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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,...

Anionic Chain-Growth Polymerization: Mechanism

Anionic Chain-Growth Polymerization: Mechanism

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 acceptor.

Step-Growth Polymerization: Overview

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...

Anionic Chain-Growth Polymerization: Overview

Anionic Chain-Growth Polymerization: Overview

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,...

Radical Chain-Growth Polymerization: Mechanism

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: Overview

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...

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Related Experiment Video

Updated: Jun 1, 2026

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

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

Published on: February 18, 2022

Tip- or electron beam-induced surface polymerization.

Sylvain Clair¹, Oualid Ourdjini, Mathieu Abel

¹IM2NP-CNRS UMR6242-Aix Marseille University, Faculté des Sciences et Techniques-Campus de saint Jérôme-Case 142, 13397 Marseille Cedex 20, France. sylvain.clair@im2np.fr

Chemical Communications (Cambridge, England)

|June 14, 2011

Summary

Researchers controlled two-dimensional polymer formation using scanning tunneling microscopy tip manipulation for precise localization. Electron irradiation was also found to significantly accelerate the polymerization reaction kinetics.

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Area of Science:

Materials Science
Surface Chemistry
Polymer Chemistry

Background:

Two-dimensional polymers offer unique properties for advanced materials.
Precise control over polymer formation is crucial for targeted applications.
Understanding reaction kinetics is key to optimizing synthesis.

Purpose of the Study:

To investigate methods for controlling the formation of two-dimensional polymers.
To explore the use of scanning tunneling microscopy for reaction localization.
To determine the effect of electron irradiation on polymerization kinetics.

Main Methods:

Utilized scanning tunneling microscopy (STM) tip manipulation to direct polymerization.
Applied electron irradiation to influence reaction rates.
Characterized the resulting two-dimensional polymer structures.

Main Results:

STM tip manipulation enabled precise spatial control over polymer formation.
Electron irradiation significantly accelerated the polymerization reaction kinetics.
Demonstrated a dual approach for controlled synthesis of 2D polymers.

Conclusions:

Precise control over 2D polymer synthesis is achievable through localized manipulation.
Electron irradiation presents a viable method for enhancing polymerization rates.
These methods provide new avenues for designing and fabricating advanced 2D materials.