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Synthesis of Bottlebrush Polymers Using the Grafting-Through and Transfer-To Methods Scott Charles Radzinski Dissertation Submit Synthesis of Bottlebrush Polymers Using the Grafting-Through and Transfer-To Methods Scott Charles Radzinski Dissertation submitted to the faculty of the Virginia Polytechnic Institute and State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy In Chemistry John B. Matson, Chair Timothy E. Long Harry Gibson Guoliang Liu March 23rd 2017 Blacksburg, VA Keywords: Comb polymer, Controlled radical polymerization, Z-RAFT Scott Radzinski Copyright 2017 Abstract: Synthesis of Bottlebrush Polymers Using the Grafting-Through and Transfer-To Methods Scott Radzinski Bottlebrush polymers are interesting topologies that have become increasingly relevant in various applications including rheology modifiers, super-soft elastomers, photonic crystals, anti- fouling coatings, the in vivo delivery of therapeutic agents, and as promising substrates in lithographic printing. These macromolecules are comprised of numerous polymeric side-chains densely grafted to a polymer backbone. The densely grafted nature of bottlebrush polymers results in steric repulsion between neighboring polymer chains, forcing these macromolecules to adopt a chain-extended conformation. Although these remarkable macromolecules have a many different applications, the transformative potential of the bottlebrush polymer topology has not been realized because the synthesis of high molecular weight bottlebrush polymers is challenging. This dissertation focusses on improving the synthesis of these large macromolecules using the grafting-through strategy in the first section and the transfer-to strategy in the second section. For the first time the effect of anchor group chemistry—the configuration of atoms linking the polymer to a polymerizable norbornene— was studied on the kinetics of ring-opening metathesis polymerization (ROMP) of macromonomers (MMs) initiated by Grubbs 3rd generation catalyst. A variance in the rate of propagation of >4-fold between similar MMs with different anchor groups was observed. This phenomenon was conserved across all MMs tested, regardless of solvent, molecular weight (MW), or repeat unit identity. Experimental and computational studies indicated that the rate differences likely resulted from a combination of varying steric demands and electronic structure among the different anchor groups. This new insight will allow others to achieve high MM conversion and prepare pure, high MW bottlebrush polymers by ROMP grafting-through. The second section of this dissertation deals with a little studied bottlebrush synthesis technique called the transfer-to method. This method is a hybrid of the grafting-from and grafting-to approaches in which the growing polymer side chains detach from the backbone, propagate freely in solution, and then reattach to the backbone in a chain transfer step. Several parameters were investigated to determine optimal conditions for this process. This study provides for the first time a guide to use the transfer-to method to produce high purity bottlebrush polymers with controllable backbone and side chain length. General Abstract: Synthesis of Bottlebrush Polymers Using the Grafting-Through and Transfer-To Methods Scott Radzinski Bottlebrush polymers are interesting topologies that have become increasingly relevant in various applications including super-soft elastomers and drug delivery agents. These macromolecules are comprised of numerous polymeric side-chains densely grafted to a polymer backbone. The densely grafted nature of bottlebrush polymers results in steric repulsion between neighboring polymer chains, forcing these macromolecules to adopt a chain-extended or worm like conformation. Although these remarkable macromolecules have a many different applications, the transformative potential of the bottlebrush polymer topology has not been realized because the synthesis of large bottlebrush polymers is challenging. This dissertation focusses on improving the synthesis of these big macromolecules using the grafting-through strategy in the first section and the transfer-to strategy in the second section. For the first time the effect of anchor group chemistry—the configuration of atoms linking the polymer to a polymerizable norbornene—was studied on bottlebrush synthesis. A variance in how fast the polymerization took between similar MMs with different anchor groups was observed. Experimental and computational studies indicated that the differences likely resulted from a combination of varying steric demands and electronic structure among the different anchor groups. This new insight will allow others to achieve high MM conversion and prepare pure, high MW bottlebrush polymers by ROMP grafting-through. The second section of this dissertation deals with a little studied bottlebrush synthesis technique called the transfer-to method. This method is a hybrid of two well-known methods, grafting-from and grafting-to approaches, in which the growing polymer side chains detach from the backbone, polymerize freely in solution, and then reattach to the backbone in a chain transfer step. Several parameters were investigated to determine optimal conditions for this process. This study provides for the first time a guide to use the transfer-to method to produce high purity bottlebrush polymers with controllable sizes. Dedication This dissertation is dedicated to my son Brogan Scott Radzinski vi Acknowledgments I would like to first thank my advisor Dr. John Matson for his continued support throughout my career at Virginia Tech. He has taught me immensely and helped me grow into the scientist I am today. I would also like to thank my committee members Dr. Gibson, Dr. Long, Dr. Turner, and Dr. Liu for guidance. A special thanks goes to my beautiful wife Christine for her patience throughout my academic career. Without her support none of this would have been possible and now she looks forward to me getting a “real” job. Thank you to fellow graduate student Jeff Foster for wonderful collaborations and keeping me sane during this endeavor. To my colleagues in the Matson lab thank you for constant laughs and breaking the GPC so I always have something to fix in the lab. To my family that has supported me during my time here, thank you very much; I could not have done this without your support. Lastly, to all my friends that have helped me and supported me along the way, thank you. vii Table of Contents Dedication ...................................................................................................................................... vi Acknowledgments......................................................................................................................... vii Table of Contents ......................................................................................................................... viii Attribution ..................................................................................................................................... xii Section I: Synthesis of Bottlebrush Polymers Using Grafting-Through. ....................................... 1 Chapter 1: Introduction to Bottlebrush Polymers ....................................................................... 1 1.1 Polymerization Techniques in Bottlebrush Synthesis .................................................. 2 1.2 Bottlebrush Polymer Synthesis Techniques ................................................................. 7 1.3 Unique Bottlebrush Polymers ..................................................................................... 14 1.4 References .................................................................................................................. 21 Chapter 2: Bottlebrush Polymer Synthesis by Ring-Opening Metathesis Polymerization: The Significance of the Anchor Group ............................................................................................ 24 2.1 Authors ............................................................................................................................ 24 2.2 Abstract ........................................................................................................................... 24 2.3 Introduction ..................................................................................................................... 25 2.4 Results and Discussion ................................................................................................... 29 2.5 Conclusions ..................................................................................................................... 39 2.6 References ....................................................................................................................... 40 2.7 Appendix ......................................................................................................................... 45 Chapter 3: Preparation of Bottlebrush Polymers via a One-Pot Ring-Opening Polymerization (ROP) and Ring-Opening Metathesis Polymerization (ROMP) Grafting-Through Strategy ... 81 3.1 Authors ............................................................................................................................ 81 viii 3.2 Abstract ........................................................................................................................... 81 3.3 Introduction ..................................................................................................................... 82 3.4 Results and Discussion ..................................................................................................
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