4.7 Article

Synthesis of poly(vinyl pivalate) by atom transfer radical polymerization in supercritical carbon dioxide

Journal

EUROPEAN POLYMER JOURNAL
Volume 61, Issue -, Pages 93-104

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.eurpolymj.2014.09.003

Keywords

Atom transfer radical polymerization (ATRP); Poly(vinyl pivalate); Supercritical carbon dioxide; Copper halide; Terpyridine; Poly(vinyl alcohol)

Funding

  1. DG Economic Circle Leading Industry R&D Program of the Ministry of the Knowledge and Economy (MOKE) [R0001657]

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Atom transfer radical polymerization of vinyl pivalate was carried out in supercritical carbon dioxide using CuBr or CuCl/terpyridine (tpy) complex system and ethyl 2-bromoisobutyrate as an initiator. The reaction kinetics of the two different catalytic systems (CuBr/tpy and CuCl/tpy) was investigated. In addition, the effects of temperature, pressure, and catalyst/ligand concentration were examined systematically to obtain an acceptable rate of polymerization and control over the number-average molecular weight (MO and polydispersity index (PDI). The result showed that relatively low PDIs were obtained and polymerization rates were enhanced at higher pressures. The CuCl/tpy complex exhibited the maximum conversion of 90% with a M., and PDI of 60.2 kg/mol and 1.29, respectively. The CuCl/tpy catalyst system showed better agreement between theoretical and experimental M-n compared to the CuBr/tpy. The living character of poly(vinyl pivalate) (PVPi) was proven by H-1 NMR spectrum and chain extension reaction. The formation of poly(vinyl alcohol) via saponification of the resulting PVPi was also carried out. The structures of both PVPi and PVA were examined by H-1 NMR and FTIR spectra. (C) 2014 Elsevier Ltd. All rights reserved.

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