Influence of counteranion on the thermal and solution behavior of poly (2-(dimethylamino)ethyl methacrylate)-Based polyelectrolytes

Matthew T. Hunley, Jeneffer P. England, Timothy E. Long

Research output: Contribution to journalArticlepeer-review

54 Scopus citations


Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) was synthesized and subsequently neutralized with various acids to form PDMAEMA · HCl, PDMAEMA · HBF4,and PDMAEMA · HOTf polyelectrolytes. In addition, ion exchange of the chloride anion provided polyelectrolytes with NO3-,N(CN)2-, PF6 -,and Tf2N- anions. The glass transition temperature (Tg) varied significantly with anion in the order Cl - > PF6- > BF4- >NO3- >TfO- >Tf2N -. The polyelectrolytes with larger, weakly coordinated anions required less thermal energy to dissociate ionic interactions, leading to tailored thermal behavior. Solution conductivity of the water-soluble polyelectrolytes decreased in the order Cl- >NO3 - >BF4- >N(CN)2- >TfO-,which was consistent with counteranion mobility. Solution rheology revealed polyelectrolyte behavior for PDMAEMA · HCl, PDMAEMA 3 HBF4, and PDMAEMA HOTf. PDMAEMA HCl underwent an electrospraying-electrospinning transition at three times the critical concentration for entanglement (Ce), which was consistent with other cationic polyelectrolytes. However, the BF4- and TfO - polyelectrolytes exhibited an onset of fiber formation at (1.4-1.8)Ce, much closer to the behavior of neutral, nonassociating polymers. Fiber diameters for all polyelectrolytes were 1-2 orders of magnitude smaller than those for neutral polymers due to increased conductivities of the electrospinning solutions.

Original languageEnglish (US)
Pages (from-to)9998-10005
Number of pages8
Issue number23
StatePublished - Dec 14 2010
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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