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Related Concept Videos

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

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

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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...
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Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
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Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)00:53

Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)

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Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
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Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

2.8K
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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Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

2.1K
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...
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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

2.4K
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...
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Related Experiment Video

Updated: Sep 16, 2025

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes
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Active light-controlled frontal ring-opening metathesis polymerization.

D R Darby1, A J Greenlee1,2, R H Bean1

  • 1Sandia National Laboratories, Albuquerque, NM, USA.

Nature Communications
|July 8, 2025
PubMed
Summary
This summary is machine-generated.

Photochemical methods enable precise control over frontal ring-opening metathesis polymerization (FROMP) of dicyclopentadiene (DCPD). This innovation allows for tunable front velocity and patterned polymerizations, advancing manufacturing techniques.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Photochemistry

Background:

  • Frontal ring-opening metathesis polymerization (FROMP) is an energy-efficient method for polymer fabrication.
  • Current FROMP control relies on resin composition or environmental factors, limiting precise manipulation.
  • Diverse applications exist for FROMP, including additive manufacturing, composites, and foams.

Purpose of the Study:

  • To develop photochemical methods for controlling FROMP of dicyclopentadiene (DCPD).
  • To achieve orthogonal control over the frontal polymerization velocity using light.
  • To demonstrate photoinhibition-enabled patterning and spatial control of frontal polymerizations.

Main Methods:

  • Utilized a photobase generator to inhibit FROMP with UV light.
  • Employed a photosensitizer and co-initiator to accelerate FROMP with blue light.
  • Demonstrated photoinhibition for lithographic patterning and spatial manipulation of polymerization fronts.

Main Results:

  • Achieved orthogonal active photocontrol of FROMP front velocity using UV and blue light.
  • Successfully demonstrated photoinhibition-enabled lithographic patterning of frontal polymerizations.
  • Showcased spatial control, redirection, and splitting of frontal polymerization fronts.

Conclusions:

  • Established a foundation for advanced photochemical control of frontal polymerizations.
  • This approach enables innovation in traditional and additive manufacturing processes.
  • Opens possibilities for novel applications such as morphogenic manufacturing.