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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

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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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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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Cationic Chain-Growth Polymerization: Mechanism

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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 generated carbocation,...

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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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Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers

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Polymer chain generation for coarse-grained models using radical-like polymerization.

Michel Perez¹, Olivier Lame, Fabien Leonforte

¹Université de Lyon, INSA de Lyon, MATEIS, CNRS, UMR 5510, 69621 Villeurbanne, France. michel.perez@insa-lyon.fr

The Journal of Chemical Physics

|June 24, 2008

Summary

This summary is machine-generated.

A novel radical polymerization-inspired method generates equilibrated polymer melt configurations. This versatile technique efficiently creates polymer melts and nanostructured polymers with built-in relaxation.

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Area of Science:

Polymer Science
Computational Chemistry
Materials Science

Background:

Generating equilibrated polymer melt configurations is crucial for accurate simulations.
Existing methods like the push-off method have limitations.
Coarse-grained models require efficient configuration generation techniques.

Purpose of the Study:

To introduce a new, versatile method for generating polymer melt configurations.
To enable relaxation during chain generation for improved equilibration.
To demonstrate the method's applicability to various polymer architectures.

Main Methods:

A three-stage method inspired by radical polymerization: nucleation, chain growth, and termination.
Monomer-solvent system with radical species to build polymer chains.
Comparison with the established push-off method for validation.

Main Results:

Successfully generated pure mono- and polydisperse polymer melts.
Static properties (radius of gyration, entanglement length) confirm melt equilibration.
Demonstrated flexibility for creating diblock and triblock copolymers.

Conclusions:

The radical polymerization-inspired technique is effective for generating equilibrated polymer melts.
The method offers a flexible and efficient alternative for polymer model generation.
Applicable to both simple polymer melts and complex nanostructured copolymers.