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Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
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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...
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For any given polymer, the weight average molecular weight (Mw) is higher than, if not equal to, the number average molecular weight (Mn). The only situation in which the weight average molecular weight and the number average molecular weight are equal is when a polymer consists only of chains with equal molecular weight. However, this never happens in a synthetic polymer, since it is difficult to control the polymerization process up to a molecular level with accuracy to a hundred percent.
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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...
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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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Un polímero covalente dinámico 1D cristalino

Elisabet De Bolòs1, Marta Martínez-Abadía1, Félix Hernández-Culebras1

  • 1POLYMAT, University of the Basque Country UPV/EHU, Avenida de Tolosa 72, Donostia-San Sebastián 20018, Spain.

Journal of the American Chemical Society
|August 22, 2022
PubMed
Resumen
Este resumen es generado por máquina.

Los investigadores sintetizaron un polímero cristalino unidimensional utilizando la química covalente dinámica. Este avance permite una mejor comprensión de las propiedades de los polímeros y crea materiales con capacidades de transporte de carga mejoradas.

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Área de la Ciencia:

  • Química de los polímeros
  • Ciencias de los materiales
  • Física del estado sólido

Sus antecedentes:

  • Los polímeros cristalinos unidimensionales son cruciales para comprender las relaciones estructura-propiedad en los materiales.
  • Lograr polímeros cristalinos unidimensionales es un desafío debido a la tendencia a las fases amorfas o semicristalinas.
  • Estos materiales ofrecen potencial para propiedades térmicas, mecánicas y conductoras mejoradas.

Objetivo del estudio:

  • Para reportar la síntesis de un polímero unidimensional cristalino en solución.
  • Para investigar la relación estructura-propiedad, en particular el transporte de carga.
  • Para demostrar un método para crear materiales poliméricos ordenados.

Principales métodos:

  • Química covalente dinámica para la síntesis de polímeros.
  • Difracción de electrones de microcristal para la confirmación estructural.
  • Estudios de transporte de carga y cálculos teóricos.

Principales resultados:

  • Con éxito sintetizó un polímero unidimensional cristalino en solución.
  • Se confirmó inequívocamente la estructura del polímero mediante difracción de electrones de microcristal.
  • Demostró que las cadenas apiladas π crean canales óptimos para el transporte de cargas.

Conclusiones:

  • La síntesis de polímeros cristalinos unidimensionales se puede lograr a través de la química covalente dinámica.
  • La estructura apilada en π es clave para las excelentes propiedades de transporte de carga del polímero.
  • Este trabajo avanza en el desarrollo de materiales poliméricos avanzados con propiedades electrónicas a medida.