Bis-hydrophilic block terpolymers via RAFT polymerization: Toward dynamic micelles with tunable corona properties

Walther, A., Millard, P. E., Goldmann, A. S., Lovestead, T. M., Schacher, F., Barner-Kowollik, C., & Müller, A. H. E. (2008) Bis-hydrophilic block terpolymers via RAFT polymerization: Toward dynamic micelles with tunable corona properties. Macromolecules, 41(22).

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We present the synthesis of well-defined bis-hydrophilic block terpolymers with two outer hydrophilic blocks and an inner hydrophobic block together with studies concerning their colloidal aggregates formed in water. The investigations aim at preparation of dynamic micelles with tunable corona properties. Highly functionalized polyethylene oxide) macro-chain-transfer agents (PEO-CTAs) of two molecular weights (2 and 5 kDa) are used as mediating agents in reversible addition fragmentation chain transfer (RAFT) polymerization. The synthesis is accomplished by first polymerizing n-butyl acrylate as a hydrophobic block and then chain extending the diblock copolymers further with various (meth)acrylamide derivatives, acrylamide (AAm), N-isopropylacrylamide (NIPAAm), N,N-diethylacrylamide (DEAAm,) and N-(2-hydroxypropyl)methacrylamide (HPMA). Due to the high degree of functionalization of the PEO-CTA, the blocking efficiency is near quantitative and the diblock copolymers can be obtained easily in a wide range of compositions and with an excellent control of the molecular weights and polydispersities (<1.15). Similarly, chain extension with the different (meth)acrylamide proceeds with very high blocking efficiencies to obtain well-defined block terpolymers. The hydrophilic-to-hydrophobic balance as well as the chain lengths of the hydrophilic blocks can be adjusted as desired. The second part of this study describes the aqueous solution characteristics of the micellar aggregates of the block terpolymers. A significant effect of the preparation pathway (direct dissolution or dialysis from a common solvent) on the type of formed aggregates is found, indicating a strong influence of the dissolution kinetics. The self-assembled aggregates are of dynamic character as they can undergo fusion and fission processes, induced by both temperature and time. Large-scale rearrangement of the architectures are possible as ensured by the low glass-transition temperature of the hydrophobic block, poly(n-butyl acrylate). Depending on the hydrophilic-to-hydrophobic balance and the pair of hydrophilic end blocks employed, spherical micelles, worm-like micelles, and vesicles can be found. The corona structure of the micelles can be tuned by changing the length and type of hydrophilic polymers used. © 2008 American Chemical Society.

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ID Code: 99197
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :32 Export Date: 5 September 2016 CODEN: MAMOB Correspondence Address: Müller, A. H. E.; Makromolekulare Chemie II, Bayreuther Zentrum für Kolloide and Grenzflächen, Universität Bayreuth, D-95440 Bayreuth, Germany; email: References: Rao, J., Luo, Z., Ge, Z., Liu, H., Liu, S., (2007) Biomacromolecules, 8, pp. 3871-3878; Wang, D., Wu, T., Wan, X., Wang, X., Liu, S., (2007) Langmuir, 23, pp. 11866-11874; Wang, D., Yin, J., Zhu, Z., Ge, Z., Liu, H., Armes, S.P., Liu, S., (2006) Macromolecules, 39, pp. 7378-7385; Cai, Y., Armes, S.P., (2005) Macromolecules, 38, pp. 271-279; Liu, S., Armes, S.P., (2003) Langmuir, 19, pp. 4432-4438; Weaver, J.V.M., Armes, S.P., Bütün, V., (2002) Chem. Commun, pp. 2122-2123; Liu, S., Armes, S.P., (2002) Angew. Chem., Int. Ed, 41, pp. 1413-1416; Zhang, L., Bernard, J., Davis, T.P., Barner-Kowollik, C., Stenzel, M.H., (2008) Macromol. 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Keywords: Acrylic monomers, Acrylics, Agglomeration, Aggregates, Amides, Chemical reactions, Colloids, Copolymerization, Copolymers, Dialysis, Dissolution, Free radical polymerization, Functional polymers, Glass transition, Hydrophobicity, Living polymerization, Micelles, Molecular weight, Monomers, Polydispersity, Polyethylene glycols, Polyethylene oxides, Polymerization, Polymers, Acrylamide, Aqueous solutions, Block terpolymers, Butyl acrylates, Chain extensions, Colloidal aggregates, Common solvents, Degree of functionalization, Diblock copolymers, Dissolution kinetics, Dynamic characters, Fission processes, Functionalized, Hydrophilic blocks, Hydrophilic polymers, Hydrophobic blocks, Isopropylacryl amides, Mediating agents, Methacrylamide, Micellar aggregates, Raft polymerizations, Reversible Addition Fragmentation Chain transfers, Scale rearrangements, Spherical micelles, Synthesis of, Transfer agents, Transition temperatures, Hydrophilicity
DOI: 10.1021/ma801215q
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: 10 Oct 2016 05:08

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