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Related Concept Videos

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

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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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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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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: Steric Effects01:10

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The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
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Radical Chain-Growth Polymerization: Chain Branching01:17

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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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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Can We Push Rapid Reversible Deactivation Radical Polymerizations toward Immortality?

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Summary

This study challenges assumptions in reversible deactivation radical polymerization (RDRP) by showing fast deactivation can reduce termination. This allows for better control over polymerization rates and chain end functionality.

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Area of Science:

  • Polymer Chemistry
  • Radical Polymerization
  • Physical Chemistry

Background:

  • Reversible deactivation radical polymerization (RDRP) balances polymerization rate and chain end functionality.
  • High radical concentration favors rate, while low concentration preserves functionality.

Purpose of the Study:

  • To investigate if the compromise in RDRP can be overcome.
  • To explore the impact of rapid deactivation on polymerization kinetics and control.

Main Methods:

  • Adjusting probability density functions for termination reactions to include radical diffusion time.
  • Developing a theoretical framework based on modified reaction kinetics.
  • Applying the framework to experimental data from copper(0)-mediated acrylamide polymerization.

Main Results:

  • Contrary to classical kinetics, rapid deactivation can reduce termination events.
  • Theoretical predictions align with experimental observations in acrylamide polymerization.
  • Demonstrated a potential to mitigate the inherent compromise in RDRP.

Conclusions:

  • Fast deactivation offers a pathway to circumvent limitations in RDRP.
  • This approach suggests enhanced control over radical polymerization processes.
  • Challenges conventional understanding of radical reaction limitations.