A detailed on-line FT/NIR and 1H NMR spectroscopic investigation into factors causing inhibition in xanthate-mediated vinyl acetate polymerization

Favier, A., Barner-Kowollik, C., Davis, T. P., & Stenzel, M. H. (2004) A detailed on-line FT/NIR and 1H NMR spectroscopic investigation into factors causing inhibition in xanthate-mediated vinyl acetate polymerization. Macromolecular Chemistry and Physics, 205(7).

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Potential sources of inhibition have been investigated via in situ Fourier transform - near infra-red (FT-NIR) and off-line 1H NMR spectroscopy in the RAFT/MADIX bulk polymerization of vinyl acetate (VA) in the presence of an O-isopropyl xanthate, i.e. methyl (isopropoxycarbonothioyl)sulfanyl acetate. The very high reactivity of the vinyl acetate propagating radical makes it vulnerable to oxygen, by-products generated during the xanthate synthesis, and stabilizers present as impurities. These impurities induce strong and variable inhibition periods in the polymerization. In addition, the MADIX process, using xanthates as reversible chain transfer agents, has been confirmed to be an efficient method for living VA polymerization. Congruent data are obtained when the monomer consumption with time is followed via both 1H NMR and in situ FT-NIR spectroscopy. The xanthate-mediated polymerization of VA exhibits no retardation effects and excellent control of the molecular weight distribution can be achieved, leading to poly(VA) of molecular weights exceeding 50 000 g · mol-1 with relatively low polydispersities.

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ID Code: 99083
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :84
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Ctr. for Adv. Macromolecular Design, Sch. of Chem. Eng. and Indust. Chem., University of New South Wales, Sydney, NSW 2052, Australia; email: camd@unsw.edu.au
Chemicals/CAS: vinyl acetate, 108-05-4
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Keywords: Free radical polymerization, In-situ FT/NIR spectroscopy, NMR spectroscopy, Polymerization kinetics, Reversible addition fragmentation chain transfer (RAFT), Byproducts, Free radicals, Molecular weight distribution, Monomers, Nuclear magnetic resonance spectroscopy, Oxygen, Polymerization, Chain transfer agents, Polydispersities, Polyvinyl acetates, vinyl acetate, xanthic acid derivative, article, chemical reaction, Fourier transformation, infrared spectroscopy, macromolecule, molecular weight, proton nuclear magnetic resonance, purification, reaction analysis, synthesis
DOI: 10.1002/macp.200300179
ISSN: 10221352
Divisions: Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 28 Jun 2017 14:01

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