Controlled Macromolecular Heterogeneity by ATRP Krzysztof Matyjaszewski, Carnegie Mellon University, DMR 0969301

1. Controlled Macromolecular Heterogeneity by ATRPKrzysztof Matyjaszewski, Carnegie Mellon University, DMR 0969301 The main activity is focused on synthesis, characterization and potential applications of polymers with controlled heterogeneities. Three major elements of molecular heterogeneity: chain uniformity (dispersity), composition (gradients) and chain topology (branching / crosslinking) are explored and their effect on nanostructured morphology and macroscopic properties studied. • The left slide illustrates the effect of the introduced porosity on swelling ratio of hydrogels prepared by ATRP. Gels with thermoresponsive polymers contained covalently incorporated stars with disulfide degradable cores. After degradation and generated porosity, swelling ratio increased 6 times for stars with hydrophilic segments and 5 times with neutral stars. Also swelling kinetics was very strongly accelerated, with 90% of water released in <10 min, instead of 2 h. (Chem. Asian J., (2011), p. 128) • The right slide illustrates the concept of electrochemically controlled ATRP (eATRP). It can be started and stopped at any time by changing the electrical potential. It is a new benign ARGET ATRP process with electrical current as reducing agent, compensating the radical termination reactions. It results in well defined polymers in organic and aqueous media. (Science, vol. 332, (2011), p. 81.)

2. Controlled Macromolecular Heterogeneity by ATRPKrzysztof Matyjaszewski, Carnegie Mellon University, DMR 0969301 Education and Outreach: -Over 40 international chemical companies have been participating in Controlled Radical Polymerization Consortium at CMU. Current members include: ATRP Solutions, Dainippon Ink, Dionex, DSM, Evonik, Henkel, Kaneka, Kilimanjaro Energy, Merck, Mitsubishi, PPG, Seeo, and Silberline. 13 commercial licenses have been signed for ATRP technology and production of polymers by ATRP process has been started in U.S., Japan and Europe. -Matyjaszewski co-organized in March 2011 Hybrid Materials Meeting, in Strasbourg, France with 1000 participants (707 posters and 198 oral presentations); in April 2011 Controlled/Living Polymerization Meeting in Antalya, Turkey with 95 participants, and in August 2011 6th Controlled Radical Polymerization Meeting at ACS Meeting in Denver with 90 oral presentations and 92 posters. Proceedings from the ACS Meetings will be published as a volume within ACS Symposia series, as from previous CRP Symposia. -Wenwen Li received 2011 Chinese Government Award for Outstanding Self-Financed Students Abroad, KM received 2011 Wolf Prize in Chemistry, Japanese Polymer Society Award, 2011 ACS Applied Polymer Science Award and Hermann F. Mark Award.