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Nano-Composite Proton Exchange Membrane ©2014 LONGHE ZHANG ALL RIGHTS RESERVED SUPRAMOLECULAR BLOCK COPOLYMERS VIA IONIC INTERACTIONS A Dissertation Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Longhe Zhang August, 2014 SUPRAMOLECULAR BLOCK COPOLYMERS VIA IONIC INTERACTIONS Longhe Zhang Dissertation Approved: Accepted: ______________________ _______________________ Advisor Department Chair Dr. Robert A. Weiss Dr. Robert A. Weiss ______________________ _______________________ Co-advisor Dean of the College Dr. Kevin A. Cavicchi Dr. Stephen Z. D. Cheng ______________________ _______________________ Committee Member Dean of the Graduate School Dr. Alamgir Karim Dr. George R. Newkome ______________________ _______________________ Committee Member Date Dr. Coleen Pugh ______________________ Committee Member Dr. Wiley J. Youngs ii ABSTRACT Supramolecular block copolymers, which are the supramolecular analog of covalently-bonded block copolymers, consist of individual polymer blocks connected by non-covalent bonds. They can be produced by self-assembly of telechelic oligomers or polymers with complementary end-groups, such that a variety of block combinations may be achieved by simple mixing of the appropriate polymers. Supramolecular block copolymers are advantageous for fabricating nanostructured functional materials, since they can exhibit morphologies mimicking conventional covalently-bonded block copolymers and the reversible nature of the supramolecular bonds between blocks allows for unique responses to external stimuli. In the first part, a supramolecular multiblock copolymer was synthesized by mixing two telechelic oligomers, α,ω-sulfonated polystyrene, derived from reversible addition−fragmentation chain-transfer (RAFT) polymerization, and α,ω-amino- polyisobutylene, prepared by cationic polymerization. Proton transfer from the sulfonic acid to the amine formed ionic bonds that produced a multiblock copolymer that formed free-standing flexible films. Small angle X-ray scattering characterization showed a lamellar morphology, whose domain spacing was consistent with the formation of a multiblock copolymer based on comparison to the chain dimensions. A reversible order-disorder transition occurred between 190°C and 210°C, but the sulfonic acid and amine functional groups decomposed at those elevated temperatures. For high non-linear strains, the dynamic modulus, G’, decreased by nearly an order of iii magnitude and the loss modulus, but recovered to the original values once the strain was reduced to 1%. In the second part, two groups of RAFT agents that contain either quaternary ammonium or quaternary phosphonium groups were prepared. At first, a series of trithiocarbonate RAFT agents containing quaternary ammonium functionality in the “R-group” were synthesized. The synthetic route involves the optimized synthesis of 4-(bromomethyl)-N,N,N-trialkyl benzyl ammonium bromide compounds, which were subsequently reacted with the alkyl trithiocarbonate anion to directly produce the trithiocarbonate RAFT agent. However, quaternary ammonium group partially degraded when the RAFT agents were used in polymerizations at 120 oC. This issue was overcome by using lower polymerization temperature. On the other hand, quaternary phosphonium-containing, trithiocarbonate RAFT agents were also synthesized via similar synthetic method. Thermal stabilities of RAFT-PR3 were enhanced compared to their ammonium analogues, which significantly improved the retention of the cationic end-functionality of the polystyrene obtained at 120 oC. For both classes of RAFT agents, the crude polystyrene can be further purified via column chromatography to afford high purity hemi-telechelic cationomers. In the third part, matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-ToF MS) was used to quantify the sulfonation level and sulfonation distribution of sulfonated polystyrene ionomers prepared by homogeneous solution sulfonation. The sulfonation levels obtained by MALDI ToF-MS and acid- base titration were compared, and the sulfonate distributions determined by MALDI- ToF MS were compared with theoretical random distributions. The results indicate that the sulfonation reaction used produces a sample with a random sulfonate distribution. iv DEDICATION To my parents, my brother, and my wife Zhouying He v ACKNOWLEDGEMENTS I am very grateful to all people who have provided me with advice, encouragement and support over my graduate career. First of all, I would like to thank my advisors, Professor Robert A. Weiss and Professor Kevin A. Cavicchi, for providing me guidance and inspiration throughout this journey. It has been a great pleasure working with both of you. I have been enjoying my research because of all the freedom, opportunities and trust that you gave me. You are always willing to share your experience, knowledge and wisdom. From your advice and suggestions, I have learned many things that are essential for being an excellent scientist. I would like to thank my committee members, Professor Alamgir Karim, Professor Coleen Pugh and Professor Wiley Youngs. I appreciate all the time you spent on this dissertation and all the advice you provided to me. I am also grateful to the group members in both labs and all other faculty members and students in the University of Akron. There are too many people to list here. Without your constant friendship and support, I cannot enjoy my life and research in Akron. I would especially like to thank Yuqing Liu who offered me a lot of help in research and daily life when he was in Akron. I also need to thank all the friends who are not in Akron but kindly provide great support for my research. vi TABLE OF CONTENTS Page LIST OF TABLES ............................................................................................................. xi LIST OF FIGURES .......................................................................................................... xii LIST OF ABBREVIATIONS ........................................................................................... xx CHAPTER I. INTRODUCTION ........................................................................................................... 1 II.BACKGROUND* ........................................................................................................... 4 2.1 Block copolymers ................................................................................................. 4 2.1.1 Phase behavior ........................................................................................... 6 2.1.2 Small angle X-ray scattering .................................................................... 11 2.1.3 Linear viscoelastic behavior .................................................................... 12 2.2 Supramolecular block polymer ........................................................................... 15 2.2.1 Supramolecular chemistry ....................................................................... 15 2.2.2 Supramolecular polymer .......................................................................... 18 2.2.3 Supramolecular block copolymer ............................................................ 20 2.3 Ionomers ............................................................................................................. 24 2.3.1 General introduction of ionomers ............................................................ 24 2.3.2 Synthesis of ionomers .............................................................................. 26 2.4 Cationic polymerization technique ..................................................................... 29 2.5 RAFT polymerization technique......................................................................... 31 2.5.1 Controlled free radical polymerization .................................................... 31 2.5.2 RAFT polymerization .............................................................................. 33 vii 2.5.3 Complex macromolecular architecture via RAFT polymerization .......... 36 2.5.4 End-functional polymer via RAFT approach .......................................... 39 III. SUPRAMOLECULAR MULTIBLOCK POLYSTYRENE- POLYISOBUTYLENE COPOLYMER VIA IONIC INTERACTIONS......................... 42 3.1 Introduction ......................................................................................................... 42 3.2. Experimental Section ......................................................................................... 46 3.2.1 Materials .................................................................................................. 46 3.2.2 Synthesis of end-functionalized (telechelic) oligomers ........................... 47 3.2.3 Preparation of the Supramolecular Block Copolymer ............................. 54 3.2.4 Characterization ....................................................................................... 55 3.3 Results and discussion ........................................................................................ 57 3.3.1 Analytical Evidence for the Formation of a Supramolecular Block Copolymer......................................................................................................... 59 3.3.2 Morphology of the blend ......................................................................... 63 3.3.3 Mechanical Properties .............................................................................. 72 3.3.4 Nonlinear Rheological Behavior.............................................................
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