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Related Concept Videos

Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

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...
Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

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 the...
Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

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...
Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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...
Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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 generated carbocation,...
Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

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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Related Experiment Video

Updated: May 29, 2026

3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization
07:28

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

Published on: February 18, 2022

Enhanced volumetric additive manufacturing via Reversible Addition-Fragmentation Chain Transfer (RAFT)

Eduards Krumins1, Yaxuan Sun2, Long Jiang3

  • 1Centre of Additive Manufacturing, Faculty of Engineering, Engineering, University Park, University of Nottingham, Nottingham, NG7 2RD, UK.

Nature Communications
|May 27, 2026
PubMed
Summary
This summary is machine-generated.

Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization in Computed Axial Lithography (CAL) reduces heat generation and auto-acceleration during 3D printing. This advancement enables the fabrication of complex, thermally stable structures with enhanced chemical versatility.

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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

Published on: April 22, 2016

Area of Science:

  • Additive Manufacturing
  • Polymer Chemistry
  • Photopolymerization

Background:

  • Computed Axial Lithography (CAL) is a Volumetric Additive Manufacturing (VAM) technique for rapid, layer-less 3D printing.
  • Conventional CAL uses free radical polymerization (FRP), an exothermic process leading to auto-acceleration, reduced print fidelity, and scalability issues due to significant heat generation (ΔT > 60°C).

Purpose of the Study:

  • To introduce Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization into CAL systems.
  • To mitigate heat generation and suppress auto-acceleration during CAL photopolymerization.
  • To enhance the chemical versatility and thermal stability of CAL-fabricated objects.

Main Methods:

  • Incorporation of RAFT polymerization into (meth)acrylate-based resins for CAL.
  • In-situ thermal monitoring to assess temperature changes during printing.
  • Evaluation of buoyancy effects to confirm suppression of thermally induced phenomena.

Main Results:

  • RAFT polymerization significantly reduced temperature rise and suppressed auto-acceleration compared to FRP in CAL.
  • Thermally induced buoyancy was mitigated, indicating improved print stability.
  • Post-printing functionalization of printed objects was achieved, demonstrating expanded chemical versatility.

Conclusions:

  • RAFT-mediated CAL effectively controls polymerization kinetics, reducing exothermic heat and improving print fidelity.
  • This approach enables the fabrication of complex structures not achievable with FRP-based CAL.
  • RAFT-mediated CAL advances the development of thermally stable and functionally tunable volumetric additive manufacturing.