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Related Concept Videos

Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
Polymer Classification: Architecture01:14

Polymer Classification: Architecture

Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...
Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
Polymer Classification: Stereospecificity01:26

Polymer Classification: Stereospecificity

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...
Polymer Classification: Crystallinity01:21

Polymer Classification: Crystallinity

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...
Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

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 acceptor.

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Updated: Jul 3, 2026

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
08:12

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers

Published on: December 16, 2022

The phase behavior of polyethylene ring chains.

Jiaye Su1, Linxi Zhang, Haojun Liang

  • 1Department of Physics, Zhejiang University, Hangzhou 310027, People's Republic of China.

The Journal of Chemical Physics
|August 7, 2008
PubMed
Summary
This summary is machine-generated.

Molecular dynamics simulations reveal polyethylene ring chains collapse in two stages. High temperatures form oblate structures, while decreasing temperatures induce gas-liquid and liquid-solid-like transitions due to internal energy barriers.

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Area of Science:

  • Polymer Physics
  • Computational Chemistry
  • Materials Science

Background:

  • Understanding the equilibrium properties and conformational changes of polymer chains is crucial in polymer physics.
  • Polyethylene, a widely used polymer, exhibits complex behavior in ring structures that differs from linear chains.
  • Previous studies on simpler models like square-well and Lennard-Jones chains provide a basis for comparison.

Purpose of the Study:

  • To investigate the equilibrium properties and collapse behavior of isolated polyethylene ring chains using molecular dynamics simulations.
  • To characterize the structural transitions and thermodynamic properties of polyethylene rings at various temperatures.
  • To compare the collapse mechanism of polyethylene rings with that of other model polymer systems.

Main Methods:

  • Molecular Dynamics (MD) simulations were employed to study polyethylene ring chains of varying lengths.
  • The simulations focused on analyzing equilibrium properties, structural conformations, and heat capacity.
  • Results were compared with theoretical predictions and data from linear chains and other model systems.

Main Results:

  • At high temperatures, polyethylene ring chains adopt a fully oblate structure, consistent with theoretical predictions of a shape factor (delta(*)=0.25) and rodlike scaling.
  • A significant energy barrier emerges at lower temperatures, leading to a gas-liquid-like transition indicated by a peak in heat capacity, primarily driven by local monomer interactions.
  • A subsequent liquid-solid-like transition is observed at even lower temperatures, suggesting a two-stage collapse mechanism unique to polyethylene rings.

Conclusions:

  • Polyethylene ring chains undergo a distinct two-stage collapse process, differing from square-well and Lennard-Jones ring chains.
  • The observed transitions are governed by internal energy barriers arising from local monomer interactions.
  • Molecular dynamics simulations provide valuable insights into the complex conformational behavior of polyethylene ring structures.