[en] The successful controlled homopolymerization of acrylonitrile (AN) by cobalt-mediated radical polymerization (CMRP) is reported for the first time. As a rule, initiation of the polymerization was carried out starting from a conventional azo-initiator (V-70) in the presence of bis(acetylacetonato)cobalt(II) ([Co(acac)2]) but also by using organocobalt(III) adducts. Molar concentration ratios of the reactants, the temperature, and the solvent were tuned, and the effect of these parameters on the course of the polymerization is discussed in detail. The best level of control was observed when the AN polymerization was initiated by an organocobalt(III) adduct at 0 °C in dimethyl sulfoxide. Under these conditions, poly(acrylonitrile) with a predictable molar mass and molar mass distribution as low as 1.1 was prepared. A combination of kinetic data, X-ray analyses, and DFT calculations were used to rationalize the results and to draw conclusions on the key role played by the solvent molecules in the process. These important mechanistic insights also permit an explanation of the unexpected solvent effect that allows the preparation of well-defined poly(vinyl acetate)-b-poly(acrylonitrile) by CMRP.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Debuigne, Antoine ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Michaux, Catherine; Facultés Universitaires Notre-Dame de la Paix (FUNDP), Namur, Belgium > Chimie Biologique Structurale lab, CPTS group
Jérôme, Christine ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Poli, Rinaldo; UPR CNRS 8241 lié par convention à l’Université Paul Sabatier et à l’Institut National Polytechnique de Toulouse, France > Laboratoire de Chimie de Coordination
Detrembleur, Christophe ; Université de Liège - ULiège > Department of chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Cobalt-mediated radical polymerization of acrylonitrile: Kinetics investigations and DFT calculations
BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE]
Braunecker, W.A., Matyjaszewski, K., (2007) Prog. Polym. Sci, 32, pp. 93-146
Hawker, C.J., Bosman, A.W., Harth, E., (2001) Chem. Rev, 101, pp. 3661-3688
Sciannamea, V., Jérôme, R., Detrembleur, C., (2008) Chem. Rev, 108, pp. 1104-1126
(2008) Handbook of RAFT polymerization, , Ed: C. Barner-Kowollik, Wiley-VCH
Wayland, B.B., Poszmik, G., Mukerjee, S.L., Fryd, M., (1994) J. Am. Chem. Soc, 116, pp. 7943-7944
Wayland, B.B., Basickes, L., Mukerjee, S., Wei, M., Fryd, M., (1997) Macromolecules, 30, pp. 8109-8112
Wayland, B.B., Peng, C.-H., Fu, X., Lu, Z., Fryd, M., (2006) Macromolecules, 39, pp. 8219-8222
Debuigne, A., Caille, J.-R., Jérôme, R., (2005) Angew. Chem, 117, pp. 1125-1128
(2005) Angew. Chem. Int. Ed, 44, pp. 1101-1104
Bryaskova, R., Detrembleur, C., Debuigne, A., Jérôme, R., (2006) Macromolecules, 39, pp. 8263-8268
Kaneyoshi, H., Matyjaszewski, K., (2005) Macromolecules, 38, pp. 8163-8169
Maria, S., Kaneyoshi, H., Matyjaszewski, K., Poli, R., (2007) Chem. Eur. J, 13, pp. 2480-2492
Debuigne, A., Caille, J.-R., Jérôme, R., (2005) Macromolecules, 38, pp. 5452-5458
Debuigne, A., Caille, J.-R., Detrembleur, C., Jérôme, R., (2005) Angew. Chem, 117, pp. 3505-3508
(2005) Angew. Chem. Int. Ed, 44, pp. 3439-3442
Detrembleur, C., Debuigne, A., Bryaskova, R., Charleux, B., Jérôme, R., (2006) Macromol. Rapid Commun, 27, pp. 37-41
Debuigne, A., Champouret, Y., Jérôme, R., Poli, R., Detrembleur, C., (2008) Chem. Eur. J, 14, pp. 4046-4059
Debuigne, A., Caille, J.-R., Willet, N., Jérôme, R., (2005) Macromolecules, 38, pp. 9488-9496
Bryaskova, R., Willet, N., Debuigne, A., Jérôme, R., Detrembleur, C., (2006) J. Polym. Sci. Polym. Chem, 45, pp. 81-89
Bryaskova, R., Willet, N., Degee, P., Dubois, P., Jérôme, R., Detrembleur, C., (2007) J. Polym. Sci. Part A: Polym. Chem, 45, pp. 2532-2542
Debuigne, A., Willet, N., Jérôme, R., Detrembleur, C., (2007) Macromolecules, 40, pp. 7111-7118
Debuigne, A., Warnant, J., Jérôme, R., Voets, I., Keizer, A.D., Stuart, M.A.C., Detrembleur, C., (2008) Macromolecules, 41, pp. 2353-2360
Benoit, D., Chaplinski, V., Braslau, R., Hawker, C.J., (1999) J. Am. Chem. Soc, 121, pp. 3904-3920
Tang, C., Kowalewski, T., Matyjaszewski, K., (2003) Macromolecules, 36, pp. 1465-1473
Kaim, A., (2006) J. Polym. Sci. Polym. Chem, 45, pp. 232-241
Matyjaszewski, K., Jo, S.M., Paik, H.-J., Gaynor, S.G., (1997) Macromolecules, 30, pp. 6398-6400
Matyjaszewski, K., Jo, S.M., Paik, H.-J., Shipp, D.A., (1999) Macromolecules, 32, pp. 6431-6438
Barboiu, B., Percec, V., (2001) Macromolecules, 34, pp. 8626-8636
Tang, C., Kowalewski, T., Matyjaszewski, K., (2003) Macromolecules, 36, pp. 8587-8589
An, Q., Qian, J., Yu, L., Luo, Y., Liu, X., (2005) J. Polym. Sci. Polym. Chem, 43, pp. 1973-1977
Liu, X.-H., Li, Y.-G., Lin, Y., Li, Y.-S., (2001) J. Polym. Sci. Polym. Chem. Ed, 45, pp. 1272-1281
Liu, X.-H., Zhang, G.-B., Lu, X.-F., Liu, J.-Y., Pan, D., Li, Y.-S., (2005) J. Polym. Sci. Polym. Chem, 44, pp. 490-498
Aqil, A., Detrembleur, C., Gilbert, B., Jérôme, R., Jérôme, C., (2007) Chem. Mater, 19, pp. 2150-2154
Minagawa, M., Miyano, K., Morita, T., Yoshii, F., (1989) Macromolecules, 22, pp. 2054-2058
Calderazzo, F., Pampaloni, G., Vitali, D., Collamati, I., Dessy, G., Fares, V., (1980) J. Chem. Soc. Dalton Trans, pp. 1965-1969
Carini, C., Pelizzi, C., Pelizzi, G., Predieri, G., Tarasconi, P., Vitali, F., (1990) J. Chem. Soc. Chem. Commun, pp. 613-614
Chiarella, G.M., Melgarejo, D.Y., Koch, S.A., (2006) J. Am. Chem. Soc, 128, pp. 1416-1417
Conradie, J., Ghosh, A., (2007) J. Chem. Theory Comput, 3, pp. 689-702
Wasbotten, I.H., Ghosh, A., (2007) Inorg. Chem, 46, pp. 7890-7898
Salomon, O., Reiher, M., Hess, B.A., (2002) J. Chem. Phys, 117, pp. 4729-4737
Harvey, J.N., Aschi, M., (2003) Faraday Discuss, 124, pp. 129-143
Harvey, J.N., Poli, R., (2003) Dalton Trans, pp. 4100-4106
Carréon-Macedo, J.L., Harvey, J.N., (2004) J. Am. Chem. Soc, 126, pp. 5789-5797
Gillies, M.B., Matyjaszewski, K., Norrby, P.-O., Pintauer, T., Poli, R., Richard, P., (2003) Macromolecules, 36, pp. 8551-8559
Matyjaszewski, K., Poli, R., (2005) Macromolecules, 38, pp. 8093-8100
Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED, Versions 1.171.32.5. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., (1993) J. Appl. Crystallogr, 26, pp. 343-350
G. M. Sheldrick, SHELXL-97, A program for crystal structure refinement. University of Göttingen, Germany, release 97-2, 1997
Becke, A.D., (1993) J. Chem. Phys, 98, pp. 5648-5652
Gaussian 03, Revision C.02, G. W. T. M. J. Frisch, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. Montgomery, J. A, T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa. M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challac
Hay, P.J., Wadt, W.R., (1985) J. Chem. Phys, 82, pp. 270-283
