Poly(p- phenylene )

1. Highly Functionalized Macromolecules Based on Copolymerization of Substituted Stilbene MonomersS. Richard Turner, Virginia Polytechnic Institute and State University, DMR 0905231 Our studies on stilbene based alternating copolymers show that the addition of the extra phenyl group (vis-à-vis styrene copolymers) enhances chain stiffness (persistence length) as measured by SAXS and SEC. These data suggest that these copolymers are “semi-rigid” since they assume a position between flexible chains and rod-like chains as shown in the continuum shown below. We have discovered that sterically crowded stilbene containing copolymers can exhibit high negative birefringence (potential application in displays) and that these highly functionalized structures can yield high surface areas suggesting that they are new examples of polymers with intrinsic microporosity. Our data suggest a strong correlation between persistence length and surface area for a series of tert-butyl carboxylate functionalized copolymers. Incorporation of stilbene alternating copolymers into vinyl benzyl chloride suspension copolymerized hypercrosslinked polymer particles was successfully accomplished and surface areas up to 2100 m2/g were obtained. High surface area functionalized nanoporous polymer particles have potential for applications in the sustainability sector for carbon dioxide capture and hydrogen storage. The preparation and solution characterization of doubly hydrophilic block copolymers for investigating “like-charge attractions” and other solution properties is in progress. The new copolymers, with precisely placed charges and systematically varied charge densities, in linear copolymers and in new block copolymers, have generated interest as novel polymeric microbicides and as drug delivery agents. Surface Area Vs. Chain Stiffness 2 Poly(methyl methacrylate) Stilbene containing copolymers Poly(p-phenylene) Surface Area (m2/g) 0.50 1.0 10.0 50.0 1 Stilbene Containing Copolymers DNA 20.0 4 Poly(propylene) Poly(ethylene oxide) SEM of High Surface Area of Hypercrosslinked Particle PaPaOCopolymers Persistence Length (nm) (chain stiffness) 3 Persistence Length (nm) (chain stiffness) Poly(styrene) Poly(ethylene) 1 2 4 3

2. Highly Functionalized Macromolecules Based on Copolymerization of Substituted Stilbene MonomersS. Richard Turner, Virginia Polytechnic Institute and State University, DMR 0905231 Education: Four graduate students, Jenny England, Yi Li, Alice Savage, and Xu Zhou contributed to progress on this project this past year. Results were summarized in two oral presentations at ACS meetings, four posters at the Virginia Tech Technical Conference and Review of the Macromolecules and Interfaces Institute, and one accepted publication in POLYMER. Two other manuscripts will be submitted soon to leading journals in polymer science. Two NSF REU students, Lindsay Matolyak (Indiana University of Pennsylvania) and Kristina Caldwell (St. Paul’s College) were mentored in the summer of 2011 by Yi Li and Alice Savage respectively. A recent graduate from Virginia Tech, Kevin Barr, worked with Xu Zhou. Mr. Barr will attend graduate school in chemistry at Virginia Tech beginning fall semester 2011. Kevin Barr and Xu Zhou determining the surface are of a polymer Outreach: Prof. Turner, as Director of the Macromolecules and Interfaces Institute (MII) at Virginia Tech, participates in many outreach programs. He is the “outreach chair” of the organizing committee of the IUPAC World Polymer Congress to be held at Virginia Tech in June 2012. He serves on the board of directors for the Virginia Tech Intellectual Properties Group and is a committee member for the Interdisciplinary Graduate Education Program of the Virginia Tech Graduate School. He is editor for the Americas (chemistry and synthesis) for POLYMER and is on the editorial boards of two other polymer journals. He led a successful outreach program for industrial stakeholders (22 companies represented) in MII in October 2010 which featured 24 faculty lectures, 103 student posters, and three outstanding visitors including Profs. Mark Hillmyer (U. Minnesota), Robert Weiss (Akron), and Dr. Larry Wendling (Senior VP Corporate Research 3M). He actively participates in augmenting the MII NSF-REU program by sponsoring picnics, team building exercises, and presenting lectures on intellectual property. He chaired the ACS PMSE Division Cooperative Research Award Symposium at the Anaheim Spring 2011 National ACS meeting. He organizes and teaches in an American Chemical Society sponsored short course “Fundamentals of Polymers and Interfaces for Adhesives, Composites, and Sustainable Structures.” Lindsay Matolyak, Yi Li, Kristina Caldwell, and Alice Savage characterizing a polymer sample using TGA and DSC.