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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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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...
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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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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.
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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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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Un sintetizador de polirotaxano de precisión

Yunyan Qiu1, Bo Song1,2, Cristian Pezzato1

  • 1Department of Chemistry, Northwestern University, Evanston, IL 60208, USA.

Science (New York, N.Y.)
|June 13, 2020
PubMed
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Los investigadores desarrollaron un método programable utilizando bombas moleculares artificiales para controlar con precisión el número de anillos en las cadenas de polímero, avanzando en el diseño de máquinas moleculares.

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Área de la Ciencia:

  • Química supramolecular
  • Ciencias de los materiales

Sus antecedentes:

  • Las moléculas mecánicamente entrelazadas son la clave para las máquinas moleculares artificiales.
  • Los polirotaxanos tienen aplicaciones especializadas pero carecen de una síntesis eficiente para un recuento preciso de anillos.

Objetivo del estudio:

  • Desarrollar protocolos sintéticos eficientes para los polirotaxanos con un número controlado de anillos.
  • Para aprovechar las bombas moleculares artificiales para la síntesis programable.

Principales métodos:

  • Se utilizaron procesos cíclicos basados en redox con bombas moleculares artificiales.
  • Entregaba anillos en pares a las pesas de polímero.
  • Incorporación controlada del anillo mediante ciclos redox químicos o electroquímicos.

Principales resultados:

  • Se logró la incorporación precisa de 2, 4, 6, 8 y 10 anillos en pesas de polímero hexacationales.
  • Control programable demostrado del número de anillos basado en ciclos redox.
  • Los polirotaxanos sintetizados con cargas crecientes (8+ a 40+).

Conclusiones:

  • La estrategia desarrollada permite una síntesis precisa y programable de polirotaxanos.
  • Esto hace avanzar el diseño y la construcción de máquinas moleculares complejas.
  • Ofrece potencial para nuevos materiales con propiedades mecánicas a medida.