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Synthesis and self-assembly of amphiphilic semi-brush and dual brush block copolymers in solution and on surfaces

  • The combination of two techniques of controlled free radical polymerization, namely the reversible addition fragmentation chain transfer (RAFT) and the atom transfer radical polymerization (ATRP) techniques, together with the use of a macromonomer allowed the synthesis of symmetrical triblock copolymers, designed as amphiphilic dual brushes. One type of brush was made of poly(n-butyl acrylate) as soft hydrophobic block, i.e. characterized by a low glass transition temperature, while the other one was made of hydrophilic poly(ethylene glycol) (PEG). The new triblock polymers represent "giant surfactants" according to their molecular architecture. The hydrophobic and hydrophilic blocks microphase separate in the bulk. In aqueous solution, they aggregate into globular micellar aggregates, their size being determined by the length of the stretched polymer molecules. As determined by the combination of various scattering techniques for the dual brush copolymer, a rather compact structure is formed, which is dominated by the largeThe combination of two techniques of controlled free radical polymerization, namely the reversible addition fragmentation chain transfer (RAFT) and the atom transfer radical polymerization (ATRP) techniques, together with the use of a macromonomer allowed the synthesis of symmetrical triblock copolymers, designed as amphiphilic dual brushes. One type of brush was made of poly(n-butyl acrylate) as soft hydrophobic block, i.e. characterized by a low glass transition temperature, while the other one was made of hydrophilic poly(ethylene glycol) (PEG). The new triblock polymers represent "giant surfactants" according to their molecular architecture. The hydrophobic and hydrophilic blocks microphase separate in the bulk. In aqueous solution, they aggregate into globular micellar aggregates, their size being determined by the length of the stretched polymer molecules. As determined by the combination of various scattering techniques for the dual brush copolymer, a rather compact structure is formed, which is dominated by the large hydrophobic poly(n-butyl acrylate) block. The aggregation number for the dual brush is about 10 times larger than for the "semi-brush" precursor copolymer, due to the packing requirements for the much bulkier hydrophobic core. On mica surfaces the triblock copolymers adsorb with worm-like backbones and stretched out side chains.show moreshow less

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Metadaten
Author:Daniel Zehm, André LaschewskyORCiDGND, Peggy Heunemann, Michael Gradzielski, Sylvain Prevost, Hua Liang, Jürgen P. Rabe, Jean-Francois Lutz
DOI:https://doi.org/10.1039/c0py00200c
ISSN:1759-9954 (print)
Parent Title (English):Polymer Chemistry
Publisher:Royal Society of Chemistry
Place of publication:Cambridge
Document Type:Article
Language:English
Year of first Publication:2011
Year of Completion:2011
Release Date:2017/03/26
Volume:2
Issue:1
Pagenumber:11
First Page:137
Last Page:147
Funder:Deutsche Forschungsgemeinschaft DFG [Sfb 448]; Fonds der Chemischen Industrie
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer Review:Referiert