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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 species into...
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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

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 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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Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
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Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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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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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Recent advances in light-regulated non-radical polymerisations.

Haiwang Lai1, Jing Zhang2, Feiyue Xing3

  • 1Department of Immunobiology, College of Life Science and Technology, Jinan University, #601 Huangpu West Avenue, Guangzhou 510632, China and Research School of Chemistry, The Australian National University, Canberra, ACT 2601, Australia. pu.xiao@anu.edu.au.

Chemical Society Reviews
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Summary

Light triggers non-radical polymerizations, offering advantages over traditional methods for advanced material development. This review explores light-regulated techniques and their applications in polymer science.

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Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes
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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Photochemistry

Background:

  • Light offers non-invasive spatiotemporal control for chemical reactions.
  • Light-regulated polymerization is crucial in polymer synthesis, drug delivery, and sensor development.
  • Existing reviews primarily focus on free radical photopolymerization.

Purpose of the Study:

  • To review recent advancements in light-regulated non-radical polymerizations.
  • To highlight novel polymerization techniques and material science applications.
  • To discuss challenges and future perspectives in the field.

Main Methods:

  • Focus on non-radical polymerization methods including ionic, ring-opening, metathesis, step-growth, and supramolecular photopolymerizations.
  • Discuss light-regulation techniques based on photolinking reactions and photoactivation of latent species.
  • Analyze the production of initiators, catalysts, or monomers upon light irradiation for polymer formation.

Main Results:

  • Non-radical photopolymerizations overcome oxygen inhibition and enable novel polymer structures.
  • Light-regulated techniques allow for the fabrication of degradable and dynamic polymers.
  • Successful implementation of conditional polymerizations and precise control over polymer architecture.

Conclusions:

  • Light-regulated non-radical polymerization is a rapidly advancing field with significant potential.
  • Further research is needed to address current challenges and unlock new applications.
  • This review provides a comprehensive overview of progress and future directions.