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The Synthesis and Characterization of Binuclear Zirconocene Complexes and Their Study As Initiators in the Polymerization of M

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The Synthesis and Characterization of Binuclear Zirconocene Complexes and Their Study As Initiators in the Polymerization of M END-GROUP FUNCTIONALIZATION OF ANIONICALLY SYNTHESIZED POLYMERS VIA HYDROSILATION REACTIONS A Dissertation Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Hoon Kim May, 2006 END-GROUP FUNCTIONALIZATION OF ANIONICALLY SYNTHESIZED POLYMERS VIA HYDROSILATION REACTIONS Hoon Kim Dissertation Approved: Accepted: Advisor Department Chair Dr. Roderic P. Quirk Dr. Mark D. Foster Committee Member Dean of the College Dr. Joseph P. Kennedy Dr. Frank N. Kelley Committee Member Dean of the Graduate School Dr. William Brittain Dr. George R. Newkome Committee Member Date Dr. Coleen Pugh Committee Member Dr. Chrys Wesdemiotis ii ABSTRACT One of the unique features of living, alkyllithium-initiated, anionic polymerization is the ability to produce a stable carbanionic chain end after complete monomer consumption, which can be followed by reaction with electrophiles to form various end- functionalized polymers. Although a variety of functional polymers have been synthesized in the last few decades, each specific functionalization has had to be designed and optimized individually. Consequently, the development of general functionalization methodologies has drawn recent interest. However, even these general functionalization methods require the use of protecting groups, and the complexity in synthetic routes and the thermal/moisture instability of many protected functional agents have restricted their practical application. This thesis describes a new, general functionalization methodology, combining well-defined, living anionic polymerization with efficient and highly selective, platinum-catalyzed hydrosilation reactions with functionalized alkenes. Well-defined, Si-H functionalized polymers (P-SiH) have been synthesized by sec- butyllithium-initiated, living anionic polymerization in benzene followed by termination with dimethylchlorosilane. Even though the Si-H bond is polar and labile, it is stable with respect to reactions with organolithium compounds in hydrocarbon solvents. These Si-H bonds are also stable to oxygen and moisture in the atmosphere so that iii Si-H functionalized polymers can be isolated and handled in air. These silyl hydride- functionalized polymers were isolated simply by precipitation into methanol, in which they are also stable. Silyl hydride-functionalized polystyrenes and polyisoprenes have been prepared and characterized by SEC, 1H, 13C and 29Si NMR spectroscopy, FT-IR spectroscopy and MALDI-TOF mass spectrometry. For quantitative analysis, the ratio of the integration area of 1H NMR resonances for the six methyl protons of the dimethylsilane unit at δ –0.1 ppm to the other six methyl protons from the sec-butyl end group from the initiator at about δ 0.7 and 0.9 ppm for the silyl hydride-functionalized polystyrene and polyisoprene, respectively has been used. The MALDI-TOF mass analysis of silyl hydride-functionalized polystyrene produces the corresponding Si-OH functionalized polymer from oxidation of Si-H functional group by the silver cation as the cationizing agent. Reliable mass spectra were obtained using sodium ion as the cationizing agent. The utility of this method for the preparation of ω-functionalized polymers was demonstrated by the hydrosilation of both a protected allylamine derivative, 3-[N,N–bis(trimethylsilyl)amino]-1-propene, and allyamine itself with a silyl hydride-functionalized polystyrene in the presence of Karstedt’s catalyst, 1,3- divinyltetramethldisiloxane-platinum. Quantitative functionalization for each of these functionalizations was proven by 1H NMR and TLC analyses as well as end group titration, and further supported by 13C, 29Si and 13C DEPT NMR, FT-IR and mass spectral analyses. The usefulness of this general functionalization methodology was also demonstrated by phenol functionalization of polystyrene by the hydrosilation reaction of the unprotected phenol, 2-allylphenol, with silane-functionalized polystyrene. The hydrosilation product was characterized by SEC, TLC, NMR (1H, 13C and 13C DEPT), iv FT-IR and mass spectral analyses. The resulting data indicated the successful preparation of phenol-functionalized polystyrene. In addition, epoxy-functionalized polystyrene was synthesized by hydrosilation of 1,2-epoxy-5-hexene with silane-functionalized polystyrene without protection, and characterized by SEC, 1H and 13C NMR spectroscopy, FT-IR spectroscopy and MALDI-TOF mass spectrometry. All characterization results were consistent with an efficient incorporation of epoxy functionality at the chain end. Similarly to other functionalizations, perfluoroalkyl functionalization of polystyrene was effected by hydrosilation of 1H,1H,2H-perfluoro-1- octene with silane-functionalized polystyrene without protection. The perfluoroalkyl- functionalized polymer was characterized by SEC, NMR (1H, 13C and 19F), FT-IR and MALDI-TOF mass spectral analyses. No evidence for any side reactions was found. The applicability of this functionalization methodology to the preparation of well- defined star-branched polymers was investigated by the reaction of octavinyl-T8- silsesquioxane with silane-functionalized polystyrene in the presence of Karstedt’s catalyst. A novel POSS (Polyhedral Oligomeric Silsesquioxane) cored, 8-arm, star- branched polystyrene was isolated by fractionation in a methanol/toluene mixture. The successful formation of POSS core was evidenced by SEC, 1H and 13C NMR, and FT-IR spectral analyses. However, the results from MALDI-TOF mass spectrometric analysis were not consistent with the predominant formation of the 8-arm, star polymer. The thermal properties of this polymer were also investigated by TGA and DSC analyses, and the star-branched polymer exhibited improved thermal stability compared to a linear standard polymer with similar molecular weight. v One limitation of this method is the use with polydienes such as polybutadiene and polyisoprene because of competing self-induced inter- or intramolecular hydrosilation of silane-functionalized polydienes during functionalization with external, substituted alkenes. Along this line, the functionalization of silyl hydride-functionalized polyisoprene has been examined in detail. Amine functionalization of polyisoprene was effected by the hydrosilation of both a protected allylamine derivative, 3-[N,N– bis(trimethylsilyl)amino]-1-propene, and allyamine itself with a silyl hydride- functionalized polyisoprene in the presence of Karstedt’s catalyst. The hydrosilation product was characterized by SEC, NMR (1H, 13C and 1H-1H COSY) and FT-IR spectral analyses. Surprisingly, the results indicated the successful preparation of amine- functionalized polyisoprene (protected and non-protected) using this method. No evidence for self-induced inter- or intramolecular hydrosilation reactions was found. vi ACKNOWLEDGEMENTS First of all, I thank my advisor, Professor Roderic P. Quirk, with all my heart for his endless encouragement, precious advice and financial support throughout my degree. I also thank all my group members for their co-operation and discussions. Especially, I thank Michael Olechnowicz for his friendship that I will not forget during my life. I truly wish to thank my wife and daughter for their great patience and the sacrifices they have made through my course of study. Their loving support truly made this possible. To my mother having lived alone in my hometown since my father’s sudden death, I really appreciate her great patience, warmhearted regard and financial support throughout my study. I thank my father-in-law for his warm encouragement and generous financial support. With my heart and soul, I apologize to my late father for my absence at the last moment of his life and thank him for his constant enthusiasm and unlimited support for me even in his period of struggle against lung cancer before he passed away. Finally, I thank God, my Lord, in heaven. vii TABLE OF CONTENTS Page LIST OF TABLES .………...…………………………………………………….…..…xiv LIST OF FIGURES ……...…………………………………………………………...…xv LIST OF SCHEMES .………………………………………………………….………..xx CHAPTER I. INTRODUCTION ...………...………………………………….…...………………..1 1.1 Living anionic polymerization……..……..……...……………………....….…….1 1.1.1 General aspects……….……………..……………………………...……….1 1.1.2 Living polymerization……………………...………………...……………...2 1.1.3 Monomers………………………………………………...……..………..…8 1.1.4 The nature and stability of organolithium compounds..…………...……....10 1.1.5 Reaction media…..…….……….…...…………………...……….………...13 1.1.6 Initiation…………….…………………………..……….…………………14 1.1.7 Propagation.…………………………………………….………………….17 1.1.8 Lewis bases.…...……………………………….…………………………..18 1.1.9 Alkali metal alkoxides….………………………………………………….19 1.1.10 Lithium halides……………………………………..………….……..…..20 1.2 End-group functionalization…….……………….……………………………...…21 1.2.1 General aspects…. …….……………...…………………….………...…...21 1.2.2 Amination………………….…...…………………………….…………....25 viii 1.2.3 Fluorination…………..……...…………….……..………………...…....…28 1.2.4 Epoxidation…………………...…..…………………………………...…...31 1.2.5 Phenol functionalization………….……………...……….……………..…33 1.3 Hydrosilation……………..………………………………………………….…...34 1.3.1 General aspects……….………….………….…………...…...……...….....34 1.3.2 Transition metal catalyzed hydrosilation………..…………………………35 1.3.3 Development of a new general functionalization methodology by the combination of anionic polymerization with hydrosilation reactions….…..37 II. EXPERIMENTAL….…….…………….....…………..…………….….….…….....42 2.1 Inert atmosphere techniques ……..……..……...………………….………….…42
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