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Radical Reactivity: Overview01:11

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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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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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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: 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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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...
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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.
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Reversible deactivation radical polymerization mediated by cobalt complexes: recent progress and perspectives.

Chi-How Peng1, Tsung-Yao Yang, Yaguang Zhao

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Cobalt-mediated radical polymerization (CMRP) efficiently controls acrylate and vinyl acetate polymerization. This review details CMRP mechanisms, including aqueous phase and photo-initiation advancements.

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Area of Science:

  • Polymer Chemistry
  • Organometallic Chemistry
  • Radical Polymerization

Background:

  • Cobalt-mediated radical polymerization (CMRP) is a key organometallic-mediated radical polymerization (OMRP) technique.
  • CMRP demonstrates high efficiency in controlling acrylate and vinyl acetate polymerization.
  • It enables the synthesis of homo- and block copolymers with controlled molecular weights and narrow distributions.

Purpose of the Study:

  • To review the polymerization behavior and control mechanisms of cobalt complexes in reversible deactivation radical polymerization (RDRP).
  • To highlight emerging developments in aqueous phase CMRP and photo-initiated CMRP.
  • To discuss the challenges and future applications of CMRP.

Main Methods:

  • Review of existing literature on CMRP mechanisms.
  • Analysis of reaction pathways involving cobalt(II) metallo-radicals and organo-cobalt(III) complexes.
  • Examination of polymerization control via reversible deactivation and degenerative transfer pathways.

Main Results:

  • Cobalt(II) complexes effectively mediate RDRP, controlling polymerization through reversible deactivation.
  • Degenerative transfer becomes dominant when cobalt(II) fully converts to organo-cobalt(III) species.
  • CMRP allows for predictable molecular weight and narrow molecular weight distribution in polymers.

Conclusions:

  • CMRP offers precise control over radical polymerization processes.
  • Advancements in aqueous and photo-initiated CMRP expand its applicability.
  • Further research into CMRP holds promise for novel polymer synthesis and applications.