Living free radical polymerization (RAFT) of dodecyl acrylate: Chain length dependent termination, mid-chain radicals and monomer reaction order

Theis, A., Feldermann, A., Charton, N., Davis, T. P., Stenzel, M. H., & Barner-Kowollik, C. (2005) Living free radical polymerization (RAFT) of dodecyl acrylate: Chain length dependent termination, mid-chain radicals and monomer reaction order. Polymer, 46(18).

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The reversible addition fragmentation chain transfer-chain length dependent-termination (RAFT-CLD-T) methodology was employed to map chain length dependent termination rate coefficient, kti,i, in dodecyl acrylate (DA) free radical polymerization at 60 and 80 °C. The chain length of the propagating DA radicals was controlled by the RAFT agents methoxycarbonylethyl phenyldithioacetate (MCEPDA) and dimethoxycarbonylethyl trithiocarbonate (DMCETC). In addition, the reaction order of the polymerization process with respect to the monomer concentration was determined at both temperatures and found to be close to 1.55 (60 °C) and 1.75 (80 °C), commensurate with the increased presence of mid-chain radicals. A modeling study demonstrates that the obtained data for the reaction order can be transferred to RAFT polymerization systems. The RAFT-CLD-T procedure was modified to account for the determined reaction orders. The obtained chain length dependence of k t in dodecyl acrylate polymerizations is in good agreement with the composite model for chain length dependent termination, showing two distinct regions: For the initial chain-length regime up to a degree of polymerization of 20, kt decreases rapidly with α (in the expression kti,i=kt0·i-α) being close to 1.15 at 80 °C. At chain lengths exceeding 20, the decrease is significantly less pronounced (α close to 0.22 at 80 °C). At 60 °C, the chain length dependence in both regions is somewhat more pronounced. The RAFT agent DMCETC may not be as suited to map out CLD kt values in the DA system, since it induces some limited rate retardation effects. © 2005 Elsevier Ltd. All rights reserved.

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ID Code: 99111
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :59 Export Date: 5 September 2016 CODEN: POLMA Correspondence Address: Barner-Kowollik, C.; Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, University of New South Wales, Sydney, NSW 2052, Australia; email: References: Asua, J.M., Beuermann, S., Buback, M., Castignolles, P., Charleux, B., Gilbert, R.G., (2004) Macromol Chem Phys, 205 (16), pp. 2151-2160; Busch, M., Müller, M., (2004) Macromol Symp, 206 (1), pp. 399-418; Nikitin, A.N., Hutchinson, R.A., (2005) Macromolecules, 38 (5), pp. 1581-1590; Buback, M., Busch, M., Kowollik, C., (2000) Macromol Theory Simul, 9 (8), pp. 442-452; Olaj, O.F., Kornherr, A., Zifferer, G., (1997) Macromol Rapid Commun, 18 (12), pp. 997-1007; Olaj, O.F., Vana, P., (1998) Macromol Rapid Commun, 19 (8), pp. 433-439; Olaj, O.F., Vana, P., Kornherr, A., Zifferer, G., (1999) Macromol Chem Phys, 200 (9), pp. 2031-2039; Olaj, O.F., Vana, P., (1998) Macromol Rapid Commun, 19 (10), pp. 533-538; Olaj, O.F., Vana, P., (2000) J Polym Sci Polym Chem, 38 (4), pp. 697-705; De Kock, J.B.L., Van Herk, A.M., German, A.L., (2001) J Macromol Sci Polym Rev, 41 (3), pp. 199-252; De Kock, J.B.L., Klumperman, B., Van Herk, A.M., German, A.L., (1997) Macromolecules, 30 (22), pp. 6743-6753; Buback, M., Egorov, M., Feldermann, A., (2004) Macromolecules, 37 (5), pp. 1768-1776; Kowollik, C., (1999), PhD Thesis, University of Göttingen; ISBN 3-89712-705-9Buback, M., Egerov, M., Junkers, T., Panchenko, E., (2004) Macromol Rapid Commun, 25 (10), pp. 1004-1009; Buback, M., Junkers, T., Vana, P., (2005) Macromol Rapid Commun, 26 (10), pp. 796-802; Vana, P., Davis, T.P., Barner-Kowollik, C., (2002) Macromol Rapid Commun, 23 (16), pp. 952-956; Mayadunne, R.T.A., Rizzardo, E., Chiefari, J., Chong, Y.K., Moad, G., Thang, S.H., (1999) Macromolecules, 32 (21), pp. 6977-6980; Moad, G., Chiefari, J., Chong, Y.K., Krstina, J., Mayadunne, R.T.A., Postma, A., (2000) Polym Int, 49 (9), pp. 993-1001; Chong, Y.K., Le, T.P.T., Moad, G., Rizzardo, E., Thang, S.H., (1999) Macromolecules, 32 (6), pp. 2071-2074; Barner-Kowollik, C., Davis, T.P., Heuts, J.P.A., Stenzel, M.H., Vana, P., Whittaker, M., (2003) J Polym Sci Polym Chem, 41 (3), pp. 365-375; Destarac, M., Charmot, D., Franck, X., Zard, S.Z., (2000) Macromol Rapid Commun, 21 (15), pp. 1035-1039; Taton, D., Wilczewska, A.Z., Destarac, M., (2001) Macromol Rapid Comm, 22 (18), pp. 1497-1503; Feldermann, A., Stenzel, M.H., Davis, T.P., Vana, P., Barner-Kowollik, C., (2004) Macromolecules, 37 (7), pp. 2404-2410; Theis, A., Feldermann, A., Charton, N., Stenzel, M.H., Davis, T.P., Barner-Kowollik, C., (2005) Macromolecules, 38 (7), pp. 2595-2605; Buback, M., Kurz, C.H., Schmaltz, C., (1998) Macromol Chem Phys, 199 (8), pp. 1721-1727; Buback, M., Kowollik, C., (1999) Macromol Chem Phys, 200 (7), pp. 1764-1770; Beuermann, S., Buback, M., Schmaltz, C., (1999) Ind Eng Chem Res, 38 (9), pp. 3338-3344; Buback, M., Kuelpmann, A., Kurz, C., (2002) Macromol Chem Phys, 203 (8), pp. 1065-1070; Buback, M., Barner-Kowollik, C., Kuelpmann, A., (2002) Macromol Chem Phys, 203 (13), pp. 1887-1894; Charton, N., Feldermann, A., Theis, A., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2004) J Polym Sci Polym Chem, 42 (20), pp. 5170-5179; Beuermann, S., Paquet Jr., D.A., McMinn, J.H., Hutchinson, R.A., (1996) Macromolecules, 29 (12), pp. 4206-4215; Scott, G.E., Senogles, E.J., (1970) Macromol Sci Chem, 4 (5), pp. 1105-1117; Rätzsch, M., Zschach, I., (1968) Plaste Kautsch, 15 (1), pp. 12-14; Wunderlich, W., (1976) Makromolek Chem, 177 (4), pp. 973-989; Strazielle, C., Benoit, H., Vogl, O., (1978) Eur Polym J, 14 (5), pp. 331-334; Madorsky, S.L., Hart, V.E., Strauss, S., (1956) J Res Natl Bur Std, 56, pp. 343-349; Czajlik, I., Földes-Berezsnich, T., Tüdos, F., Vértes, E., (1981) Eur Polym J, 17 (2), pp. 131-135; Willemse, R.X.E., Van Herk, A., Panchenko, E., Junkers, T., Buback, M., (2005) Macromolecules, 38 (12), pp. 5098-5103; Wulkow, M., Busch, M., Davis, T.P., Barner-Kowollik, C., (2003) J Polym Sci, Polym Chem, 42 (6), pp. 1441-1448; Fracet, C., Belleney, J., Charleux, B., Pirri, R., (2002) Macromolecules, 35 (13), pp. 4912-4918; Arzamendi, G., Plessis, C., Leiza, J.R., Asua, J.M., (2003) Macromol Theory Simul, 12 (5), pp. 315-324; Fischer, H., Radom, L., (2001) Angew Chem Int Ed, 40 (8), pp. 1340-1371; Plessis, C., Arzamendi, G., Alberdi, J.M., Van Herk, A., Leiza, J.R., Asua, J.M., (2003) Macromol Rapid Commun, 24 (2), pp. 173-177; Tanaka, K., Yamada, B., Fellows, C.M., Gilbert, R.G., Davis, T.P., Yee, L.H., (2001) J Polym Sci, Part A: Polym Chem, 39 (22), pp. 3902-3915; Barner-Kowollik, C., Vana, P., Davis, T.P., (2002) Handbook of Radical Polymerization, p. 209. , K. 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Keywords: Dodecyl acrylate, Kinetics (Polym.), Reversible addition fragmentation chain transfer polymerization (RAFT), Composite materials, Free radical polymerization, Free radicals, Monomers, Reaction kinetics, Chain length, Dodecul acrylate (DA), Mid-chain radicals, Reaction order, Polyacrylates, polymer science
DOI: 10.1016/j.polymer.2005.06.004
ISSN: 00323861
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: 22 Sep 2016 04:50

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