A Detailed investigation of the experimental conditions for the reversible addition fragmentation chain transfer-mediated copolymerization of acrylonitrile and butadiene

Dürr, C. J., Emmerling, S. G. J., Kaiser, A., Brandau, S., Habicht, A. K. T., Klimpel, M., & Barner-Kowollik, C. (2012) A Detailed investigation of the experimental conditions for the reversible addition fragmentation chain transfer-mediated copolymerization of acrylonitrile and butadiene. Journal of Polymer Science, Part A: Polymer Chemistry, 50(1).

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The synthesis of acrylonitrile-butadiene rubbers (NBRs) via trithiocarbonate-mediated reversible addition fragmentation chain transfer (RAFT) polymerization of acrylonitrile (ACN) and 1,3-butadiene (BD) in solution under azeotropic conditions (38/62) was investigated for a broad range of common solvents: N,N-dimethylacetamide (DMAc), chlorobenzene, 1,4-dioxane, tert-butanol, isobutyronitrile, toluene, trimethylacetonitrile, dimethyl carbonate, acetonitrile, methyl acetate, acetone, and tert-butyl methyl ether. The gravimetrically determined conversions for the free radical polymerizations of ACN/BD after 22 h at 100 °C were in the range of 15% for methyl acetate to 35% for DMAc. The origin of the differences in conversion is attributed to the unequal decomposition behavior of the employed azo initiator 2,2′-azobis(N-butyl-2-methylpropionamide) (1) in the solvents under investigation, as determined by ultraviolet-visible (UV-vis) spectroscopy. Relative decomposition of 1 in solution (0.1 mol L-1) at 100 °C was calculated from the UV-vis spectra for selected solvents. 90% of 1 in DMAc was decomposed after 22 h, 83% in tert-butanol, 57% in 1,4-dioxane, 53% in isobutyronitrile, 45% in chlorobenzene, and 21% in toluene. The evolution of molecular weight with conversion using the initiator 1 was in accordance with the theoretically expected values, regardless of the solvent studied. Moreover, the RAFT-mediated copolymerization of ACN/BD in DMAc with azo initiators 1, 1-[(1-cyano-1-methylethyl)azo]formamide (2) and 1,1′- azobis(cyclohexanecarbonitrile) (3) was investigated. A strong deviation from the linear evolution of molecular weight due to a fast decomposition of these initiators - congruent with high primary radical delivery rates - at the selected temperature was observed when using 2 and 3. The deviation was not observed when using 1. © 2011 Wiley Periodicals, Inc.

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ID Code: 99306
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :12 Export Date: 5 September 2016 CODEN: JPACE Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany; email: christopher.barner-kowollik@kit.edu References: (2009), International Institute of Synthetic Rubber ProducersChiefari, J., Chong, Y.K., Ercole, F., Krstina, J., Jeffery, J., Le, T.P.T., Mayadunne, R.T.A., Thang, S.H., (1998) Macromolecules, 31, pp. 5559-5562; Moad, G., Barner-Kowollik, C., (2008) Handbook of RAFT Polymerization, p. 51. , In; Barner-Kowollik, C. Ed.; Wiley-VCH: Weinheim, p ff; Moad, G., Rizzardo, E., Thang, S.H., (2005) Aust. J. Chem., 58, pp. 379-410; Moad, G., Rizzardo, E., Thang, S.H., (2006) Aust. J. Chem., 59, pp. 669-692; Moad, G., Rizzardo, E., Thang, S.H., (2009) Aust. J. Chem., 62, pp. 1402-1472; 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; Moad, G., Rizzardo, E., Thang, S.H., (2008) Polymer, 49, pp. 1079-1131; Ahmad, N.M., Charleux, B., Farcet, C., Ferguson, C.J., Gaynor, S.G., Hawkett, B.S., Heatley, F., Venkatesh, R.M., (2009) Rapid Commun., 30, pp. 2002-2021; Kaiser, A., Brandau, S., Klimpel, M., Barner-Kowollik, C., (2010) Macromol. Rapid Commun., 31, pp. 1616-1621; Hollbeck, C., Bandermann, F., Gunther, C., (1996) Angew. Makromol. Chem., 242, pp. 47-64; Bardeck, S., (1996) University of Essen, , Kinetik der Nitril-Butadien-Kautschuk-Synthese in Lösung; In Kinetik der Nitril-Butadien-Kautschuk-Synthese in Lösung; Cherubin, T., (1999) Ãber Die Bestimmung von Copolymerisationsparametern in der Radikalischen Copolymerisation von Acrylnitril Mit Butadien, , In; University of Essen; Coote, M.L., Davis, T.P., (2000) Eur. Polym. J., 36, pp. 2423-2427; Coote, M.L., Davis, T.P., Klumperman, B., Monteiro, M.J., (1998) J. Macromol. Sci. Polym. Rev., 38, pp. 567-593; Beuermann, S., (2009) Macromol. Rapid Commun., 30, pp. 1066-1088; Beuermann, S., Garcia, N., (2004) Macromolecules, 37, pp. 3018-3025; Zhang, X., Giani, O., Monge, S., Robin, J.-J., (2010) Polymer, 51, pp. 2947-2953; Liu, Z., Hu, J., Sun, J., He, G., Li, Y., Zhang, G., (2010) J. Polym. Sci. Part A Polym. Chem., 48, pp. 3573-3586; París, R., De La Fuente, J.L., (2005) J. Polym. Sci. Part A: Polym. Chem., 43, pp. 6247-6261; Benaglia, M., Rizzardo, E., Alberti, A., Guerra, M., (2005) Macromolecules, 38, pp. 3129-3140; Lin, C.Y., Coote, M.L., (2009) Aust. J. Chem., 62, pp. 1479-1483; Chastrette, M., Rajzmann, M., Chanon, M., (1985) J. Am. Chem. Soc., 107, pp. 1-11; Gu, C.H., Li, H., Gandhi, R.B., Raghavan, K., (2004) Int. J. Pharm., 283, pp. 117-125; Lewis, F.M., Matheson, M.S., (1949) J. Am. Chem. Soc., 71, pp. 747-748; Roy, J.C., Nash, J.R., Williams, R.R., Hamill, W.H., (1956) J. Am. Chem. Soc., 78, pp. 519-521; Hammond, G.S., Sen, J.N., Boozer, C.E., (1955) J. Am. Chem. Soc., 77, pp. 3244-3248; Barner-Kowollik, C., Quinn, J.F., Nguyen, T.L.U., Heuts, J.P.A., Davis, T.P., (2001) Macromolecules, 34, pp. 7849-7857; Jain, M., Vora, R.A., Satpathy, U.S., (2003) Eur. Polym. J., 39, pp. 2069-2076; Strazielle, C., Benoit, H., Vogl, O., (1978) Eur. Polym. J., 14, pp. 331-334
Keywords: acrylonitrile butadiene copolymerization, acrylonitrile-butadiene rubber (NBR), controlled/living radical polymerization, high temperature initiators, initiator decay, initiators, reversible addition fragmentation chain transfer (RAFT), rubber, solvent study, 1 ,3-butadiene, 1 ,4-Dioxane, Acrylonitrile-butadiene rubber, Azoinitiator, Common solvents, Decomposition behaviors, Dimethyl carbonate, Expected values, Experimental conditions, Fast decomposition, Formamides, High temperature, Methyl acetates, N ,N-Dimethylacetamide, Primary radicals, Reversible addition fragmentation, Reversible addition fragmentation chain transfer, Reversible addition-fragmentation chain transfer polymerization, Tert butanol, Tert-butyl methyl ethers, UV-vis spectra, Acetone, Acetonitrile, Alcohols, Amides, Butadiene, Copolymerization, Copolymers, Ethers, Free radicals, Initiators (explosives), Molecular weight, Organic solvents, Polymers, Solvents, Toluene, Volatile fatty acids, Free radical polymerization
DOI: 10.1002/pola.25033
ISSN: 0887624X
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: 04 Oct 2016 04:19

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