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Videos de Conceptos Relacionados

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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Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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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: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

2.9K
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: 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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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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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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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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3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization
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Fragmentación por adición reversible de la transferencia de la cadena de crecimiento por etapas polimerización

Joji Tanaka1, Noel Edward Archer1, Michael Jeffery Grant1

  • 1Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599, United States.

Journal of the American Chemical Society
|September 28, 2021
PubMed
Resumen

Este estudio introduce la polimerización de crecimiento gradual de RAFT, creando polímeros únicos con agentes RAFT colgantes. Estos polímeros pueden formar cepillos moleculares o transformarse en cadenas lineales, mejorando las posibilidades de diseño de polímeros.

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Área de la Ciencia:

  • Química de los polímeros
  • Ciencias macromoleculares

Sus antecedentes:

  • La polimerización por transferencia de cadena de fragmentación por adición reversible (RAFT) ofrece un control preciso de la estructura del polímero.
  • Las limitaciones en la afinidad de la columna vertebral del polímero restringen el ámbito de aplicación de la polimerización RAFT tradicional.
  • La combinación de técnicas de polimerización es crucial para el desarrollo de arquitecturas poliméricas avanzadas.

Objetivo del estudio:

  • Desarrollar un nuevo método de polimerización mediante la combinación sinérgica de RAFT y polimerización por crecimiento gradual.
  • Para crear polímeros con estructuras de columna vertebral ajustables y sitios reactivos colgantes.
  • Demostrar la síntesis de polímeros moleculares y su posterior transformación.

Principales métodos:

  • Utilizando un proceso de inserción altamente selectivo de un solo monómero con un agente RAFT.
  • Implementación de una estrategia de polimerización dual: crecimiento escalonado RAFT seguido de injerto.
  • Utilizando una funcionalidad de columna vertebral para la modificación posterior a la polimerización.

Principales resultados:

  • Se logró con éxito la polimerización por crecimiento escalonado de RAFT, obteniendo polímeros con agentes RAFT colgantes en cada unidad vertebral.
  • Polímeros de cepillo moleculares sintetizados mediante el injerto de cadenas laterales en los agentes RAFT colgantes.
  • Demostró la transformación de polímeros tipo cepillo en cadenas lineales uniformes utilizando un mecanismo de escisión sensible al estímulo.

Conclusiones:

  • La polimerización por crecimiento escalonado RAFT proporciona una plataforma versátil para crear arquitecturas complejas de polímeros.
  • El método desarrollado permite la síntesis de cepillos moleculares con cadenas laterales ajustables.
  • La escisión sensible al estímulo de la columna vertebral del polímero permite una transformación estructural controlada.