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Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen...
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Pore transport and ion-pair formation are critical mechanisms for the absorption and distribution of drugs in the body.
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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
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Ion exchange chromatography separates charged molecules from a solution by reversibly exchanging them with mobile, or 'active', ions associated with the oppositely charged stationary phase. This method can be used to separate ions, soften and deionize water, and purify solutions. The polymers comprising the ion-exchange column are high-molecular-weight and chemically stable polymers, crosslinked to be porous and essentially insoluble. They are also functionalized with either acidic or...
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Cationic Chain-Growth Polymerization: Mechanism00:57

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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Updated: Jan 6, 2026

Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications
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Ion transport in backbone-embedded polymerized ionic liquids.

Jordan R Keith1, Venkat Ganesan1

  • 1McKetta Department of Chemical Engineering, University of Texas at Austin, Austin, Texas 78712, USA.

The Journal of Chemical Physics
|October 3, 2019
PubMed
Summary
This summary is machine-generated.

Computer simulations reveal that longer spacers in backbone polymerized ionic liquids decrease anion mobility. Backbone polymers show more intermolecular hopping than pendant types, despite similar ion dynamics.

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Area of Science:

  • Polymer Chemistry
  • Computational Materials Science
  • Ionic Liquids

Background:

  • Polymerized ionic liquids (PILs) are advanced materials with tunable properties.
  • Understanding ion transport in PILs is crucial for applications like batteries and fuel cells.
  • Backbone and pendant PIL architectures exhibit distinct ion transport characteristics.

Purpose of the Study:

  • To investigate ion transport phenomena in backbone polymerized ionic liquids.
  • To analyze the effect of spacer length on ion mobility and coordination.
  • To compare backbone PILs with pendant PILs regarding ion hopping and association.

Main Methods:

  • Atomistic computer simulations were employed.
  • Simulations focused on backbone polymerized cationic liquids with bistrifluoromethylesulfonylimide (TFSI-) counterions.
  • Structural characteristics and ion mobilities were analyzed for varying methylene spacer lengths (four, six, eight) and compared to a pendant PIL.

Main Results:

  • Anion diffusivity in backbone PILs decreases with increasing spacer length.
  • Decreased anion mobility is attributed to reduced intramolecular and intermolecular hopping frequencies.
  • Backbone PILs exhibit higher intermolecular hopping rates than pendant PILs.
  • TFSI- anions in pendant PILs show higher coordination with multiple imidazolium cations compared to backbone PILs.

Conclusions:

  • Spacer length significantly impacts ion transport in backbone PILs.
  • Backbone and pendant PILs display different ion coordination and hopping behaviors.
  • Despite structural differences, backbone PILs exhibit correlated diffusivity and ion-association relaxation times, similar to pendant variants.