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Videos de Conceptos Relacionados

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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Olefin Metathesis Polymerization: Overview01:13

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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 of a...
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Anionic Chain-Growth Polymerization: Overview01:20

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Cycloaddition Reactions: Overview01:16

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Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
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Types of Step-Growth Polymers: Polyesters01:20

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The introduction of polyesters has brought major development to the textile industry. The wrinkle-free behavior of polyester blends has eliminated the need for starching and ironing clothes.
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[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement01:21

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The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
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La catálisis conmutable mejora las propiedades de los polímeros derivados del CO2 (poly (carbonato de ciclohexeno) -

Gregory S Sulley1, Georgina L Gregory1, Thomas T D Chen1

  • 1Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, U.K.

Journal of the American Chemical Society
|February 21, 2020
PubMed
Resumen

Este estudio introduce un nuevo proceso catalítico para crear polímeros de bloque degradables a partir de desechos de dióxido de carbono (CO2) y materiales de base biológica. Estos nuevos polímeros derivados del CO2 presentan una mayor resistencia y flexibilidad, ofreciendo alternativas sostenibles para aplicaciones de materiales.

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Área de la Ciencia:

  • Química de los polímeros
  • Catálisis
  • Materiales sostenibles

Sus antecedentes:

  • La copolimización de dióxido de carbono (CO2) con epóxidos ofrece una vía para valorar el CO2 residual y reducir la contaminación.
  • Los policarbonatos de alta masa molar de CO2 existentes, como el policarbonato de ciclohexeno, a menudo carecen de las propiedades mecánicas deseables y muestran fragilidad.
  • Los polioles de policarbonato de baja masa molar son comercialmente relevantes para los termofijos y los poliuretanos.

Objetivo del estudio:

  • Desarrollar un nuevo proceso de polimerización catalítica para la síntesis de polímeros de bloque ABA degradables que incorporen dióxido de carbono.
  • Crear polímeros derivados del CO2 con propiedades mecánicas mejoradas en comparación con el carbonato de poli (ciclohexeno) existente.
  • Explorar el potencial de estos nuevos materiales en diversas aplicaciones.

Principales métodos:

  • Se utilizó un nuevo catalizador heterodinuclear organometálico altamente activo Zn{II}/Mg{II}.
  • Se utilizó un procedimiento de un solo recipiente, combinando ε-decalactona de base biológica, óxido de ciclohexeno y dióxido de carbono.
  • Síntesis de polímeros de bloque de carbonato de ciclohexeno-b-decalactona-b-carbonato de ciclohexeno [PCHC-PDL-PCHC].

Principales resultados:

  • Síntesis selectiva y eficiente de polímeros de bloque ABA degradables con una incorporación de CO2 del 6 al 23% en peso.
  • Se logró una alta selectividad de CO2 (> 99%) y conversiones de monómeros (> 90%).
  • Los polímeros resultantes exhibieron composiciones predecibles, masas molares (38-71 kg mol-1), extremos de la cadena dihidroxila telecélica, buena estabilidad térmica (~ 280 °C), alta tenacidad (112 MJ m-3) y excelente alargamiento en la ruptura (> 900%).

Conclusiones:

  • El proceso catalítico desarrollado produce nuevos polímeros de bloque derivados del CO2 con propiedades mecánicas significativamente mejoradas.
  • El control preciso de la cantidad y ubicación de CO2 en la cadena de polímeros mejora el rendimiento del material.
  • El proceso es versátil, aplicable a varios monómeros y abre caminos para nuevas aplicaciones de polímeros derivados de CO2.