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Issue 44, 2018
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Thiol–ene photopolymerization of vinyl-functionalized metal–organic frameworks towards mixed-matrix membranes

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Abstract

We developed a facile methodology for fabricating a free-standing mixed-matrix membrane (MMM) containing covalently incorporated metal–organic framework (MOF) particles up to 60 wt% by utilizing thiol–ene photopolymerization with the MOF consisting of vinyl functionality. Vinyl-functionalized UiO-66 (UiO-66-CH[double bond, length as m-dash]CH2) was synthesized from 2-vinyl-1,4-dicarboxylic acid with ZrCl4, and a free-standing MMM was readily produced by irradiation of a polymerization mixture containing UiO-66-CH[double bond, length as m-dash]CH2, poly(ethylene glycol) divinyl ether (PEO-250), pentaerythritol tetra(3-mercaptopropionate) (PETM), 2,2′-(ethylenedioxy)diethanethiol (EDDT), and 2,2-dimethoxy-2-phenylacetophenone (DMPA) as a photoradical initiator. Assorted analyses combining FTIR, thermogravimetric analysis, scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction strongly supported the fact that the desired MMM containing well-dispersed UiO-66-CH[double bond, length as m-dash]CH2 particles was successfully produced by C–S bond formation, which provided strong union of the MOF with the polymer matrix without interfacial voids. The produced MMM was highly flexible and showed improved mechanical properties as compared to the pristine polymeric membrane, indicating that the covalently immobilized UiO-66-CH[double bond, length as m-dash]CH2 particles were homogeneously distributed in the polymer matrix. Gas permeability across the MMM was significantly enhanced compared with the pristine polymeric membrane as diffusion of the gas molecules was facilitated in the porous space in the MOF.

Graphical abstract: Thiol–ene photopolymerization of vinyl-functionalized metal–organic frameworks towards mixed-matrix membranes

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Supplementary files

Article information


Submitted
25 Apr 2018
Accepted
15 Aug 2018
First published
15 Aug 2018

J. Mater. Chem. A, 2018,6, 21961-21968
Article type
Paper

Thiol–ene photopolymerization of vinyl-functionalized metal–organic frameworks towards mixed-matrix membranes

C. Satheeshkumar, H. J. Yu, H. Park, M. Kim, J. S. Lee and M. Seo, J. Mater. Chem. A, 2018, 6, 21961
DOI: 10.1039/C8TA03803A

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