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Related Concept Videos

Molecular Weight of Step-Growth Polymers01:08

Molecular Weight of Step-Growth Polymers

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Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...
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Radical Chain-Growth Polymerization: Overview01:10

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Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

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The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this...
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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
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Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

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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...
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Related Experiment Video

Updated: Apr 14, 2026

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

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Slowing down of ring polymer diffusion caused by inter-ring threading.

Eunsang Lee1, Soree Kim1, YounJoon Jung1

  • 1Department of Chemistry, Seoul National University, Seoul, 151-747, Korea.

Macromolecular Rapid Communications
|April 18, 2015
PubMed
Summary
This summary is machine-generated.

Ring polymer melts diffuse slowly due to threading, not internal structure changes. Molecular dynamics simulations reveal that increased polymerization degree significantly slows diffusion by hindering unthreading events.

Keywords:
diffusionpersistence and exchange timering polymersscalingthreading dynamics

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Area of Science:

  • Polymer Physics
  • Materials Science

Background:

  • Ring polymers exhibit slower diffusion in melts compared to their internal structural reorganization.
  • Unlike linear polymers, direct evidence of entanglements is absent in ring polymers, but inter-ring threading is hypothesized to impede diffusion.

Purpose of the Study:

  • To provide evidence for threading dynamics in ring polymers.
  • To investigate the relationship between polymerization degree and threading in ring polymer melts.

Main Methods:

  • Utilized molecular dynamics simulations.
  • Applied a novel analysis method focusing on persistence and exchange times, adapted from studies of glassy systems.

Main Results:

  • Found that threading time in ring polymer melts escalates more rapidly with polymerization degree than in linear polymer melts.
  • Demonstrated that threaded ring polymers require an unthreading event to diffuse, directly linking threading to diffusion hindrance.

Conclusions:

  • Threading is a critical factor limiting the diffusion of ring polymers.
  • The rate of diffusion in ring polymer melts is strongly dependent on the degree of polymerization due to threading dynamics.