Transport and structural characteristics of crosslinked poly(ethylene oxide) rubbers

Haiqing Lin, Elizabeth Van Wagner, John S. Swinnea, Benny D. Freeman, Steven J. Pas, Anita J. Hill, Sumod Kalakkunnath, Douglass S. Kalika

Research output: Contribution to journalArticlepeer-review

100 Scopus citations


Three series of crosslinked poly(ethylene oxide) rubbers have been prepared by photopolymerization of prepolymer solutions containing: (1) poly(ethylene glycol) diacrylate (PEGDA) and H2O, (2) PEGDA and poly(ethylene glycol) methyl ether acrylate (PEGMEA), and (3) PEGDA and poly(ethylene glycol) acrylate (PEGA). All of these polymers have similar chemical composition (approximately 82 wt.% ethylene oxide), but the crosslink density and the content and chemistry of chain end groups are different. The effect of chain end groups and crosslink density on mass density, glass transition temperature (Tg), free volume, and H2, N2, CH4 and CO2 transport properties of the polymers was determined. The effect of temperature on gas permeability and solubility was also investigated. Many of the samples were amorphous. However, samples with high concentrations of PEGMEA could crystallize, and the formation of crystalline regions significantly decreased permeability. A generalized free volume model was used to interpret the effect of crosslink density and chain end groups on gas permeability and diffusivity, where free volume was characterized using two techniques: (1) density and group contribution theory, and (2) positron annihilation lifetime spectroscopy. Finally, the potential application of these materials for CO2/light gas separations was explored.

Original languageEnglish
Pages (from-to)145-161
Number of pages17
JournalJournal of Membrane Science
Issue number1-2
StatePublished - May 1 2006

Bibliographical note

Funding Information:
We gratefully acknowledge use of the facilities in the Department of Chemistry and Biochemistry at The University of Texas at Austin. Mr. Steven Sorey conducted the 1 H NMR measurements, and Dr. Mehdi Moini performed the FAB-MS studies. We gratefully acknowledge partial support of this work by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy (Grant No. DE-FG03-02ER15362). This research was also partially supported by the United States Department of Energy's National Energy Technology Laboratory under a subcontract from Research Triangle Institute through their Prime Contract No.: DE-AC26-99FT40675. This work was prepared with the partial support of the U.S. Department of Energy, under Award No. DE-FG26-01NT41280. However, any opinions, findings, conclusions, or recommendations expressed herein are those of the authors and do not necessarily reflect the views of the DOE. Partial support from the National Science Foundation under grant number CTS-0515425 is also acknowledged.

Funding Information:
Activities at the University of Kentucky were supported by a grant from the Kentucky Science and Engineering Foundation as per Grant Agreement KSEF-148-502-05-130 with the Kentucky Science and Technology Corporation. We are also pleased to acknowledge support provided through a Kentucky Opportunity Fellowship administered by the University of Kentucky Graduate School (SK).

Funding Information:
PALS experiments were performed with funding from the Australian Research Council within the framework of the ARC Centers of Excellence program through the Centre for Nanostructured Electromaterials.


  • Carbon dioxide
  • Free volume
  • Membrane
  • Poly(ethylene oxide)
  • Separation

ASJC Scopus subject areas

  • Biochemistry
  • General Materials Science
  • Physical and Theoretical Chemistry
  • Filtration and Separation


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