Design and Synthesis of Polymer-Based Advanced Nanomaterials Usin

University of South Carolina Scholar Commons Theses and Dissertations 1-1-2013 Design and Synthesis of Polymer-Based Advanced Nanomaterials Using Raft Polymerization and Click Reaction Junting Li University of South Carolina Follow this and additional works at: https://scholarcommons.sc.edu/etd Part of the Chemistry Commons Recommended Citation Li, J.(2013) Design and Synthesis of Polymer-Based Advanced Nanomaterials Using Raft Polymerization and Click Reaction (Doctoral dissertation) Retrieved from https://scholarcommons.sc.edu/etd/2393 This Open Access Dissertation is brought to you by Scholar Commons It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of Scholar Commons For more information, please contact dillarda@mailbox.sc.edu DESIGN AND SYNTHESIS OF POLYMER-BASED ADVANCED NANOMATERIALS USING RAFT POLYMERIZATION AND CLICK REACTION by Junting Li Bachelor of Science East China University of Science and Technology, 2006 Master of Science East China University of Science and Technology, 2008 Submitted in Partial Fulfillment of the Requirements For the Degree of Doctor of Philosophy in Chemistry and Biochemistry College of Arts and Sciences University of South Carolina 2013 Accepted by: Brian C Benicewicz, Major Professor Chuanbing Tang, Committee Member Thomas Vogt, Committee Member Harry Ploehn, Committee Member Lacy Ford, Vice Provost and Dean of Graduate Studies © Copyright by Junting Li, 2013 All Rights Reserved ii  ACKNOWLEDGEMENTS First, I would like to thank my advisor Prof Brian Benicewicz for giving me the opportunities to achieve this intriguing and innovative research His support and encouragement for me had never changed even after many times of failures in my experiments, and his insight and profound expertise served as the best guidance throughout my Ph.D studies I also want to thank all my committee members: Prof Chuanbing Tang, Prof Tomas Vogt and Prof Harry Ploehn for their useful suggestions regarding my proposal and my Ph.D research I would like to acknowledge my collaborators – Prof Linda Shadler and Dr Jianing Gao at Rensselaer Polytechnic Institute, Prof Sanat Kumar and Dr Yuping Xie at Columbia University for their valuable contributions and advices to this work The experience working with these knowledgeable and helpful people in the interdisciplinary projects let me have a higher version of the material science and learn more extensive beyond chemistry Many thanks are due to the members of Benicewicz group past and present for their constant assistance and suggestions In particular, I want to thank Dr Yu Li and Dr Cash Brandon for being the best mentors I could have had Last but not least, I want to express my greatest gratitude to my parents and my fiancée – Di Song This achievement could not have been possible without their love, encouragement, and support iii  ABSTRACT This research focuses on exploring new synthetic approaches to prepare polymerbased advanced nanomaterials using highly efficient chemical tools, such as reversible addition-fragmentation chain transfer (RAFT) polymerization and click reactions In the first project, novel synthetic routes to produce fullerene-based polymers were designed First, mono-alkynyl functionalized fullerene was prepared starting with pristine fullerene (C60) Methyl methacrylate and 6-azido hexyl methacrylate were then randomly copolymerized via RAFT polymerization with well-controlled molecular weights and copolymer compositions Finally, the two moieties were covalently assembled into a series of well-defined side-chain fullerene polymers (SFP’s) via the copper-catalyzed click reaction The TGA and UV-vis analyses demonstrated consistent and high conversions for most of the samples Furthermore, the SEM images of these polymers showed the formation of various supramolecular nanoparticle assemblies and crystalline-like clusters depending on the fullerene contents and polymer chain lengths Additionally, “tadpole-like” fullerene polymers (TFP) were generated from bi-alkynyl functionalized fullerene, followed by a click reaction to anchor azido-capped polymers as “tails” The resultant polymers behaved as surfactants to significantly improve the solubility of graphene The UV-vis and FT-IR spectra indicated the strong π-π stacking interactions between the TFP’s and graphene TEM images also displayed different dispersions of the complexes of TFP’s and graphene in various solvents iv  Another aspect of this Ph.D research was the fabrication of Janus nanoparticles (NP’s) A critical challenge in NP functionalization has been the preparation of polymergrafted asymmetric (Janus) NP’s (dia