Effect of monomer structure on the gelation of a class of metallo-supramolecular polymers

Wengui Weng, Zheng Li, Alex M. Jamieson, Stuart J. Rowan

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

Gelation of metallo-supramolecular polymers prepared from three ditopic ligand monomers, 1, 2 and 3, derived, respectively, from tetra-, penta-, and hexaethylene glycols, in the presence of the transition metal ion Zn II, as well as the properties of the resulting gels, are investigated and compared. It is found that these slight changes in the core length of the monomer lead to substantial variations in the gel characteristics, which can be attributed to solubility differences between the corresponding metallo-supramolecular polymers. Observations of gelation kinetics indicate 3:Zn has the slowest and 1:Zn the fastest rate. Rheological measurements of the gelation kinetics of 1:Zn indicate unusual behavior in that the modulus exhibits a distinct maximum at a gel time of around 15-30 min. The origin of this phenomenon is suggested to be the transient formation of a metastable colloidal structure which occurs on account of the fast phase separation kinetics of 1:Zn and subsequent particle densification via redistribution of solvent. Under equivalent conditions of solvent quality and polymer concentration, the shear modulus of 2:Zn gels is substantially higher than that of 1:Zn and 3:Zn. It appears that the lower modulus of 1:Zn is a consequence of its lower solubility, which results in smaller, more dense colloidal particles and hence a lower particle volume fraction. On the other hand, 3:Zn gels also have a lower modulus than 2:Zn on account of their higher solubility, resulting in a larger sol fraction under the equivalent conditions.

Original languageEnglish
Pages (from-to)4647-4657
Number of pages11
JournalSoft Matter
Volume5
Issue number23
DOIs
Publication statusPublished - 2009
Externally publishedYes

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gelation
Gelation
Polymers
monomers
Monomers
Gels
gels
polymers
solubility
Solubility
Kinetics
kinetics
Polymethyl Methacrylate
densification
Densification
Phase separation
Transition metals
Metal ions
glycols
Volume fraction

ASJC Scopus subject areas

  • Chemistry(all)
  • Condensed Matter Physics

Cite this

Effect of monomer structure on the gelation of a class of metallo-supramolecular polymers. / Weng, Wengui; Li, Zheng; Jamieson, Alex M.; Rowan, Stuart J.

In: Soft Matter, Vol. 5, No. 23, 2009, p. 4647-4657.

Research output: Contribution to journalArticle

Weng, Wengui ; Li, Zheng ; Jamieson, Alex M. ; Rowan, Stuart J. / Effect of monomer structure on the gelation of a class of metallo-supramolecular polymers. In: Soft Matter. 2009 ; Vol. 5, No. 23. pp. 4647-4657.
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