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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.
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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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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 generated carbocation,...
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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 acceptor.
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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 species into the...
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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.
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Conocimientos mecánicos sobre la polimerización de inserción de acrilato.

Damien Guironnet1, Lucia Caporaso, Boris Neuwald

  • 1Department of Chemistry, University of Konstanz, 78464 Konstanz, Germany.

Journal of the American Chemical Society
|March 9, 2010
PubMed
Resumen

Este estudio detalla la oligomerización catalítica de los acrilatos utilizando nuevos complejos de paladio. Los investigadores exploraron los mecanismos de inserción del acrilato de metilo y el etileno, revelando información clave sobre las vías de polimerización y las barreras energéticas.

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Área de la Ciencia:

  • Química organometálica Química orgánica de los metales.
  • Catálisis de polimerización por catálisis de polimerización.
  • Coordinación Química de la Coordinación

Sus antecedentes:

  • Los complejos de paládio con ligandos PwedgeO sirven como precursores de un solo componente para la oligomerización catalítica del acrilato.
  • La comprensión del mecanismo de inserción de acrilato en enlaces alquilo-paladio es crucial para controlar la polimerización.

Objetivo del estudio:

  • Para investigar la oligomerización catalítica de los acrilatos utilizando nuevos complejos de paladio.
  • Para dilucidar el mecanismo de las inserciones consecutivas de acrilato en enlaces de metilo-paladio.
  • Para modelar los intermediarios involucrados en la polimerización de inserción de acrilato y la copolimerización de etileno-acrilato.

Principales métodos:

  • Síntesis y caracterización de complejos de paladio, incluida la espectroscopia de RMN y la difracción de rayos X de cristal único.
  • Estudios cinéticos de la unión al sustrato y la inhibición de la polimerización.
  • Cálculos de la Teoría Funcional de Densidad (DFT) para modelar vías de reacción y barreras energéticas.

Principales resultados:

  • Se formaron dos complejos de quelato diastereoméricos a través de inserciones consecutivas de 2,1-metilacrilato en el enlace Pd-Me.
  • Los estudios vinculantes revelaron que la coordinación de monómeros dificulta la inserción de acrilato, retrasando significativamente la polimerización.
  • Los estudios de DFT proporcionaron información detallada sobre las vías y las barreras energéticas de múltiples inserciones consecutivas de acrilato.

Conclusiones:

  • Los complejos de paladio sintetizados son modelos efectivos para los intermediarios en la polimerización de inserción de acrilato.
  • La coordinación de los monómeros juega un papel crítico en la regulación de la tasa de polimerización.
  • Los cálculos teóricos apoyan las observaciones experimentales, ofreciendo una comprensión más profunda del proceso catalítico.