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Cationic Chain-Growth Polymerization: Mechanism

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,...

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 the...

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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.
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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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Related Experiment Video

Updated: Jun 24, 2026

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

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

Published on: November 21, 2017

Achieving lambda/20 resolution by one-color initiation and deactivation of polymerization.

Linjie Li¹, Rafael R Gattass, Erez Gershgoren

¹Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742, USA.

Science (New York, N.Y.)

|April 11, 2009

Summary

This study introduces a novel photolithography technique using multiphoton absorption for cross-linking and one-photon absorption for deactivation. This method achieves scalable sub-wavelength feature fabrication, enabling advanced 2D and 3D nanostructure manufacturing.

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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

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Published on: September 26, 2016

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Last Updated: Jun 24, 2026

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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

Published on: September 26, 2016

Area of Science:

Nanotechnology
Materials Science
Optics

Background:

Conventional photolithography is limited by diffraction, restricting feature resolution.
Achieving sub-wavelength feature sizes is crucial for advanced microelectronics and nanophotonics.

Purpose of the Study:

To develop a photolithography technique that overcomes diffraction limits.
To enable the fabrication of nanoscale features with high precision.

Main Methods:

Utilizing multiphoton absorption of pulsed 800-nm light to initiate polymer cross-linking.
Employing simultaneous one-photon absorption of continuous-wave 800-nm light to deactivate photopolymerization.
Implementing spatial phase-shaping of the deactivation beam for precise control.

Main Results:

Demonstrated fabrication of features with scalable resolution along the beam axis.
Achieved a minimum feature size of 40 nanometers.
Successfully created structures with feature sizes significantly smaller than the wavelength of light used.

Conclusions:

The developed photolithography approach overcomes traditional diffraction limitations.
This technique allows for the precise fabrication of complex 2D and 3D nanostructures.
Anticipated applications include advanced semiconductor manufacturing and nanophotonics.