Usually ionomer synthesis consists of two steps – the introduction of acid groups to the polymer backbone and the neutralization of some of the acid groups by a metal cation. In very rare cases, the groups introduced are already neutralized by a metal cation. The first step (introduction of acid groups) can be done in two ways; a neutral non-ionic monomer can be copolymerized with a monomer that contains pendant acid groups or acid groups can be added to a non-ionic polymer through post-reaction modifications. For example, ethylene-methacrylic acid and sulfonated perfluorocarbon (Nafion) are synthesized through copolymerization while polystyrene sulfonate is synthesized through post-reaction modifications.
In most cases, the acid form of the copolymer is synthesized (i.e. 100% of the carboxylic acid groups are neutralized by hydrogen cations) and the ionomer is formed through subsequent neutralization by the appropriate metal cation. The identity of the neutralizing metal cation has an effect on the physical properties of the ionomer; the most commonly used metal cations (at least in academic research) are zinc, sodium, and magnesium. Neutralization or ionomerization, can also be accomplished in two ways: the acid copolymer can be melt-mixed with a basic metal or neutralization can be achieved through solution processes. The former method is preferred commercially. However, as commercial manufacturers are reluctant to share their procedures, little is known about the exact conditions of the melt-mixing neutralization process other than that hydroxides are generally used to provide the metal cation. The latter solution neutralization process is generally used in academic settings. The acid copolymer is dissolved and a basic salt with the appropriate metal cation is added to this solution. Where dissolution of the acid copolymer is difficult, simply swelling the polymer in the solvent is sufficient, though dissolving is always preferred. Because basic salts are polar and are not soluble in the non-polar solvents used to dissolve most polymers, mixed solvents (e.g. 90:10 toluene/alcohol) are often used.
Neutralization level must be determined after an ionomer is synthesized as varying the neutralization level varies the morphological and physical properties of the ionomer. One method used to do this is to examine the peak heights of infrared vibrations of the acid form. However, there may be substantial error in determining peak height, especially since small amounts of water appear in the same wavenumber range. Titration of the acid groups is another method that can be used, though this is not possible in some systems.
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"Properties of Ionomers". polymerdatabase.com. Retrieved 2019-12-10. http://polymerdatabase.com/polymer%20classes/Ionomers.html
Zhang, Longhe; Brostowitz, Nicole R.; Cavicchi, Kevin A.; Weiss, R. A. (2014-02-01). "Perspective: Ionomer Research and Applications". Macromolecular Reaction Engineering. 8 (2): 81–99. doi:10.1002/mren.201300181. ISSN 1862-8338. /wiki/Doi_(identifier)
"Properties of Ionomers". polymerdatabase.com. Retrieved 2019-12-10. http://polymerdatabase.com/polymer%20classes/Ionomers.html
Zhang, Longhe; Brostowitz, Nicole R.; Cavicchi, Kevin A.; Weiss, R. A. (2014-02-01). "Perspective: Ionomer Research and Applications". Macromolecular Reaction Engineering. 8 (2): 81–99. doi:10.1002/mren.201300181. ISSN 1862-8338. /wiki/Doi_(identifier)
"Properties of Ionomers". polymerdatabase.com. Retrieved 2019-12-10. http://polymerdatabase.com/polymer%20classes/Ionomers.html
Zhang, Longhe; Brostowitz, Nicole R.; Cavicchi, Kevin A.; Weiss, R. A. (2014-02-01). "Perspective: Ionomer Research and Applications". Macromolecular Reaction Engineering. 8 (2): 81–99. doi:10.1002/mren.201300181. ISSN 1862-8338. /wiki/Doi_(identifier)
Xu, Wu; Scott, Keith (2010-11-01). "The effects of ionomer content on PEM water electrolyser membrane electrode assembly performance". International Journal of Hydrogen Energy. VIII symposium of the Mexican Hydrogen Society. 35 (21): 12029–12037. Bibcode:2010IJHE...3512029X. doi:10.1016/j.ijhydene.2010.08.055. ISSN 0360-3199. /wiki/Bibcode_(identifier)