Polymer membranes with ultrahigh CO2 permeabilities and high selectivities are needed to address some of the critical separation challenges related to energy and the environment, especially in natural gas purification and post-combustion carbon capture. However, very few solution-processable, linear polymers are known today that access these types of characteristics, and all of the known structures achieve their separation performance through the design of rigid backbone chemistries that concomitantly increase chain stiff-ness and interchain spacing, thereby resulting in ultramicroporosity in solid-state chain-entangled films. Herein, the separation performance of a porous polymer obtained via ring-opening metathesis polymerization is reported, which possesses a flexible backbone with rigid, fluorinated side chains. This polymer exhibits ultrahigh CO2 permeability (>21 000 Barrer) and exceptional plasticization resistance (CO2 plasticization pressure > 51 bar). Compared to traditional polymers of intrinsic microporosity, the rate of physical aging is slower, especially for gases with small effective diameters (i.e., He, H2, and O2). This structural design strategy, coupled with studies on fluorination, demon-strates a generalizable approach to create new polymers with flexible backbones and pore-forming side chains that have unexplored promise for small-molecule separations.

Polymers with Side Chain Porosity for Ultrapermeable and Plasticization Resistant Materials for Gas Separations

Francesco M. Benedetti;Maria Grazia De Angelis;
2019

Abstract

Polymer membranes with ultrahigh CO2 permeabilities and high selectivities are needed to address some of the critical separation challenges related to energy and the environment, especially in natural gas purification and post-combustion carbon capture. However, very few solution-processable, linear polymers are known today that access these types of characteristics, and all of the known structures achieve their separation performance through the design of rigid backbone chemistries that concomitantly increase chain stiff-ness and interchain spacing, thereby resulting in ultramicroporosity in solid-state chain-entangled films. Herein, the separation performance of a porous polymer obtained via ring-opening metathesis polymerization is reported, which possesses a flexible backbone with rigid, fluorinated side chains. This polymer exhibits ultrahigh CO2 permeability (>21 000 Barrer) and exceptional plasticization resistance (CO2 plasticization pressure > 51 bar). Compared to traditional polymers of intrinsic microporosity, the rate of physical aging is slower, especially for gases with small effective diameters (i.e., He, H2, and O2). This structural design strategy, coupled with studies on fluorination, demon-strates a generalizable approach to create new polymers with flexible backbones and pore-forming side chains that have unexplored promise for small-molecule separations.
2019
Yuan He, Francesco M. Benedetti, Sharon Lin, Chao Liu, Yanchuan Zhao, Hong‐Zhou Ye, Troy Van Voorhis, Maria Grazia De Angelis, Timothy M. Swager, Zachary P. Smith
File in questo prodotto:
File Dimensione Formato  
adma.201807871.pdf

accesso aperto

Tipo: Postprint
Licenza: Licenza per accesso libero gratuito
Dimensione 2.01 MB
Formato Adobe PDF
2.01 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/688299
Citazioni
  • ???jsp.display-item.citation.pmc??? 5
  • Scopus 58
  • ???jsp.display-item.citation.isi??? 62
social impact