Quantifying photoinitiation efficiencies in a multiphotoinitiated free-radical polymerization

Voll, D., Hufendiek, A., Junkers, T., & Barner-Kowollik, C. (2012) Quantifying photoinitiation efficiencies in a multiphotoinitiated free-radical polymerization. Macromolecular Rapid Communications, 33(1).

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Online size exclusion chromatography-electrospray ionization-mass spectrometry (SEC/ESI-MS) is employed for quantifying the overall initiation efficiencies of photolytically generated radical fragments. In a unique experiment, we present the first quantitative and systematic study of methyl-substituted acetophenone-type photoinitiators being employed in a single cocktail to initiate the free-radical polymerization of methyl methacrylate (MMA) in bulk. The photoinitiators are constituted of a set of two known and four new molecules, which represent an increasing number of methyl substituents on their benzoyl fragment, that is, benzoin, 4-methylbenzoin, 2,4-dimethylbenzoin, 2,4,6-trimethylbenzoin, 2,3,5,6-tetramethylbenzoin, and 2,3,4,5,6-pentamethylbenzoin. The absolute quantitative evaluation of the mass spectra shows a clear difference in the initiation ability of the differently substituted benzoyl-type radical fragments: Increasing the number of methyl substituents leads to a decrease in incorporation of the radical fragments. The first systematic study of six (methyl substituted) acetophenone-type photoinitiators employed in a single cocktail experiment is presented. PLP synthesis in conjunction with coupled online SEC/ESI-MS is the method of choice to obtain absolute quantitative information regarding the initiation ability of the derived radical fragments. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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ID Code: 99326
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :10 Export Date: 5 September 2016 CODEN: MRCOE Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische, Chemie und Polymerchemie, Karlsruhe Institute of Technology, Engesserstr. 18, 76128 Karlsruhe, Germany; email: christopher.barner-kowollik@kit.edu Chemicals/CAS: methacrylic acid methyl ester, 80-62-6; Free Radicals; Methylmethacrylate, 80-62-6 References: Yilmaz, G., Tuzun, A., Yagci, Y., (2010) J. Polym. Sci., Part A: Polym. Chem., 48, p. 5120; Balta, D.K., Cetiner, N., Temel, G., Turgut, Z., Arsu, N., (2008) J. Photochem. Photobiol., A, 199, p. 316; Balta, D.K., Temel, G., Aydin, M., Arsu, N., (2010) Eur. Polym. J., 46, p. 1374; Yilmaz, G., Aydogan, B., Temel, G., Arsu, N., Moszner, N., Yagci, Y., (2010) Macromolecules, 43, p. 4520; Saraiva, M.F., Couri, M.R.C., Le Hyaric, M., De Almeida, M.V., (2009) Tetrahedron, 65, p. 3563; Dietlin, C., Allonas, X., Morlet-Savary, F., Fouassier, J.P., Visconti, M., Norcini, G., Romagnano, S., (2008) J. Appl. Polym. Sci., 109, p. 825; Lalevée, J., Morlet-Savary, F., Roz, M.E., Allonas, X., Fouassier, J.P., (2009) Macromol. Chem. Phys., 210, p. 311; Lalevee, J., Blanchard, N., Tehfe, M.A., Fries, C., Morlet-Savary, F., Gigmes, D., Fouassier, J.P., (2011) Polym. Chem., 2, p. 1077; Lalevee, J., Roz, M.E.I., Tehfe, M.A., Alaaeddine, M., Allonas, X., Fouassier, J.P., (2009) J. Photopolym. Sci. Technol., 22, p. 587; Günzler, F., Wong, E.H.H., Koo, S.P.S., Junkers, T., Barner-Kowollik, C., (2009) Macromolecules, 42, p. 1488; Voll, D., Junkers, T., Barner-Kowollik, C., (2011) Macromolecules, 44, p. 2542; Szablan, Z., Junkers, T., Koo, S.P.S., Lovestead, T.M., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2007) Macromolecules, 40, p. 6820; Szablan, Z., Lovestead, T.M., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2007) Macromolecules, 40, p. 26; Vana, P., Davis, T.P., Barner-Kowollik, C., (2002) Aust. J. Chem., 55, p. 315; Gruendling, T., Guilhaus, M., Barner-Kowollik, C., (2009) Macromol. Rapid Commun., 30, p. 589; Gruendling, T., Guilhaus, M., Barner-Kowollik, C., (2008) Anal. Chem., 80, p. 6915; Weinstock, H.H., Fuson, R.C., (1936) J. Am. Chem. Soc., 58, p. 1986; Gray, A.R., Fuson, R.C., (1934) J. Am. Chem. Soc., 56, p. 739; Fuson, R.C., Weinstock, H.H., Ullyot, G.E., (1935) J. Am. Chem. Soc., 57, p. 1803; Wolf, T., Voll, D., Unterreiner, A.-N., Barner-Kowollik, C., UnpublishedUR - https://www.scopus.com/inward/record.uri?eid=2-s2.0-84855393981&partnerID=40&md5=976be8e0f5103070fcc671ab90a7d6d7
Keywords: free-radical polymerization of methyl methacrylate, multiphotoinitiated pulsed laser polymerization, pulsed laser polymerization-online size-exclusion chromatography-electrospray ionization-mass spectrometry, quantifying initiator efficiencies, substituted benzoins, Initiation efficiency, Mass spectra, Photoinitiation, Photoinitiators, Quantitative evaluation, Quantitative information, Size exclusion, Systematic study, Acrylic monomers, Atom transfer radical polymerization, Efficiency, Electrospray ionization, Esters, Experiments, Ionization, Ketones, Mass spectrometry, Organic polymers, Pulsed lasers, Size exclusion chromatography, Free radical polymerization, free radical, methacrylic acid methyl ester, article, chemistry, electrospray mass spectrometry, gel chromatography, photochemistry, polymerization, radiation exposure, Chromatography, Gel, Free Radicals, Methylmethacrylate, Photochemical Processes, Spectrometry, Mass, Electrospray Ionization
DOI: 10.1002/marc.201100655
ISSN: 10221336
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 30 Sep 2016 04:36

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