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Related Concept Videos

Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

3.7K
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

3.8K
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...
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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.
10.2K
Radical Reactivity: Overview01:11

Radical Reactivity: Overview

3.0K
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...
3.0K
Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

2.6K
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...
2.6K
Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

3.0K
The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
3.0K

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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

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Light-Controlled Radical Polymerization: Mechanisms, Methods, and Applications.

Mao Chen1, Mingjiang Zhong1, Jeremiah A Johnson1

  • 1Department of Chemistry and ‡Department of Chemical Engineering, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.

Chemical Reviews
|March 16, 2016
PubMed
Summary
This summary is machine-generated.

This review surveys photocontrolled, living radical polymerizations (photo-CRPs), detailing intramolecular photochemical and photoredox mechanisms. It highlights applications in advanced materials, aiming to inspire new research directions.

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Area of Science:

  • Polymer Chemistry
  • Photochemistry
  • Materials Science

Background:

  • Controlled radical polymerization (CRP) is crucial for polymer synthesis and materials fabrication.
  • Light-mediated polymerization offers precise control over polymer architecture.
  • Photocontrolled, living radical polymerization (photo-CRP) is an emerging powerful strategy.

Purpose of the Study:

  • To provide a comprehensive survey of known photo-CRPs.
  • To classify photo-CRP methods based on their underlying mechanisms.
  • To summarize current applications and stimulate future research.

Main Methods:

  • Categorization of photo-CRPs into intramolecular photochemical and photoredox processes.
  • Detailed discussion of reaction mechanisms for each subcategory.
  • Summary of reported applications in various fields.

Main Results:

  • Photo-CRPs are systematically divided into two primary mechanistic categories.
  • Numerous specific methods within these categories are summarized and classified.
  • Key applications including surface fabrication and continuous flow technology are highlighted.

Conclusions:

  • Photo-CRP is a versatile technique for advanced polymer synthesis.
  • Understanding mechanistic pathways is key to developing new photo-CRP methods.
  • This review serves as a knowledge base and catalyst for innovation in photocontrolled polymerization.