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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...
3.4K
Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

2.8K
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 of a...
2.8K
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...
2.3K
Base-Catalyzed Ring-Opening of Epoxides02:26

Base-Catalyzed Ring-Opening of Epoxides

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Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
11.3K
Acid-Catalyzed Ring-Opening of Epoxides02:24

Acid-Catalyzed Ring-Opening of Epoxides

10.0K
Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
10.0K
Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

4.4K
Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Updated: Apr 18, 2026

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
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Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers

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Metátesis de abertura de anillo libre de metales polimerización de la polimerización.

Kelli A Ogawa1, Adam E Goetz, Andrew J Boydston

  • 1Department of Chemistry, University of Washington , Seattle, Washington 98195, United States.

Journal of the American Chemical Society
|January 10, 2015
PubMed
Resumen

Este estudio introduce un nuevo método de polimerización de metástasis de apertura de anillo libre de metales (ROMP). Los iniciadores orgánicos se oxidan para crear cationes radicales, lo que permite una polimerización controlada sin metales de transición.

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Área de la Ciencia:

  • Química de Polímeros La química de los polímeros es la química de los polímeros.
  • Síntesis orgánica La síntesis orgánica.
  • Ciencia de los materiales Ciencia de los materiales.

Sus antecedentes:

  • La polimerización por metástasis de apertura de anillo (ROMP) tradicionalmente se basa en catalizadores de metales de transición.
  • El desarrollo de métodos de polimerización libres de metales es crucial para la sostenibilidad y evitar la contaminación de metales en los productos.

Objetivo del estudio:

  • Establecer un nuevo enfoque libre de metales para el ROMP controlado.
  • Para demostrar la eficacia de la oxidación del iniciador orgánico para la ROMP.
  • Para lograr el control temporal de la polimerización mediante la catálisis fotorredóxica.

Principales métodos:

  • Generación de cationes radicales a través de la oxidación de un electrón de éteres de vinilo utilizando un mediador orgánico de fotoredox.
  • Reacción de los cationes radicales generados con el norboreneno para iniciar la ROMP.
  • Utilizando ciclos de encendido/apagado de la exposición a la luz para el control temporal del crecimiento del polímero.

Principales resultados:

  • ROMP logrado con microestructuras idénticas a las ROMP mediadas por metales.
  • Se obtienen altos rendimientos de polímero en condiciones de reacción suaves.
  • Se ha demostrado una buena correlación entre el peso molecular y las relaciones monómero-catalizador.
  • Mostró el control temporal sobre la reiniciación de la polimerización a través de la exposición a la luz.

Conclusiones:

  • Este trabajo presenta el primer método libre de metales para el ROMP controlado.
  • El método desarrollado ofrece una alternativa sostenible y eficiente a la tradicional ROMP mediada por metales.
  • La oxidación mediada por fotorredóxido de iniciadores orgánicos proporciona una plataforma versátil para la polimerización controlada.