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Controlled radical polymerization of styrene initiated by diethyldithiocarbamate‐mediated iniferters
Author(s) -
Ishizu Koji,
Katsuhara Hideya,
Kawauchi Susumu,
Furo Masahito
Publication year - 2004
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.21417
Subject(s) - styrene , polymerization , copolymer , monomer , polystyrene , polymer chemistry , radical polymerization , photopolymer , radical , molar mass distribution , methacrylic acid , chemistry , photochemistry , dissociation (chemistry) , materials science , polymer , organic chemistry
We demonstrated that density functional theory calculations provide a prediction of the trends in C‐S bond dissociation energies and atomic spin densities for radicals using two model compounds as diethyldithiocarbamate (DC)‐mediated iniferters. On the basis of this information, we synthesized 2‐( N,N ‐diethyldithiocarbamyl)isobutylic acid (DTCA) and (4‐cyano‐4‐diethyldithiocarbamyl)pentanoic acid (CDPA) as DC‐mediated iniferters. Free‐radical polymerizations of styrene (St) were carried out in benzene initiated by DTCA or CDPA under UV irradiation. The first‐order time‐conversion plots showed the straight line for the UV irradiation system initiated by CDPA indicating the first order in monomer. The number‐average molecular weight ( M n ) of the polystyrene (PSt) increased in direct proportion to monomer conversion. The molecular weight distribution ( M w / M n ) of the PSt was in the range of 1.3–1.7. It was concluded this polymerization system proceeded with a controlled radical mechanism. However, photopolymerization of styrene initiated by DTCA showed nonliving polymerization consistent with UV initiation. Theoretical predictions supported these experimental results. Methacrylic acid (MA) could also be polymerized in a living fashion with such a PSt precursor as a macroinitiator because PSt exhibited a DC group at its terminal end. This system could be applied to the architecture of block copolymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 413–418, 2005