Limitations of cyclodextrin-mediated RAFT homopolymerization and block copolymer formation

Hetzer, M., Schmidt, B. V. K. J., Barner-Kowollik, C., & Ritter, H. (2013) Limitations of cyclodextrin-mediated RAFT homopolymerization and block copolymer formation. Journal of Polymer Science, Part A: Polymer Chemistry, 51(11).

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The design and synthesis of a new hydrophobic monomer, that is, 4-(tert-butyl)phenyl 6-acrylamidohexanoate (TBP-AA-HO) and its ability to form supramolecular host/guest complexes with β-cyclodextrin (CD) is described. The aqueous CD-mediated reversible addition fragmentation chain transfer (RAFT) polymerization affords molecular masses up to 8600 g mol-1 with polydispersities between 1.2 and 1.4. The surprisingly low molecular weights for higher monomer/chain transfer agent (CTA) ratios are investigated by comparing results obtained from free radical and RAFT radical polymerization in aqueous and organic media. The results indicate a steric hindrance caused by attached CD molecules on the growing polymer chain leading to stagnation of the polymerization process due to a restricted accessibility of the reactive chain end. This hypothesis is supported by matrix-assisted laser desorption/ionization time of flight mass spectrometry. Furthermore, the CD-mediated synthesis of amphiphilic diblock copolymers in variable aqueous media is described. Hydrophilic poly(N,N-dimethylacrylamide) macro-CTAs with different molecular weights are used to polymerize TBP-AA-HO at 50 °C. The diblock copolymers are analyzed by 1H-nuclear magnetic resonance spectroscopy and size exclusion chromatography. The results confirm the polymer structure and reveal similar limitations of chain growth as observed for the CD-mediated homopolymerization with a limit of 7000 g mol-1 for efficient chain extension. © 2013 Wiley Periodicals, Inc.

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ID Code: 99353
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :5 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), Engesserstraße 18, 76128 Karlsruhe, Germany; email: References: 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; Grubbs, R.B., (2011) Polym. Rev., 51, pp. 104-137; Ouchi, M., Terashima, T., Sawamoto, M., (2009) Chem. Rev., 109, pp. 4963-5050; Matyjaszewski, K., Xia, J.H., (2001) Chem. Rev., 101, pp. 2921-2990; Barner-Kowollik, C., Perrier, S., (2008) J. Polym. Sci. Part A: Polym. 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Keywords: amphiphiles, aqueous solution, block copolymers, cyclodextrin, reversible addition fragmentation chain transfer (RAFT), Amphiphilic diblock copolymers, Hydrophobic monomers, Matrix-assisted laser desorption/ionization time of flights, Poly(N ,N-dimethylacrylamide), Polymerization process, RAFT radical polymerization, Reversible addition fragmentation chain transfer, Reversible addition-fragmentation chain transfer polymerization, Cyclodextrins, Free radical polymerization, Free radicals, Homopolymerization, Mass spectrometry, Molecular weight, Nuclear magnetic resonance spectroscopy, Polymers, Solutions
DOI: 10.1002/pola.26644
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: 29 Sep 2016 23:40

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