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

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

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

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
Pages (from-to)9998-10005
Number of pages8
JournalMacromolecules
Volume43
Issue number23
DOIs
Publication statusPublished - 2010 Dec 14
Externally publishedYes

ASJC Scopus subject areas

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

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