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Related Concept Videos

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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Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
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Polymer Classification: Crystallinity01:21

Polymer Classification: Crystallinity

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Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...
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Phase Transitions02:31

Phase Transitions

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Whether solid, liquid, or gas, a substance's state depends on the order and arrangement of its particles (atoms, molecules, or ions). Particles in the solid pack closely together, generally in a pattern. The particles vibrate about their fixed positions but do not move or squeeze past their neighbors. In liquids, although the particles are closely spaced, they are randomly arranged. The position of the particles are not fixed—that is, they are free to move past their neighbors to...
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Anionic Chain-Growth Polymerization: Mechanism01:04

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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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Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

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The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
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Multiple interaction regulated phase transition behavior of thermo-responsive copolymers containing cationic

Yingna Zhang1, Hui Tang, Peiyi Wu

  • 1The State Key Laboratory of Molecular Engineering of Polymers and Department of Macromolecular Science and Laboratory for Advanced Materials, Fudan University, Shanghai 200433, China. peiyiwu@fudan.edu.cn huitang@fudan.edu.cn.

Physical Chemistry Chemical Physics : PCCP
|November 15, 2017
PubMed
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This study reveals how interactions influence copolymer phase transitions. Anion-dipole interactions drive phase changes in P(OEGMA-co-BVIm[SCN]), while hydrophobic interactions govern P(OEGMA-co-BVIm[NTf2]) aggregation.

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Area of Science:

  • Polymer Science
  • Materials Chemistry
  • Physical Chemistry

Background:

  • Random copolymers of oligo(ethylene glycol)methacrylate (OEGMA) and imidazolium-based ionic liquids (ILs) exhibit complex phase transition behaviors.
  • Understanding these transitions is crucial for designing advanced functional materials.

Purpose of the Study:

  • To investigate the influence of anion-macromolecule, water-mediated ion-macromolecule, and hydrophobic interactions on the phase transition behaviors of P(OEGMA-co-BVIm[X]) copolymers.
  • To elucidate the specific roles of different interactions in driving phase transitions and self-assembly.

Main Methods:

  • Temperature-variable 1H NMR spectroscopy to study molecular dynamics and hydration changes.
  • Fourier-transform infrared (FT-IR) spectroscopy to analyze chemical interactions and hydrogen bonding.
  • Analysis of phase transition mechanisms in copolymers with different ionic liquid anions (SCN- and NTf2-).

Main Results:

  • In P(OEGMA-co-BVIm[SCN]), anion-dipole interactions between SCN- and CH2 groups enhance hydration, while C=O dehydration drives phase transition.
  • Water-mediated hydrogen bonds (C=O-D2O-PIL) form in P(OEGMA-co-BVIm[SCN]), linking polymers and leading to micelle formation.
  • In P(OEGMA-co-BVIm[NTf2]), heating causes sequential water expulsion, and hydrophobic interactions between OEGMA and IL segments drive self-aggregation.

Conclusions:

  • The phase transition behavior of P(OEGMA-co-BVIm[X]) copolymers is dictated by a combination of specific intermolecular interactions.
  • Anion type significantly influences the dominant interaction mechanism, leading to distinct phase transition pathways and self-assembly structures.
  • These findings provide insights into the design principles for stimuli-responsive polymer materials based on ionic liquid copolymers.