The long and the short of radical polymerization

Derboven, P., D'Hooge, D. R., Reyniers, M. F., Marin, G. B., & Barner-Kowollik, C. (2015) The long and the short of radical polymerization. Macromolecules, 48(3).

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Precision functionality is the key feature of next-generation radical polymerization enabling the implementation of applications such as controlled drug delivery, self-healing material design, and optoelectronic materials. The incorporation of functionality is however diametrically opposed to diffusion-controlled growth-inhibiting termination reactions. The fundamental bottleneck remains the identification of a generic and flexible protocol to accurately map the short-long termination reactivity. Herein, we introduce a unique framework based on the reversible addition-fragmentation chain transfer-chain length dependent-termination (RAFT-CLD-T) method that encompasses an extension of state-of-the-art fundamental theories and a correction for possible polymer matrix effects. Applied to methyl methacrylate (MMA) polymerization, the short-long termination reactivity is accurately quantified for the first time. Data analysis reveals the deficiency of currently used simplified models to describe the true short-long termination reactivity and the dominance of short-chain diffusivity. The proposed framework and insights are a turnkey prerequisite for the fundamental understanding of radical polymerization processes and to complete current macromolecular diffusion theories. © 2015 American Chemical Society.

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19 citations in Scopus
20 citations in Web of Science®
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ID Code: 99427
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :12
Export Date: 5 September 2016
Correspondence Address: D'Hooge, D.R.; Laboratory for Chemical Technology, Ghent University, Technologiepark 914, Belgium
References: Bajpai, A.K., Shukla, S.K., Bhanu, S., Kankane, S., (2008) Prog. Polym. Sci., 33, pp. 1088-1118; Fick, A., (1855) Poggendorff's Ann. Phys. Chem., 94, pp. 59-86; Einstein, A., (1905) Ann. Phys., 322, pp. 549-560; Von Smoluchowski, M., (1906) Ann. Phys., 326, pp. 756-780; Hawker, C.J., Wooley, K.L., (2005) Science, 309, pp. 1200-1205; Barner-Kowollik, C., Russell, G.T., (2009) Prog. Polym. Sci., 34, pp. 1211-1259; Barner-Kowollik, C., (2008) Handbook of RAFT Polymerization, , Wiley-VCH: Weinheim; Braunecker, W.A., Matyjaszewski, K., (2007) Prog. Polym. Sci., 32, pp. 93-146; 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; Hawker, C.J., Bosman, A.W., Harth, E., (2001) Chem. Rev., 101, pp. 3661-3688; Kruse, T.M., Souleimonova, R., Cho, A., Gray, M.K., Torkelson, J.M., Broadbelt, L.J., (2003) Macromolecules, 36, pp. 7812-7823; Matyjaszewski, K., (2009) Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP, , American Chemical Society: Washington, DC; Matyjaszewski, K., Tsarevsky, N.V., (2014) J. Am. Chem. Soc., 136, pp. 6513-6533; Patten, T.E., Xia, J.H., Abernathy, T., Matyjaszewski, K., (1996) Science, 272, pp. 866-868; Barner-Kowollik, C., Du Prez, F.E., Espeel, P., Hawker, C.J., Junkers, T., Schlaad, H., Van Camp, W., (2011) Angew. Chem., Int. Ed., 50, pp. 60-62; Gregory, A., Stenzel, M.H., (2012) Prog. Polym. Sci., 37, pp. 38-105; Kolb, H.C., Finn, M.G., Sharpless, K.B., (2001) Angew. Chem., Int. Ed., 40, p. 2004; Hansell, C.F., Espeel, P., Stamenovic, M.M., Barker, I.A., Dove, A.P., Du Prez, F.E., O'Reilly, R.K., (2011) J. Am. Chem. Soc., 133, pp. 13828-13831; Gody, G., Maschmeyer, T., Zetterlund, P.B., Perrier, S., (2013) Nat. Commun., 4, p. 2505; Lutz, J.F., Ouchi, M., Liu, D.R., Sawamoto, M., (2013) Science, 341, p. 628; Pfeifer, S., Zarafshani, Z., Badi, N., Lutz, J.-F., (2009) J. Am. Chem. Soc., 131, pp. 9195-9197; Soeriyadi, A.H., Boyer, C., Nyström, F., Zetterlund, P.B., Whittaker, M.R., (2011) J. Am. Chem. Soc., 133, pp. 11128-11131; Buback, M., Hippler, H., Schweer, J., Vogele, H.P., (1986) Macromol. Rapid Commun., 7, pp. 261-265; Buback, M., Kowollik, C., (1998) Macromolecules, 31, pp. 3211-3215; Beuermann, S., Buback, M., (2002) Prog. Polym. Sci., 27, pp. 191-254; Buback, M., Egorov, M., Junkers, T., Panchenko, E., (2004) Macromol. Rapid Commun., 25, pp. 1004-1009; Barth, J., Buback, M., Barner-Kowollik, C., Junkers, T., Russell, G.T., (2012) J. Polym. Sci., Part A: Polym. Chem., 50, pp. 4740-4748; Barth, J., Buback, M., Russell, G.T., Smolne, S., (2011) Macromol. Chem. Phys., 212, pp. 1366-1378; Buback, M., Junkers, T., Vana, P., (2005) Macromol. Rapid Commun., 26, pp. 796-802; Johnston-Hall, G., Stenzel, M.H., Davis, T.P., Barner-Kowollik, C., Monteiro, M.J., (2007) Macromolecules, 40, pp. 2730-2736; Johnston-Hall, G., Theis, A., Monteiro, M.J., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2005) Macromol. Chem. Phys., 206, pp. 2047-2053; Vana, P., Davis, T.P., Barner-Kowollik, C., (2002) Macromol. Rapid Commun., 23, pp. 952-956; Junkers, T., Theis, A., Buback, M., Davis, T.P., Stenzel, M.H., Vana, P., Barner-Kowollik, C., (2005) Macromolecules, 38, pp. 9497-9508; Theis, A., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2005) Macromolecules, 38, pp. 10323-10327; Theis, A., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2006) Polymer, 47, pp. 999-1010; Theis, A., Feldermann, A., Charton, N., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2005) Polymer, 46, pp. 6797-6809; Theis, A., Feldermann, A., Charton, N., Stenzel, M.H., Davis, T.P., Barner-Kowollik, C., (2005) Macromolecules, 38, pp. 2595-2605; Feldermann, A., Stenzel, M.H., Davis, T.P., Vana, P., Barner-Kowollik, C., (2004) Macromolecules, 37, pp. 2404-2410; Lovestead, T.M., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2007) Macromol. Symp., 248, pp. 82-93; Lovestead, T.M., Theis, A., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2006) Macromolecules, 39, pp. 4975-4982; Vana, P., Davis, T.P., Barner-Kowollik, C., (2002) Macromol. Theory Simul., 11, pp. 823-835; Mills, I., Cvitas, T., Homann, K., Kallay, N., Kuchitsu, K., (1988) Quantities, Units and Symbols in Physical Chemistry, , Blackwell Scientific Publications: Oxford; Johnston-Hall, G., Monteiro, M.J., (2008) J. Polym. Sci., Part A: Polym. Chem., 46, pp. 3155-3173; Buback, M., Egorov, M., Gilbert, R.G., Kaminsky, V., Olaj, O.F., Russell, G.T., Vana, P., Zifferer, G., (2002) Macromol. Chem. Phys., 203, pp. 2570-2582; Russell, G.T., Napper, D.H., Gilbert, R.G., (1988) Macromolecules, 21, pp. 2141-2148; Faldi, A., Tirrell, M., Lodge, T.P., Vonmeerwall, E., (1994) Macromolecules, 27, pp. 4184-4192; Zetterlund, P.B., Yamazoe, H., Yamada, B., (2002) Polymer, 43, pp. 7027-7035; Achilias, D.S., (2007) Macromol. Theory Simul, 16, pp. 319-347; D'Hooge, D.R., Reyniers, M.F., Marin, G.B., (2013) Macromol. React. Eng., 7, pp. 362-379; Faldi, A., Tirrell, M., Lodge, T.P., (1994) Macromolecules, 27, pp. 4176-4183; O'Neil, G.A., Torkelson, J.M., (1999) Macromolecules, 32, pp. 411-422
Keywords: Atom transfer radical polymerization, Chain length, Chains, Controlled drug delivery, Drug delivery, Esters, Free radical polymerization, Optoelectronic devices, Polymerization, Self-healing materials, Transfer matrix method, Chain length dependent terminations, Diffusion controlled growth, Fundamental theory, Methyl methacrylates, Opto-electronic materials, Polymerization process, Reversible addition fragmentation chain transfer, Termination reactions, Acrylic monomers
DOI: 10.1021/ma5017659
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: 26 Sep 2016 05:26

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