A detailed investigation of the free radical copolymerization behavior of n -butyl acrylate macromonomers

Zorn, A. M., Junkers, T., & Barner-Kowollik, C. (2011) A detailed investigation of the free radical copolymerization behavior of n -butyl acrylate macromonomers. Macromolecules, 44(17).

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The free radical copolymerization of macromonomers with low molecular weight monomers represents a versatile tool for the formation of statistical copolymers featuring pendant side chains. In the current study n-butyl acrylate macromonomer (BAMM) has been synthesized via high temperature acrylate synthesis in a one-pot-one-step procedure and copolymerized with benzyl acrylate (BzA) as a comonomer up to 40% conversion in a free radical copolymerization with 1,1′-azobis(isobutyronitrile) (AIBN) as a source of radicals. The copolymers poly(BAMM)-co-poly(BzA) are fully characterized via size exclusion chromatography (SEC), nuclear magnetic resonance spectroscopy (NMR), and liquid adsorption chromatography at critical conditions (LACCC). The achievable molecular weight of the synthesized poly(BAMM)-co-poly(BzA) lies between 8000 and 77000 g mol-1 with a polydispersity of 1.30-2.12. Calculated copolymer compositions from the integrals of the specific resonances H ar and CH2 of the BzA compared to CH2 of the BAMM have been subjected to a (terminal model) Mayo-Lewis analysis, resulting in estimated reactivity ratios at ∼40% conversion of rBzA = 2.46 and rBAMM = 1.79, indicating a copolymer composition of F BA < 0.65 for the copolymers derived from fBzA > 0.9 up to a copolymer composition of FBA > 0.9 for copolymers with a comonomer feed of fBzA < 0.6. The poly(BAMM)-co-poly(BzA) have been analyzed under critical conditions of n-butyl acrylate (BA) on a normal phase column to obtain an image of the generated poly(BAMM)-co-poly(BzA). © 2011 American Chemical Society.

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ID Code: 99288
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :8
Export Date: 5 September 2016
Correspondence Address: Junkers, T.; Institute for Materials Research (IMO), Polymer Reaction Design Group, Universiteit Hasselt, Agoralaan, Gebouw D, BE-3590 Diepenbeek, Belgium; email: christopher.barner-kowollik@kit.edu
References: Hadjichristidis, N., Pitsikalis, M., Iatrou, H., Pispas, S., (2003) Macromol. Rapid Commun., 24, pp. 979-1013; Li, D., Grady, M.C., Hutchinson, R.A., (2005) Ind. Eng. Chem. Res., 44, pp. 2506-2517; Li, D., Leiza, J.R., Hutchinson, R.A., (2005) Macromol. Theory Simul., 14, pp. 554-559; McHale, R., Aldabbagh, F., Carroll, W.M., Yamada, B., (2005) Macromol. Chem. Phys., 206, pp. 2054-2066; Quan, C.L., Soroush, M., Grady, M.C., Hansen, J.E., Simonsick, W.J., (2005) Macromolecules, 38, pp. 7619-7628; Yamada, B., Zetterlund, P.B., Sato, E., (2006) Prog. Polym. Sci., 31, pp. 835-877; Matyjaszewski, K., Xia, J.H., (2001) Chem. Rev., 101, pp. 2921-2990; Schön, F., Hartenstein, M., Müller, A.H.E., (2001) Macromolecules, 34, pp. 5394-5397; Topham, P.D., Sandon, N., Read, E.S., Madsen, J., Ryan, A.J., Armes, S.P., (2008) Macromolecules, 41, pp. 9542-9547; Chiefari, J., Jeffery, J., Mayadunne, R.T.A., Moad, G., Rizzardo, E., Thang, S.H., (1999) Macromolecules, 32, pp. 7700-7702; Chiefari, J.; Moad, G.; Rizzardo, E.; Gridnev, A. A. US 98/47927, 1998Willemse, R.X.E., Van Herk, A.M., Panchenko, E., Junkers, T., Buback, M., (2005) Macromolecules, 38, pp. 5098-5103; Nikitin, A.N., Hutchinson, R.A., Buback, M., Hesse, P., (2007) Macromolecules, 40, pp. 8631-8641; Junkers, T., Bennet, F., Koo, S.P.S., Barner-Kowollik, C., (2008) J. Polym. Sci., Part A: Polym. Chem., 46, pp. 3433-3437; Barner-Kowollik, C., Davis, T.P., Stenzel, M.H., (2004) Polymer, 45, pp. 7791-7805; Junkers, T., Barner-Kowollik, C., (2008) J. Polym. Sci., Part A: Polym. Chem., 46, pp. 7585-7605; Koo, S.P.S., Junkers, T., Barner-Kowollik, C., (2009) Macromolecules, 42, pp. 62-69; Junkers, T., Koo, S.P.S., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2007) Macromolecules, 40, pp. 8906-8912; Junkers, T., Barner-Kowollik, C., (2009) Macromol. Theory Simul., 18, pp. 421-433; Zorn, A.-M., Junkers, T., Barner-Kowollik, C., (2009) Macromol. Rapid Commun., 30, pp. 2028-2035; Zorn, A.-M., Malkoch, M., Carlmark, A., Barner-Kowollik, C., (2011) Polym. Chem., 2, pp. 1163-1173; Grady, M.C., Simonsick, W.J., Hutchinson, R.A., (2002) Macromol. Symp., 182, pp. 149-168; Cai, Y.L., Hartenstein, M., Muller, A.H.E., (2004) Macromolecules, 37, pp. 7484-7490; Krivorotova, T., Vareikis, A., Gromadzki, D., Netopilik, M., Makuska, R., (2010) Eur. Polym. J., 46, pp. 546-556; Nguyen, S., Marchessault, R.H., (2005) Macromolecules, 38, pp. 290-296; Norman, J., Moratti, S.C., Slark, A.T., Irvine, D.J., Jackson, A.T., (2002) Macromolecules, 35, pp. 8954-8961; Ohno, S., Matyjaszewski, K., (2006) J. Polym. Sci., Part A: Polym. Chem., 44, pp. 5454-5467; Roos, S.G., Muller, A.H.E., Matyjaszewski, K., (1999) Macromolecules, 32, pp. 8331-8335; Ryan, J., Aldabbagh, F., Zetterlund, P.B., Yamada, B., (2008) React. Funct. Polym., 68, pp. 692-700; Meijs, G.F., Rizzardo, E., (1990) J. Macromol. Sci., Rev. Macromol. Chem. Phys., 30, pp. 305-377; Merz, E., Alfrey, T., Goldfinger, G., (1946) J. Polym. Sci., 1, pp. 75-82; Fukuda, T., Ma, Y.D., Inagaki, H., (1985) Macromolecules, 18, pp. 17-26; Davis, T.P., O'Driscoll, K.F., Piton, M.C., Winnik, M.A., (1991) Polym. Int., 24, pp. 65-70; Coote, M.L., Johnston, L.P.M., Davis, T.P., (1997) Macromolecules, 30, pp. 8191-8204; Coote, M.L., Zammit, M.D., Davis, T.P., Willett, G.D., (1997) Macromolecules, 30, pp. 8182-8190; Gao, H.F., Min, K., Matyjaszewski, K., (2006) Macromol. Chem. Phys., 207, pp. 1709-1717; Falkenhagen, J., Much, H., Stauf, W., Muller, A.H.E., (2000) Macromolecules, 33, pp. 3687-3693; Pasch, H., (1993) Polymer, 34, pp. 4095-4099; Wong, E.H.H., Stenzel, M.H., Junkers, T., Barner-Kowollik, C., (2010) Macromolecules, 43, pp. 3785-3793; Inglis, A.J., Barner-Kowollik, C., (2011) Polym. Chem., 2, pp. 126-136; Schmid, C., Falkenhagen, J., Barner-Kowollik, C., (2011) J. Polym. Sci., Part A: Polym. Chem., 49, pp. 1-10; Roos, S.G., Müller, A.H.E., Matyjaszewski, K., (2000) Controlled/Living Radical Polymerization, 768, pp. 361-371. , American Chemical Society: Washington, DC, Vol; Roos, S.G., Schmitt, B., Müller, A.H.E., (1999) Polym. Prepr., 40, p. 984; Strazielle, C., Benoit, H., Vogl, O., (1978) Eur. Polym. J., 14, pp. 331-334; Penzel, E., Goetz, N., (1990) Angew. Makromol. Chem., 178, pp. 191-200; Gruendling, T., Guilhaus, M., Barner-Kowollik, C., (2008) Anal. Chem., 80, pp. 6915-6927; Lewis, F.M., Walling, C., Cummings, W., Briggs, E.R., Mayo, F.R., (1948) J. Am. Chem. Soc., 70, pp. 1519-1523; Mayo, F.R., Lewis, F.M., (1944) J. Am. Chem. Soc., 66, pp. 1594-1601; Wang, W., Nikitin, A.N., Hutchinson, R.A., (2009) Macromol. Rapid Commun., 30, pp. 2022-2027; Hirano, T., Zetterlund, P.B., Yamada, B., (2003) Polym. J., 35, pp. 491-500; Chiefari, 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; Barner-Kowollik, C., (2008) Handbook of RAFT Polymerization, , Wiley-VCH: Weinheim
Keywords: Benzyl acrylate, Butyl acrylates, Co-monomer, Copolymer compositions, Critical condition, Free radical copolymerization, High temperature, Liquid adsorption chromatography, Low molecular weight, Macro-monomers, Macromonomer, N-butyl acrylate, Normal phase, Reactivity ratio, Side-chains, Statistical copolymers, Terminal model, Versatile tools, Adsorption, Copolymerization, Free radicals, Gel permeation chromatography, Molecular weight, Monomers, Nuclear magnetic resonance spectroscopy, Plastic products, Polydispersity, Resonance, Size exclusion chromatography, Copolymers
DOI: 10.1021/ma201345m
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: 05 Oct 2016 01:33

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