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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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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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Free-Radical Chain Reaction and Polymerization of Alkenes02:35

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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 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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Anionic Chain-Growth Polymerization: Overview01:20

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Olefin Metathesis Polymerization: Overview01:13

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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.
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Updated: Oct 3, 2025

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Toward Green Atom Transfer Radical Polymerization: Current Status and Future Challenges.

Sylwia Dworakowska1,2, Francesca Lorandi1,3, Adam Gorczyński1,4

  • 1Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA, 15213, USA.

Advanced Science (Weinheim, Baden-Wurttemberg, Germany)
|February 17, 2022
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Atom transfer radical polymerization (ATRP) offers controlled polymer synthesis, aligning with green chemistry principles. This review explores ATRP

Keywords:
atom transfer radical polymerizationbiobased polymersdegradable polymersdepolymerizationgreen chemistry

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Area of Science:

  • Polymer Chemistry
  • Green Chemistry

Background:

  • Reversible-deactivation radical polymerizations (RDRPs) enable precise control over polymer architecture, composition, and functionality.
  • Atom transfer radical polymerization (ATRP) is a key RDRP technique with diverse applications, including advanced materials for electronics and energy.

Purpose of the Study:

  • To review the alignment of Atom transfer radical polymerization (ATRP) technology with the 12 principles of green chemistry.
  • To highlight advancements and challenges in developing environmentally sustainable ATRP methods.

Main Methods:

  • Review of existing literature on ATRP and green chemistry principles.
  • Analysis of environmental and health impacts associated with ATRP processes.
  • Identification of key discoveries and recent developments in green ATRP.

Main Results:

  • ATRP demonstrates significant green features, contributing to sustainable polymer synthesis.
  • Discussion of environmental benefits and remaining challenges in implementing green ATRP.
  • Highlighting innovations that reduce waste and improve safety in ATRP.

Conclusions:

  • ATRP can be effectively integrated with green chemistry principles for sustainable material development.
  • Continued research is needed to overcome existing challenges and fully realize the potential of green ATRP.
  • Future opportunities lie in further optimizing ATRP for broader environmentally relevant applications.