Division of Polymer Chemistry (POLY) Graphical Abstracts Submitted for the 247th ACS National Meeting & Exposition March 16-20, 2014 | Dallas, Texas • Chemistry & Materials for Energy Division of Polymer Chemistry (POLY) Table of Contents [click on a session time (AM/PM/EVE) for link to abstracts] Session SUN MON TUE WED THU AM AM Excellence in Graduate Polymer Research** EVE PM PM AM Materials for Energy Harvesting EVE PM AM Polymers for Oil and Gas Energy Operations EVE PM Sustainable Polymers, Processes and Product AM AM AM Applications** PM PM EVE AM Undergraduate Research in Polymer Science EVE PM Frontiers in Polymer Characterization AM EVE AM General Topics: New Synthesis and Characterization of AM AM AM PM Polymers** PM PM EVE Paul J. Flory Polymer Education Award: Symposium in AM Honor of George Odian AM AM AM 12th International Symposium on Biorelated Polymers PM PM PM PM EVE ACS Award in Polymer Chemistry: Symposium in Honor PM of Karen L. Wooley** AM AM AM Responsive Nanostructures and Nanocomposites PM PM PM PM EVE Sci-Mix EVE AM Synthesis and Applications of Conjugated Materials: AM PM Contributions from Texas and Beyond** PM EVE PM AM AM Peptide-Based Materials for Nanomedicine** EVE PM PM POLY/PMSE Plenary Lecture and Awards Reception** EVE **Primary organizer of Cosponsored symposium. Note: ACS does not own copyrights to the individual abstracts. For permission, please contact the author(s) of the abstract. POLY Scott Iacono, Dylan Boday, Jeffrey Youngblood Sunday, March 16, 2014 1 - Environmentally-friendly flame retardants for polymeric materials containing phosphorus and nitrogen Simone T. Lazar, [email protected], Bob Howell. Department of Chemistry, Central Michigan University, Mt. Pleasant, MI 48858, United States There is a growing need for environmentally-friendly flame retardants for polymeric materials that are both effective and non- toxic. Traditional organohalogen flame retardants are effective, readily available, and inexpensive. However, they are stable, persist in the environment, and tend to bioaccumulate. Because of this they may pose a risk to human health. Phosphorus compounds are the most likely replacements for these older flame retardants. Since the effectiveness of phosphorus compounds is often enhanced by the presence of nitrogen, it would be desirable to generate materials containing an abundance of both elements. Further, the generation of such materials from a renewable biosource is attractive for several reasons. It would likely degrade in the environment and would not be dependent on a non-renewable petrochemical source. Natural oils are available from several sources and contain unsaturation which may be converted to epoxides. The epoxides may be opened with nitrogen nucleophiles to generate alcohols which can be converted to a variety of phosphorus compounds. This is illustrated below for a commercially-available triepoxide. Sunday, March 16, 2014 09:00 AM Undergraduate Research in Polymer Science (09:00 AM - 11:30 AM) Location: Hyatt Regency Dallas Room: Moreno A POLY Scott Iacono, Dylan Boday, Jeffrey Youngblood Sunday, March 16, 2014 2 - Intumescent multilayer nanocoating, made with renewable polyelectrolytes, for flame-retardant cotton Galina Laufer1, Christopher Kirkland1, Shannon Murray1, [email protected], Alexander Morgan2, Jaime C. Grunlan1, [email protected]. (1) Mechanical Engineering, Texas A&M University, College Station, Texas 77843, United States, (2) Energy Technology and Materials Division, University of Dayton Research Institute, Dayton, Ohio 45469, United States Thin films of fully renewable and environmentally benign electrolytes, cationic chitosan (CH) and anionic phytic acid (PA), were deposited on cotton fabric via layer-by-layer (LbL) assembly in an effort to reduce flammability. Altering the pH of aqueous deposition solutions modifies both thickness and composition of the final nanocoating. In a vertical flame test, fabrics coated with high PA content multilayers completely extinguished the flame, while uncoated cotton was completely consumed. Microcombustion calorimetry confirmed that all coated fabric reduces peak heat release rate (pkHRR) by at least 50% relative to the uncoated control. This superior performance is believed to be due to high phosphorus content that enhances the intumescent behavior of these nanocoatings. These results demonstrate the first completely renewable intumescent LbL assembly, which conformally coats every fiber in cotton fabric and provides an effective alternative to current flame retardant treatments. Sunday, March 16, 2014 09:15 AM Undergraduate Research in Polymer Science (09:00 AM - 11:30 AM) Location: Hyatt Regency Dallas Room: Moreno A POLY Scott Iacono, Dylan Boday, Jeffrey Youngblood Sunday, March 16, 2014 3 - Synthetic design of block copolymer amphiphiles for nanomaterial dispersion Guilhem X Dehoe, [email protected], Thaddeus P Formal, Anton D Chavez, Philip J Costanzo. Chemistry and Biochemistry, California Polytechnic State University, San Luis Obispo, CA 93407, United States Amphiphilic block copolymers were prepared with a variety of controlled radical polymerization techniques, including RAFT and ATRP. Length of the hydrophobic and hydrophilic block were adjusted to determine optimum dispersion of various hydrophobic nanomaterials. The prepared water-borne dispersions were subsequently utilized for a wide variety of applications. Sunday, March 16, 2014 09:30 AM Undergraduate Research in Polymer Science (09:00 AM - 11:30 AM) Location: Hyatt Regency Dallas Room: Moreno A POLY Scott Iacono, Dylan Boday, Jeffrey Youngblood Sunday, March 16, 2014 4 - Investigation of microphase separated dicarboximide-functionalized oxanorbornyl diblock copolymers exhibiting nanostructure Marisa Adams, [email protected], Dean Waldow. Department of Chemistry, Pacific Lutheran University, Tacoma, WA 98447, United States Solid-state polymer electrolytes offer a promising alternative to liquid electrolyte supports in lithium ion batteries. Herein, we investigate a diblock system which may offer a nanostructured approach to membrane electrolytes. We have synthesized dicarboximide-functionalized oxanorbornyl diblock copolymers with varying ratios of ethylene oxide (EO)2 and phenyl side groups. Polymerization was conducted under living conditions using a Grubbs third generation catalyst through a ring opening metathesis mechanism. The diblocks were characterized using NMR, GPC, and DSC which shows two glass transition temperatures that correlate with those observed in the phenyl and ethylene oxide (EO)2 homopolymers. Small angle x-ray scattering and AFM of spun cast films will be used to characterize microphase-separated nanostructures, which may be useful in lithium ion conduction. Sunday, March 16, 2014 09:45 AM Undergraduate Research in Polymer Science (09:00 AM - 11:30 AM) Location: Hyatt Regency Dallas Room: Moreno A POLY Scott Iacono, Dylan Boday, Jeffrey Youngblood Sunday, March 16, 2014 5 - Nanoparticle-decorated honeycomb-structured polymeric films via breath figures with Janus particles Sophie E Miller1,2, [email protected], Wei Sun1,3, Julia A Kornfield1. (1) Department of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, United States, (2) Department of Chemical Engineering, Stanford University, Stanford, CA 94305, United States, (3) Department of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, China Microporous polymer scaffolds decorated with nanoparticles could provide functional membranes that are needed in solar-to-fuel technologies. Therefore, efficient production processes are needed for high surface area, porous membranes with distinct catalytic nanoparticles on opposite sides of a support that resists oxidation and separates the products, e.g., hydrogen and oxygen. Breath figure (BF) patterning is an established method to create microstructured honeycomb-patterned porous polymer films. This research shows that surface-active nanoparticles can self-assemble onto the interfaces between the templating BF water droplets and the polymer solution to control micrometer and nanometerscale hierarchical structure. Here, amphiphilic “Janus” nanoparticles serve as both solid surfactants and Pickering emulsion stabilizing agents, thus able to optimize ordering degree of the honeycomb structures and nanoparticle enrichment in the pore walls. Janus nanoparticles were synthesized using literature methods (with improvements that will be presented): functionalizing only the exposed surface of particles embedded on the surface of wax microspheres (colloidosomes) renders half of the particle hydrophobic. They were then employed in the BFs templating method for the first time, resulting in regular, porous films with uniform, high nanoparticle density. Humble materials (silica and polystyrene) demonstrate the method, and can now be replaced by catalyst nanoparticles (e.g., nickel, molybdenum sulfide, or cobalt-based) embedded in a semiconducting polymer to create membranes for photocatalytic water splitting. Sunday, March 16, 2014 10:15 AM Undergraduate Research in Polymer Science (09:00 AM - 11:30 AM) Location: Hyatt Regency Dallas Room: Moreno A POLY Scott Iacono, Dylan Boday, Jeffrey Youngblood Sunday, March 16, 2014 6 - Top coats confer orientation control of block copolymer domains Matthew Carlson1, [email protected], Michael Maher2, Christopher Bates2, Jeffrey Self1,2, Christopher Ellison1, C. Grant Willson1,2. (1) Mcketta Department