Fig. 1: Functionality of copolymers per backbone carbon

1. Highly Functionalized Macromolecules Based on Copolymerization of Substituted Stilbene MonomersRichard Turner, Virginia Polytechnic Institute and State University, DMR 0905231 • Stilbene based alternating copolymers exhibit semi-rigid backbones due to the steric crowding of the extra phenyl group (vis-à-vis styrene copolymers) from persistence lengths as measured by SAXS and SEC. • The rigidity and functionality per backbone carbon were readily tuned by synthesizing the copolymers as shown in the continuum Fig. 1 and the solution properties of the polyelectrolytes showed traditional polyelectrolyte behavior. A two-step dissociation behavior of the two carboxylic acid groups in the succinic acid units within these polyelectrolytes was observed using pH titrations. • Alternating sequences of stilbene and maleimide were incorporated into hyper-crosslinked polymer particles and particles with high surface area, up to 1000 m2/g, were obtained from suspension polymerized precursor particles. Incorporation of these sequences increased the Tg of the precursor lightly-crosslinked precursor polymer particles as shown in Fig. 2. • Incorporation of various functional groups, selected for enhancing specific properties such as hydrogen adsorption or carbon dioxide capture, into hyper-crosslinked polymer particles was demonstrated. • Controlled radical polymerization was used to prepare new doubly hydrophilic block copolymers containing stilbene derivatives with semi-rigid-b-flexible chains for solution property characterizations. Fig. 1: Functionality of copolymers per backbone carbon Fig. 2: Tg of precursor polymer particles vs. content of alternating sequences

2. Highly Functionalized Macromolecules Based on Copolymerization of Substituted Stilbene MonomersRichard Turner, Virginia Polytechnic Institute and State University, DMR 0905231 Education: Three graduate students, Yi Li, Alice Savage, and Xu Zhou contributed to progress on this project this past year. Yi Li graduated (PhD) spring 2012 and is employed by Celanese. Results were summarized in two oral presentations at ACS meetings, two posters at the IUPAC World Polymer Congress at Virginia Tech in June 2012, and two accepted publications in Macromolecules and ACS Macro Letters. Two NSF REU students, Stacey Chin (Carnegie Mellon University) and Abbysinia Davis (St. Paul’s College) were mentored in the summer of 2012 by Alice Savage and Xu Zhou respectively. Undergraduate student, Zach Kiernan, was also mentored in the fall of 2011 and spring of 2012 by Alice Savage. Alice Savage and Xu Zhou synthesized copolymers. Outreach: Prof. Turner, as Director of the Macromolecules and Interfaces Institute (MII) at Virginia Tech, participates in many outreach programs. He served as a co-chair of the IUPAC World Polymer Congress (WPC) which was held at Virginia Tech June 24-29, 2012. With approximately 1500 attendees (60% international), 770 oral presentations and 445 posters, this WPC was one of the largest and most successful of these prestigious biennial international meetings. 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 actively participates in augmenting the MII NSF-REU program by sponsoring picnics, team building exercises, and presenting lectures on intellectual property. He chairs the ACS PMSE Division’s Distinguished Service Award Committee. He participates with the VT Office of Economic Development bridging MII research capabilities with small polymer based companies in south and southwest Virginia. He teaches in the MII outreach short course on adhesion science. Abbysinia Davis, Xu Zhou, Stacey Chin and Alice Savage participated in the IUPAC World Polymer Congress.