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Videos de Conceptos Relacionados

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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Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

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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

Free-Radical Chain Reaction and Polymerization of Alkenes

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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

Radical Chain-Growth Polymerization: Chain Branching

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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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Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

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Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
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Radical Formation: Addition00:47

Radical Formation: Addition

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Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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La polimerización del radical de transferencia atómica libre de metales por transferencia de átomos es una

Nicolas J Treat1, Hazel Sprafke, John W Kramer

  • 1Materials Department, Materials Research Laboratory, University of California , Santa Barbara, California 93106, United States.

Journal of the American Chemical Society
|November 1, 2014
PubMed
Resumen
Este resumen es generado por máquina.

Este estudio introduce un método de polimerización radical de transferencia atómica libre de metales (ATRP) utilizando catalizadores fotorredóxicos ligeros y orgánicos. Este enfoque ofrece un excelente control sobre las propiedades del polímero y permite la síntesis versátil de copolímero de bloque.

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Área de la Ciencia:

  • Química de Polímeros La Química de Polímeros es la química de los polímeros.
  • Catálisis orgánica por catálisis orgánica.
  • La fotoquímica es la fotoquímica.

Sus antecedentes:

  • Los métodos tradicionales de polimerización radical por transferencia atómica (ATRP) a menudo sufren de contaminación por metales.
  • El desarrollo de técnicas de polimerización libre de metales es crucial para aplicaciones que requieren alta pureza.

Objetivo del estudio:

  • Informar sobre un nuevo proceso ATRP sin metales que utiliza luz y catalizadores orgánicos fotorredóxicos.
  • Para demostrar un control eficiente sobre el peso molecular del polímero, la polidispersidad y los extremos de la cadena.
  • Mostrar la fácil síntesis de copolímeros de bloque e integración con otros procesos radicales controlados.

Principales métodos:

  • El uso de luz visible para mediar la polimerización.
  • Utilizando catalizadores fotoredox de base orgánica para ciclos de activación y desactivación.
  • Investigando la polimerización de los monómeros de vinilo.

Principales resultados:

  • Se logró una polimerización eficiente de monómeros de vinilo con un excelente control.
  • Ha demostrado un control preciso sobre el peso molecular, la polidispersidad y los extremos de la cadena.
  • Facilitó la síntesis directa de copolímeros de bloque con alta versatilidad estructural.

Conclusiones:

  • El sistema ATRP sin metales desarrollado supera los problemas de contaminación por metales.
  • Los catalizadores orgánicos fotorredóxicos ofrecen una plataforma versátil para la polimerización radical controlada.
  • Esta metodología es prometedora para la síntesis avanzada de polímeros y la química de moléculas pequeñas.