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

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Electrochemically mediated atom transfer radical polymerization on nonconducting substrates: controlled brush growth

Bin Li¹, Bo Yu, Wilhelm T S Huck

¹State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 China.

Journal of the American Chemical Society

|January 25, 2013

Summary

Surface initiated atom transfer radical polymerization (SI-ATRP) uses a Cu(I)/L activator gradient to control polymer growth. Polymer brushes were grafted by controlling the gap distance and substrate angle for tunable polymer kinetics.

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Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates

Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates

Published on: January 17, 2018

Area of Science:

Polymer Chemistry
Surface Science
Electrochemistry

Background:

Atom Transfer Radical Polymerization (ATRP) is a controlled polymerization technique.
Surface-initiated ATRP (SI-ATRP) allows for polymer grafting from surfaces.
Controlling polymerization kinetics is crucial for tailoring material properties.

Purpose of the Study:

To investigate surface-initiated atom transfer radical polymerization (SI-ATRP) triggered by an electrochemical activator gradient.
To explore the effect of activator concentration gradients on polymer growth kinetics.
To achieve gradient polymer brushes with tunable properties.

Main Methods:

Generation of a Cu(I)/L activator at a working electrode.
Formation of a stable [Cu(II)L]/[Cu(I)L] ratio gradient via ion diffusion in a defined gap.
Grafting polymer brushes onto initiator-terminated substrates at varying gap distances and tilting angles.

Main Results:

SI-ATRP was successfully initiated by the diffusion of the electrochemically generated activator.
A stable concentration gradient of the copper catalyst ([Cu(II)L]/[Cu(I)L]) was established.
Polymer growth kinetics were dictated by the gap distance, enabling control over polymer chain length and density.
Gradient polymer brushes were synthesized by positioning the substrate along the established gradient.

Conclusions:

Electrochemical generation of activator gradients provides a novel method for controlling SI-ATRP.
The gap distance and substrate orientation are key parameters for tuning polymer brush architecture.
This approach allows for the creation of materials with spatially controlled polymer properties.