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Surface Engineering and Monomer Design for Light- Mediated Ring Opening Metathesis Polymerization

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Surface Engineering and Monomer Design for Light- Mediated Ring Opening Metathesis Polymerization University of Kentucky UKnowledge Theses and Dissertations--Chemical and Materials Engineering Chemical and Materials Engineering 2018 SURFACE ENGINEERING AND MONOMER DESIGN FOR LIGHT- MEDIATED RING OPENING METATHESIS POLYMERIZATION Ishan A. Fursule University of Kentucky, [email protected] Digital Object Identifier: https://doi.org/10.13023/ETD.2018.028 Right click to open a feedback form in a new tab to let us know how this document benefits ou.y Recommended Citation Fursule, Ishan A., "SURFACE ENGINEERING AND MONOMER DESIGN FOR LIGHT-MEDIATED RING OPENING METATHESIS POLYMERIZATION" (2018). Theses and Dissertations--Chemical and Materials Engineering. 82. https://uknowledge.uky.edu/cme_etds/82 This Doctoral Dissertation is brought to you for free and open access by the Chemical and Materials Engineering at UKnowledge. It has been accepted for inclusion in Theses and Dissertations--Chemical and Materials Engineering by an authorized administrator of UKnowledge. For more information, please contact [email protected]. STUDENT AGREEMENT: I represent that my thesis or dissertation and abstract are my original work. Proper attribution has been given to all outside sources. I understand that I am solely responsible for obtaining any needed copyright permissions. I have obtained needed written permission statement(s) from the owner(s) of each third-party copyrighted matter to be included in my work, allowing electronic distribution (if such use is not permitted by the fair use doctrine) which will be submitted to UKnowledge as Additional File. I hereby grant to The University of Kentucky and its agents the irrevocable, non-exclusive, and royalty-free license to archive and make accessible my work in whole or in part in all forms of media, now or hereafter known. I agree that the document mentioned above may be made available immediately for worldwide access unless an embargo applies. I retain all other ownership rights to the copyright of my work. I also retain the right to use in future works (such as articles or books) all or part of my work. I understand that I am free to register the copyright to my work. REVIEW, APPROVAL AND ACCEPTANCE The document mentioned above has been reviewed and accepted by the student’s advisor, on behalf of the advisory committee, and by the Director of Graduate Studies (DGS), on behalf of the program; we verify that this is the final, approved version of the student’s thesis including all changes required by the advisory committee. The undersigned agree to abide by the statements above. Ishan A. Fursule, Student Dr. Bradley Berron, Major Professor Dr. Thomas Dziubla, Director of Graduate Studies SURFACE ENGINEERING AND MONOMER DESIGN FOR LIGHT-MEDIATED RING OPENING METATHESIS POLYMERIZATION DISSERTATION Dissertation submitted to the faculty of the graduate school in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the College of Engineering at the University of Kentucky By Ishan A. Fursule Director: Dr. Bradley Berron, Associate Professor of Chemical and Materials Engineering, University of Kentucky, Lexington, Kentucky 2017 Copyright © Ishan A. Fursule 2017 ABSTRACT OF DISSERTATION SURFACE ENGINEERING AND MONOMER DESIGN FOR LIGHT-MEDIATED RING OPENING METATHESIS POLYMERIZATION Stimuli-responsive materials are changing the landscape of actuated materials, optoelectronics, molecular machines, solar cells, temporary memory storage, and biomedical materials. Specifically, photo-responsive polymers have gained acceleration in research and application since the last two decades in the form of a surface coating and micro-patterns. Light as a stimulus can be coherent, mono or polychromatic, tunable for power (intensity) and energy (wavelength), and has precise spatiotemporal control. Conventional surface coating techniques such as spin coating are unable to impart properties to the coatings in terms of sturdiness, homogeneity, uniformity over the complex surface, post deposition modification, and process efficiency. Also, in the field of photoreponsive polymers, there is no simple technique for surface-patterning of photo- responsive polymers, which is an important missing link between current research and future potential applications. This dissertation designs new strategies for light-mediated ring opening metathesis polymerization (ROMP) to synthesize a diverse class of stable photo-responsive polymers and coatings. Firstly, we propose a new synthetic route to functionalize surface-initiated ring opening metathesis polymerization (SI ROMP) coatings. The backbone of ROMP polymers has internal carbon-carbon double bonds which are potential sites to introduce additional functionalities like stimuli-responsive functional groups. We leverage these unsaturated bonds to incorporate functionalized side chains using thiol-ene click chemistry. Thiol-ene chemistry is a versatile approach to attach diverse functional groups at the site of a carbon- carbon double bond. This approach was tested by grafting 3 types of thiols with different functional tail groups and can be readily used for any polyolefin coatings. Secondly, oxidative degradation of SI ROMP coatings in the organic solvent is a common problem resulting in a decrease in the film thickness due to polymer chain cleavage. We incorporated a custom designed crosslinker to the polynorbornene (pNB) coatings to prepare in situ crosslinked pNB coatings. This approach provides a crosslinked coating of pNB with significantly increased stability against organic solvents by decreasing the film loss from 73 % to 28 %. Lastly, a novel approach of making photo-responsive polymer by light mediated ROMP is demonstrated. Light mediated control over rate of polymerization is the key feature required for patterning surface with photoresponsive polymers. We achieved this goal by designing and synthesizing a monomer that effectively controls the activity of the catalyst by temporarily deactivating it on irradiation with UV 365 nm light and reactivating it back by irradiation with blue 455 nm light to resume the ROMP. Keywords: Azobenzene, polynorbornene, photoresponsive ROMP, SI ROMP, crosslinker, coating. Ishan A. Fursule 12/01/2017 SURFACE ENGINEERING AND MONOMER DESIGN FOR LIGHT-MEDIATED RING OPENING METATHESIS POLYMERIZATION By Ishan A. Fursule Dr. Bradley Berron Director of Dissertation Dr. Thomas Dziubla Director of Graduate Studies Date 12/01/2017 To my Mother, Father, and Brother. ACKNOWLEDGEMENTS The very first person to whom I would like to express my deepest gratitude is Dr. Bradley Berron. He has not only guided me throughout my doctoral research work by his profound knowledge, creative ideas, and welcoming new projects proposed by me but also has been a ‘Mentor’ to me. During my research, I did take time to learn new laboratory practices, using instruments, and getting results through the highs and lows, but he has always been encouraging, positive and very patient. Being ahead of time, the importance of hard work and having a big vision towards your work are the three things that I learned from him and will be the pillars for my future career. To summarize, without his support, insight, and vision, my journey through Ph.D. would have been much difficult. I am really honored to work with him and thankful for being my research advisor. I am also extremely thankful to all my committee members Dr. Matthew Beck, Dr. Stephen Rankin, and Dr. Mark Watson for their guidance, valuable suggestions, and oversee completion of my dissertation thesis. Many thanks to Dr. Marcelo I. Guzman for agreeing to serve as my external examiner. Secondly, I would like to thank my parents, late mother Mrs. Manda Fursule, and father Mr. Anupkumar Fursule for shaping me into a person who I am with their love, encouragement, and belief in me. Also, I would like to thank my elder brother, Dr. Anurag Fursule who is the biggest inspiration for me for his hardworking and helping nature. Special thanks to all my friends ‘Virginia Mandal’ especially Shreya, Abhishek, Prachi, Raghava, Priyesh, and everyone who made my life in Lexington very exciting and unforgettable. I am also grateful to my fellow lab members, Dr. Aman Preet Kaur, Dr. Leila Safazadeh, Dr. Jacob Lilly, Charles Watkins Jr., Calvin Cahall, Dr. Anuhya Gottipati, Pei- Jung Wu, Cong Li and Landon Mills. They have made my time in laboratory fun and enjoyable. Finally, I would like to acknowledge CeNSE, ERTL, NMR facility at UKy, and other academic laboratories for allowing me to use their analytical instruments and professors who spent their precious time in discussing and providing their valuable suggestion on my research ideas. Finally, this work was supported by National Science iii Foundation under Award CMMI-1334403. Acknowledgment is also made to the Donors of the American Chemical Society Petroleum Research Fund (52743-DNI5 and 57619- DNI10) for partial support of this research. iv Table of contents ACKNOWLEDGEMENTS ............................................................................................... iii Table of contents ................................................................................................................. v List of tables ....................................................................................................................... ix List of figures ...................................................................................................................... x List of Abbreviations ......................................................................................................
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