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Organocatalyzed Ring Opening Polymerization and the Design of Materials for Topological Trapping

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Organocatalyzed Ring Opening Polymerization and the Design of Materials for Topological Trapping ORGANOCATALYZED RING OPENING POLYMERIZATION AND THE DESIGN OF MATERIALS FOR TOPOLOGICAL TRAPPING A DISSERTATION SUBMITTED TO THE DEPARTMENT OF CHEMISTRY AND THE COMMITTEE ON GRADUATE STUDIES OF STANFORD UNIVERSITY IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY TYLER STUKENBROEKER JANUARY 2016 © 2016 by Tyler Scott Stukenbroeker. All Rights Reserved. Re-distributed by Stanford University under license with the author. This work is licensed under a Creative Commons Attribution- Noncommercial 3.0 United States License. http://creativecommons.org/licenses/by-nc/3.0/us/ This dissertation is online at: http://purl.stanford.edu/jd110qd1669 ii I certify that I have read this dissertation and that, in my opinion, it is fully adequate in scope and quality as a dissertation for the degree of Doctor of Philosophy. Robert Waymouth, Primary Adviser I certify that I have read this dissertation and that, in my opinion, it is fully adequate in scope and quality as a dissertation for the degree of Doctor of Philosophy. Eric Kool I certify that I have read this dissertation and that, in my opinion, it is fully adequate in scope and quality as a dissertation for the degree of Doctor of Philosophy. Paul Wender Approved for the Stanford University Committee on Graduate Studies. Patricia J. Gumport, Vice Provost for Graduate Education This signature page was generated electronically upon submission of this dissertation in electronic format. An original signed hard copy of the signature page is on file in University Archives. iii iv Abstract Ring-opening polymerization (ROP) is a highly useful route to well-defined, high molecular weight polymers. In recent years, strongly nucleophilic neutral bases such as N-heterocyclic carbenes (NHCs) have been shown to catalyze ring opening polymerization with control over the topology of the polymer product. This mechanism has been termed Zwitterionic Ring Opening Polymerization (ZROP). Here, new catalysts and monomers have been explored for these processes. Two types of organocatalysts were developed. A recently reported superbase, cyclopropenimine, was tested for activity with a number of monomers. It was discovered that this catalyst polymerizes lactide not through ZROP, but through anionic ROP initiated by a previously unreported mechanism. It was demonstrated that cyclopropenimines deprotonate lactide to form the corresponding enolate, which serves as the initiator and endgroup for the polymerization. Additionally, an electrophilic co- catalyst for lactide polymerization based on a cationic bis(imidazolium) structure was discovered. Furthermore, a class of cyclic phosphotriesters was synthesized as a substrate for NHC-catalyzed polymerization. Mechanistic studies were consistent with the existing interpretation of ZROP. The topology of the polymer products was found to be highly impacted by slight changes in monomer structure. One of these monomers, 2-isoproxy- 1,3,2-dioxophospholane 2-oxide (iPP), yielded high molecular weight cyclic products. To further interrogate the polymer architecture, a crosslinked polyacrylate network was formed in-situ with the poly(iPP). In this way cyclic macromolecules were topologically trapped, preventing their extraction by solvent washing. The gel platform used for this trapping protocol was optimized and this process was explored as a way to sort polymers based on their topology. Finally, the properties of these gels, a unique form of interpenetrating network, were studied. v vi Acknowledgements My time at Stanford coincided with an unprecedented period of Stanford football dominance (three Rose Bowls), wonderfully sunny weather (albeit due to an ecologically devastating drought), and three faculty members receiving the Nobel Prize in Chemistry. Despite these auspicious concurrences, I am most thankful to have overlapped on the Farm with many smart, kind, and fun individuals whom I am eager to acknowledge. The research presented here was funded by multiple agencies. I was personally supported by a National Defense Science and Engineering Graduate Fellowship on behalf of the Army Research Office. The operational budget was provided by the National Science Foundation via two grants, DMR-1001903 and DMR-1407658. Work done at the Molecular Foundry (LBNL) was supported by the US Department of Energy. I was particularly fortunate to find Bob Waymouth’s lab when I arrived at Stanford. Over the past five years Bob has allowed me the freedom to learn about organocatalysis and polymer physics and develop a project that incorporates both fields. I am lucky to have had him as a scientific role model. If children eventually turn into their parents then graduate students turn into their advisors; recently I have caught myself dropping “Bob-isms” with alarming frequency. I am grateful to my reading committee, Paul Wender and Eric Kool, for taking the time to read and critique various proposals and ideas. Undoubtedly their wisdom will prove invaluable as I move forward in my career. Other professors I have had the pleasure of working with include Yan Xia and Do Yoon who offered their insight regarding my projects. Tristan Lambert and especially his former student Jeff Bandar were incredibly patient with me on our collaborative project. Redouane Borsali was a cordial host when I visited France. Many other people inside and outside of the chemistry department enabled the experiments and findings presented in this thesis. Steve Lynch, Theresa McLaughlin, vii Theresa Pick, and Jeff Tok all helped me to make important measurements. Without the assistance Roger Kuhn, Marie Herbert, Orlando Martinez, and most of all Dewi Fernandez there is no way I could have kept all my requirements in order. I will miss the students and post-docs in the Waymouth Lab. Naomi, Eric and Jelena have been terrific desk-neighbors. Besides stimulating chemistry discussions, I have enjoyed having lunch, grabbing a beer, and going skiing with them. Kevin, Kate, Tim and I share the bond of spending all five years together in lab and I couldn’t think of a better set of classmates to be paired with. Young is a wonderfully witty travel buddy. James is my favorite Irishman and I will miss his astute observations of life in lab. Xiangyi and Colin offered gracious help with polymerization questions and experiments on many occasions. Many postdocs deserve my gratitude, most recently Andrey, Chris, Gregg, and Antonio. With Wilson, Weiwei, Liz, Katherine, Ben, and Rebecca around I am sure the lab will remain both entertaining and innovative. In other labs, Ben Elling, Jingxian Li, and Tadanori Kurosawa have shared the agony and the ecstasy of maintaining GPCs with me. Special acknowledgement is necessary for my friend and mentor Hayley Brown. It is no exaggeration to say that everything I know about air-free technique, glove-box polymerizations, solvent drying, cyclic polymers, reading and writing manuscripts, giving group meetings, applying for fellowships, and much, much more came from Hayley. I am indebted to her for walking me through countless procedures and taking me under her wing when experiments weren’t working. Most of all, I enjoyed getting to know her as a friend both in lab, on camping trips, and during several drives up to Berkeley. Stanford has offered me tremendous opportunities to teach and learn about science outside of my research. I have enjoyed tutoring athletes through the AARC program and visiting high schools with the chemistry outreach program. I had a blast viii making the Goggles Optional show with a group of zany people who tolerated my brief stint as a podcasting personality. Without my friends, I am sure I would have a very different experience in graduate school. There are far too many to list here, but I especially want to shout out the Reno Boys (Honk! Honk!) and the movie night crew (and the Moooovie goes to…) for all the fun memories. The brilliant and lovely Tali has probably spent the most time listening to me babble on about lab, so I thank her for that and much more. My good friends, near and far, have all been wonderfully supportive during my time here. Finally, I would be nowhere without my family. My brother Wesley visited me in California several times. I am constantly blown away hearing about his accomplishments. My parents, George and Susan, always made education a priority. This included reading my essays, helping with my projects, checking my homework and teaching me to be a hard-working student. They made sure I went to the best high school, the college of my choosing, and don’t complain that my chemistry career seems to be taking me to progressively more distant locations. Thank you! ix x Table of Contents Chapter 1: Topological Materials 1.1 Introduction 3 1.2 Topological Trapping 4 1.3 Slip-Link Gel 7 1.4 Summary 10 1.5 References 11 Chapter 2: Organocatalysts for Polymerization of Lactide 2.1 Introduction 15 2.2 Results and Discussion Bis-Imidazolium Salts as Electrophilic Co-Catalysts 2.2.1 17 for Lactide Polymerization Cyclopropenimines as Superbase Catalysts for Ring 2.2.2 21 Opening Polymerization 2.3 Experimental Procedures 35 2.4 References 44 Chapter 3: Polymerization of Phosphotriester Monomers 3.1 Introduction 49 3.2 Results and Discussion 3.2.1 Benzyl Phospholane Monomer 51 3.2.2 Isopropoxy Phospholane Monomer 60 3.2.3 Mechanistic Studies 63 3.3 Experimental Procedures 69 3.4 References 85 xi Chapter 4: Stimuli-Responsive Organogels 4.1 Introduction 91 4.2 Results and Discussion 4.2.1 Acid-Induced Transition from Organogel to Hydrogel 93 4.2.2 Reduction-Induced Degradation of Organogel 95 4.2.3 Organogels Synthesized from 1,2-Dithiolanes 98 4.3 Experimental Procedures 100 4.4 References 104 Chapter 5: Topological Trapping of Cyclic Polymers 5.1 Introduction 109 5.2 Results and Discussion 5.2.1 Poly(iPP) Trapping 110 5.2.1a Selective Polymer Retention Not a Molecular Weight Effect 117 5.2.2 Catch-and-Release Gels 120 5.2.3 Physical Properties of Topological Gels 126 5.2.4 Poly(valerolactone) Trapping 131 5.3 Experimental Procedures 136 5.4 References 142 xii List of Figures Fig.
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