University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 8-2016 Synthesis and Characterization of New Multifunctional Initiators for Anionic Polymerization and the Use of Poly(4-hydroxystyrene) as a Template for new Polymers Christopher Michael Hurley 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 Hurley, Christopher Michael, "Synthesis and Characterization of New Multifunctional Initiators for Anionic Polymerization and the Use of Poly(4-hydroxystyrene) as a Template for new Polymers. " PhD diss., University of Tennessee, 2016. https://trace.tennessee.edu/utk_graddiss/3929 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 Christopher Michael Hurley entitled "Synthesis and Characterization of New Multifunctional Initiators for Anionic Polymerization and the Use of Poly(4-hydroxystyrene) as a Template for new Polymers." 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: Kevin Kit, Brian Long, George Kabalka Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) Synthesis and Characterization of New Multifunctional Initiators for Anionic Polymerization and the Use of Poly(4-hydroxystyrene) as a Template for New Polymers A Dissertation Presented for the Doctor of Philosophy Degree The University of Tennessee, Knoxville Christopher Michael Hurley August 2016 Copyright © 2016 by Christopher M. Hurley All rights reserved. ii DEDICATION This work is dedicated to my father, Dr. John P. Hurley, whose commitment to hard work and enduring attitude has been a guiding light to his children. iii ACKNOWLEDGEMENTS I would like to express my sincerest appreciation towards all the individuals who contributed to making this dissertation a possibility. A work of this nature is impossible without the direct and indirect contributions of a large number of great people. I am grateful for the effort and the dedication of my committee: Professor Jimmy W. Mays, Dr. George W. Kabalka, Dr. Brian Long and Dr. Kevin M. Kit. I would like to give special thanks to my advisor, Dr. Jimmy W. Mays for all that he has provided and done to assist in this work. In addition I would like to acknowledge all the members and non-members of the Mays’ group that have assisted in my development including Dr. Nam-Goo Kang, Dr. Mohammad Changez, Dr. Georgios Sakellariou, Dr. Kostas Misichronis, Dr. Shahinur Rahman, Dr. Durairaj Baskaran, Dr. Sachin Bobade, Dr. Vikram Srivastiva, Dr. Andrew Goodwin, Dr. Justin Roop, Dr. Beom-Goo Kang, Mr. Tom Malgren, Dr. Brad Miller, Dr. John Dunlap, Dr. Weiyu Wang, Xinyi Lu, Wei Lu, Hongbo Feng, Benjamin Ripy, and Huiqun Wang. I would like to thank all the members of the department that I have interacted with and my friends outside of the department for their encouragement and friendship. Lastly, I would like to thank my family for their gracious understanding and the countless things they have done to help me along this path. Especially my mother, Mary Ellen and my siblings Patrick and Meagan. I would also like to thank my girlfriend, Megan Johnstone, for all her efforts, understanding and patience during my pursuit of this goal. iv ABSTRACT This dissertation explores the synthesis and use of multifunctional anionic polymerization initiators for the purpose of opening the gateway to the synthesis of polymer architectures of greater complexity. First the multifunctional oxyanion initiator generated by reacting poly(4-hydroxystyrene) with sodium hydride was used to synthesize a previously unknown polymer containing an aryl halide functional group. The homopolymer solution self-assembly behavior of poly(4-hydroxystyrene) and the newly synthesized poly (4-(4-bromophenyloxy)styrene) were both investigated. This is followed by the synthesis and characterization of multifunctional alkyne core molecules and random copolymers of polystyrene-co-poly(4-hydroxystyrene) which served as templates for the synthesis of new random copolymers of polystyrene-co-poly(4-(2- propynyloxy)styrene). The newly formed multifunctional alkyne core molecules and alkyne functionalized random copolymers served as polymer backbones in a “grafting to” strategy. Previously prepared azide terminated polymers were grafted to the multifunctional alkyne core molecules and polymer backbones by copper (I) catalyzed alkyne-azide cycloaddition reactions. Lastly, the synthesis of a new hydrocarbon soluble multifunctional initiator was undertaken. The resulting molecule was shown to be an efficient initiator of anionic polymerization in non-polar solvent in the absence of polar additives, necessary in all previous attempts to combat large scale aggregation of such multifunctional initiator. This new initiator will open the way to facile synthesis of well- defined star polymers, star-block copolymers, and more complex polymer architectures. v TABLE OF CONTENTS Chapter 1 Introduction .................................................................................................. 1 Background ................................................................................................................... 2 Multifunctional Initiators ............................................................................................... 7 Functionalized 1,1-Diphenylethylene ........................................................................ 10 Difunctional Double 1,1-Diphenylethylene Initiators ................................................ 13 Higher Complexity Polymer Architecture ................................................................. 19 Functionalized Styrene Monomers ............................................................................ 29 Conclusions ................................................................................................................. 40 References ................................................................................................................... 42 Chapter 2 Synthesis, Characterization and Application of the Self-assembly of amphiphilic homopolymers poly(4-hydroxystyrene) and poly(4-(4- bromophenyloxy)styrene) .......................................................................................... 49 Abstract ........................................................................................................................ 50 Introduction ................................................................................................................. 50 Experimental Section .................................................................................................. 53 Chemicals ............................................................................................................. 53 Characterization ................................................................................................... 54 Anionic Polymerization of 4-(1-ethoxyethoxy)styrene ...................................... 55 Deprotection of poly(4-(1-ethoxyethoxy)styrene) ............................................. 55 Williamson Etherification Reaction of poly(4-hydroxystyrene) and 4- bromobenzyl bromide .......................................................................................... 55 Self-assembly of homopolymers in solvent mixtures ...................................... 56 Formation of gold nanoparticles ........................................................................ 56 Preparation of doxorubicin loaded poly(4-hydroxystyrene) Vesicles ............. 57 Cell Culture ........................................................................................................... 57 Treatment of HCT-116 cancer cells with Doxorubicin loaded Poly(4- hydroxystyrene) Vesicles .................................................................................... 57 Results and Discussion .............................................................................................. 58 Conclusions ................................................................................................................. 77 References ................................................................................................................... 78 Chapter 3 Synthesis and characterization of star and graft copolymers of poly(4- (1-ethoxyethoxy)styrene) and poly(methyl acrylate) via click reaction .................. 81 Abstract ........................................................................................................................ 82 Introduction ................................................................................................................. 82 Experimental Section .................................................................................................. 85 Chemicals