Chain length dependent termination in butyl acrylate free-radical polymerization studied via stationary and pulsed laser initiated RAFT polymerization

Junkers, T., Theis, A., Buback, M., Davis, T. P., Stenzel, M. H., Vana, P., & Barner-Kowollik, C. (2005) Chain length dependent termination in butyl acrylate free-radical polymerization studied via stationary and pulsed laser initiated RAFT polymerization. Macromolecules, 38(23).

View at publisher

Abstract

The chain-length dependence of the termination rate coefficient, k t, in butyl acrylate free-radical polymerization has been determined by two independent methods, RAFT-SP-PLP and RAFT-CLD-T, both employing control of radical chain length by reversible addition fragmentation chain transfer (RAFT) polymerization. Within RAFT-SP-PLP, the polymerization induced by a laser single pulse is monitored via near-IR spectroscopy with a time resolution of microseconds. In RAFT-CLD-T, isothermal reaction rate measurements are carried out via DSC under stationary polymerization conditions. The resulting k t data refer to the situation of living/controlled radical polymerization, where both radical chain length and monomer conversion increase during the course of the reaction. The RAFT-SP-PLP measurements were carried out at 60°C and two pressures, 5 and 1000 bar. The RAFT-CLD-T experiments were run at ambient pressure and at two temperatures, 60 and 80°C, respectively. In absolute value, the termination rate coefficients for identical pressure and temperature deduced from the two methods differ by less than a factor of 2. For the dependence of kt on chain length, i, almost identical information is provided by the two techniques. The chain-length dependence of kt may be described by the power-law expression kt(i) = k t(1,1)i-α with, however, α being different for short-chain and long-chain radicals. RAFT-SP-PLP yields α1 = 1.25 for the short-chain regime from 1 < i < 30, and α2 = 0.22 for chain lengths above i = 50. RAFT-CLD-T results in α1 = 1.04 and α2 = 0.20 in identical chain length regimes. k t(1,1) values are found to be close to 1 × 109 L mol-1 s-1. © 2005 American Chemical Society.

Impact and interest:

69 citations in Scopus
Search Google Scholar™
63 citations in Web of Science®

Citation counts are sourced monthly from Scopus and Web of Science® citation databases.

These databases contain citations from different subsets of available publications and different time periods and thus the citation count from each is usually different. Some works are not in either database and no count is displayed. Scopus includes citations from articles published in 1996 onwards, and Web of Science® generally from 1980 onwards.

Citations counts from the Google Scholar™ indexing service can be viewed at the linked Google Scholar™ search.

ID Code: 99108
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :69
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: Vana, P.; Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstr. 6, D-37077 Göttingen, Germany; email: pvana@uni-goettingen.de
References: Barner-Kowollik, C., Buback, M., Egerov, M., Fukuda, T., Goto, A., Olaj, O.F., Russell, G.T., Zetterlund, P.B., (2005) Prog. Polym. Sci., 30, pp. 605-643; Buback, M., Egorov, M., Kaminsky, V., Olaj, O.F., Russell, G.T., Vana, P., Zifferer, G., (2002) Macromol. Chem. Phys., 203, pp. 2570-2582; Barner-Kowollik, C., Vana, P., Davis, T.P., Kinetics of free radical polymerization (2002) Handbook of Radical Polymerization, p. 209. , Matyjaszewski, K., Davis, T. P., Eds.; Wiley and Sons: New York; Smith, G.B., Russell, G.T., Heuts, J.P.A., (2003) Macromol. Theory Simul., 12, pp. 299-314; Olaj, O.F., Vana, P., (1998) Macromol. Rapid Commun., 19, pp. 433-439; Olaj, O.F., Vana, P., (1998) Macromol. Rapid Commun., 19, pp. 533-538; De Kock, J.B.L., Klumperman, B., Van Herk, A.M., German, A.L., (1997) Macromolecules, 30, pp. 6743-6753; Buback, M., Busch, M., Kowollik, C., (2000) Macromol. Theory Simul., 9, pp. 442-452; Buback, M., Egorov, M., Feldermann, A., (2004) Macromolecules, 37, pp. 1768-1776; Buback, M., Egorov, M., Junkers, T., Panchenko, E., (2004) Macromol Rapid Commun., 25, pp. 1004-1009; Buback, M., Egorov, M., Junkers, T., Panchenko, E., (2005) Macromol. Chem. Phys., 206, pp. 333-341; Smith, G.B., Russell, G.T., Yin, M., Heuts, J.P.A., (2005) Eur. Polym. J., 41, pp. 225-230; Vana, P., Davis, T.P., Barner-Kowollik, C., (2002) Macromol. Rapid Commun., 23, pp. 952-956; Theis, A., Feldermann, A., Charton, N., Stenzel, M.H., Davis, T.P., Barner-Kowollik, C., (2005) Macromolecules, 38, pp. 2595-2605; Theis, A., Feldermann, A., Charton, N., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2005) Polymer, 46, pp. 6797-6809; Johnston-Hall, G., Theis, A., Monteiro, M., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2005) Macromol. Chem. Phys., 206, pp. 2047-2053; Mayadunne, R.T.A., Rizzardo, E., Chiefari, J., Chong, Y.K., Moad, G., Thang, S.H., (1999) Macromolecules, 32, pp. 6977-6980; Chiefari, J., Mayadunne, R.T.A., Moad, C.L., Moad, G., Rizzardo, E., Postma, A., Skidmore, A., Thang, S.H., (2003) Macromolecules, 36, pp. 2273-2283; Moad, G., Chiefari, J., Mayadunne, R.T.A., Moad, C.L., Postma, A., Rizzardo, E., Thang, S.H., (2002) Macromol. Symp., 182, pp. 65-80; Moad, G., Chiefari, J., Chong, Y.K., Krstina, J., Mayadunne, R.T.A., Postma, A., Rizzardo, E., Thang, S.H., (2000) Polym. Int., 49, pp. 993-1001; Krstina, J., Moad, G., Rizzardo, E., Winzor, C.L., Berge, C.T., Fryd, M., (1995) Macromolecules, 28, pp. 5381-5385; Delduc, P., Tailhan, C., Zard, S.Z., (1988) J. Chem. Soc., Chem. Commun., pp. 308-310; Moad, G., Rizzardo, E., Thang, S.H., (2005) Aust. J. Chem., 58, pp. 379-410; Vana, P., Davis, T.P., Barner-Kowollik, C., (2002) Macromol. Theory Simul., 11, pp. 823-835; Buback, M., Hippler, H., Schweer, J., Vögele, H.P., (1986) Makromol. Chem., Rapid Commun., 7, pp. 261-265; Olaj, O.F., Bitai, I., Hinkelmann, F., (1987) Makromol. Chem., 188, p. 1689; Beuermann, S., Buback, M., Davis, T.P., Gilbert, R.G., Hutchison, R.A., Olaj, O.F., Russell, G.T., Van Herk, A.M., (1997) Macromol. Chem. Phys., 198, pp. 1545-1560; Buback, M., Junkers, T., Vana, P., (2005) Macromol. Rapid Commun., 26, pp. 796-802; Wulkow, M., Busch, M., Davis, T.P., Barner-Kowollik, C., (2003) J. Polym. Sci., Polym. Chem., 42, pp. 1441-1448; Busch, M., Müller, M., (2004) Macromol. Symp., 206, pp. 399-418; Nikitin, A.N., Hutchinson, R.A., (2005) Macromolecules, 38, pp. 1581-1590; Plessis, C., Arzamendi, G., Alberdi, J.M., Van Herk, A.M., Leiza, J.R., Asua, J.M., (2003) Macromol. Rapid Commun., 24, pp. 173-177; Arzamendi, G., Plessis, C., Leiza, J.R., Asua, J.M., (2003) Macromol. Theory Simul., 12, pp. 315-324; Willemse, R.X.E., Van Herk, A.M., Panchenko, E., Junkers, T., Buback, M., (2005) Macromolecules, 38, pp. 5098-5103; Tamami, B., Kiasat, A.R., (1998) J. Chem. Res., Synop., pp. 454-455; Buback, M., (1991) Angew. Chem., Int. Ed. Engl., 30, pp. 641-653; Penzel, E., Götz, N., (1990) Angew. Makromol. Chem., 178, pp. 191-200; Strazielle, C., Benoit, H., Vogl, O., (1978) Eur. Polym. J., 14, pp. 331-334; Madorsky, S.L., Hart, V.E., Strauss, S.J., (1956) Res. Natl. Bur. Stand., 56, pp. 343-354; Arita, T., Buback, M., Janssen, O., Vana, P., (2004) Macromol. Rapid Commun., 25, pp. 1376-1381; Asua, J.M., Beuermann, S., Buback, M., Castignolles, P., Charleux, B., Gilbert, R.G., Hutchinson, R.A., Van Herk, A.M., (2004) Macromol. Chem. Phys., 205, pp. 2151-2160; Sato, E., Emoto, T., Zetterlund, P.B., Yamada, B., (2004) Macromol Chem. Phys., 205, pp. 1829-1839; Tanaka, K., Yamada, B., Fellows, C.M., Gilbert, R.G., Davis, T.P., Yee, L.H., Smith, G.B., Russel, G.T., (2001) J. Polym. Sci., Part A: Polym. Chem., 39, pp. 3902-3915; Beuermann, S., Buback, M., Schmaltz, C., (1998) Macromolecules, 31, pp. 8096-18074; Wunderlich, W., (1976) Makromol. Chem., 177, pp. 973-989; Wang, A.R., Zhu, S., Kwak, Y., Goto, A., Fukuda, T., Monteiro, M.S., (2003) J. Polym. Sci., Part A: Polym. Chem., 41, p. 2833; Beuermann, S., Buback, M., (2002) Prog. Polym. Sci., 27, pp. 191-254; Kurz, C., (1999), Ph.D. Thesis, GöttingenFeldermann, A., Stenzel, M.H., Davis, T.P., Vana, P., Barner-Kowollik, C., (2004) Macromolecules, 37, pp. 2404-2410; Barner-Kowollik, C., Quinn, J.F., Nguyen, T.L.U., Heuts, J.P.A., Davis, T.P., (2001) Macromolecules, 34, pp. 7849-7857; Charton, N., Feldermann, A., Theis, A., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2004) J. Polym. Sci., Part A: Polym. Chem., 42, pp. 5170-5179; Buback, M., Huckestein, B., Kuchta, F.D., Russell, G.T., Schmid, E., (1994) Macromol. Chem. Phys., 195, pp. 2117-2140; Kuchta, F.D., (1996), Ph.D. Thesis, GöttingenFeldermann, A., Ah Toy, A., Davis, T.P., Stenzel, M.H., Barner Kowollik, C., (2005) Polymer, 46, pp. 8448-8457; Smoluchowski, M., (1917) Z. Phys. Chem. (Munich), 92, p. 129; De Kock, J.B.L., Van Herk, A.M., German, A.L., (2001) J. Macromol. Sci., Polym. Rev., C41, pp. 199-252; McLeary, J.B., McKenzie, J.M., Tonge, M.P., Sanderson, R.D., Klumpermann, B., (2004) Chem. Commun., pp. 1950-1951; Willemse, R.X.E., Staal, B.B.P., Van Herk, A.M., Pierik, S.C.J., Klumperman, B., (2003) Macromolecules, 36, pp. 9797-9803; Olaj, O.F., Vana, P., Zoder, M., Kornherr, A., Zifferer, G., (2000) Macromol. Rapid Commun., 21, pp. 913-920; Olaj, O.F., Vana, P., Zoder, M., (2002) Macromolecules, 35, pp. 1208-1214; Zetterlund, P.B., Busfield, W.K., Jenkins, I.D., (2002) Macromolecules, 35, pp. 7232-7237; Smith, G.B., Russell, G.T., Yin, M., Heuts, J.P.A., (2004) Eur. Polym. J., 41, pp. 225-230
Keywords: Data acquisition, Hydrocarbons, Laser pulses, Monomers, Pressure effects, Rate constants, Temperature distribution, Chain length, Identical pressures, Monomer conversion, Power law, Free radical polymerization
DOI: 10.1021/ma051485k
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: 22 Sep 2016 04:50

Export: EndNote | Dublin Core | BibTeX

Repository Staff Only: item control page