Thermoresponsive behavior of amphiphilic diblock co-oligomers of ethylene glycol and styrene in aqueous solution

Meiliana Siauw, Paul A. Fitzgerald, Brian S. Hawkett, Sebastien Perrier

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We report the thermoresponsive behavior in aqueous solution of amphiphilic diblock co-oligomers of ethylene glycol (EG) and styrene (S) obtained by reversible addition fragmentation chain transfer (RAFT) polymerization (mPEG16-b-PS2, mPEG16-b-PS4 and mPEG16-b-PS6). The block co-oligomers were obtained from the polymerization of styrene mediated by a PEG macro-RAFT agent, mPEG-PBTC. The precise control offered by RAFT polymerization over the length of the short hydrophobic chain permits tuning of the thermoresponsive behavior for all the studied methoxy poly(ethylene glycol)-block-polystyrene copolymers. mPEG 16-b-PS2 was shown to self-assemble into micelles at temperatures below the lower critical solution temperature (LCST) of the block co-oligomer, whilst no such critical temperature was observed for solutions of self-assembled mPEG16-b-PS4 and mPEG16-b- PS6. mPEG16-b-PS4 self-assembles into relatively mobile spherical particles which evolve into prolate spheroids with increasing temperature, whilst mPEG16-b-PS6 forms particle clusters, which have lower mobility than the mPEG16-b-PS4 particles. This work is the first study on the aggregation behavior of such short chain lengths of mPEG-b-PS as a function of temperature, and shows how tuning the PS oligomer length permits control of the thermoresponsive behavior of mPEG-b-PS assemblies in water.

Original languageEnglish
Pages (from-to)7007-7015
Number of pages9
JournalSoft Matter
Issue number29
Publication statusPublished - 7 Aug 2013
Externally publishedYes

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