Compositionally Controlled Polyether Membranes via Mono(μ-alkoxo)bis(alkylaluminum)-Initiated Chain-Growth Network Epoxide Polymerization: Synthesis and Transport Properties

Christina G. Rodriguez, Malgorzata Chwatko, Jaesung Park, Caitlin L. Bentley, Benny D. Freeman, Nathaniel A. Lynd

Research output: Contribution to journalArticlepeer-review

10 Scopus citations


The addition of a diglycidyl-ether to a mono(μ-alkoxo)bis(alkylaluminum)-initiated epoxide polymerization presents a strategy for amorphous polyether-based membrane synthesis. In situ kinetic 1H NMR spectroscopy was used to monitor model network copolymerizations of epichlorohydrin (ECH) with 1,4-butanediol-diglycidyl ether (Butyl-dGE) or poly(ethylene oxide)-diglycidyl ether (PEO-dGE). Reactivity ratios were extracted from the evolution of polymer composition from the monomer feed during copolymerization. Quantitative conversion and nearly random comonomer incorporation was achieved. The generality of this synthetic technique was supported by the polymerization of Butyl-dGE and a range of epoxide monomers such as n-butyl glycidyl ether (nBGE), allyl glycidyl ether, ECH, and glycidol. The copolymerizations produced optically clear, flexible films in all cases. We investigated the potential for this synthetic platform to provide compositional control of structure-property relationships within the context of industrially relevant membrane separations for CO2. Given the affinity of PEO for CO2 and water, we explored using nBGE as a hydrophobic diluent, which was copolymerized with varying incorporations of PEO-dGE. The resultant cross-linked polyether membranes exhibited high CO2 permeabilities (150-300 barrer) and selectivity over N2CO2/N2 = 20-30) and H2CO2/H2 ≈ 6). CO2 sorption isotherms could be described by Henry's law and did not vary across the series of nBGE/PEO-dGE films. The similar sorption coefficients suggested that differences in permeability among these samples were driven by differences in diffusion coefficients. The diffusivity of CO2 increased with cross-link density, and permeability was unaffected by humidity for this series of hydrophobic cross-linked polyether membranes.

Original languageEnglish
Pages (from-to)1191-1198
Number of pages8
Issue number4
StatePublished - Feb 25 2020

Bibliographical note

Funding Information:
This research was funded in part by the Sandia Laboratory Directed Research and Development (LDRD) program, including student support through the Academic Alliance LDRD program (C.G.R.). The authors thank the Welch Foundation (F-1904) and a 3M Nontenured Faculty Award for partial support of this research. This research was partially supported by the National Science Foundation through the Center for Dynamics and Control of Materials: an NSF MRSEC under Cooperative Agreement no. DMR-1720595. The authors wish to thank Dr. Joan Brennecke for the use of a thermogravimetric analyzer.

Publisher Copyright:
© 2020 American Chemical Society.

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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