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POLYDIMETHYLSILOXANE CONTAINING BLOCK COPOLYMERS: SYNTHESIS AND CHARACTERIZATION OF ALTERNATING POLY(ARYLENE ETHER PHOSPHINE OXIDE)-b-SILOXANE AND SEGMENTED NYLON 6,6 –b-SILOXANE COPOLYMERS by W. David Polk Dissertation submitted to the Faculty of the Virginia Polytechnic Institute and State University In partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in Chemistry Dr. James E. McGrath, Chairman Dr.JudyS.Riffle Dr.AllanR.Shultz Dr. John G. Dillard Dr.PaulA.Deck July 2, 2001 Blacksburg, Virginia Keywords: Polydimethylsiloxane, Polyarylene Ether, Phenyl Phosphine Oxide, Polyamide, Nylon 6,6, Block Copolymer, Fire Resistance, Optical Materials, Nanoparticles Copyright 2001, W. David Polk POLY(DIMETHYLSILOXANE) CONTAINING BLOCK COPOLYMERS: SYNTHESIS AND CHARACTERIZATION OF ALTERNATING POLY(ARYLENE ETHER PHOSPHINE OXIDE)-B-SILOXANE AND SEGMENTED NYLON 6,6-B- SILOXANE COPOLYMERS W. David Polk (ABSTRACT) Two novel classes of siloxane containing, organic-inorganic block copolymers were prepared using different synthetic approaches. The first copolymers were alternating poly(arylene ether phosphine oxide)-poly(dimethylsiloxane) systems, prepared via oligomeric silylamine-hydroxyl reactions. Secondly, segmented nylon 6,6- poly(dimethylsiloxane) block copolymers were synthesized via a non-aqueous adaptation of the “nylon 6,6 salt” hydrolytic polyamidization, using bis(aminopropyl) dimethylsiloxane oligomer as a co-reactant. Three series of “perfectly” alternating block copolymers were produced from well characterized hydroxyl-terminated poly(arylene ether phosphine oxide) and dimethylamine-terminated poly(dimethylsiloxane) oligomers, in order to investigate both block length and chemical composition effects. Copolymerization in chlorobenzene resulted in high molecular weight materials capable of forming optically clear, nanophase separated films, which displayed unusual morphologies and good mechanical strength. Thermal gravimetric analysis showed high thermo-oxidative stability and increasing char yield with increasing siloxane content. Additional thermal and mechanical investigations provided evidence of selective phase mixing, particularly at shorter block lengths. Surface analysis showed an enrichment of the siloxane blocks at the air-polymer interface in comparison to the bulk state. This behavior increased in proportion to the length of the parent siloxane oligomers. Evaluation of selected optical properties, e.g., refractive indices, revealed linear trends resulting in values of compositionally weighted averages. Conversely, a series of nylon 6,6-siloxane copolymers were produced from the polycondensation of preformed propylamine-terminated poly(dimethylsiloxane)s, solid ii nylon 6,6 salt and a corresponding amount of adipic acid to afford siloxane-amide semi- crystalline copolymers with siloxane content ranging from 10 to ~45 wt%. The characterization of high molecular weight and covalent siloxane-amide linkages was hindered by insolubility. For example, crystallinity of the nylon 6,6 precluded the use of common solution techniques, while the susceptibility of the siloxane blocks towards ionic redistribution prevented the use of strongly acidic solvents. However, development of a novel analytical technique using solid state 13C NMR and liquid–solid extraction provided evidence for the presence of covalent bonding between the dissimilar oligomer chains. Thermal gravimetric analysis of resultant copolymers revealed an increase in char yield with increasing siloxane content, a preliminary indicator of increased fire resistance, which was supported by subsequent qualitative Bunsen burner observations. Differential scanning calorimetry showed retention of the polyamide crystalline melt with levels of siloxane incorporation of up to 45 weight %. In conclusion, two novel classes of polydimethylsiloxane containing block copolymers have been successfully synthesized, despite the complications created as a result of the polar/non-polar interactions developed between a semi-inorganic polydimethylsiloxane and the hydrocarbon based polyarylene ethers and nylon 6,6. iii Acknowledgements First and foremost, I would like to thank my advisor, Dr. James E. McGrath, for all of his support and guidance throughout my education at Virginia Tech. Words cannot express how much I have gained his wisdom, as well as from the many learning opportunities he afforded me during my tenure. Additionally, I would like to thank my graduate committee, Dr. Judy S. Riffle, Dr. Alan R. Schultz, Dr. John G. Dillard and Dr. Paul A. Deck, and all of the faculty with whom I have interacted, for without their insight, patience, and helpful suggestions that have shaped my development as a scientist, this thesis would not have been possible. Likewise, I must express a great deal of gratitude to Dr. Kay Turner, Dr. Jerry Adduci, and the Chemistry Faculty of the Rochester Institute of Technology. Their collective vision, which saw potential in a sophomore, gave me my first taste of research, instilled in me the desire to truly understand reactions atomistically instead of simply performing them. I am indebted to many colleagues dispersed throughout the Virginia Tech Polymer Community -- each for multiple reasons. Those who gave the greatest direct assistance in the acquisition of data for this dissertation include Matt O’Sickey, Dave Godshall, Emmet O’Brien, Tom Glass, Steve McCartney and Dr. Y.S. Kim. Also, many thanks are owed to my former fellow graduate students and post-docs of the McGrath group, from whom I have learned so much. In particular, I am grateful to Dr. M. Sankarapandian, Dr. H. Shobha, Dr. Feng Wang, and Dr. Sue Mecham, who helped refine my synthesis techniques; and my fellow labmates, Dr. Jeff Mecham, Mike Hickner, and William Harrison, whose camaraderie and advice provided inspiration when obstacles arose. Much appreciation is due to the secretaries, Millie Ryan, Esther Brann, Joyce Moyer, Angie Flynn, and Laurie Good; the McGrath Group would simply not function without them. However, my deepest gratitude must to go to my parents, for encouraging my curiosity, instilling a thirst for knowledge, and infusing in me the perseverance that has enabled me to attain all that I have accomplished. iv Table of Contents 1 INTRODUCTION......................................................................................... 1 2 LITERATURE REVIEW ............................................................................ 4 2.1. BLOCK COPOLYMERS............................................................. 4 2.1.1 Classes of Hybrid Materials and Copolymers: A Brief Review...... 4 2.1.1.1 Physical Blends..................................................................... 4 2.1.1.2 Random / Statistical Copolymers.......................................... 7 2.1.1.3 Graft Copolymers.................................................................. 9 2.1.1.4 Block Copolymers .............................................................. 10 2.1.2 Synthesis of Block Copolymers ........................................... 11 2.1.2.1 Chain-Growth (Addition) Copolymerizations .................... 12 2.1.2.1.1 Reactivity Ratios..................................................................12 2.1.2.1.2 Sequential Addition of Monomers.......................................13 2.1.2.2 Step-Growth (Condensation) Block Copolymers ............... 14 2.1.2.2.1 Preformed Reactive Oligomers............................................14 2.1.2.2.2 Interfacial Copolymerization ...............................................16 2.1.3 Major Characteristics of Block Copolymers ...................... 16 2.1.3.1 Block Copolymer Morphologies......................................... 17 2.1.3.1.1 Miscible vs. Immiscible Copolymer Segments ...................17 2.1.3.1.2 Effects of Segment Length on Phase Separation .................18 2.1.3.1.3 Theoretical Basis for Micro- or Nanoscopic Phase Separation ............................................................................19 2.1.3.2 Structure –Property Relationships of Block Copolymers... 20 2.1.3.3 Thermoplastic Elastomers................................................... 22 2.2 POLY(ARYLENE ETHER)S AND POLY(ARYLENE ETHER PHOSPHINE OXIDE)S 25 2.2.1 General Structure and Characteristics............................... 25 2.2.2 Commercialized Examples.................................................. 27 2.2.3 Synthetic Approaches and Mechanisms for Poly(arylene ether)s 28 2.2.3.1 Electrophilic Aromatic Substitution. .................................. 29 2.2.3.2 Nucleophilic Aromatic Substitution. .................................. 32 2.2.3.2.1 SN1 and SN2 Mechanisms ....................................................32 v 2.2.3.2.2 Aryne and SNAr mechanisms...............................................34 2.2.3.2.2.1 “Aryne” Elimination-Addition Mechanism.................... 35 2.2.3.2.2.2 SNAr – Addition-Elimination Mechanism ................... 36 2.2.3.2.3 Additional Nucleophilic Aromatic Substitution Processes..39 2.2.3.2.3.1 Silyl-displacement........................................................ 39 2.2.3.2.3.2 SRN1 - A Radical Side Reaction................................... 40 2.2.3.2.3.3 Metal Mediated Coupling Reactions ........................... 42 2.2.4 Phosphine and Phosphine Oxide Containing Organic Polymers..... 43 2.2.5 Overview of Selected Optical Properties of Polymers........ 48 2.3 POLYDIMETHYLSILOXANES AND SILOXANE CONTAINING COPOLYMERS ... 53 2.3.1 Historical Development and Nomenclature.......................
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