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Related Concept Videos

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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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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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: 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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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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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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Updated: Oct 14, 2025

3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization
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Photo-Iniferter RAFT Polymerization.

Matthias Hartlieb1,2

  • 1Institute of Chemistry, University of Potsdam, Karl-Liebknecht-Straße 24-25, 14476, Potsdam, Germany.

Macromolecular Rapid Communications
|November 9, 2021
PubMed
Summary

Photo-iniferter Reversible Addition-Fragmentation chain-Transfer (PI-RAFT) polymerization uses light to control radical polymerization. This method offers advantages over traditional thermal methods, enabling precise control over polymer synthesis.

Keywords:
lightphoto-iniferter reversible addition-fragmentation chain-transferphoto-mediated polymerizationradical polymerizationreversible addition-fragmentation chain-transfer polymerization

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Area of Science:

  • Polymer Chemistry
  • Photochemistry
  • Materials Science

Background:

  • Light-mediated polymerization offers superior spatial and temporal control compared to thermal methods.
  • Reversible Addition-Fragmentation chain-Transfer (RAFT) polymerization is a versatile technique for controlled radical polymerization, producing complex macromolecular structures.
  • RAFT polymerization can be initiated by light through various pathways, including photo-initiators and photo-catalysts.

Purpose of the Study:

  • To review the Photo-Iniferter Reversible Addition-Fragmentation chain-Transfer (PI-RAFT) polymerization technique.
  • To highlight the advantages of PI-RAFT polymerization over conventional RAFT processes.
  • To discuss the direct activation of chain transfer agents using light in RAFT polymerization.

Main Methods:

  • Review of literature on light-mediated polymerization techniques.
  • Detailed discussion of the Photo-Iniferter (PI) approach for RAFT polymerization.
  • Comparison of PI-RAFT polymerization with conventional thermal RAFT methods.

Main Results:

  • PI-RAFT polymerization allows for direct light-based initiation and control of the RAFT process.
  • This method provides enhanced spatial and temporal control over polymerization.
  • PI-RAFT polymerization can be performed under mild reaction conditions.

Conclusions:

  • PI-RAFT polymerization represents an elegant and effective strategy for controlled radical polymerization.
  • The direct activation of chain transfer agents by light offers significant advantages for polymer synthesis.
  • This technique expands the utility of RAFT polymerization for creating advanced materials.