High-Throughput Evaluation of Atom Transfer Radical Polymerization: Towards a Directed Design and Understanding of Optimal Catalytic Systems

Zhang, Huiqi; Marin, Veronica; Fijten, Martin W. M.; Schubert, Ulrich S.

Abstract:

High-throughput experimentation (HTE) was successfully applied in atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) for the rapid screening and optimization of different reaction conditions. A library of 108 different reactions was designed for this purpose, which used four different initiators [ethyl 2-bromoisobutyrate, methyl 2-bromopropionate, (1-bromoethyl)benzene, and p-toluenesulfonyl chloride], five metal salts (CuBr, CuCl, CuSCN, FeBr2, and FeCl2), and nine ligands (2,2
-bipyridine and its derivatives). The optimal reaction conditions for Cu(I) halide, CuSCN, and Fe(II) halide-mediated ATRP systems with 2,2
-bipyridine and its 4,4
-dialkyl-substituted derivatives as ligands were determined. Cu(I)-mediated systems were better controlled than Fe(II)-mediated ones under the examined conditions. A bipyridine-type ligand with a critical length of the substituted alkyl group (i.e., 4,4
-dihexyl 2,2
-bipyridine) exhibited the best performance in Cu(I)-mediated systems, and p-toluenesulfonyl chloride and ethyl 2-bromoisobutyrate could effectively initiate Cu(I)-mediated ATRP of MMA, resulting in polymers with low polydispersities in most cases. Besides, Cu(I) halide-mediated ATRP with 4,5
-dimethyl 2,2
-bipyridine as the ligand and p-toluenesulfonyl chloride as the initiator proved to be better controlled than those with 4,4
-dimethyl 2,2
-bipyridine as the ligand, and polymers with much lower polydispersities were obtained in the former cases. This successful HTE example opens up a way to significantly accelerate the development of new catalytic systems for ATRP and to improve the understanding of structure–property relationships of the reaction systems.

Year:

2004

Type of Publication:

Article

Keywords:

atom transfer radical polymerization ATRP; high throughput experimentation HTE; catalysis; methyl methacrylate; bipyridine derivatives; structureproperty relation

Journal:

Journal of Polymer Science: Part A: Polymer Chemistry

Volume:

42

Pages:

1876 - 1885