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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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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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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 species into...
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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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Anionic Chain-Growth Polymerization: Mechanism01:04

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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
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Cationic Chain-Growth Polymerization: Mechanism00:57

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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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Updated: Feb 8, 2026

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

Yi Wang1, Marco Fantin1, Sangwoo Park1

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

Macromolecules
|July 7, 2018
PubMed
Summary
This summary is machine-generated.

Electrochemically mediated reversible addition-fragmentation chain-transfer polymerization (eRAFT) was achieved using aryl radicals generated via electroreduction. This method enables controlled synthesis of polymers and copolymers with high conversion rates.

Keywords:
Electroreductionchain extensioncontrolled radical polymerizationdiazonium salteRAFTelectrochemistry

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Area of Science:

  • Polymer Chemistry
  • Electrochemistry

Background:

  • Reversible addition-fragmentation chain-transfer (RAFT) polymerization is a versatile method for controlled radical polymerization.
  • Electrochemical methods offer a tunable and potentially greener alternative for initiating polymerization reactions.

Purpose of the Study:

  • To develop an electrochemically mediated RAFT polymerization (eRAFT) for (meth)acrylates.
  • To investigate the efficacy of aryl radical generation via electroreduction as initiators for eRAFT.
  • To compare controlled potential vs. controlled current conditions for eRAFT.

Main Methods:

  • Electrochemical reduction of benzoyl peroxide (BPO) or 4-bromobenzenediazonium tetrafluoroborate (BrPhN2+) to generate aryl radicals.
  • RAFT polymerization of (meth)acrylates initiated by electrogenerated aryl radicals.
  • Comparison of polymerization control and conversion under fixed potential and fixed current electrolysis.

Main Results:

  • Successful eRAFT polymerization of (meth)acrylates was achieved.
  • Electroreduction of BPO and BrPhN2+ yielded aryl radicals that initiated RAFT polymerization.
  • Direct electroreduction of chain transfer agents was unsuccessful.
  • Fixed current electrolysis provided higher conversions (>80%) compared to fixed potential, which suffered from electrode passivation.
  • Well-defined homopolymers and block copolymers with controlled molecular weights were synthesized.

Conclusions:

  • Electrochemical initiation of RAFT polymerization is feasible using aryl radicals generated by electroreduction.
  • Fixed current electrolysis offers a practical and efficient method for eRAFT, overcoming limitations of fixed potential electrolysis.
  • This eRAFT approach provides good control over polymer architecture and molecular weight for (meth)acrylate monomers.