Atom transfer radical polymerization in the presence of Cu0 – mechanism and kinetics study

POLY 123

Wei Tang, wtang1@andrew.cmu.edu, Hongchen Dong, hdong@andrew.cmu.edu, Yungwan Kwak, ywkwak@andrew.cmu.edu, and Krzysztof Matyjaszewski, km3b@andrew.cmu.edu. Department of Chemistry, Carnegie Mellon University, 4400 Fifth Ave, Mailbox 50, Pittsburgh, PA 15208
Detailed investigation on the atom transfer radical polymerization (ATRP) in the presence of Cu0 was carried to clarify the mechanism and kinetics of this process. Polymerization of MA was successfully reached to high conversion within a very short time in both DMSO and acetonitrile (MeCN). Disproportionation study of CuIBr/tris(2-dimethylaminoethyl)amine suggested that disproportionation is limited in DMSO and negligible in MeCN. Activation constant for Cu0 and comproportionation constant were obtained by fitting the model reaction data. Contribution of activation with Cu0 is below 1% in most cases. By implementing chain length and conversion dependent termination coefficient, simulations demonstrated that this process obeys activators re-generated by electron transfer (ARGET) ATRP rather than single-electron-transfer living radical polymerization (SET-LRP) process mechanism
 

General Papers: Functional Materials
6:00 PM-8:00 PM, Sunday, August 19, 2007 BCEC -- Exhibit Hall - B2, Poster

Sci-Mix
8:00 PM-10:00 PM, Monday, August 20, 2007 BCEC -- Exhibit Hall - B2, Sci-Mix

Division of Polymer Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007