UV-triggered end group conversion of photo-initiated poly(methyl methacrylate)

Voll, D., Neshchadin, D., Hiltebrandt, K., Gescheidt, G., & Barner-Kowollik, C. (2012) UV-triggered end group conversion of photo-initiated poly(methyl methacrylate). Macromolecules, 45(15).

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Abstract

The analysis of photo-initiated poly(methyl methacrylate) via electrospray ionization-mass spectrometry (ESI-MS) (synthesized by pulsed laser polymerization (PLP, at λ = 351 nm) of methyl methacrylate (MMA) and benzoin as photoinitiator at 6 mJ/pulse laser energy) evidences the presence of unidentified species. The determination of the origin of these species requires a detailed investigation via size exclusion chromatography-electrospray ionization-mass spectrometry (SEC/ESI-MS) and chemically induced dynamic nuclear polarization-nuclear magnetic resonance spectroscopy (CIDNP-NMR). It was found that post-irradiation of benzoin-initiated poly(methyl methacrylate) leads to α-cleavage of the benzoyl fragment leading to a sequence of cascade reactions, including the formation of an additional double bond within the polymer chain as evidenced via ESI-MS. Furthermore, the reaction products of the benzoyl radical post α-cleavage (e.g., benzaldehyde, phenyl methyl ketone, methyl formate, or methane) as well as the formed macroradical can be followed by CIDNP-NMR, which allows establishing a reaction mechanism for the UV-induced cleavage process. The study thus evidence that-if the integrity of UV initiated polymers is to be kept intact during their synthesis-very low irradiation energies need to be employed. © 2012 American Chemical Society.

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ID Code: 99328
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :5
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: Gescheidt, G.; Institute of Physical and Theoretical Chemistry, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria; email: g.gescheidt-demner@tugraz.at
References: Gruber, H.F., (1992) Prog. Polym. Sci., 17, pp. 953-1044; Tunc, D., Yagci, Y., (2011) Polym. Chem., 2, pp. 2557-2563; Lalevee, J., Blanchard, N., Tehfe, M.A., Fries, C., Morlet-Savary, F., Gigmes, D., Fouassier, J.P., (2011) Polym. Chem., 2, pp. 1077-1084; Yagci, Y., Jockusch, S., Turro, N.J., (2010) Macromolecules, 43, pp. 6245-6260; Goez, M., (1995) Concepts Magn. Reson., 7, pp. 69-86; Griesser, M., Dworak, C., Jauk, S., Höfer, M., Rosspeintner, A., Grabner, G., Liska, R., Gescheidt, G., (2012) Macromolecules, 45, pp. 1737-1745; Buback, M., Gilbert, R.G., Hutchinson, R.A., Klumperman, B., Kuchta, F.-D., Manders, B.G., O'Driscoll, K.F., Schweer, J., (1995) Macromol. Chem. Phys., 196, pp. 3267-3280; Beuermann, S., Buback, M., Davis, T.P., Gilbert, R.G., Hutchinson, R.A., Olaj, O.F., Russell, G.T., Van Herk, A.M., (1997) Macromol. Chem. Phys., 198, pp. 1545-1560; Aaserud, D.J., Prokai, L., Simonsick, W.J., (1999) Anal. Chem., 71, pp. 4793-4799; Gruendling, T., Guilhaus, M., Barner-Kowollik, C., (2008) Anal. Chem., 80, pp. 6915-6927; Gruendling, T., Guilhaus, M., Barner-Kowollik, C., (2009) Macromolecules, 42, pp. 6366-6374; Voll, D., Junkers, T., Barner-Kowollik, C., (2011) Macromolecules, 44, pp. 2542-2551; Voll, D., Hufendiek, A., Junkers, T., Barner-Kowollik, C., (2012) Macromol. Rapid Commun., 33, pp. 47-53; Wolf, T.J.A., Voll, D., Barner-Kowollik, C., Unterreiner, A.-N., (2012) Macromolecules, 45, pp. 2257-2266; Voll, D., Junkers, T., Barner-Kowollik, C., (2012) J. Polym. Sci., Part A: Polym. Chem., 50, pp. 2739-2757; Szablan, Z., Lovestead, T.M., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2006) Macromolecules, 40, pp. 26-39; Szablan, Z., Junkers, T., Koo, S.P.S., Lovestead, T.M., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2007) Macromolecules, 40, pp. 6820-6833; Günzler, F., Wong, E.H.H., Koo, S.P.S., Junkers, T., Barner-Kowollik, C., (2009) Macromolecules, 42, pp. 1488-1493; Gruendling, T., Guilhaus, M., Barner-Kowollik, C., (2009) Macromol. Rapid Commun., 30, pp. 589-597; Kaptein, R., Oosterhoff, L.J., (1969) Chem. Phys. Lett., 4, pp. 214-216; Closs, G.L., (1969) J. Am. Chem. Soc., 91, pp. 4552-4554; Yurkovskaya, A., Morozova, O., Gescheidt, G., Structures and Reactivity of Radicals Followed by Magnetic Resonance (2012) Encyclopedia of Radicals in Chemistry, Biology and Materials, , In; Chatgilialoglu, C. Studer, A. John Wiley & Sons, Ltd. London; Salikhov, K.M., Molin, Y.N., Sagdeev, R.Z., Buchachenko, A.L., (1984) Spin Polarization and Magnetic Effects in Radical Reactions, p. 419. , Elsevier: Amsterdam; AIST: Integrated Spectral Database System of Organic CompoundsNosova, V.M., Ustynyuk, Y.A., Bruk, L.G., Temkin, O.N., Kisin, A.V., Storozhenko, P.A., (2011) Inorg. Chem., 50, pp. 9300-9310; Kaiser, T., Grossi, L., Fischer, H., (1978) Helv. Chim. Acta, 61, pp. 223-233; Wendt, H.R., Hunziker, H.E., (1984) J. Chem. Phys., 81, pp. 717-723; Gupta, A., Liang, R., Tsay, F.D., Moacanin, J., (1980) Macromolecules, 13, pp. 1696-1700; Wöll, D., Laimgruber, S., Galetskaya, M., Smirnova, J., Pfleiderer, W., Heinz, B., Gilch, P., Steiner, U.E., (2007) J. Am. Chem. Soc., 129, pp. 12148-12158
Keywords: Benzoyl radicals, Cascade reactions, Double bonds, Electrospray ionization mass spectrometry, End groups, Irradiation energy, Laser energies, Methyl formate, Methyl ketones, Methyl methacrylates, Photo-initiator, Polymer chains, Postirradiation, Pulsed laser polymerization, Reaction mechanism, Size exclusion, Acetone, Aldehydes, Electrospray ionization, Esters, Irradiation, Mass spectrometry, Methane, Nuclear magnetic resonance spectroscopy, Polymers, Synthesis (chemical), Acrylic monomers
DOI: 10.1021/ma301275b
ISSN: 00249297
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 04:20

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