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Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

3.5K
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...
3.5K
Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

3.6K
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 species into...
3.6K
Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

9.6K
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.
9.6K
Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

2.5K
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...
2.5K
Mixtures of Acids03:27

Mixtures of Acids

21.9K
The pH of a solution containing an acid can be determined using its acid dissociation constant and its initial concentration. If a solution contains two different acids, then its pH can be determined using one of several methods depending upon the relative strength of the acids and their dissociation constants.
A Mixture of a Strong Acid and a Weak Acid
In a mixture of a strong acid and a weak acid, the strong acid dissociates completely and becomes a source of almost all the hydronium ions...
21.9K
Mixtures of Acids01:19

Mixtures of Acids

1.1K
The pH of a solution containing an acid can be determined using its acid dissociation constant and initial concentration. If a solution contains two different acids, then its pH can be determined using one of several methods depending on the relative strength of the acids and their dissociation constants.
In a strong and weak acid mixture, the strong acid dissociates completely and becomes a source of almost all the hydronium ions present in the solution. In contrast, the weak acid shows...
1.1K

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Related Experiment Video

Updated: Feb 11, 2026

Author Spotlight: Advancing Cell Membrane Biophysics - Exploring Interactions and Challenges Through Experimental and Computational Approaches
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Author Spotlight: Advancing Cell Membrane Biophysics - Exploring Interactions and Challenges Through Experimental and Computational Approaches

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Radical initiated polymerization in a bifunctional mixture via computer simulation.

Keri L Diamond1, Ras B Pandey, Shelby F Thames

  • 1School of Polymers and High Performance Materials, University of Southern Mississippi, Hattiesburg, Mississippi 39406, USA.

The Journal of Chemical Physics
|July 23, 2004
PubMed
Summary

Computer simulations reveal polymerization behavior in vegetable oil derived macromonomers (VOMMs). Free radical initiation influences reaction rates and polymer growth, showing patterns consistent with experimental observations.

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Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
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Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development

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Area of Science:

  • Polymer Chemistry
  • Computational Materials Science
  • Chemical Engineering

Background:

  • Vegetable oil derived macromonomers (VOMMs) offer sustainable alternatives in polymer applications.
  • Understanding the polymerization kinetics of VOMMs is crucial for controlling material properties.
  • Computer simulations provide a powerful tool to investigate complex polymerization processes.

Purpose of the Study:

  • To investigate the polymerization behavior of bifunctional monomers (olefins and acrylates) in a VOMM-simulating solvent.
  • To model the effects of free radical initiation on polymerization kinetics and polymer growth.
  • To compare simulation results with experimental observations and assess model dependency.

Main Methods:

  • Utilized computer simulations on a cubic lattice to model monomer interactions and solvent effects.
  • Employed the Metropolis algorithm for sample equilibration.
  • Implemented free radical-initiated reaction pathways to simulate covalent bonding.
  • Analyzed reaction rate decay patterns (power laws, exponential decays) and polymer growth as a function of monomer concentration.

Main Results:

  • Reaction rates exhibit characteristic decay patterns with time, including power-law and exponential behaviors.
  • Polymer growth (A-B bonding) was studied across different polymer concentrations for four VOMM-relevant model systems.
  • Free radical-initiated polymerization simulations showed consistency with homopolymerization models and experimental data.
  • Observed variations in simulation outcomes were found to be dependent on the specific model system used.

Conclusions:

  • Computer simulations effectively model VOMM polymerization, including free radical initiation effects.
  • The study provides insights into reaction kinetics and polymer growth relevant to VOMM applications.
  • Simulation results align with experimental findings, though model-specific variations warrant further investigation.