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Versus Pairwise- Association of Telechelic Polymers Ring/Chain versus Network: Architecture Induced by Self- versus Pairwise- Association of Telechelic Polymers Thesis by Boyu Li In Partial Fulfillment of the Requirements for the degree of Doctor of Philosophy CALIFORNIA INSTITUTE OF TECHNOLOGY Pasadena, California 2016 (Defended May 10th, 2016) ii 2016 Boyu Li ORCID: orcid.org/0000-0002-7648-3745 iii ACKNOWLEDGEMENTS Coming to Caltech five years ago was like entering a new world for me: new country, new language and a fantastic new environment for science. I am grateful to all of the people who have helped me complete this thesis, academically or personally. First, I would like to thank my advisor, Prof. Julie Kornfield, for being such a caring, encouraging, and inspiring mentor. I felt a strong match with Julie the first time I talked with her during my first quarter at Caltech. Over the years, she has enlightened me with her passion for beautiful science, her pursuit for accuracy, and her insights in polymer sciences. “Be quantitative!” She always says. And indeed, I will carry it with me for my whole life. I treasure the great advice from the members of my committee (Professors David Tirrell, Dan Weitekamp and Bob Grubbs), for example, the gestures in giving presentations and tips in writing a NSF-level proposal, etc. There are not that many places on earth where a student can learn from world-renowned scientists. And I appreciate their time and energy spent in reviewing my proposals and thesis. I would also like to thank Prof. Zhen-Gang Wang for his wonderful course of Polymer Physics, which was illuminating, intuitive, and fun. It is one of the direct reasons that I fell in love with polymer physics coming from an organic chemistry background. I enjoyed the time working and living at Caltech, thanks to the people around me. It was also a great pleasure to have the awesome former and current lab-mates in the Kornfield lab. For the first half of my PhD thesis, I worked with other great scientists on a polymeric fuel additive for mist-control and drag-reduction. Dr. Ming-Hsin (Jeremy Wei) taught me ring- opening metathesis polymerization (ROMP) and how to use chain-transfer agents (CTA) to install associative end groups. Dr. Simon Jones gave me great advices on polymer synthesis and writing. I was inspired by Dr. Virendra Sarohia, who was involved in the major US-UK collaboration in the late-1970s and early-1980s, for inspiring me to work on associative polymers for mist control to improve aviation safety. I cherish the conversations with Zuli on topics from women in science to daily life. I enjoyed discussing polymer physics with Joey and Paul, and the trips we had together for beam-time. The MRS conference trips with iv Karthik and Tiziana will always be among my happy memories. It has been fun chatting with Dan, Amy, and Artemis about almost everything in life. Nothing is more enjoyable than delicious Asian food. I love our exploration of Asian restaurants with Dennis, Bo, and Zach. I am happy to have been able to talk with Rachel, Ben, and Red during recruitment and then work with them now. I am really grateful for the help and support from these wonderful people. I have always been amazed at how people all over the campus, or even off campus, can be so helpful. Bilin Zhuang, a PhD at Prof. Zhen-Gang Wang’s group, has been a great friend and shared her positive attitude to life with me. Dr. Xuelian He, a visiting scholar from East China University of Science and Technology (ECUST), helped synthesize the polymer backbone control used in my thesis. Kuang Shen, a former PhD at Prof. Shu-ou Shan’s lab, taught me experimental techniques involving proteins and helped me settle down when I first started. Alex Tucker-Schwartz, a former postdoc from Prof. Rustem Ismagilov’s group, has been a nice big-brother and provided enormous help for job searching. Jeff Groseth offered his insights when our ancient instruments were down. Jayesh Patel is such an amazing expert and teacher, and kept all of our rheometers functioning beautifully. Andy Meyer came to rescue, helping us switch the Wyatt light scattering device to batch mode, when we had only two weeks left for manuscript submission. Marcy Fowler, Andrea Arias, Yvette Grant, Sarah Mojarad, and Kate Davies have kept the Kornfield group in pace and organized. Last but not least, I would love to thank my family for supporting and loving me under any circumstances. The life wisdoms shared with me by my parents are so valuable, keeping me positive during all of the years. I especially want to thank my husband, who is everything I ever wanted. He is a great listener, even when I complained about similar issues over and over again. I am grateful that we have had a chance to share our PhD experience, and understand each other so well. v ABSTRACT Non-covalent associations, including hydrophobic interaction or ionic interaction for self- association, and metal coordination or hydrogen-bonding for complementary-association, have been widely used as key interactions in supramolecules formation with telechelic associative polymers. And a specific application of long associative telechelic polymers has been developed by our group for the mist-control and drag-reduction of liquid fuels. During the research on this project, self- and pairwise-associative telechelic polymers are able to be compared for the first time, and are shown to display distinct associative patterns. In order to design materials with the desired properties, it is imperative to understand the relationships between polymer chemical structure and their topology and dynamics. In this thesis, self-associative telechelic polymer refers to α,ω-di(isophthalic acid) polycyclooctadiene (DA-PCOD), which can associate with itself through its acid ends. When tertiary amine-ended polymer is added into the mixture, isophthalic acid preferably associates pairwisely with tertiary amine due to the higher binding strength of charge-assisted hydrogen bond. And the 1:1 molar ratio mixture of α,ω-di(isophthalic acid) and α,ω- di(di(tertiary amine)) PCOD (DA/DB-PCOD) is named as pairwise-associative telechelic polymers. DA-PCOD is capable of multimeric association via directional hydrogen bonding due to the specific chemical structure of the isophthalic acid end, while DA/DB-PCOD exhibits dynamics that strikingly resembles that for linear covalent polymers. Temperature determines the binding strength of self- and pairwise- end association, and furthermore, the fraction of unbound ends and the distribution and topology of formed supramolecules/aggregates. Polymer length affects the dynamics of DA-PCOD mainly through determining the concentration of the end groups. And the net effect of chain length on the dynamics of DA/DB-PCOD is non-monotonic and varies with the specific temperature and concentration. The knowledge of structure-property relationships obtained from this work will enable future design of end group entities and other properties of these associative telechelic polymers for their specific applications. vi PUBLISHED CONTENT AND CONTRIBUTIONS M.-H. Wei*, B. Li*, R. L. A. David, S. C. Jones, V. Sarohia, J. A. Schmitigal & J. A. Kornfield (*: authors contributed equally), “Mega-supramolecules for safer, cleaner fuel by end-association of long telechelic polymers”, Science, 2015, 350, 72-75. DOI: 10.1126/science.aab0642 B. Li focused on the viscometry, multi-angle laser light scattering (MALLS) and small angle neutron scattering (SANS) characterization of the supramolecules, participated in the polymer synthesis, preliminary diesel generator test and high speed impact experiment, and prepared the manuscript and supplementary information. B. Li, J. Kim, J. A. Kornfield, “A Molecular Picture for the Thermo-Reversibility of Gels Formed by Isophthalic Acid-Ended Telechelic Polymers”, MRS Proceedings, 2015, 1794, 9-14. DOI: 10.1557/opl.2015.638 B. Li performed the experiments (rheology and SANS) in this work, and prepared the manuscript. Materials Research Society Fall Meeting, Boston, Massachusetts (Dec 2015) Temperature and Chain Length Effects on the Topology and Thermodynamics of Soft Gels Formed by Telechelic Polymers with Hydrogen-Bonding Ends (talk) B. Li performed the experiments in this work, and gave the oral presentation. Materials Research Society Spring Meeting, San Francisco, California (April 2015) End-Associative Polymers in Organic Liquids: From Mist Control to Ultra-Soft Gels (talk) B. Li performed the experiments (rheology and SANS) in this work, and gave the oral presentation. vii TABLE OF CONTENTS Acknowledgements……………………………………………......................iii Abstract ……………………………………………………………....………v Published Content and Contributions…………………………………...........vi Table of Contents……………………………………………………..……. vii List of Figures………………………………………………………...………ix List of Tables..………………………………………………………………xvi List of Schemes...……………………………………………………..……xviii Chapter I: Introduction to Association of Telechelic Polymers ...................... I-1 1.1 Literature on self-associative telechelic polymers .............................. I-2 1.2 Literature on complementary-associative telechelic polymers ......... I-13 1.3 Mega-supramolecules developed for mist-control and drag-reduction ... ……………………………………………………………… ………I-15 1.4 From mist control to polymer physics ............................................... I-13 1.5 Conformation and dynamics of linear covalent polymer solutions .. I-25 1.6 Nature of the end associations of DA-PCOD and DA/DB-PCOD ... I-43 1.7 Scope of each chapter ........................................................................
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