Phosphonium ionenes from well-defined step-growth polymerization: Thermal and melt rheological properties

Sean T. Hemp, Musan Zhang, Mana Tamami, Timothy Edward Long

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

Step-growth polymerization of ditertiary phosphines with dibromoalkanes enabled the synthesis of novel phosphonium ionenes. In situ FTIR spectroscopy monitored the increase in absorbance as a function of time at 1116 cm -1, which corresponded to the polymeric P+-Ph stretch. Aqueous size-exclusion chromatography (SEC) provided absolute molecular weights and confirmed expected molecular weight growth for difunctional, step-growth polymerization. Phosphonium ionenes exhibited improved thermal and base stability compared to ammonium ionenes, which was attributed to the propensity of the ammonium cation towards Hofmann elimination. Melt rheology examined phosphonium ionene viscous flow and the influence of charge density on melt viscosity as a function of shear rate and temperature. Time-temperature superposition (TTS) resulted in both master curves and pseudomaster curves depending on phosphonium ionene composition. Two primary relaxations occurred: (1) onset of long-range segmental motion at Tg, and (2) relaxation attributed to electrostatic interactions. Higher charge densities shifted these two relaxations to longer time scales and increased flow activation energies. Phosphonium ionenes also readily bound pDNA effectively (± ratios of 1), and base stability suggested applications in energy generation.

Original languageEnglish
Pages (from-to)3582-3590
Number of pages9
JournalPolymer Chemistry
Volume4
Issue number12
DOIs
Publication statusPublished - 2013 Jun 21
Externally publishedYes

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Polymerization
Hot Temperature
Charge density
Ammonium Compounds
Growth
Molecular Weight
Molecular weight
Phosphines
Temperature
Size exclusion chromatography
Rheology
Base Composition
Viscous flow
Fourier Transform Infrared Spectroscopy
Articular Range of Motion
Coulomb interactions
Static Electricity
Viscosity
Shear deformation
Gel Chromatography

ASJC Scopus subject areas

  • Bioengineering
  • Biochemistry
  • Biomedical Engineering
  • Polymers and Plastics
  • Organic Chemistry

Cite this

Phosphonium ionenes from well-defined step-growth polymerization : Thermal and melt rheological properties. / Hemp, Sean T.; Zhang, Musan; Tamami, Mana; Long, Timothy Edward.

In: Polymer Chemistry, Vol. 4, No. 12, 21.06.2013, p. 3582-3590.

Research output: Contribution to journalArticle

Hemp, Sean T. ; Zhang, Musan ; Tamami, Mana ; Long, Timothy Edward. / Phosphonium ionenes from well-defined step-growth polymerization : Thermal and melt rheological properties. In: Polymer Chemistry. 2013 ; Vol. 4, No. 12. pp. 3582-3590.
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