University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 5-2017 Hetero-Atom Containing Functional Polymers: Synthesis, Characterization and Applications Hongbo Feng University of Tennessee, Knoxville, [email protected] Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Polymer Chemistry Commons Recommended Citation Feng, Hongbo, "Hetero-Atom Containing Functional Polymers: Synthesis, Characterization and Applications. " PhD diss., University of Tennessee, 2017. https://trace.tennessee.edu/utk_graddiss/4397 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Hongbo Feng entitled "Hetero-Atom Containing Functional Polymers: Synthesis, Characterization and Applications." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Chemistry. Jimmy W. Mays, Major Professor We have read this dissertation and recommend its acceptance: Alexei Sokolov, Ziling Xue, Brian Long, Joshua Sangoro Accepted for the Council: Dixie L. Thompson Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) Hetero-Atom Containing Functional Polymers: Synthesis, Characterization and Applications A Dissertation Presented for the Doctor of Philosophy Degree The University of Tennessee, Knoxville Hongbo Feng May 2017 Copyright © 2017 by Hongbo Feng. All rights reserved. ii DEDICATION This thesis is dedicated to my beloved family. iii ACKNOWLEDGEMENTS First of all, I would like to thank my advisor, Dr. Jimmy Mays for his guidance, encouragement, and constant support throughout my research. I also appreciate this valuable opportunity to study and research in this wonderful laboratory. I feel proud and honored to work with world-class experts in living anionic polymerization. I also thank Dr. Alexi Sokolov, Dr. Brain Long, Dr. Xue Ben, and Dr. Joshua Sangoro for their valuable time and for serving as my committee members. I also want to thank Dr. Nam-goo Kang for being not only a mentor but also a good friend. I wouldn’t be able to perform any living anionic polymerization without him. He taught me important glass-blowing and high vacuum techniques. My research wouldn’t be completed without Dr. Kunlun Hong’s kind help. He is a wonderful friend and mentor. I thank Dr. Yangyang Wang, Dr. Fei Fan for helping me with characterizations. Dr. Weiyu Wang is a true friend. I thank him for helpful discussions from time to time. I couldn’t not forget how we encourage each other when facing failures and frustrations. I would like to thank my fellow colleagues, Mr. Wei Lu, Dr. Xinyi Lu, Miss Huiqun Wang and previous group members for making the lab time enjoyable. Finally, I want to thank my family. All of this wouldn’t be possible without their support and love. iv ABSTRACT A mission to manage ever increased energy demands and reduce carbon foot print has challenged scientists and engineers to develop new materials with superior characteristics. In this scenario, lithium-ion batteries have been the dominating technology for not only applications in consumer electronics but also are essential for clean energy storage. On the other hand, the capture and separation of CO2 [carbon dioxide] in power generation and in industrial processes is considered to be a key to reduce the carbon footprint. Living anionic polymerization along with controlled polymerization techniques has realized the preparation of a wide variety of functional polymers with tunable properties. In this dissertation, we will present preparation of hetero-atom containing polymers using various polymerization techniques and post-polymerization modifications. We also want to explore: how can we employ these functional polymers to solve the current challenging problems? In chapter 1, we present the review of the state of the art polymer electrolytes for next-generation lithium ion batteries followed by the introduction of current CO2 [carbon dioxide] fixation and CO2/N2 [carbon dioxide/ nitrogen] gas separation techniques. In chapter 2, we discuss the synthetic methodology and experimental techniques including living anionic polymerization using high vacuum techniques, cationic ring opening polymerization techniques and hydrosilylation. v In chapter 3 and chapter 4, we discuss the preparation of ambipolar polymer electrolytes and polymerized ionic liquids based on polydimethylsiloxane. The characterization, lithium ionic conductivity and structure-properties relationship are discussed. Chapter 5 describes a novel method to obtain living anionic polymerization of 2- isopropenyl-2-oxazoline. Through our modified synthetic conditions, block copolymers of IPOx are also prepared and microphase separations are studied. In chapter 6, we investigate the synthesis gold nanoparticle using PIPOx as template. The size of god nanoparticles will be analyzed using TEM [transmission electron microscopy] and AFM [atomic force microscopy]. Furthermore, the interactions between PIPOx [poly(2-isopropenyl-2-oxazoline)] template and AuNPs [gold nano particles] is studied using XPS [X-ray photoelectron spectroscopy]. In chapter 7, we introduce the preparation of amidoxime-modified PTMSP [poly(1- trimethylsilyl-1-propyne)] and its applications on CO2/N2 [carbon dioxide/ nitrogen] separation. Finally, the research in this dissertation is summarized and future work is presented in chapter 8. vi TABLE OF CONTENTS Chapter 1 Introduction ......................................................................................... 1 1.1 Motivation .................................................................................................... 2 1.1.1 Energy Storage- Lithium Ion Battery .................................................... 4 1.1.2 Reduce Carbon Footprint-CO2 Capture, fixation and Separation ........ 10 1.2 Literature Review- State of The Art in The Field of Polymer Electrolyte for Lithium Conduction ..................................................................................................... 12 1.2.1 Types of Lithium-Conducting Polymer Electrolytes ........................... 12 1.2.2 Solid Polymer Electrolytes-The Effect of Polymer Matrix ................. 22 1.2.3 Ionic Liquids and Polymerized Ionic Liquids ...................................... 30 1.2.4 Lithium Ion Transport Mechanism ...................................................... 48 1.3 CO2/N2 Gas Separation .............................................................................. 55 1.4 References .................................................................................................. 69 Chapter 2 Synthetic Methodology and Characterization ............................... 83 Abstract ............................................................................................................ 84 2.1 Introduction ................................................................................................ 85 2.2 Synthetic Methodology and Experimental Techniques ............................. 86 2.2.1 Living Anionic Polymerization and High Vacuum Techniques .......... 86 2.2.2 Living Cationic Ring Opening Polymerization. .................................. 90 2.2.3 Hydrosilylation .................................................................................... 98 2.3 Characterization ....................................................................................... 100 vii 2.3.1 Molecular Weight Characterization ................................................... 100 2.3.2 Thermal Properties Characterization ................................................. 104 2.4 References ................................................................................................ 107 Chapter 3 PDMS-Based Ambipolar Polymer Electrolytes: Preparation and Characterization ........................................................................................................... 113 Abstract .......................................................................................................... 114 3.1 Introduction .............................................................................................. 115 3.2 Experimental Section ............................................................................... 116 3.2.1 Synthesis of Polyhydromethylsiloxane (PHMS). .............................. 118 3.2.2 Synthesis of 2-Allyltetrahydrothiophene 1,1-Dioxide (ACS). .......... 119 3.2.3 Synthesis of Polyhydromethylsiloxane Based Polymer Electrolytes. 119 3.3 Results and Discussion ............................................................................. 120 3.3.1 Synthesis of Polyhydromethylsiloxane (PHMS). .............................. 120 3.3.2 Synthesis of 2-Allyltetrahydrothiophene 1,1-Dioxide (ACS). .......... 123 3.3.3 Synthesis of PDMS-Based Polymer Electrolytes .............................. 123 3.3.4 Ionic Conductivity and Ion Transport Mechanism ............................ 123 3.4 Conclusion...............................................................................................