Mapping free radical reactivity: A high-resolution electrospray ionization-mass spectrometry study of photoinitiation processes in methyl methacrylate free radical polymerization

Szablan, Z., Lovestead, T. M., Davis, T. P., Stenzel, M. H., & Barner-Kowollik, C. (2007) Mapping free radical reactivity: A high-resolution electrospray ionization-mass spectrometry study of photoinitiation processes in methyl methacrylate free radical polymerization. Macromolecules, 40(1).

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Abstract

High-resolution electrospray ionization-mass spectrometry (ESI-MS) was applied to study the polymeric product spectrum generated by the pulsed laser polymerization (PLP) of methyl methacrylate (MMA) at temperatures ≤0 °C in the presence of the photoinitiators 2,2-dimethoxy-2-phenylacetophenone (DMPA), benzoin, benzil, benzoin ethyl ether (BEE), and 2,2- azobisisobutylnitrile (AIBN). Termination products, both combination and disproportionation, were identified with high accuracy. Both the benzoyl and acetal fragments generated as a result of DMPA photocleavage were found to initiate and highly likely terminate polymerization. Under the conditions studied, the acetal radical produced upon DMPA photolysis fragments further to yield methyl radicals which seem to act predominantly as terminating moieties. Both the benzoyl and ether fragments produced as a result of benzoin photocleavage were found to act as initiating and probable terminating species, indicating that the ether radical fragment does not act exclusively as a terminating species. Additionally, increasing laser intensity and/or irradiation repetition rate (i.e., energy deposition into the system) results in more complex product distributions of the MMA polymers produced via photoinitiation (with the exception of AIBN). Temperature was determined to have a minor influence on the resulting product distribution under the conditions examined. © 2007 American Chemical Society.

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ID Code: 99161
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :45
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: Barner-Kowollik, C.; Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, University of New South Wales, Sydney, NSW 2052, Australia; email: camd@unsw.edu.au
References: Gruber, H.F., (1992) Prog. Polym. Sci, 17, pp. 953-1044; Kaur, M., Srivastava, A.K., (2002) J. Macromol. Sci. Part C: Polym. Rev, 42, pp. 481-512; Ge, J., Trujillo, M., Stansbury, J.W., (2005) J. Dent. Mater, 21, pp. 1163-1169; Anseth, K.S., Newman, S.M., Bowman, C.N., (1995) Adv. Polym. Sci, 122, pp. 177-217; Fisher, J.P., Dean, D., Engel, P.S., Mikos, A.G., (2001) Annu. Rev. Mater. Res, 31, pp. 171-181; Anseth, K.S., Metters, A.T., Bryant, S.J., Martens, P.J., Elisseeff, J.H., Bowman, C.N., (2002) J. Controlled Release, 78, pp. 199-209; Buback, M., Feldermann, A., Barner-Kowollik, C., Lacik, I., (2001) Macromolecules, 34, pp. 5439-5448; Buback, M., Egorov, M., Felderman, A., (2004) Macromolecules, 37, pp. 1768-1776; Szablan, Z., Stenzel, M.H., Davis, T.P., Barner, L., Barner-Kowollik, C., (2005) Macromolecules, 38, pp. 5944-5954; Lissi, E.A., Garrido, J., (1984) J. Polym. Sci., Polym. Lett. Ed, 22, pp. 391-393; 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; Buback, M., Kowollik, C., (1998) Macromolecules, 31, pp. 3211-3215; Stickler, M., Meyerhoff, G., (1978) Makromol. Chem, 179, pp. 2729-2745; Corner, T., (1984) Adv. Polym. Sci, 62, pp. 95-142; Caykara, T., Guven, O., (1999) Polym. Degrad. Stab, 65, pp. 225-229; Schultz, A.R., (1961) J. Phys. Chem, 65, pp. 967-972; Simha, R., (1952) J. Polym. Sci, 9, pp. 465-467; David, C., Fuld, D., Geuskens, G., Charlesby, A., (1969) Eur. Polym. J, 5, pp. 641-648; Wochnowski, C., Shams Eldin, M.A., Metev, S., (2005) Polym. Degrad. Stab, 89, pp. 252-264; Hu, Y., Chen, C., (2003) Polym. Degrad. Stab, 82, pp. 81-88; Odian, G., (1991) Principles of Polymerization, , Wiley-Interscience: New York; Fouassier, J.P., Merlin, A., (1980) J. Photochem, 12, pp. 17-23; Luís Faria, J., Steenken, S., (1997) J. Chem. Soc., Perkin Trans. 2, pp. 1153-1159; Heine, H.G., (1972) Tetrahedron Lett, 47, pp. 4755-4758; Yee, L.H., Coote, M.L., Davis, T.P., Chaplin, R.P., (2000) J. Polym. Sci., Part A: Polym. Chem, 38, pp. 2192-2200; Szablan, Z., Ah Toy, A., Terrenoire, A., Davis, T.P., Stenzel, M.H., Müller, A.H.E., Barner-Kowollik, C., (2006) J. Polym. Sci., Polym. Chem, 44, pp. 3692-3710; Davis, T.P., Matyjaszewski, K., (2002) Handbook of Radical Polymerization, , Wiley-Interscience: New York; Pappas, S.P., Asmus, R.A., (1982) J. Polym. Sci., Polym. Chem, 20, pp. 2643-2653; Carlblom, L.H., Pappas, S.P., (1977) J. Polym. Sci, 15, pp. 1381-1391; Hageman, H.J., van der Maeden, F.B.J., Janssen, P.C., (1979) Makromol. Chem, 180, pp. 2531-2537; Willemse, R.X.E., (2005), Ph.D. Thesis, Technical University of EindhovenWillemse, R.X.E., van Herk, A.M., (2006) J. Am. Chem. Soc, 128, pp. 4471-4480; Kowollik, C., (1999), Ph.D. Thesis, Göttingen, ISBN 3-89712-705-9Sander, M.R., Osborn, C.L., (1974) Tetrahedron Lett, 5, pp. 415-418; Jaegermann, P., Lendzian, F., Rist, G., Mõbius, K., (1987) Chem. Phys. Lett, 140, pp. 615-619; Fischer, H.; Baer, R.; Hany, R.; Verhoolen. I.; M. J. Walnier, M. J. J. Chem. Soc., Perkin Trans. 2 1990, 787-798Buback, M., Busch, M., Kowollik, C., (2000) Macromol. Theory Simul, 9, pp. 442-452; Barner-Kowollik, C., Vana, P., Davis, T.P., (2002) J. Polym. Sci., Part A: Polym. Chem, 40, pp. 675-681; Kaji, M., Muramatsu, Y., Unno, A., Hirai, O., (2005) J. Photopolym. Sci. Technol, 18, pp. 135-140; Hanton, S.D., (2001) Chem. Rev, 101, pp. 527-569; Montaudo, G., (1996) Trends Polym. Sci, 4, pp. 81-86; Scrivens, J.H., Jackson, A.T., (2000) Int. J. Mass Spectrom, 200, pp. 261-276; Barner-Kowollik, C., Davis, T.P., Stenzel, M.H., (2004) Polymer, 45, pp. 7791-7805; Nielen, M.W.F., (1999) Mass Spectrosc. Rev, 18, pp. 309-344; Raeder, H.J., Schrepp, W., (1998) Acta Polym, 49, pp. 272-293; Tanaka, K., (2003) Angew. Chem., Int. Ed, 42, pp. 3861-3870; Saf, R., Mirtl, C., Hummel, K., (1997) Acta Polym, 48, pp. 513-526; McEwen, C.N., Simonsick Jr., W.J., Larsen, B.S., Ute, K., Hatada, K., (1995) J. Am. Soc. Mass Spectrom, 6, pp. 906-911; Vana, P., Albertin, L., Davis, T.P., Barner-Kowollik, C., (2002) J. Polym. Sci., Polym. Chem, 40, pp. 4032-4037; Felderman, A., Ah Toy, A., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2005) Polymer, 46, pp. 8448-8457; Ah Toy, A., Vana, P., Davis, T.P., Barner-Kowollik, C., (2004) Macromolecules, 37, pp. 744-751; Vana, P., Davis, T.P., Barner-Kowollik, (2002) C. Aust. J. Chem, 55, pp. 315-318; Deleted in proofCoote, M.L., Zammit, M.D., Davis, T.P., (1996) Trends Polym. Sci, 4, pp. 189-196; Olaj, O.F., Bitai, I., Hinkelmann, F., (1987) Makromol. Chem, 188, pp. 1689-1702; Guittard, J., Tessier, M., Biais, J.C., Bolbach, G., Rozes, L., Maréchal, E., Tabet, J.C., (1996) J. Mass Spectrom, 31, pp. 1409-1421; Chowdhury, S.K., Katta, V., Chait, B.T., (1990) J. Am. Chem. Soc, 112, pp. 9012-9013; Kaur, M., Srivastava, A.K., (2002) J. Macromol. Sci., Part C: Polym. Rev, 42 (4), pp. 481-512; Hatada, K., Kitayama, T., Ute, K., (1988) Prog. Polym. Sci, 13, pp. 189-276; Phan, X.T.P., (1986) J. Radiat. Curing, 18, pp. 23-25; Phan, X.T.P., (1986) J. Radiat. Curing, 13, pp. 11-17; Borer, A., Kirchmayer, R., Rist, G., (1978) Helv. Chim. Acta, 61, pp. 305-324; Groenenboom, C.J., Hageman, H.J., Overreem, T., Weber, A.J.M., (1982) Makromol. Chem, 183, pp. 281-292; Baxter, J.E., Davidson, R.S., Hageman, H.J., Havkoort, G.T.M., (1988) Polymer, 29, pp. 1575-1580; The intensity of the incident radiation is beset with an error of ±30% over the course of a single reaction (20 min) due to gradual heating of the reaction gas in the laser system and/or degradation of laser gas over time as well as some condensation which may occur on the reaction vials due to the low temperatures usedHutchinson, J., Ledwith, A., (1973) Polymer, 14, pp. 405-408; Mukai, M., Yamauchi, S., Hirota, N., (1989) J. Phys. Chem, 93, pp. 4411-4413
Keywords: Free radical polymerization, Ionization, Mass spectrometry, Photolysis, Pulsed laser applications, Thermal effects, High-resolution electrospray ionization-mass spectrometry (ESI-MS), Methyl methacrylate, Photoinitiation processes, Pulsed laser polymerization (PLP), Acrylics
DOI: 10.1021/ma0616559
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: 11 Oct 2016 04:55

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