Chemistry Seminar: Understanding of the Glass Transition in Ionic Liquid Polymers

Toward an Understanding of the Glass Transition in Ionic Liquid Polymers Derived from New Tri-Substituted and Tetra-Substituted Vinylimidazolium Salts

Dr. Thomas W. Smith
Professor of Chemistry
School of Chemistry and Materials Science, RIT

Dr. Smith will discuss the synthesis of new highly-substituted ionic liquid monomers, specifically triflate salts of 3-butyl-2-methyl-1-vinylimidazolium, 3-ethyl-2-methyl-1-vinylimidazolium, and 2-ethyl-3,4-dimethyl-1-vinylimidazolium ionic liquids, in order to investigate certain glass transition properties.

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Abstract:
The glass transition in polymers derived from tetra-substituted 1-butyl-2,3-dimethyl-4-vinylimidazolium salts has been found to be substantially invariant. This unexpected result is attributed to a combination of minimal H-bonding interactions in the 2-substituted imidazolium polymer salt and steric separation between ion pairs enforced by having substituents on the 1, 2, 3, and 4 positions of the imidazolium moiety that dramatically diminishes the contribution of counterion size to the equilibrium distance between the center of the anion and cation. If this is the case, similar invariance in glass transition characteristics may be observed in polymers derived from other tri-substituted and tetra-substituted imidazolium monomers. In order to explore this possibility in more depth, new highly-substituted ionic liquid monomers, specifically triflate salts of 3-butyl-2-methyl-1-vinylimidazolium, 3-ethyl-2-methyl-1-vinylimidazolium, and 2-ethyl-3,4-dimethyl-1-vinylimidazolium ionic liquids were synthesized by alkylation of 2-methyl-1-vinylimidazole and 2-ethyl-4-methyl-1-vinylimidazole. Specifics on the glass transition in these polymer salts with anions of varying size will be presented along with details on monomer synthesis and polymerization.

Speaker Bio:
Thomas W. Smith (Tom) is a Professor of Chemistry and Microsystems Engineering, at the Rochester Institute of Technology and a well-known researcher in the field of polymer chemistry. He began his career in chemistry at the Lubrizol Corporation (Wickliffe, Ohio), received his B.S. degree in Chemistry from John Carroll University (Cleveland, Ohio) and his Ph.D. in Organic Chemistry from the University of Michigan. He is an ACS Fellow (inducted in the inaugural class of Fellows in 2009) and a Fellow of the ACS Division of Polymer Chemistry (2010). Prior to joining the faculty at RIT, Dr. Smith spent 28 years in research, and technology management at the Xerox Corporation. In 1986, he was made a Research Fellow and from 1986-2001 he held a variety of strategic positions as a Manager and Fellow in the Xerox Corporate Research Group and the historic Ink Jet Business Unit. At Xerox, Tom made seminal contributions in the synthesis of stable nanoparticulate dispersion of metals and semiconductors; chemical alloying of semiconductors; ion-binding with polymers in two dimensions; and, the use of electric field to control the morphology of block copolymer systems. Dr. Smith transitioned to academia in 2002; his research activities at RIT have centered on the design, synthesis and study of the reactivity, physical chemistry and device applications of functional polymer systems, including:, conductive and electroactive polymer composites; ion-binding polymers and block copolymers; and, poly(ionic liquids). He is the author of 56 papers and 73 U.S. Patents on these subjects. Topics of notable publications and patents emanating from research conducted at RIT include: phosphoric acid induced micellization of styrene-ethylene oxide block copolymers, the photo-Fries rearrangement in vinyl and acrylic polymer systems, photoplastic siloxane-based thiol-ene polymers, enhancement of femtosecond laser micromachining speed in dye-doped hydrogel polymers, alternatives to chemical amplification for 193 nm lithography, PVDF-based polymer blend films for fuel cell membranes, pseudo-polyelectrolytes in multilayered films and ionic liquid 4-vinylimidazolium salts. Tom has advised and graduated twelve M.S. Chemistry and MS&E students and two Microsystems Engineering Ph.D. students. He has also provided research experiences for numerous undergraduate students. From July 2010 through June 2012, Tom served as Interim Academic Director of the Golisano Institute for Sustainability.

Intended Audience:
Undergraduates, graduates, experts. Those with interest in the topic.

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