unforgotten experience in my life. Thanks for everything we went through and I will wish you the best for the future. iii TABLE OF CONTENTS ACKNOWLEDGEMENTS ........................................................................ II TABLE OF CONTENTS ........................................................................... IV LIST OF TABLES ................................................................................... XIII LIST OF FIGURES .............................................................................. XVIII DISCLAIMER ...................................................................................... XXIV DISSERTATION FORMAT ................................................................. XXV ABSTRACT .......................................................................................... XXVII CHAPTER 1 ...................................................................................................1 INTRODUCTION .........................................................................................1 1.1. INTRODUCTION......................................................................................1 1.2. POLYURETHANES ..................................................................................2 1.3. POLYOLS................................................................................................4 1.3.1. Polyols Properties ............................................................................................ 4 1.3.2. Petroleum-based Polyols ................................................................................ 5 1.3.3. Vegetable-based Polyols ................................................................................. 5 1.4. BACKGROUND LITERATURE ................................................................. 7 1.5. REFERENCES .........................................................................................8 iv CHAPTER 2 .................................................................................................11 SOYBEAN OIL POLYMERIZATION AND SOY-BASED POLYOLS .......................................................................................................................11 2.1. ABSTRACT ...........................................................................................11 2.2. INTRODUCTION....................................................................................12 2.3. EXPERIMENTAL ...................................................................................14 2.3.1. Materials ........................................................................................................ 14 2.3.2. Bodying reaction experimental setup .......................................................... 14 2.3.2.1. Batch reactor setup ................................................................................. 14 2.3.2.2. Continuous flow-reactor setup ............................................................... 15 2.3.3. Soy-based polyol reaction experimental setup ........................................... 15 2.3.3.1. Alcohol addition ....................................................................................... 15 2.3.3.2. Acid reduction with ESBO ..................................................................... 16 2.3.4. Analytical methods ........................................................................................ 16 2.4. RESULTS AND DISCUSSION ..................................................................18 2.4.1. Polymerization of soybean oil ...................................................................... 18 2.4.2. Soy-based polyols .......................................................................................... 26 2.4.3. GC-FID, GPC and FT-IR analytical results ............................................... 29 2.5. CONCLUSION .......................................................................................34 2.6. ACKNOWLEGMENT .............................................................................35 2.7. REFERENCES .......................................................................................35 v CHAPTER 3 .................................................................................................39 SOY-BASED POLYOLS FOR POLYURETHANE APPLICATIONS 39 3.1. ABSTRACT ...........................................................................................39 3.2. INTRODUCTION....................................................................................40 3.3. EXPERIMENTAL SET UP .......................................................................42 3.3.1. Materials ........................................................................................................ 42 3.3.2. Reaction Synthesis ........................................................................................ 43 3.3.2.1. Polymerization Reaction ......................................................................... 43 3.3.2.2. Alcohol Addition Reaction ...................................................................... 43 3.3.3. Analytical Methods ....................................................................................... 43 3.3.4. Characterization Analyses ........................................................................... 44 3.3.5. Extractability Analysis ................................................................................. 45 3.4. FLEXIBLE POLYURETHANE FOAM APPLICATION ...............................45 3.4.1. Foam Procedure ............................................................................................ 45 3.4.2. Foam Properties ............................................................................................ 47 3.5. RESULTS ..............................................................................................47 3.5.1. Reaction Synthesis Results ........................................................................... 47 3.5.2. Synthesis Characterization Results ............................................................. 57 3.5.3. Extractability Results ................................................................................... 60 3.5.4. PU Foam Results ........................................................................................... 64 3.6. CONCLUSION .......................................................................................67 vi 3.7. ACKNOWLEDGMENTS .........................................................................67 3.8. REFERENCES .......................................................................................68 CHAPTER 4 .................................................................................................72