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Renewable Polymers from Itaconic Acid

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Renewable Polymers from Itaconic Acid RENEWABLE POLYMERS FROM ITACONIC ACID A Dissertation Presented to the Faculty of the Graduate School of Cornell University In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy by Jacob Thomas Trotta August 2019 © 2019 Jacob Thomas Trotta ii RENEWABLE POLYMERS FROM ITACONIC ACID Jacob Thomas Trotta, Ph. D. Cornell University 2019 Itaconic acid (IA) is a biorenewable compound that is generated inexpensively and in large amounts by the fermentation of biomass. While a variety of structurally diverse polymers have been accessed from IA, continued exploration of efficient syntheses and polymerizations of novel monomers could lead to the development of sustainable materials that can help reduce society’s dependence of petroleum (Chapter 1). We show that from β-monomethyl itaconate, an IA derivative, we can utilize a selective addition strategy that allows access to both α-methylene-γ-butyrolactone (MBL, tulipalin A) and α-methylene-γ,γ-dimethyl-γ-butyrolactone (Me2MBL), which serve as high value biorenewable analogues to petroleum-derived methyl methacrylate. Subsequent polymerization of both Me2MBL and MBL through reversible addition- fragmentation chain-transfer (RAFT) polymerization generates well defined poly(Me2MBL) (PMe2MBL) and poly(MBL) (PMBL) polymers. Through physiochemical characterization, we show that PMe2MBL has desirable properties comparable with known PMBL materials (Chapter 2). We then extend our strategy to produce triblock polymers using PMBL end blocks with an IA-derived polyester mid- block. Using catalytic, solvent-free, and high yielding transformations from an itaconate source, we efficiently synthesize a saturated diol, a saturated diester, and an unsaturated diester. Subsequent step-growth polycondensation polymerizations of these monomers leads to polyesters with relatively high molar masses (> 10 kg/mol). Chain-end iii functionalization and chain-extension of the saturated polyesters with MBL then provides access to an almost completely IA-derived triblock polymer thermoplastic. Alternatively, we show that thiol-ene cross-linking of unsaturated polyesters allows access to thermosets with tunable mechanical properties based on the cross-linking density. In most cases, high isolated yields, high atom economies, and low process mass intensities for these reactions reflect green and sustainable processes (Chapter 3). We then explore sustainable methods for the oxidation of MBL to its oxide, MBLO. Ring- opening polymerizations of MBLO to PMBLO is performed and gives access to a new, biorenewable, and amorphous polyether that exhibits a high glass transition temperature (106 °C). Comparisons with other common polyethers highlights the potential utility of this new material, and the polymerization of similar renewable epoxide monomers are studied (Chapter 4). iv BIOGRAPHICAL SKETCH Jacob Trotta was born in Boston, Massachusetts in 1992. He grew up in Peabody, Massachusetts and then graduated from Concord-Carlisle Regional High School in Concord, Massachusetts in 2010 before attending college at Villanova University in Pennsylvania. During his time as an undergraduate, Jacob worked as an intern at Alkermes, Inc. during summer and winter breaks, beginning in 2011. He obtained his B.S. from Villanova University in the of Spring 2014 with a major in chemistry and a minor in mathematics. Following this, Jacob began his graduate career at Cornell University in the laboratory of Brett Fors, where he worked on the synthesis and characterization of renewable polymeric materials largely derived from itaconic acid. Starting in the summer of 2019, Jacob will return to Alkermes to work full-time. In his free time, Jacob enjoys running, hiking, playing board games, and watching Game of Thrones. v ACKNOWLEDGMENTS I never really questioned my decision to pursue chemistry during my undergraduate and then graduate career, and this is probably because I had such a positive experience with the subject as a teenager – it turns out that having good science teachers in high school matters quite a bit. So, because of that, I owe a huge thanks to Mrs. McCaffrey-Clark, a truly phenomenal high school chemistry teacher, who got me interested in chemistry in the first place. Once I got to college, I met many people who helped me on my path to graduate school. In particular, I would like to thank Professor Deanna Zubris, Professor Eduard Casillas, Professor Nicholas Piro, and Professor Scott Kassel for their support and instruction along the way. I also need to thank my undergraduate roommates for their continued friendships through the years: Francis Polignano (honorary roommate), Connor McGuckin, Matthew Whalen, Steven Stagliano, and Brian Selitto, you all are the best, and I look forward to many more years of friendship. While I got my undergraduate degree in chemistry from Villanova University, I did most of my undergraduate research at Alkermes, Inc. as an intern. Alkermes fostered an incredibly supportive environment where I first developed an interest in research. I am grateful to everyone at Alkermes that I interacted with, especially Dr. Tarek Zeidan, whose role as a mentor made a hugely positive impact on my development as a scientist. I am very much looking forward to beginning my career at Alkermes this summer. After graduating from Villanova University, I entered the graduate program in Chemistry and Chemical Biology at Cornell University, in part because I wanted to work with Professor Brett Fors. Joining the lab of a brand-new assistant professor was vi a potentially risky move, but looking back, I know I made the right decision. So thank you, Brett, for your instruction, support, and patience over the last five years. I’m glad I spent it making as many things as possible from corn in your lab. It wasn’t just me in the Fors group, and I have many others to thank. Thanks to Dr. Dillon Gentekos: the past five years have had their highs and lows, and several “phases” were gone through, but it was nice to have someone to get through it with. Thanks to Stephen Parker Singleton: though you left the group, your presence was still felt. Righ. Thanks to Vernoika Kottisch, whose editing skills made this thesis possible. Thanks to Michael Supej, who promised to trim my rune armor for free. Thanks to Renee Sifri, who inspired me to pick up the piano again and learn to swing dance. Thanks to Stephanie Rosenbloom and her bird Petrie, who’s still learning how to say my name. Thanks to Scott Spring for his love of all things renewable. Thanks to Luis Melecio-Zambrano (here’s to another 10 years of friendship). Thanks to Yuting Ma, who always managed to make me laugh. There were also some postdocs in the Fors group. Thanks to Professor Dongbing Zhao, who supervised my first-year self and always helped when I, panicked, would ask if an experiment was dangerous. Thanks to Professor Quentin Michaudel, who I think about every postdoc appreciation day. Thanks to Dr. Erin Stache, who got me out of my running hiatus. I am especially grateful to all the undergraduates who have both worked with me and put up with me over the past five years. Mengyuan Jin, Katherine Stawiasz, Allison Wu, Teresa Datta, Zachary Vaughn, and Amanda Innamorato: thank you for your hard work and for the contributions you all made to the research I’ve worked on vii during graduate school. I’m sorry that I made you all clean so many NMR tubes. And although I did not work with them directly, I am grateful to have interacted with both Kathleen Naeher (the most chill undergrad) and Mason Wu. As a first-year graduate student, I sometimes wasn’t 100% sure of what I was doing, and there weren’t any older graduate students in the Fors group to turn to for help. So a huge thanks to Dr. Matthew Moschitto, Dr. Tony Tierno, and Dr. Cathy Mulzer for being around late and helping me find chemicals, for answering my many chemistry questions, and for helping me locate products I managed to lose track of during column purification. I’d also like to thank Professor Geoffrey Coates and Professor David Collum for sitting on my special committee, as well as Professor Phillip Milner for serving as a special committee member proxy for my B exam. Thanks also to Professor Bruce Ganem as well, who always let me walk into his office, unannounced, to talk chemistry. Another thanks goes out to Professor Frank Schroeder, an excellent teacher who always answered my NMR questions (even years after taking his course!) and would discuss immortality and space science with me during visit weekends. I’d also like to thank both Dr. Cynthia Kinsland, whose support and free candy helped get me through my first year, and Dr. Ivan Keresztes, without whom many of my monomers and polymers might have gone uncharacterized. A big thank also goes out to Pat Hine for her support over the years. I’ve had the great opportunity to collaborate with a number of people during graduate school. I am particularly thankful to Dr. Annabelle Watts, whose contributions to our work on the generation of thermosets and thermoplastics from itaconic acid viii significantly accelerated its progress, and who taught me a lot about the mechanical testing of polymers. I’d also like to thank both Dr. Angelika Neitzel and Dr. Leonel Barreda for the opportunity to contribute to their research on hemicyclic acetal esters. Also a huge thanks to Professor Marc Hillymer, whose group I was very fortunate to collaborate with. And thanks to Professor Christopher Ellison and Aditya Banerji for the use of the Ellison group’s DMF SEC. Of course, graduate school wasn’t just about chemistry. Thanks to Dr. Kristina Hugar for running my first half-marathon with me (and for running it at my much slower pace!). Thanks to Dr. Anton Chavez, who was always very quiet during Game of Thrones and never laughed at critical, dramatic moments.
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