Influence of Counteranion on the Thermal and Solution Behavior of Poly(2-(dimethylamino)ethyl methacrylate)-Based Polyelectrolytes

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

doi:10.1021/ma1017499

Cited by 55 publications

(77 citation statements)

References 43 publications

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“…Long and co-workers also investigated the impact of counteranion on the solution and thermal properties of ammoniumbased polyelectrolytes. [ 11 ] Our study revealed the important infl uence of anion selection on the T g of the polyelectrolyte, and we observed polyelectrolyte electrospinning …”

supporting

confidence: 53%

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Alkyl‐Substituted N‐Vinylimidazolium Polymerized Ionic Liquids: Thermal Properties and Ionic Conductivities

Green

Cruz

et al. 2011

Macro Chemistry & Physics

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Structure-property relationships for polymerized ionic liquids (PILs) relate chemical structure to ionic conductivity and reveal the importance of glass transition temperature ( T g ) and the energy associated with an ion-hopping mechanism for ion conduction for a series of alkyl-substituted vinylimidazolium PILs. The alkyl-substituted vinylimidazolium-based PILs with varying lengths of n -alkyl substituents provide diverse precursors with exchangeable anions to further enhance thermal stability and ionic conductivity. As the anion size increases, regardless of alkyl substituent length, T g decreases and the onset of weight loss, T D , increases. As the length of the alkyl substituent increases, T g decreases for PILs with Br − and BF 4 − counteranions. Ionic conductivity increases over an order of magnitude upon exchange of the counteranion from TfO − < Tf 2 N − . due to their unique combination of physical properties including high thermal stability, wide electrochemical window, negligible vapor pressure, and potentially high ionic conductivities. [3][4][5][6][7] Two particular classes of ILs are polymerizable ILs (PILs) that contain polymerizable functional groups and room temperature ILs (RTILs) with melting temperatures at or below room temperature. [ 8 ] Potential applications have included electrolytes in electromechanical transducers, artifi cial muscle fabrication, and non-volatile solvents for a myriad of chemical reactions. [ 9 ] Chen and Elabd investigated the solution properties and subsequent formation of electrospun fi bers of an imidazolium-containing methacrylate-based PIL. [ 10 ] This study revealed solution properties similar to polyelectrolyte solutions, and electrospun fi bers formed with intermediate fi ber diameters and onset of fi ber formation between polyelectrolyte and neutral polymers. The fi brous mats exhibited promising ionic conductivities at room temperature, and upon swelling with a RTIL, ionic conductivities were on the order of 10 mS cm − 1 . Long and co-workers also investigated the impact of counteranion on the solution and thermal properties of ammoniumbased polyelectrolytes. [ 11 ] Our study revealed the important infl uence of anion selection on the T g of the polyelectrolyte, and we observed polyelectrolyte electrospinning

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supporting

confidence: 53%

“…Our previous studies established the significant impact of counteranion selection on the thermal stability of cationic polyelectrolytes. [ 11 ] TGA of imidazolium-based PILs also displayed a similar trend with anion selection. Decreasing the basicity of the counteranion in the following order Br − > BF 4…”

Section: Methodsmentioning

confidence: 59%

Alkyl‐Substituted N‐Vinylimidazolium Polymerized Ionic Liquids: Thermal Properties and Ionic Conductivities

Green

Cruz

et al. 2011

Macro Chemistry & Physics

Self Cite

146

189

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“…This fact was related to the 193 zwitterionic nature of the lecithin which presents asymmetric positive and negative electric 194 charges. These charges were dissociated in aqueous solution and thus, led to an increase of 195 the electrical conductivity (Hunley, England & Long, 2010). Concerning the viscosity, it was 196 seen that very low values were obtained regardless the absence or presence of the 197 surfactants.…”

Section: Characterization Of the Carbohydrate-based Solutions 107mentioning

confidence: 99%

Surfactant-aided electrospraying of low molecular weight carbohydrate polymers from aqueous solutions

Pérez-Masiá

Lagarón

López‐Rubio

2014

Carbohydrate Polymers

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In this work it is demonstrated, for the first time, that it is feasible to develop, using the electrospraying technique, low molecular weight carbohydrate-based capsule morphologies from aqueous solutions through the rational use of surfactants. Two different low molecular weight carbohydrate polymers were used, a maltodextrin and a commercial resistant starch. The solution properties and subsequent high voltage sprayability was evaluated upon addition of non-ionic (Tween20, and Span20) and zwitterionic (lecithin) surfactants. The morphology and molecular organization of the structures obtained was characterized and related to the solution properties. Results showed that, while unstable jetting and dropping occurred from the pure carbohydrate solutions without surfactant, the addition of some surface active molecules above their critical micelle concentration facilitated capsule formation. Higher surfactant concentrations led to smaller and more homogeneous capsule morphologies, related to lower surface tension and higher conductivity of the solutions. In this work it is demonstrated, for the first time, that it is feasible to develop, using the 13 electrospraying technique, low molecular weight carbohydrate-based capsule morphologies 14 from aqueous solutions through the rational use of surfactants. Two different low molecular 15 weight carbohydrate polymers were used, a maltodextrin and a commercial resistant starch. 16The solution properties and subsequent high voltage sprayability was evaluated upon addition 17 of non-ionic (Tween20, and Span20) and zwitterionic (lecithin) surfactants. The morphology 18 and molecular organization of the structures obtained was characterized and related to the 19 solution properties. Results showed that, while unstable jetting and dropping occurred from 20 the pure carbohydrate solutions without surfactant, the addition of some surface active 21 molecules above their critical micelle concentration facilitated capsule formation. Higher 22 surfactant concentrations led to smaller and more homogeneous capsule morphologies, 23 related to lower surface tension and higher conductivity of the solutions. 24 25

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“…For example, the samples poly (BImBHCS-Br) and poly(BImBHCS-BF 4 ) with relative small volume have stable LC ordered structure when varying the temperature. The volume of PF 6 " is bigger than that of Br" and BF 4 " [57,58] and the poly(BImBHCS-PF 6 ) exhibited an isotropic transition temperature during the heating process. The counter-anion TFSI" had the largest volume and not only can it weaken the intramolecular stacking of biphenyl but it was shown to destroy the scaffold of main chain LC properties.…”

Section: Thermal Properties and Liquid Crystalmentioning

confidence: 94%

“…The observed T g trend resulted from the different nucleophilicity and steric effect of counter-anions [56]. For example, the TFSI" anion, which has relatively large steric hindrance and weak nucleophilicity, aided in the segmentmovement strengthening of the material [57,58], and thus this material (poly(BImBHCS-TFSI)) gave the lowest T g temperature among the four samples. To study the LC properties of the class of MCSCILCPs prepared herein, we performed PLM to investigate their birefringence phenomena.…”

Section: Thermal Properties and Liquid Crystalmentioning

confidence: 99%

Combined main-chain/side-chain ionic liquid crystalline polymer based on ‘jacketing’ effect: Design, synthesis, supra-molecular self-assembly and photophysical properties

Weng¹,

Xie²,

Arges³

et al. 2015

Express Polym. Lett.

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Ionic liquid crystalline polymers (ILCPs) are a class of macromolecular architectures with mesogenic groups and ionic species and they have attracted great interest in the fields of polymer chemistry and materials science lately [1][2][3]. The combination of electrostatic interaction with liquid crystalline (LC) ordering yields ILCPs with excellent mechanical properties, rheological processability, piezoelectric performance, and optical variable performance [1][2][3][4][5][6][7]. Generally, ionic interaction promotes the ILCPs to form ionic clusters resulting in a reversible physical gelation [1,8,9]. Moreover, incorporation of the ions and selection of the type of ion chemistry can effectively improve the miscibility with other polymers. Therefore, ILCPs are versatile candidates to construct new high-performance functional mate- 536Combined main-chain/side-chain ionic liquid crystalline polymer based on 'jacketing' effect: Design, synthesis, supra-molecular self-assembly and photophysical properties Abstract. Reasonably fabricating ordered structures of ionic polymers is very important for the development of novel functional materials. By combining the ions and liquid cry stalline polymer, we successfully designed and synthesized a series of novel combined main-chain/side-chain ionic liquid crystalline polymer (MCSC-ILCPs) containing imidazolium groups and different counter-anions, poly (2,5-bis{[6-(4-butoxy-4!-imidazolium biphenyl)hexyl]oxycarbonyl}styrene salts) poly(BImBHCS-X) with the following types of counter-anions (Br", BF 4 ", PF 6 " and TFSI"). Combined technologies confirmed the chemical structures of the monomers and polymers with imidazolium cation and different counter-anions. Differential scanning calorimetry (DSC), polarized light microscopy (PLM) and one-and two-dimensional wide-angle X-ray diffraction (1D and 2D WAXD) results illustrated that the LC structures and the transitions of ordered structures depended on the nature of the counter-anion employed. The polymers with Br" and BF 4 " counter-anions exhibited smectic A (SmA) LC behavior below the isotropic temperature. The another one, poly(BImBHCS-TFSI) with the large volume of the TFSI" anion destroyed the packing of the LC ordered structure resulting in an amorphous structure. The photophysical properties of the polymers prepared can be adjusted by tuning the ionic interaction of the polymers by switching the counter-anion.

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Influence of Counteranion on the Thermal and Solution Behavior of Poly(2-(dimethylamino)ethyl methacrylate)-Based Polyelectrolytes

Cited by 55 publications

References 43 publications

Alkyl‐Substituted N‐Vinylimidazolium Polymerized Ionic Liquids: Thermal Properties and Ionic Conductivities

Alkyl‐Substituted N‐Vinylimidazolium Polymerized Ionic Liquids: Thermal Properties and Ionic Conductivities

Surfactant-aided electrospraying of low molecular weight carbohydrate polymers from aqueous solutions

Combined main-chain/side-chain ionic liquid crystalline polymer based on ‘jacketing’ effect: Design, synthesis, supra-molecular self-assembly and photophysical properties

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