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Copper‐based reverse ATRP process for the controlled radical polymerization of methyl methacrylate
Author(s) -
Pan Kai,
Jiang Long,
Zhang Juan,
Dan Yi
Publication year - 2007
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.26246
Subject(s) - polymer chemistry , methyl methacrylate , polymerization , chemistry , atom transfer radical polymerization , bipyridine , monomer , copolymer , radical polymerization , solution polymerization , polymer , organic chemistry , crystal structure
A series of copper‐based reverse atom transfer radical polymerizations (ATRP) were carried out for methyl methacrylate (MMA) at same conditions (in xylene, at 80°C) using N , N , N ′, N ′‐teramethylethylendiamine (TMEDA), N , N , N ′, N ′, N ′‐pentamethyldiethylentriamine (PMDETA), 2‐2′‐bipyridine, and 4,4′‐Di(5‐nonyl)‐2,2′‐bipyridine as ligand, respectively. 2,2′‐azobis(isobutyronitrile) (AIBN) was used as initiator. In CuBr 2 /bpy system, the polymerization is uncontrolled, because of the poor solubility of CuBr 2 /bpy complex in organic phase. But in other three systems, the polymerizations represent controlled. Especially in CuBr 2 /dNbpy system, the number‐average molecular weight increases linearly with monomer conversion from 4280 up to 14,700. During the whole polymerization, the polydispersities are quite low (in the range 1.07–1.10). The different results obtained from the four systems are due to the differences of ligands. From the point of molecular structure of ligands, it is very important to analyze deeply the two relations between (1) ligand and complex and (2) complex and polymerization. The different results obtained were discussed based on the steric effect and valence bond theory. The results can help us deep to understand the mechanism of ATRP. The presence of the bromine atoms as end groups of the poly(methyl methacrylate) (PMMA) obtained was determined by 1 H‐NMR spectroscopy. PMMA obtained could be used as macroinitiator to process chain‐extension reaction or block copolymerization reaction via a conventional ATRP process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007