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Synthesis and Interfacial Behavior of Functional Amphiphilic Graft Copolymers Prepared by Ring-Opening Metathesis Polymerization

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Synthesis and Interfacial Behavior of Functional Amphiphilic Graft Copolymers Prepared by Ring-Opening Metathesis Polymerization University of Massachusetts Amherst ScholarWorks@UMass Amherst Open Access Dissertations 2-2009 Synthesis and Interfacial Behavior of Functional Amphiphilic Graft opC olymers Prepared by Ring- opening Metathesis Polymerization Kurt E. Breitenkamp University of Massachusetts Amherst, [email protected] Follow this and additional works at: https://scholarworks.umass.edu/open_access_dissertations Part of the Polymer and Organic Materials Commons Recommended Citation Breitenkamp, Kurt E., "Synthesis and Interfacial Behavior of Functional Amphiphilic Graft opoC lymers Prepared by Ring-opening Metathesis Polymerization" (2009). Open Access Dissertations. 4. https://doi.org/10.7275/v32k-tj21 https://scholarworks.umass.edu/open_access_dissertations/4 This Open Access Dissertation is brought to you for free and open access by ScholarWorks@UMass Amherst. It has been accepted for inclusion in Open Access Dissertations by an authorized administrator of ScholarWorks@UMass Amherst. For more information, please contact [email protected]. SYNTHESIS AND INTERFACIAL BEHAVIOR OF FUNCTIONAL AMPHIPHILIC GRAFT COPOLYMERS PREPARED BY RING-OPENING METATHESIS POLYMERIZATION A Dissertation Presented by KURT E. BREITENKAMP II Submitted to the Graduate School of the University of Massachusetts Amherst in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY February 2009 Polymer Science and Engineering © Copyright by Kurt E. Breitenkamp II 2009 All Rights Reserved SYNTHESIS AND INTERFACIAL BEHAVIOR OF FUNCTIONAL AMPHIPHILIC GRAFT COPOLYMERS PREPARED BY RING-OPENING METATHESIS POLYMERIZATION A Dissertation Presented by KURT E. BREITENKAMP II Approved as to style and content by: __________________________________________ Todd S. Emrick, Chair __________________________________________ E. Bryan Coughlin, Member __________________________________________ Anthony D. Dinsmore, Member ________________________________________ Shaw L. Hsu, Department Head Polymer Science and Engineering DEDICATION In memory of my father, Kurt E. Breitenkamp, and grandmother, Frances Rogers, who made this possible and continue to inspire me everyday. ACKNOWLEDGMENTS I would like to thank my thesis advisor, Professor Todd Emrick for inspiring my love of chemistry and allowing me the freedom to test my own creativity in the lab. You have been and continue to be a great mentor and friend without condition. I would also like to thank my committee members, Professors Bryan Coughlin and Tony Dinsmore. The work contained herein would not have been possible without your assistance in many key experiments. I would also like to thank all the other members of the Polymer Science and Engineering faculty and staff for their education and assistance during my time in graduate school. I would like to thank the agencies who financially supported this research: Center for UMass-Industry Research on Polymers (CUMIRP), National Science Foundation - Materials Research Science & Engineering Center (MRSEC) at UMass-Amherst, National Science Foundation (NSF) – Chemical Transport Systems (CTS), and Office of Naval Research (EUWP). Thank you to those who contributed directly to the work contained in this thesis: Dr. Bryan Parrish, Rebecca Breitenkamp, Dr. Ravindra Revanur, Bryan McClosky, Professor Benny Freeman, Dr. Grégoire Cardoen, Dan Burke, Matt Kade, Jennifer Simeone, Euhna Jin, and Professor Denise Junge. I would also like to specifically thank members of the Polymer Science and Engineering staff who assisted me throughout the course of graduate school and who contributed to many experiments herein: Dr. Steve Eyles, Lou Raboin, Dr. Sekar Thirunavukkarasu, and Dr. Charlie Dickinson. I would like to thank all my fellow group members for their help and support. In particular, I would like to thank the early Emrick group members from whom I learned so v much: Dr. Bryan Parrish, Dr. Habib Skaff, Dr. Rui Hong, Dr. Kevin Sill, and Dr. Ken Ellzey. I would also like to thank all the current Emrick group members, especially Katrina Kratz and Brent Hammer. Thanks to my friends, Doug and Meghan Holmes, for making the second round of graduate school much more entertaining. Many thanks to my family – Mom, James, Pappy, Robin, Michael, Rudy, Becky, Ryan, Lyndi, Sean, and Ally. None of this would be possible without your continued love and moral support. Finally, I would like to thank my wife, Rebecca Breitenkamp, for all of the memories during our journey through graduate school. Words cannot describe how much you mean to me. vi ABSTRACT SYNTHESIS AND INTERFACIAL BEHAVIOR OF FUNCTIONAL AMPHIPHILIC GRAFT COPOLYMERS PREPARED BY RING-OPENING METATHESIS POLYMERIZATION FEBRUARY 2009 KURT E. BREITENKAMP II, B.S., UNIVERSITY OF SOUTHERN MISSISSIPPI M.S., UNIVERSITY OF MASSACHUSETTS-AMHERST Ph.D., UNIVERSITY OF MASSACHUSETTS-AMHERST Directed by: Professor Todd S. Emrick This thesis describes the synthesis and application of a new series of amphiphilic graft copolymers with a hydrophobic polyolefin backbone and pendent hydrophilic poly(ethylene glycol) (PEG) grafts. These copolymers are synthesized by ruthenium benzylidene-catalyzed ring-opening metathesis polymerization (ROMP) of PEG- functionalized cyclic olefin macromonomers to afford polycyclooctene-graft-PEG (PCOE-g-PEG) copolymers with a number of tunable features, such as PEG graft density and length, crystallinity, and amphiphilicity. Macromonomers of this type were prepared first by coupling chemistry using commercially available PEG monomethyl ether derivatives and a carboxylic acid-functionalized cycloctene. In a second approach, macromonomers possessing a variety of PEG lengths were prepared by anionic polymerization of ethylene oxide initiated by cyclooctene alkoxide. This methodology affords a number of benefits compared to coupling chemistry including an expanded PEG molecular weight range, improved hydrolytic stability of the PEG-polycyclooctene linkage, and a reactive hydroxyl end-group functionality for optional attachment of biomolecules and probes. vii The amphiphilic nature of these graft copolymers was exploited in oil-water interfacial assembly, and the unsaturation present in the polycyclooctene backbone was utilized in covalent cross-linking reactions to afford hollow polymer capsules. In one approach, a bis-cyclooctene PEG derivative was synthesized and co-assembled with PCOE-g-PEG at the oil-water interface. Upon addition of a ruthenium benzylidene catalyst, a cross-linked polymer shell is formed through ring-opening cross-metathesis between the bis-cyclooctene cross-linker and the residual olefins in the graft copolymer. By incorporating a fluorescent-labeled cyclooctene into the graft copolymer, both oil- water interfacial segregation and effective cross-linking were confirmed using confocal laser scanning microscopy (CLSM). In a second approach, reactive functionality capable of chemical cross-linking was incorporated directly into the polymer backbone by synthesis and copolymerization of phenyl azide and acyl hydrazine-functional cyclooctene derivatives. Upon assembly, these reactive polymers were cross-linked by photolysis (in the phenyl azide case) or by addition of glutaraldehyde (in the acyl hydrazine case) to form mechanically robust polymer capsules with tunable degradability (i.e. non-degradable or pH-dependent degradability). This process permits the preparation of both oil-in-water and water-in-oil capsules, thus enabling the encapsulation of hydrophobic or hydrophilic reagents in the capsule core. Furthermore, the assemblies can be sized from tens of microns to the 150 nm - 1 µm size range by either membrane extrusion or ultrasonication techniques. These novel capsules may be well-suited for a number of controlled release applications, where the transport of encapsulated compounds can be regulated by factors such as cross-link density, hydrolytic stability, and environmental triggers such as changes in pH. viii TABLE OF CONTENTS Page ACKNOWLEDGMENTS ...................................................................................................v ABSTRACT...................................................................................................................... vii LIST OF TABLES........................................................................................................... xiii LIST OF FIGURES ......................................................................................................... xiv LIST OF SCHEMES ...........................................................................................................v LIST OF ABBREVIATIONS..............................................................................................v 1. SYNTHETIC POLYMERS FOR ENCAPSULATION AND DELIVERY ...........1 1.1 The Role of Synthetic Polymers in Drug Delivery............................................1 1.1.1 Conjugation of Polymers to Drugs and Delivery Systems .................3 1.1.2 Encapsulation and Release Strategies using Polymeric Delivery Systems .............................................................................6 1.1.2.1 Delivery Systems Based on Polymer Microspheres ............7 1.1.2.2 Encapsulation Systems Based on Block Copolymer Assembly..............................................................................9 1.1.2.3 Polymer Capsules as Drug Delivery Platforms .................12 1.2 Thesis Outline ..................................................................................................15 1.3 References........................................................................................................18
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