Amphiphilic block copolymers featuring a reversible hetero Diels-Alder linkage

Langer, M., Brandt, J., Lederer, A., Goldmann, A. S., Schacher, F. H., & Barner-Kowollik, C. (2014) Amphiphilic block copolymers featuring a reversible hetero Diels-Alder linkage. Polymer Chemistry, 5(18).

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The present article reports the preparation of a novel class of switchable amphiphilic diblock copolymers with a temperature switchable linkage. Reversible addition fragmentation chain transfer (RAFT) polymerization was used to synthesize the individual blocks: for the preparation of the non-polar block, i.e. poly(isoprene-co-styrene) (P(I-co-S)) (9200 g mol-1 ≤ M n ≤ 50000 g mol-1, 1.22 ≤ ≤ 1.36), a chain transfer agent (CTA, 3-((2-bromo-2-methylpropanoyl)oxy)propyl 2-(((dodecylthio)carbonothioyl)thio)-2-methylpropanoate) carrying a bromine group was employed, ready for subsequent cyclopentadienyl (Cp) transformation. For the preparation of the polar block, triethylene glycol methyl ether acrylate (TEGA) was polymerized (6600 g mol-1 ≤ Mn ≤ 35000 g mol-1, 1.12 ≤ ≤ 1.30) using a RAFT agent carrying a phosphoryl Z-group, which is able to undergo hetero Diels-Alder (HDA) ligation with Cp moieties. Both building blocks were conjugated at ambient temperature in the presence of ZnCl2 as catalyst yielding the amphiphilic block copolymer P(I-co-S)-b-PTEGA (16000 g mol-1 ≤ Mn ≤ 68000 g mol-1, 1.15 ≤ ≤ 1.32). To investigate the bonding/debonding capability of the HDA linkage, high temperature nuclear magnetic resonance (HT-NMR) spectroscopy, high temperature dynamic light scattering (HT-DLS) and high temperature size exclusion chromatography (HT-SEC) were carried out, evidencing that efficiently switchable amphiphilic block copolymers were generated (>4 cycles). © 2014 the Partner Organisations.

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ID Code: 99392
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :9
Export Date: 5 September 2016
Correspondence Address: Schacher, F.H.; Institut für Organische Chemie und Makromolekulare Chemie, Jena Center for Soft Matter, Friedrich Schiller Universität Jena, 07743 Jena, Germany; email:
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Keywords: Dynamic light scattering, Free radical polymerization, Nuclear magnetic resonance spectroscopy, Styrene, Amphiphilic block copolymers, Amphiphilic diblock copolymers, Chain transfer agents, Cyclopentadienyls, High temperature dynamics, Methyl ether acrylate, Reversible addition-fragmentation chain transfer polymerization, Triethylene glycol, Block copolymers
DOI: 10.1039/c4py00644e
ISSN: 17599954
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: 27 Sep 2016 04:06

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