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Related Concept Videos

Radical Chain-Growth Polymerization: Mechanism01:09

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...
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Characteristics and Nomenclature of Copolymers01:24

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Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...
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Radical Chain-Growth Polymerization: Overview01:10

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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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Free-Radical Chain Reaction and Polymerization of Alkenes02:35

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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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Radical Chain-Growth Polymerization: Chain Branching01:17

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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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Step-Growth Polymerization: Overview01:03

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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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Related Experiment Video

Updated: Jun 18, 2025

Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers
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Solid-Phase Synthesis of Well-Defined Multiblock Copolymers by Atom Transfer Radical Polymerization.

Grzegorz Szczepaniak1,2, Kriti Kapil1, Samuel Adida1

  • 1Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States.

Journal of the American Chemical Society
|July 30, 2024
PubMed
Summary

This study introduces a novel solid-phase polymer synthesis method using amphiphilic ChemMatrix resin and atom transfer radical polymerization (ATRP) for creating sequence-controlled block copolymers.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Organic Synthesis

Background:

  • Solid-phase synthesis, originating from peptide chemistry, is a powerful technique for macromolecules.
  • Traditional solid supports often have limitations in solvent compatibility and processing.

Purpose of the Study:

  • To develop an efficient solid-phase method for sequence-controlled polymer synthesis.
  • To utilize the unique properties of ChemMatrix (CM) resin for improved polymer synthesis.

Main Methods:

  • Covalent immobilization of polymer chains onto a poly(ethylene glycol) (PEG)-based ChemMatrix (CM) resin.
  • Combination of atom transfer radical polymerization (ATRP) with solid-phase techniques.
  • Synthesis of multi-block copolymers (di-, tri-, tetra-, penta-block).

Main Results:

  • Achieved high yields of well-defined block copolymers with excellent molecular weight and dispersity control.
  • Demonstrated the versatility of the method with various monomers in organic and aqueous media.
  • Identified limitations in achieving very high molecular weights due to resin pore confinement.

Conclusions:

  • The developed solid-phase polymer synthesis approach using CM resin is effective for creating sequence-controlled block copolymers.
  • This method offers a simplified and rapid route for synthesizing tailored block copolymers with diverse functionalities.
  • The amphiphilic nature of CM resin enhances processing efficiency compared to traditional supports.