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Colloid and Polymer Science

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01-04-2013 | Original Contribution

Self-assembly behavior of fluorocarbon-end-capped poly(glycerol methacrylate) in aqueous solution

Authors: Zheng Li, Elkin Amado, Jörg Kressler

Published in: Colloid and Polymer Science | Issue 4/2013

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Abstract

Well-defined perfluoroalkyl-terminated poly(glycerol methacrylate) (R _F-PGMA) semitelechelics are prepared by atom transfer radical polymerization and copper(I)-catalyzed alkyne–azide cycloaddition reaction. R _F-PGMA has a similar architecture as the well-studied perfluorinated poly(ethylene oxide) (R _F-PEO) semitelechelics but bears two hydroxyl groups on each glycerol methacrylate unit. Because of the strong hydrophobic interaction of the perfluoroalkyl group, R _F-PGMA semitelechelics self-associate to form core–corona spherical micelles in water above the critical micellization concentration (cmc) which depends on poly(glycerol methacrylate) (PGMA) content and temperature. For comparison, the R _F-PEO semitelechelics with the same perfluoroalkyl terminal group as R _F-PGMA are also prepared. The cmc values of R _F-PGMA semitelechelics are found to increase with increasing temperature in water, which is opposite to the tendency of R _F-PEO semitelechelics. According to the thermodynamic studies, the micellization process of R _F-PGMA in aqueous solution is driven by both a negative enthalpy and an increase of entropy, whereas the micellization of R _F-PEO is an entropy-driven process exhibiting a positive micellization enthalpy. This striking different behavior originates from intra-/intermolecular hydrogen bonds between the hydroxyl groups of the PGMA chains. These strong inter- and intramolecular hydrogen bonds between PGMA segments lead to a self-aggregation of R _F-PGMA evident in temperature-dependent ¹H and ¹⁹F NMR spectroscopy and dynamic light scattering measurements.

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Title: Self-assembly behavior of fluorocarbon-end-capped poly(glycerol methacrylate) in aqueous solution
Authors: Zheng Li
Elkin Amado
Jörg Kressler
Publication date: 01-04-2013
Publisher: Springer-Verlag
Published in: Colloid and Polymer Science / Issue 4/2013
Print ISSN: 0303-402X
Electronic ISSN: 1435-1536
DOI: https://doi.org/10.1007/s00396-012-2803-y

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