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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.
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...
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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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Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...
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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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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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Competencia y Acoplamiento Entre Cristalización y Microseparación en un Copolímero Tribloque

Shichu Yang1, Zhihao Shen1, Xing-He Fan1

  • 1Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, China.

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Los copolímeros de bloque con bloques de cristal líquido y semicristalinos se autoensamblan en estructuras laminares y hexagonales. La cristalización del polímero influye significativamente en la formación de nanoestructuras, lo que lleva a transiciones de fase únicas.

Palabras clave:
copolímero de bloquecristalizacióntransición inferior de desorden a ordenmicroseparaciónpolímero semicristalino

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Área de la Ciencia:

  • Química de Polímeros
  • Ciencia de Materiales
  • Nanotecnología

Sus antecedentes:

  • Los copolímeros de bloque (BCP) se autoensamblan en diversas nanoestructuras.
  • La incorporación de polímeros de cristal líquido (LC) y semicristalinos modifica el autoensamblaje de BCP.
  • Los polímeros LC con chaqueta de mesógenos (MJLCP) ofrecen propiedades únicas.

Objetivo del estudio:

  • Sintetizar y caracterizar nuevos BCP que contienen bloques de polidimetilsiloxano (PDMS), poli(L-ácido láctico) (PLLA) y un bloque LC de PMVBP.
  • Investigar la influencia de la cristalización de PLLA en la formación de nanoestructuras de BCP.
  • Explorar el comportamiento de fase dependiente de la temperatura y las transiciones.

Principales métodos:

  • Síntesis de copolímeros tribloque (PDMS-b-PLLA-b-PMVBP).
  • Dispersión de rayos X en ángulo pequeño (SAXS) dependiente de la temperatura para análisis estructural.
  • Análisis de transiciones de fase y evolución de nanoestructuras.

Principales resultados:

  • El copolímero dibloque PLLA-b-PMVBP no mostró nanoestructuras ordenadas debido a parámetros de solubilidad similares.
  • El copolímero tribloque PDMS-b-PLLA-b-PMVBP exhibió estructuras laminares (LAM) a temperatura ambiente y hexagonales (HEX) a altas temperaturas.
  • La cristalización de PLLA impactó significativamente el autoensamblaje de BCP, compitiendo o acoplándose potencialmente con la microseparación.
  • Se observó una rara transición de desorden a orden inferior (LDOT).

Conclusiones:

  • La interacción entre la cristalización del polímero y la microseparación gobierna la nanoestructura de BCP.
  • Se observan transiciones estructurales inducidas por la temperatura (LAM a HEX).
  • El comportamiento de fase novedoso, incluido LDOT, resalta la complejidad del autoensamblaje de BCP con bloques funcionales.