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Related Concept Videos

Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

2.7K
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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Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

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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.
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Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
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Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

2.0K
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: Sep 21, 2025

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Repurposing Biocatalysts to Control Radical Polymerizations.

Kyle J Rodriguez1, Bernadetta Gajewska1, Jonas Pollard1

  • 1Adolphe Merkle Institute, University of Fribourg, Chemin des Verdiers 4, 1700 Fribourg, Switzerland.

ACS Macro Letters
|May 28, 2022
PubMed
Summary
This summary is machine-generated.

Biocatalysts like enzymes can now control advanced polymerizations, enabling greener synthesis of precision polymers and functional nanomaterials. This review covers biocatalytic controlled radical polymerizations (bioCRP) for diverse applications.

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Area of Science:

  • Polymer Chemistry
  • Biocatalysis
  • Green Chemistry

Background:

  • Enzymes and biomolecules have historically initiated free radical polymerizations.
  • Recent advances demonstrate biocatalysts' ability to control reversible-deactivation radical polymerizations.

Purpose of the Study:

  • To critically review biocatalytic controlled radical polymerizations (bioCRP).
  • To discuss the potential of bioCRP for environmentally friendly polymer synthesis and advanced applications.

Main Methods:

  • Review of biocatalytic atom transfer radical polymerization (bioATRP).
  • Review of enzyme-initiated reversible addition-fragmentation chain transfer radical polymerization (bioRAFT).
  • Review of biocatalytic organometallic-mediated radical polymerization (bioOMRP) and biocatalytic reversible complexation mediated polymerization (bioRCMP).

Main Results:

  • Biocatalysts offer a sustainable approach to controlled polymerization.
  • BioCRP methods enable the synthesis of precision polymers with defined architectures.
  • These methods are applicable to creating functional nanostructures and surface modifications.

Conclusions:

  • Biocatalytic controlled radical polymerizations represent a significant advancement in sustainable polymer synthesis.
  • BioCRP holds substantial promise for applications in nanotechnology, surface science, and biosensing.