Polymerization of ethylene oxide with a calixarene-based precursor: Synthesis of eight-arm poly(ethylene oxide) stars by the core-first methodology

Daniel Taton, Myriam Saule, Jennifer Logan, Randolph Duran, H. O.U. Sijian, Elliot L. Chaikof, Yves Gnanou*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

62 Scopus citations

Abstract

Eight-arm poly(ethylene oxide) (PEO) stars were prepared by the core-first method with a newly designed octahydroxylated precursor. This compound was readily obtained in two steps from commercially available tert-butylcalix[8]arene. The choice of the proper solvent of polymerization proved crucial to obtain PEO star materials with a narrow distribution of molar masses. For instance, the use of dimethyl sulfoxide (DMSO) resulted in PEO samples of rather large polydispersities (PDI: 1.3-1.5). In this solvent, the calix-arene-based precursor was only sparingly soluble, and an attempt to metalate its eight hydroxyl groups produced insoluble alkoxides. In addition, the presence of a side population of low-molar-mass species attributable to linear chains was detected because of the chain transfer of propagating alkoxides to DMSO. Polymerization experiments carried out in tetrahydrofuran (THF) as solvent afforded better control over the molar masses and PDIs. This was related to the better solubility of the octafunctional calixarene-based precursor in THF and to the small tendency of the alkoxides formed to aggregate in that solvent. Under such conditions, all eight hydroxyl functions efficiently initiated the polymerization of ethylene oxide. In this way, well-defined PEO stars (PDI < 1.2) of tunable molar masses incorporating a calixarene-based core could be obtained, as it was supported by the characterization of the samples by size exclusion chromatography, NMR, and viscometry.

Original languageEnglish (US)
Pages (from-to)1669-1676
Number of pages8
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume41
Issue number11
DOIs
StatePublished - Jun 1 2003

Keywords

  • Core-first method
  • Poly(ethylene oxide)
  • Stars
  • Tert-butylcalix[8]arene

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

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