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Videos de Conceptos Relacionados

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

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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

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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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Molecular Weight of Step-Growth Polymers01:08

Molecular Weight of Step-Growth Polymers

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Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...
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Polymer Classification: Architecture01:14

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Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...
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Step-Growth Polymerization: Overview01:03

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
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Radical Chain-Growth Polymerization: Overview01:10

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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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Control de la densidad de injerto y distribución en polímeros de injerto por copolimización de metástasis de apertura

Tzu-Pin Lin1, Alice B Chang1, Hsiang-Yun Chen1

  • 1Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.

Journal of the American Chemical Society
|February 22, 2017
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Resumen

Los investigadores desarrollaron un nuevo método de síntesis de polímeros utilizando la polimerización de metástasis de apertura de anillo vivo (ROMP) para controlar la densidad y distribución del injerto. Esta técnica permite un ajuste preciso de la arquitectura del polímero para el diseño de materiales avanzados.

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Área de la Ciencia:

  • Química de los polímeros
  • Ciencias de los materiales
  • Síntesis orgánica

Sus antecedentes:

  • El control preciso de la secuencia y la arquitectura del polímero es esencial para comprender las relaciones estructura-propiedad.
  • El diseño de polímeros funcionales con propiedades a medida requiere metodologías sintéticas avanzadas.
  • La polimerización de metástasis de apertura de anillo vivo (ROMP) ofrece una plataforma versátil para la síntesis de polímeros.

Objetivo del estudio:

  • Desarrollar un nuevo enfoque sintético para la manipulación fácil de la densidad y la distribución del injerto en polímeros.
  • Permitir la síntesis de polímeros con arquitecturas controladas, uniendo los regímenes lineal a brocha.
  • Establecer un método para ajustar las propiedades del polímero mediante el injerto controlado.

Principales métodos:

  • Se utilizó la polimerización de metástasis de apertura de anillo vivo (ROMP) con un catalizador de tercera generación (G3).
  • Se utilizan dialquilésteres discretos de norbornenilo (por ejemplo, DME, DEE, DBE) como diluyentes copolymerizados con macronomeros funcionalizados (PS, PLA, PDMS).
  • Determinación de las constantes de auto propagación y de propagación cruzada utilizando un modelo de copolimización terminal para analizar la distribución de secuencias.

Principales resultados:

  • Se logra un control directo de la densidad de injerto del polímero a través de la relación de alimentación de macronomeros y diluyentes.
  • Demostró que las tasas de propagación coincidentes favorecen la distribución aleatoria de la cadena lateral, mientras que las disparidades aumentan la tendencia al gradiente.
  • Polímeros monodispersos sintetizados (PLA-ran-DME) con densidades de injerto variables y longitudes de espina dorsal controladas.

Conclusiones:

  • La estrategia sintética desarrollada proporciona un método poderoso para crear polímeros con densidad de injerto ajustable y distribución de la cadena lateral.
  • Este control sobre la arquitectura del polímero es crucial para dictar las propiedades microscópicas y macroscópicas del material.
  • El enfoque facilita la síntesis de diversas arquitecturas de polímeros, desde las estructuras lineales hasta las de brocha de botella.