IONOMERS

An ionomer is a polymer that comprises repeat units of both electrically neutral repeating units
and a fraction of ionized units (usually no more than 15 mole percent) covalently bonded to the
polymer backbone as pendant group moieties. This means that most ionomers are copolymers of
the neutral segments and the ionized units, which usually consist of carboxylic acid groups.
The classification of a polymer as an ionomer depends on the level of substitution of ionic groups
as well as how the ionic groups are incorporated into the polymer structure. For example,
polyelectrolytes also have ionic groups covalently bonded to the polymer backbone, but have a
much higher ionic group molar substitution level (usually greater than 80%); ionenes are polymers
where ionic groups are part of the actual polymer backbone. These two classes of ionic-group-
containing polymers have vastly different morphological and physical properties and are therefore
not considered ionomers.
Ionomers have unique physical properties including electrical conductivity and viscosity—
increase in ionomer solution viscosity with increasing temperatures (see conducting polymer).
Ionomers also have unique morphological properties as the non-polar polymer backbone is
energetically incompatible with the polar ionic groups. As a result, the ionic groups in most
ionomers will undergo microphase separation to form ionic-rich domains.
Commercial applications for ionomers include golf ball covers, semipermeable membranes,
sealing tape and thermoplastic elastomers. Common examples of ionomers include polystyrene
sulfonate, Nafion and Hycar.
SYNTHESIS
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.
GENERAL PROPERTIES
Ionomers are synthetic polyelectrolytes that consist of both electrically neutral and ionized groups
that are randomly and or regularly distributed along the polymer backbone. They can be divided
into polycations, polyanions and polyampholytes. Like ordinary polyelectrolytes, they can bear
one or more charges depending on the pH value. However, per definition, their ion content is
usually no more than 10 to 15% and, thus, most ionomers are insolube or only slightly soluble in
water. One important characteristic of ionomers is the strong molecular aggregation of the ion-
carrying groups to ion rich domains or ion clusters which act as physical crosslinks. When heated,
the ionic bonds and clusters dissolve and when cooled, they reform. This gives ionomers a unique
structure and behavior. At low temperatures they behave like crosslinked polymers (elastomers)
and at elevated temperatures like ordinary thermoplastics.
In an ionomer, the nonpolar chains are grouped together and the polar ionic groups are attracted to
each other. This allows thermoplastic ionomers to act in ways similar to that of crosslinked
polymers or block copolymers.
However, ionomers are not crosslinked polymers, and are in fact a type of thermoplastic called a
reversible crosslinker. When heated, the ionic groups will lose their attractions for each other and
the chains will move around freely. As the temperature increases, the chains move around faster
and faster and the groups cannot stay in their clusters. This allows for a polymer with the properties
of an elastomer and the processability of a thermoplastic.

The majority of ionomers studied have a polyvinyl or polydiene backbone and carry anionic groups
(anionomers) with Na+, and Zn2+as counter ions. The three most important ionized groups are
carboxylate (–COO-), sulfonate (–SO3-) and phosphonate (–PO32-) which differ in the strength of
the ionic interaction. Usually, less than 80% of the acid groups are neutralized by a base. The
remaining acid groups provide sites for hydrogen bonding between neighboring molecules which
are weaker than ionic bonds but stronger than secondary bonds. Thus, increasing the acid and ion
content in the polymer results higher mechanical strength, modulus, and toughness. Carboxylate
ionomers with an olefin backbone are by far the most common ionic polymers followed by
sulfonate ionomers with a styrene backbone. Both types of ionomers are produced on a commercial
scale and find many applications. Other backbones that have been studied include polybutadiene,
polyacrylate, polymethacrylate, polyisoprene, and polytetrafluorethylene.
Ionomers can be either synthesized by copolymerization of ionic and neutral monomers or by
chemical modification of electrically neutral polymers. The majority of ionomers are produced via
free-radical copolymerization. For example, ethylene is copolymerized with methacrylic and/or
acrylic acid by a high pressure process similar to low-density polyethylene. These ionic
copolymers have typically a low melting point, improved toughness/flexibility and mechanical
strength and when used as films, possess a much higher clarity and gloss and provide superior hot
tack, seal strength and puncture resistance than unmodified polyethylene film. Another important
class of carboxylate ionomers are copolymers of acrylates with acrylic and/or methacrylic acid,
produced by free-radical emulsion or solution copolymerization. These ionomers are used as
pressure-sensitive adhesives. A commercially important sulfonate ionomer is sulfonated
tetrafluoroethylene (Nafion) which is produced by free-radical copolymerization of
tetrafluoroethylene (TFE is the monomer of Teflon) with a perfluorinated vinyl ether sulfonyl
fluoride co-monomer. The copolymers carries perfluoroether pendant side chains terminated by
sulfonic acid groups. These ionomers have excellent chemical and thermal stability and can absorb
large amounts of water. They are often used as ion-selective membranes. An ionomer that is
produced via chemical modification is (lightly) sulfonated polystyrene. These ionomers are
obtained by treating polystyrene with sulfonating agents such as acetyl sulfate in chlorinated
solvents (post-sulfonation). This method can also be employed to produce block-copolymers with
lightly sulfonated styrene blocks. The sulfonated ionomers form physical crosslinks that approach
the strength of covalent links which is desirable in many elastomeric applications.
COMMERCIAL IONOMERS
The largest volume ionomers are copolymers of ethylene and acrylic and/or methacrylic acid.
Commercial grades of ethylene (meth)acrylic acid (EAA, EMAA) are available from DuPont
(Surlyn®, Nucrel®), SK Global Chemical1 (Primacor™), and Ineos, (Eltex®).
Perfluorinated sulfonic acid ionomers (PFSA) are sold by DuPont (Nafion), Solfay (Aquivion),
Chemours, and 3M.

APPLICATIONS
The by far most important ionomer is ethylene acrylic acid copolymer (EAA) which is sold under
the tradename Surlyn by DuPont. It is frequently used as a food packaging material and as a tie-
layer (compatibilizer) in multi-layer films. Other important applications include coatings and
surface films for golf balls, sports equipment, and for overmolded (cosmetic) bottles.
Important applications include cation exchange membrane for fuel cells, PEM water electrolyzers,
separators for redox flow batteries, electrodialysis, and electrochemical hydrogen compressors.
One specific ion-selective membrane is a perfluorosulfonate ionomer which DuPont calls Nafion.
All perfluorosulfonate ionomers have outstanding chemical and thermal stability and the ability to
absorb incredible amounts of water. Nafion membranes can be made into films or tubes and can
be used in many caustic and dangerous processes. Some such processes are the production of
chlorine, regeneration of spent acids, separations in chemical processing, as well as uses in fuel
cells and electrodialysis.