Search research articles

ABOUT JoVE

Overview Leadership Blog JoVE Help Center

AUTHORS

Publishing Process Editorial Board Scope & Policies Peer Review FAQ Submit

LIBRARIANS

Testimonials Subscriptions Access Resources Library Advisory Board FAQ

RESEARCH

JoVE Journal Methods Collections JoVE Encyclopedia of Experiments Archive

EDUCATION

JoVE Core JoVE Business JoVE Science Education JoVE Lab Manual Faculty Resource Center Faculty Site

Terms & Conditions of Use

Related Concept Videos

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...

Radical Chain-Growth Polymerization: Chain Branching

Radical Chain-Growth Polymerization: Chain Branching

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...

Free-Radical Chain Reaction and Polymerization of Alkenes

Free-Radical Chain Reaction and Polymerization of Alkenes

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.

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,...

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by

Same author

Surface-Initiated Atom Transfer Radical Polymerization Using Hydrogel Reactors.

Langmuir : the ACS journal of surfaces and colloids·2026

Same author

PDMS aqueous leachates cause acute toxicity in <i>C. elegans</i>.

Lab on a chip·2026

Same author

Assessing PDMS Biocompatibility in Microfluidic Applications: Toxicity and Survival Outcomes in <i>C. elegans</i>.

bioRxiv : the preprint server for biology·2025

Same author

Controlled delivery of phosphate to plants with optimized chemical and physical factors.

Quantitative plant biology·2025

Same author

Functional Hydrogels for Selective Phosphate Removal from Water and Release on Demand.

Langmuir : the ACS journal of surfaces and colloids·2025

Same author

DendriPep Nanocoats: Substrate-Agnostic, Self-Assembling Constructs with Shear-Controlled Thickness and Permeability.

Langmuir : the ACS journal of surfaces and colloids·2025

Search research articles

Related Experiment Video

Updated: May 28, 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

Simultaneous bulk- and surface-initiated controlled radical polymerization from planar substrates.

Salomon Turgman-Cohen¹, Jan Genzer

¹Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, North Carolina 27695, United States.

Journal of the American Chemical Society

|October 8, 2011

Summary

Monte Carlo simulations reveal that bulk polymerization is faster and produces polymers with narrower molecular weight distribution than surface-initiated polymerization. Surface polymerization rates depend on initiator density, invalidating common assumptions about polymer grafting density.

More Related Videos

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

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

Published on: April 22, 2016

Fabricating Complex Culture Substrates Using Robotic Microcontact Printing (R-µCP) and Sequential Nucleophilic Substitution

Fabricating Complex Culture Substrates Using Robotic Microcontact Printing (R-µCP) and Sequential Nucleophilic Substitution

Published on: October 31, 2014

Related Experiment Videos

Last Updated: May 28, 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

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

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

Published on: April 22, 2016

Fabricating Complex Culture Substrates Using Robotic Microcontact Printing (R-µCP) and Sequential Nucleophilic Substitution

Fabricating Complex Culture Substrates Using Robotic Microcontact Printing (R-µCP) and Sequential Nucleophilic Substitution

Published on: October 31, 2014

Area of Science:

Polymer Chemistry
Surface Science
Computational Chemistry

Background:

Controlled radical polymerization is crucial for synthesizing polymers with defined properties.
Surface-initiated polymerization allows for the creation of polymer brushes and functionalized surfaces.
Accurate characterization of surface-bound polymers is essential for their applications.

Purpose of the Study:

To investigate the differences between controlled radical polymerization in bulk solution and from a flat surface.
To determine the factors influencing surface-initiated polymerization rates.
To challenge the assumption of equal molecular weight between bulk and surface-grown polymers.

Main Methods:

Monte Carlo computer simulations were employed.
Simulations modeled simultaneous polymerization in solution and from an impenetrable flat surface.
Variations in initiator site density on the surface were considered.

Main Results:

Bulk polymers exhibited faster growth rates and narrower molecular weight distributions compared to surface-initiated polymers.
The rate of surface-initiated polymerization was found to be dependent on the density of initiator sites.
A significant discrepancy was observed between the molecular weights of bulk and surface-grown polymers.

Conclusions:

The assumption that surface-initiated polymer molecular weight equals bulk polymer molecular weight is generally invalid.
This finding has implications for the accurate determination of grafting density in surface-bound polymer systems.
Understanding these differences is key for designing and characterizing advanced polymer materials.