Global trends for kp? Expanding the frontier of ester side chain topography in acrylates and methacrylates

Haehnel, A. P., Schneider-Baumann, M., Hiltebrandt, K. U., Misske, A. M., & Barner-Kowollik, C. (2013) Global trends for kp? Expanding the frontier of ester side chain topography in acrylates and methacrylates. Macromolecules, 46(1).

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Abstract

The Arrhenius parameters of the propagation rate coefficient for two linear methacrylates, two branched methacrylates, and two branched acrylates are determined via the pulsed laser polymerization-size exclusion chromatography (PLP-SEC) method. The Mark-Houwink-Kuhn-Sakurada parameters of these polymers are additionally determined via multidetector SEC of narrowly distributed polymer samples obtained through fractionation, allowing for a correct SEC calibration in the PLP-SEC experiment. The data obtained for stearyl methacrylate (SMA, A = 3.45 (-1.17 to +4.46) × 106 L·mol-1·s-1; Ea = 21.49 (-1.59 to +1.90) kJ·mol-1) and behenyl methacrylate (BeMA, A = 2.51 (-0.80 to +3.06) × 106 L·mol-1·s -1; Ea = 20.52 (-1.43 to +1.85) kJ·mol -1) underpin the trend of increasing kp with increasing ester side chain length. Propylheptyl methacrylate (PHMA, A = 2.83 (-0.82 to 3.15) × 106 L·mol-1·s-1; Ea = 21.72 (-1.20 to +1.64) kJ·mol-1) and heptadecanyl methacrylate (C17MA, A = 2.04 (-0.66 to +1.71) × 10 6 L·mol-1·s-1; Ea = 20.72 (-1.42 to +1.38) kJ·mol-1) can be described as a family of branched methacrylates jointly with isodecyl methacrylate and ethylhexyl methacrylate (both published previously), resulting in joint Arrhenius parameters of A = 2.39 (-0.51 to +0.84) × 106 L·mol -1·s-1 and Ea = 21.16 (-0.78 to +0.76) kJ·mol-1. In addition, the corresponding branched acrylates are studied applying high-frequency PLP at a 500 Hz laser repetition rate, resulting in Arrhenius parameters of A = 1.05 (-0.42 to +2.81) × 10 7 L·mol-1·s-1 and Ea = 16.41 (-1.99 to +2.42) kJ·mol-1 for propylheptyl acrylate (PHA) and A = 8.15 (-2.83 to +10.3) × 106 L·mol -1·s-1 and Ea = 14.66 (-1.49 to +1.66) kJ·mol-1 for heptadecanyl acrylate (C17A). © 2012 American Chemical Society.

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ID Code: 99350
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :14
Export Date: 5 September 2016
CODEN: MAMOB
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: Kornherr, A., Olaj, O.F., Schnöll-Bitai, I., Zifferer, G., (2003) Macromol. Theory Simul., 12, pp. 332-338; Olaj, O.F., Bitai, I., Hinkelmann, F., (1987) Makromol. Chem., 188, pp. 1689-1702; Schnöll-Bitai, I., Olaj, O.F., (1990) Makromol. Chem., 191, pp. 2491-2499; Aleksandrov, A.P., Vladimir, N.G., Kitaiì, M.S., Smirnova, I.M., Sokolov, V.V., (1977) Sov. J. Quantum Electron., 7, p. 547; Beuermann, S., Buback, M., (2002) Prog. Polym. Sci., 27, pp. 191-254; Van Herk, A.M., (2009) Macromol. Rapid Commun., 30, pp. 1964-1968; 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; Beuermann, S., Buback, M., El Rezzi, V., Jürgens, M., Nelke, D., (2004) Macromol. Chem. Phys., 205, pp. 876-883; Buback, M., (2009) Macromol. Symp., 275-276, pp. 90-101; Dervaux, B., Junkers, T., Schneider-Baumann, M., Du Prez, F.E., Barner-Kowollik, C., (2009) J. Polym. Sci., Part A: Polym. Chem., 47, pp. 6641-6654; Beuermann, S., Buback, M., Davis, T.P., García, N., Gilbert, R.G., Hutchinson, R.A., Kajiwara, A., Russell, G.T., (2003) Macromol. Chem. Phys., 204, pp. 1338-1350; Beuermann, S., Buback, M., Davis, T.P., Gilbert, R.G., Hutchinson, R.A., Kajiwara, A., Klumperman, B., Russell, G.T., (2000) Macromol. Chem. Phys., 201, pp. 1355-1364; 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., Gilbert, R.G., Hutchinson, R.A., Klumperman, B., Kuchta, F.-D., Manders, B.G., O'Driscoll, K.F., Schweer, J., (1995) Macromol. Chem. Phys., 196, pp. 3267-3280; Beuermann, S., (2003) Pure Appl. Chem., 75, pp. 1091-1096; Nikitin, A.N., Hutchinson, R.A., Buback, M., Hesse, P., (2007) Macromolecules, 40, pp. 8631-8641; Haehnel, A.P., Fleischmann, S., Hesse, P., Hungenberg, K.-D., Barner-Kowollik, C., (2013) Macromol. React. Eng., , 10.1002/mren.201200030; Zhong, M., Matyjaszewski, K., (2011) Macromolecules, 44, pp. 2668-2677; Coote, M.L., Barner-Kowollik, C., (2006) Aust. J. Chem., 59, pp. 712-718; Hlalele, L., Klumperman, B., (2011) Macromolecules, 44, pp. 6683-6690; Hutchinson, R.A., Beuermann, S., Paquet, D.A., McMinn, J.H., (1997) Macromolecules, 30, pp. 3490-3493; Zammit, M.D., Coote, M.L., Davis, T.P., Willett, G.D., (1998) Macromolecules, 31, pp. 955-963; Junkers, T., Schneider-Baumann, M., Koo, S.S.P., Castignolles, P., Barner-Kowollik, C., (2010) Macromolecules, 43, pp. 10427-10434; Willemse, R.X.E., Van Herk, A.M., (2010) Macromol. Chem. Phys., 211, pp. 539-545; Barner-Kowollik, C., Bennet, F., Schneider-Baumann, M., Voll, D., Rölle, T., Facke, T., Weiser, M.-S., Junkers, T., (2010) Polym. Chem., 1, pp. 470-479; Roberts, G.E., Davis, T.P., Heuts, J.P.A., Ball, G.E., (2002) Macromolecules, 35, pp. 9954-9963; Pascal, P., Winnik, M.A., Napper, D.H., Gilbert, R.G., (1993) Makromol. Chem., Rapid Commun., 14, pp. 213-215; Coote, M.L., Davis, T.P., (1999) J. Polym. Sci., Part B: Polym. Phys., 37, pp. 2557-2570; Gaborieau, M., Nicolas, J., Save, M., Charleux, B., Vairon, J.-P., Gilbert, R.G., Castignolles, P., (2008) J. Chromatogr., A, 1190, pp. 215-223; Penzel, E., Goetz, N., (1990) Angew. Makromol. Chem., 178, pp. 191-200; Xu, Z., Song, M., Hadjichristidis, N., Fetters, L.J., (1981) Macromolecules, 14, pp. 1591-1594; Stickler, M., Panke, D., Wunderlich, W., (1987) Makromol. Chem., 188, pp. 2651-2664; Junkers, T., Barner-Kowollik, C., (2008) J. Polym. Sci., Part A: Polym. Chem., 46, pp. 7585-7605; Ahmad, N.M., Charleux, B., Farcet, C., Ferguson, C.J., Gaynor, S.G., Hawkett, B.S., Heatley, F., Venkatesh, R., (2009) Macromol. Rapid Commun., 30, pp. 2002-2021; Barner-Kowollik, C., Günzler, F., Junkers, T., (2008) Macromolecules, 41, pp. 8971-8973; Obenaus, F., Droste, W., Neumeister, J., (2000) Ullmann's Encyclopedia of Industrial Chemistry, 6, pp. 445-454. , Butenes In; Wiley-VCH Verlag GmbH & Co. KGaA: Berlin, Vol; Rudolph, J., Ulonska, A., Papp, R., Paciello, R., Breitscheidel, B., Faller, K., (2009) BASF SE, , WO/2009/124979; Brandrup, J., Immergut, E.H., Grulke, E.A., Abe, A., Bloch, D.R., (1999) Polymer Handbook, , 4 th ed. John Wiley & Sons: New York; Castignolles, P., (2009) Macromol. Rapid Commun., 30, pp. 1995-2001; Xu, Z., Hadjichristidis, N., Fetters, L.J., (1984) Macromolecules, 17, pp. 2303-2306; García, N., Tiemblo, P., Guzmán, J., (2007) Macromolecules, 40, pp. 4802-4808; Nikitin, A.N., Castignolles, P., Charleux, B., Vairon, J.-P., (2003) Macromol. Rapid Commun., 24, pp. 778-782; Sato, E., Emoto, T., Zetterlund, P.B., Yamada, B., (2004) Macromol. Chem. Phys., 205, pp. 1829-1839; Bennet, F., Rölle, T., Fäcke, T., Weiser, M.-S., Bruder, F.-K., Barner-Kowollik, C., Junkers, T., (2013) Macromol. Chem. Phys., , 10.1002/macp.201200285; Vandenbergh, J., Junkers, T., (2012) Macromolecules, 45, pp. 6850-6856; (2012), https://www.coherent.com/, Coherent home page, supplier for LASER systems, viewed 26.10.2012Heuts, J.P.A., Russell, G.T., (2006) Eur. Polym. J., 42, pp. 3-20; Van Herk, A.M., Dröge, T., (1997) Macromol. Theory Simul., 6, pp. 1263-1276; Van Herk, A.M., Van Den Brand, H., Berg, I., (2012) Contour V2.0.2; Beuermann, S., Buback, M., Hesse, P., Lacík, I., (2005) Macromolecules, 39, pp. 184-193; Lin, C.Y., Izgorodina, E.I., Coote, M.L., (2009) Macromolecules, 43, pp. 553-560; Isa, D., Benjamin, B.N., Ching Yeh, L., Michelle, L.C., The mechanism of stereoregulation in free-radical polymerization of bulky methacrylates (2012) Progress in Controlled Radical Polymerization: Mechanisms and Techniques, 1100, pp. 15-32. , In; American Chemical Society: Washington, DC, Vol
Keywords: Arrhenius parameters, Exclusion chromatography, Global trends, High frequency HF, Laser repetition rate, Multi-detectors, Polymer samples, Propagation rate coefficient, Side chain lengths, Side-chains, Stearyl methacrylate, Esterification, Esters, Lasers, Polymers, Salts
DOI: 10.1021/ma302319z
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: 29 Sep 2016 22:48

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