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Related Concept Videos

Cycloaddition Reactions: MO Requirements for Photochemical Activation01:12

Cycloaddition Reactions: MO Requirements for Photochemical Activation

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Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
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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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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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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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Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

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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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Acetals and Thioacetals as Protecting Groups for Aldehydes and Ketones01:24

Acetals and Thioacetals as Protecting Groups for Aldehydes and Ketones

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Acetals are formed by reacting two equivalents of alcohol with carbonyl compounds like aldehydes or ketones. Acetals are unaffected by bases, nucleophiles, oxidizing agents, and reducing agents. They serve as protecting groups for aldehydes and ketones. Acetals can be easily formed and also easily removed via mild acid hydrolysis.
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Types of Step-Growth Polymers: Polyesters01:20

Types of Step-Growth Polymers: Polyesters

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The introduction of polyesters has brought major development to the textile industry. The wrinkle-free behavior of polyester blends has eliminated the need for starching and ironing clothes.
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Facile and Efficient Preparation of Tri-component Fluorescent Glycopolymers via RAFT-controlled Polymerization
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RAFT with Light: A User Guide to Using Thiocarbonylthio Compounds in Photopolymerizations.

Magdalena A Beres1, Cyrille Boyer2, Matthias Hartlieb3,4

  • 1Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom.

ACS Polymers Au
|June 16, 2025
PubMed
Summary

This guide details light-mediated polymerizations using thiocarbonylthio compounds, focusing on photoiniferter and photoinduced electron transfer reversible-addition-fragmentation chain-transfer (PET-RAFT) polymerization. It provides practical insights for optimizing these advanced polymerization techniques.

Keywords:
PET-RAFTReversible addition−fragmentation chain-transfer polymerizationlightphotoRDRPphotoiniferterphotomediated polymerizationphotopolymerizationradical polymerizationreversible-deactivation radical polymerization

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Area of Science:

  • Polymer Chemistry
  • Photochemistry

Background:

  • Conventional reversible-addition-fragmentation chain-transfer (RAFT) polymerization is a well-established technique.
  • Photomediated polymerizations offer unique advantages over conventional methods, including spatial and temporal control.

Purpose of the Study:

  • To provide a comprehensive guide to photopolymerizations mediated by thiocarbonylthio compounds.
  • To focus on practical aspects of photoiniferter and photoinduced electron transfer RAFT (PET-RAFT) polymerizations for both new and experienced researchers.

Main Methods:

  • Discussion of the photochemical behavior of thiocarbonylthio compounds and selection of light wavelengths.
  • Exploration of key parameters influencing polymerization: catalyst, solvent, light intensity, and temperature.
  • Review of reactor configurations, including light sources, reactor geometry (batch vs. flow), and temperature control.

Main Results:

  • Critical examination of how light wavelength impacts polymerization kinetics and polymer properties.
  • Detailed analysis of parameters affecting polymerization success, such as catalyst and solvent choice.
  • Emphasis on oxygen tolerance and end-group fidelity for achieving well-defined polymers.

Conclusions:

  • Photoiniferter and PET-RAFT polymerizations offer powerful tools for advanced polymer synthesis.
  • Optimizing reaction parameters and reactor design is crucial for efficient and controlled light-mediated polymerizations.
  • This perspective provides a framework for harnessing light-mediated polymerization for innovative applications.