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Synthesis and temperature gradient interaction chromatography of model asymmetric star polymers by the "macromonomer" approach

Agostini, Serena; Hutchings, Lian R.

Synthesis and temperature gradient interaction chromatography of model asymmetric star polymers by the "macromonomer" approach Thumbnail


Serena Agostini


We describe herein the synthesis and characterisation of a series of asymmetric three arm polystyrene stars via the “macromonomer” approach. The stars have been designed as model polymers to probe branched polymer dynamics and in particular to establish the chain-length of side-arm which precipitates a change in the rheological properties of the resulting polymers from “linear-like” to “star-like”. Thus, a homologous series of three arm stars have been prepared in which the molar mass of two (long) arms are fixed at 90,000 g mol−1 and the molar mass of the remaining (short) arm is varied from below the entanglement molecular weight (Me) to above Me. The arms were prepared by living anionic polymerisation, resulting in well-defined chain lengths with narrow molecular weight distribution. In contrast to the usual chlorosilane coupling approach, the macromonomer approach involves the introduction of reactive chain-end functionalities on each of the arms, either through the use of a functionalised (protected) initiator or a functional end-capping agent, which allows the stars to be constructed by a simple condensation coupling reaction. In this study we will compare the relative efficiency of a Williamson and ‘click’ coupling reaction in producing the stars. Most significantly, although this approach maybe a little more time-consuming than the more common silane coupling reaction, in the present study the “long” arm may be produced in sufficient quantity such that all of the asymmetric stars are produced with long arms of identical molecular weight – the only remaining variable being the molecular weight of the short arm. This will allow for a far more robust interpretation of the resulting characterisation of the dynamic properties. Temperature gradient interaction chromatography was used alongside size exclusion chromatography to characterise the structural dispersity of the resulting stars and establish the degree of structural homogeneity.

Journal Article Type Article
Publication Date Sep 1, 2013
Deposit Date Nov 20, 2013
Publicly Available Date Jul 29, 2014
Journal European Polymer Journal
Print ISSN 0014-3057
Electronic ISSN 1873-1945
Publisher Elsevier
Peer Reviewed Peer Reviewed
Volume 49
Issue 9
Pages 2769-2784
Keywords Branched polymer, Temperature gradient interaction chromatography (TGIC), Anionic polymerisation, Macromonomer.
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Accepted Journal Article (663 Kb)

Copyright Statement
NOTICE: this is the author’s version of a work that was accepted for publication in European Polymer Journal. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in European Polymer Journal, 49, 9, 2013, 10.1016/j.eurpolymj.2013.06.021.

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