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

doi:10.1021/ma1017499

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 journal › Article › peer-review

54 Scopus citations

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 (T_g) 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 (C_e), which was consistent with other cationic polyelectrolytes. However, the BF₄^- and TfO ^- polyelectrolytes exhibited an onset of fiber formation at (1.4-1.8)C_e, 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 language	English (US)
Pages (from-to)	9998-10005
Number of pages	8
Journal	Macromolecules
Volume	43
Issue number	23
DOIs	https://doi.org/10.1021/ma1017499
State	Published - Dec 14 2010
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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

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.",

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AU - Hunley, Matthew T.

AU - England, Jeneffer P.

AU - Long, Timothy E.

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N2 - 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.

AB - 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.

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

Abstract

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