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Polyisobutylene Telechelic Prepolymers by in Situ End-Quenching and Post-Polymerization Modifications

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Polyisobutylene Telechelic Prepolymers by in Situ End-Quenching and Post-Polymerization Modifications The University of Southern Mississippi The Aquila Digital Community Dissertations Spring 5-2017 Polyisobutylene Telechelic Prepolymers by In Situ End-Quenching and Post-Polymerization Modifications Bin Yang University of Southern Mississippi Follow this and additional works at: https://aquila.usm.edu/dissertations Part of the Polymer and Organic Materials Commons, Polymer Chemistry Commons, and the Polymer Science Commons Recommended Citation Yang, Bin, "Polyisobutylene Telechelic Prepolymers by In Situ End-Quenching and Post-Polymerization Modifications" (2017). Dissertations. 1327. https://aquila.usm.edu/dissertations/1327 This Dissertation is brought to you for free and open access by The Aquila Digital Community. It has been accepted for inclusion in Dissertations by an authorized administrator of The Aquila Digital Community. For more information, please contact [email protected]. POLYISOBUTYLENE TELECHELIC PREPOLYMERS BY IN SITU END- QUENCHING AND POST-POLYMERIZATION MODIFICATIONS by Bin Yang A Dissertation Submitted to the Graduate School and the School of Polymers and High Performance Materials at The University of Southern Mississippi in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Approved: ________________________________________________ Dr. Robson F. Storey, Committee Chair Professor, Polymers and High Performance Materials ________________________________________________ Dr. Derek L. Patton, Committee Member Associate Professor, Polymers and High Performance Materials ________________________________________________ Dr. James W. Rawlins, Committee Member Associate Professor, Polymers and High Performance Materials ________________________________________________ Dr. Jeffrey S. Wiggins, Committee Member Associate Professor, Polymers and High Performance Materials ________________________________________________ Dr. Jason D. Azoulay, Committee Member Assistant Professor, Polymers and High Performance Materials ________________________________________________ Dr. Karen S. Coats Dean of the Graduate School May 2017 COPYRIGHT BY Bin Yang 2017 Published by the Graduate School ABSTRACT POLYISOBUTYLENE TELECHELIC PREPOLYMERS BY IN SITU END- QUENCHING AND POST-POLYMERIZATION MODIFICATIONS by Bin Yang May 2017 This volume focuses on the development of telechelic polyisobutylene (PIB) prepolymers by combining end-capping of living carbocationic polymerization of isobutylene (IB) with suitable reactants and post-polymerization modifications. Alkylation kinetics of PIB tert-chloride with alkoxybenzenes using either TiCl4 or AlCl3 were investigated. Quantitative para-position end-capped products were only achieved if the alkoxybenzene/AlCl3 molar ratio was greater than unity; while no such molar ratio is required for TiCl4, but the alkylation rate was slower than AlCl3 under the same conditions. Photopolymerization kinetics analysis of PIB triphenol tri(meth)acrylates with low and high Mns, and control aliphatic PIB triol triacrylate with similar high Mn showed that Darocur 1173 afforded the highest photopolymerization rate and conversion. Kinetics analysis also indicated despite of end-functionality and acrylate structure, photopolymerization rate for PIB prepolymers with high Mns, attributed to reduced diffusional mobility, resulting in decreased rate of termination and autoacceleration. Structure-property relationships indicated the Tg of PIB networks decreased as the Mn of PIB macromer increased regardless of end-group type, and thermal stability remained constant regardless of end-group type. Tensile properties were characteristic of weak rubbery networks. Quantitative synthesis of PIB telechelic prepolymers with various types of epoxides, including aliphatic and phenyl glycidol ether, exo-olefin epoxide, and ii cyclohexene epoxide have been developed through post modifications. A novel method for PIB chain end functionalization was developed whereby living PIB is end-capped with the bulky comonomer, 4-(4-allyloxyphenyl)-2-methyl-1-butene (AMB) at full IB conversion. Addition is readily limited to one or two comonomer units per chain end at a low [AMB]/[chain end] ratio. The mechanism suggested that upon addition of AMB, the resulting carbocation tends to undergo terminative chain transfer consisting of alkylation of the 4-allyloxyphenyl ring at C2, via a five-membered cyclic intermediate. Grubbs 3rd generation mediated ROMP of PIB (oxa)norbornene macromonomers via a grafting “through” methodology were conducted successfully, producing PIB bottlebrush polymers with controlled molecular weight and low dispersities. Both 1H NMR and SEC kinetics analyses showed pseudo-first-order kinetic behavior for these macromonomers. Besides, both kinetic studies demonstrated that the ROMP propagation rate of PIB norbornene is at least 2.2 times greater than that of PIB oxanorborne macromonomer. iii ACKNOWLEDGMENTS I am grateful to my advisor, Dr. Robson F. Storey, for providing the guidance, support, and freedom to explore new ideas, and for being a great friend, high-point climber, and a mentor. His scientific know-how, persistence, and encouragement make my graduate career meaningful and enjoyable. I also sincerely appreciate my graduate committees for their help: Dr. Derek Patton, Dr. Jeffrey Wiggins, Dr. James Rawlins, and Dr. Jason Azoulay. I would like to thank Dr. Brooks Abel and Dr. Charles McCormick for their contribution to this work. I would also like to acknowledge Dr. Sarah Morgan for her help on looking for industrial career path, Dr. Jason Azoulay for bringing me in his research group to expand my experience and knowledge, and Dr. William Jarrett for his continuous help on NMR acquisition and interpretation. I would like to thank all of my colleagues in the Storey research group, my first- year class, and my fellow graduate students, who made my research life fruitful and interesting. In particular, I would like to thank Dr. Subramanyam Ummadisetty, Dr. Todd Hartlage, Dr. Lauren Kucera, Dr. Mark Brei, Dr. Adekunle Olubummo, Conor Roche, C.Garrett Campbell, Corey Parada, Jie Wu, Morgan Heskett, R. Hunter Cooke, Travis Holbrook, Merlin Dartez, and our secretary Melanie Heusser. I would like to thank Henkel Corp. for the generous financial support of the projects described in this volume. iv DEDICATION This work is dedicated to my parents for their endless love, care, and support for all paths I chose to pursue. Finally, much gratitude to my family and friends for their much appreciated support and understanding. v TABLE OF CONTENTS ABSTRACT ........................................................................................................................ ii ACKNOWLEDGMENTS ................................................................................................. iv DEDICATION .................................................................................................................... v LIST OF TABLES .............................................................................................................. x LIST OF ILLUSTRATIONS ............................................................................................. xi LIST OF SCHEMES....................................................................................................... xvii CHAPTER I - BACKGROUND ........................................................................................ 1 1.1 Polyisobutylenes ....................................................................................................... 1 1.2 Living Carbocationic Polymerization of Isobutylene ............................................... 3 1.2.1 Commercial Polyisobutylenes ........................................................................... 3 1.2.2 Living Carbocationic Polymerization of Isobutylene ........................................ 4 1.3 Functionalization of Polyisobutylenes ...................................................................... 6 1.3.1 Post-Polymerization Modification ..................................................................... 7 1.3.2 In-Situ Functionalization .................................................................................... 8 1.3.2.1 Functional Initiators .................................................................................... 9 1.3.2.2 In-Situ Functionalization ............................................................................. 9 1.4 Telechelic Polyisobutylenes .................................................................................... 15 1.5 Bottlebrush Polymers .............................................................................................. 17 1.6 References ............................................................................................................... 22 vi – END-QUENCHING OF TERT-CHLORIDE TERMINATED POLYISOBUTYLENE WITH ALKOXYBENZENES: COMPARISON OF ALCL3 AND TICL4 CATALYSTS............................................................................................... 32 2.1 Abstract ................................................................................................................... 32 2.2 Introduction ............................................................................................................. 33 2.3 Experimental ........................................................................................................... 35 2.4 Results and Discussion ........................................................................................... 38 2.5 Conclusions
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