antioxidants and

antiozonants

PRO T ECT IVE /

IN H I BI TO RS
Most rubber articles need protection against attack and degradation from
their environment beyond what the polymer and cure systems can provide.
Protection against exposure and decomposition from environmental conditions such
as solvents, oils, detergents, heat, cold, light, ozone, and oxygen are to name a few.
This two-part Solutions insert will deal with the Selective Protective Materials
known as Antioxidants and Antiozonants.

Part I – oxidation / ozonation of rubber

a brief history
In the late 19th and early 20th centuries, articles made from rubber had very poor
weathering characteristics. Natural rubber was the only elastomeric polymer
available for commercial use at that time. Articles made from natural rubber
would soon become soft and tacky. They would no longer be serviceable.
Chemists determined the cause of degradation and pre-mature failure of rubber
articles was due to reaction with oxygen in the atmosphere. Knowing this,
chemists worked at identifying chemicals that would extend the useful service life
of a rubber product by protecting the rubber article from “ooxidation”. Naturally
occurring materials such as waxes, coal tar, creosote and many other products
were used early on to “coat” rubber articles; providing the needed protection from
oxidation. These protective coatings would be “scuffed” or “worn” off and the
unprotected rubber would soon fail; resulting in the need to find a more
permanent solution. As a result, it was found that certain phenols, hydroxylamine
derivatives and secondary aromatic amine derivatives were useful in retarding the
degradative effects of oxygen. Instead of “coating” the surface of the rubber
article, these chemicals were incorporated into the rubber compound during
mixing. The benefit of this method would allow the protective chemical(s) to:
1) react with oxygen that was entrained in the rubber compound as a result of
mechanical mixing and 2) would bleed toward the surface over time; offering a
continuous supply of protection for the rubber article. These chemicals became
known as “AAntioxidants”.
The discovery of “AAntiozonants” occurred early in the 20th century, but it wasn’t
until mid-way through the century before they became widely used. It was
discovered that rubber articles (mainly tires) stored for several years quickly
failed when put into use. Chemists were baffled because these tires were failing
so quickly. After all, they contained antioxidants to protect them against attack
from O2. Chemists analyzed this “static storage” type of failure, and determined
it was not the result of oxygen, but due to ozone (O3) in the atmosphere that
attacked the rubber and resulted in the catastrophic failure of these tires.
 ANTIOXIDANTS AND ANTIOZONANTS: c o n t i n u e d 2

definitions
Often the terms “antioxidant” and “antiozonant” are used synonymously; even though
they have different functions in a rubber compound.
Antioxidants – are chemicals that are used to protect rubber articles
against attack from oxygen (O2 ).

Antiozonants – are chemicals and / or waxes that “bleed” to the surface of

a rubber article, to protect it against attack from ozone (O3 ).

For long-term storage protection, some rubber articles are sealed with an exterior
coating of wax or similar substance for additional protection against attack from ozone.

Oxygen comprises approximately 20 percent of the earth’s atmosphere. On the

other hand, ozone comprises only a few parts per hundred million (pphm). The attack
of ozone on unprotected rubber is much more aggressive than is oxygen. There can be a
synergistic effect between antioxidants and antiozonants. Most antiozonants have a dual
functionality. They not only protect against ozonation, but most will protect against
oxidation as well. Antioxidants however, will not protect against ozonation.

To the naked eye, a rubber article that has been degraded by either oxygen or ozone looks
like there is a “cloudy,” silver-gray film on the surface of the rubber. This is commonly
referred to as “frosting”. Often this film is mistaken for “bloom”. The key is, a chemical
that is blooming to the surface of a rubber article, resulting in a cloudy film, can be washed
or rubbed off. Surface degradation due to attack from either oxygen or ozone can not.
Upon close examination under low power microscope you can see the “cracks” on the surface
of the rubber article.

Key: A way to tell the difference between a rubber article that has
been degraded by oxygen and one that has been degraded by ozone
is by observing the direction of “cracks” that appear on the surface
of the article.

Cracks that appear due to the attack of ozone run perpendicular

to the direction of the “grain” or stress applied to the rubber article.

Cracks that appear due to the attack of oxygen upon a rubber article
are random in their orientation.

The picture on the next page shows evidence of degradation of a rubber matt due to prolonged
exposure to both ozone and oxygen.
 ANTIOXIDANTS AND ANTIOZONANTS: c o n t i n u e d 3

O3 O2

Effect of O3 on unprotected rubber Effect of O2 on unprotected rubber

Note: The orientation of the cracks on the surface of the rubber.
Photo courtesy of Akron Rubber Development Lab

Non-polar polymer systems provide the most protection against attack from either oxygen
or ozone due to the saturation of their C-C bonds in the polymer backbone. Due to
unsaturation in the polymer backbone, polar (diene) polymer systems lack the ability to
withstand prolonged exposure to weathering (exposure to oxygen and/or ozone.) An example
would be the C=C double bonds in natural rubber. The greater the degree of unsaturation in
the polymer, the more severe the degradative attack from oxygen / ozone will be upon the
rubber article. It only takes about two percent saturation of the polymer, with oxygen, for a
rubber article to fail and become unserviceable. Once oxidation of rubber has started, the
reaction becomes auto-catalytic and can only be terminated under certain conditions.

theory of oxidation
There are two chemical radicals that, when formed, work to oxidize rubber, degrading it
and causing a rubber article to fail. They are peroxide radicals and hydroperoxide radicals.
Antioxidants (and antiozonants) react with these radicals to terminate the chain reaction
causing oxidation of polar polymer systems; thereby prolonging the serviceability of a rubber
article. Antioxidants also react with hydrocarbon radicals when they are formed. In doing so,
antioxidants block the reaction sites that are available for the formation of peroxide and/or
hydroperoxide radicals; thus retarding the oxidative process.

Chemically, antioxidants work to:

1) eliminate peroxide radicals before they are able to form and do their damage.
2) destroy hydroperoxide radicals before they can do their damage. and /or
3) react with hydrocarbon radicals to “short-stop” the formation of oxy radicals.
 ANTIOXIDANTS AND ANTIOZONANTS: c o n t i n u e d 4

In a nut shell. . . . . .
•Peroxide radicals are formed when oxygen (O2 ) reacts with a
hydrocarbon radical. And, hydroperoxide radicals are formed when two
peroxide radicals react with each other.

•Hydrocarbon radicals are formed when a hydrogen atom (-H) is

“knocked off” the hydrocarbon chain.

•A hydrocarbon chain will loose a hydrogen atom when enough energy is

introduced into the system to liberate a hydrogen (–H) atom.

•Energy is introduced into a rubber system when the temperature of the rubber
is elevated.

•The temperature of a rubber article is elevated when heat, UV light

and/or motion (stress or dynamic force) is applied to the system.

There is a second way hydrocarbon radicals are formed.

Hydrocarbon radicals are formed by “mechanical” chain scissioning resulting from
the mixing process.
During mixing, the polymers’ macromolecules are “scissioned” by the shearing
action of the mixer. When this happens, these severed ends constitute
hydrocarbon free radicals.
Also, during mixing, air (O2 ) is trapped in the polymer matrix. The trapped
oxygen will react with severed ends of the hydrocarbon chains forming
destructive peroxides.
Antioxidants that are blended into the compound are available to react with the
mechanically formed hydrocarbon radicals……..thus inhibiting oxidation.

Rubber does not have to be mixed or cured for the destructive forces of oxygen to attack.
Unsaturated synthetic polymers are susceptible to attack from oxygen and/or ozone.
To protect these polymers from oxidation, manufacturers will often add small amounts
of a secondary (synergist) antioxidant (i.e. Phosphites) to the emulsion stage of polymer
processing. This ensures that the polymer is protected when it is coagulated and stored
before use. Nitrile, SBR, polychloroprene and synthetic polyisoprene are examples of
polymers that have antioxidants added to their latex phase of processing to protect them
from oxidation. Natural rubber polymers normally do not need the addition of “polymer
stabilizers” to be protected against oxidation. Natural rubber already contains naturally
occurring antioxidants that protect the polymer from oxidation.
 ANTIOXIDANTS AND ANTIOZONANTS: c o n t i n u e d 5

solubility . . . . in rubber
One of the key properties of antidegradants (antioxidants and /or antiozonants) is their
solubility in the rubber matrix. The faster the rate of bloom, the less soluble the
antidegradant is in the polymer system. The rate of bloom of antidegradants is not a
fixed constant. It varies according to the polymer system and type of antidegradant used.
Antidegradants are intended to bleed slowly to the surface of a rubber article ensuring
a continuous supply of the protecting chemical at the surface. The introduction of
long-chain aliphatic hydrocarbons into a stabilizer molecule decreases volatility and
increases the solubility of the antidegradant in hydrocarbon polymers. Slowing volatility
and increasing solubility of antidegradants improves their performance.
Other factors that have an effect on the rate of bloom are other chemical additives such
as waxes, process aids, plasticizers and cure systems. The state of cure, temperature and
dynamic conditions will also determine the rate an antidegradant bleeds toward the surface.
Generally, waxes and process aids will form a film on the exterior surface of a rubber
article; providing a temporary, physical barrier of protection against attack from ozone.
Once on the surface of the rubber, antidegradants will react with free radicals when they
are formed. A “re-freshening” of the surface with antidegradants, over time, ensures
prolonged serviceability of the rubber article.

oxidation reaction mechanism

The Oxidative Reaction Mechanism RH = hydrocarbon chain
Ro = hydrocarbon radical
Depicting the Attack of Oxygen on
an Unsaturated Hydrocarbon Chain ROo = peroxide radical
ROOo = peroxide radical
is outlined below.
ROOH = hydroperoxide
ROOR = stable bond
(ANTIOXIDANTS AND ANTIOZONANTS: cR-R
o n t=
i n stable
u e d bond

Initial Rxn:

RH + energy Ro + -
H
Hydrocarbon Chain Hydrocarbon Radical Hydrogen

In the initiation reaction, energy is used to start the reaction by severing a hydrogen atom from
the polymer chain. This forms a hydrocarbon free radical and hydrogen. At this point,
In the initiation
antioxidants reaction,
can react energy
with the is used toradicals
hydrocarbon start thetoreaction by severing
“short-stop” a hydrogen
the formation of peroxide
and / or hydroperoxide free radicals resulting in terminating the oxidation process.
atom
If leftfrom the polymer
unchecked, chain.
the next step, This forms a hydrocarbon
propagation free radical and
reaction is auto-catalytic. hydrogen.free
Hydrocarbon
Atradicals
this point, antioxidants
are reacted can react
with oxygen withperoxide
to form the hydrocarbon
radicals. radicals to “short-stop” the
formation of peroxide and/or hydroperoxide free radicals resulting in terminating the
Propagation Rxn:
oxidation process. o o
R + O2 ROO
hydrocarbon radical peroxide radical
If left unchecked, the next step, propagation reaction is auto-catalytic. Hydrocarbon free
Peroxide radicals are very unstable and react very quickly.
radicals are reactedo with oxygen to form peroxide radicals. o
ROO RH autocatalytic ROOH + R
peroxide radical polymer hydroperoxide hydrocarbon radical
ANTIOXIDANTS AND ANTIOZONANTS: c o n t i n u e d 6

Propagation Rxn:

Peroxide radiclas are very unstable and react very quickly.

If a peroxide radical reacts with a hydrocarbon, a hydroperoxide radical and a

hydrocarbon radical is produced. The production of a hydrocarbon radical starts the
process all over again.

Hydroperoxide radicals are thermally unstable and decompose to generate two new
free radicals.

When two hydroperoxide radicals are formed, they will react to form an alkoxy radical
and a peroxide radical. Then the process starts all over again! (As shown in the rxn above)

Termination Rxns:
The auto-catalytic oxidation reaction process can be terminated in either of three ways.

1) When two hydrocarbon radicals react, they form a stable cross-link.

2) When a hydrocarbon radical reacts with a peroxide radical, they will form a
stable cross-link.

3) When two peroxide radicals react, they form a stable bond.

 (ANTIOXIDANTS
ANTIOXIDANTS AND ANTIOZONANTS: c o n t i n u e d 7
ANTIOXIDANTS AND
AND ANTIOZONANTS:
ANTIOZONANTS: cc oo nn tt ii nn uu ee dd

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intermediate ion (Zwitterion).
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++ ––C
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radical ozonide
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At
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shown above
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the oxidative reaction
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Note:
Note: The
The difference
difference between
between the
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reaction mechanism
mechanism ofof oxygen
oxygen and
and ozone
ozone is
is that
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the
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reaction of
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ozone is
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surface phenomenon
phenomenon while
while the
the reaction
reaction of
of oxygen
oxygen can
can be
be both
both surface
surface
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and an
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Note:phenomenon.
internal phenomenon.
The difference between the reaction mechanism of oxygen and
ozone is that the reaction of ozone is a surface phenomenon while the
reaction of oxygen can be both surface and an internal phenomenon.
ANTIOXIDANTS AND ANTIOZONANTS: c o n t i n u e d 8

effect of heat
Elevated temperatures are another key property that plays a major role in the degradation of
rubber products. Heat is detrimental to rubber products and accelerates oxidation. Generally,
there are two conditions that will elevate the temperature of rubber articles. 1) curing and 2)
dynamic flex.

curing – certain antidegradants are designed to protect uncured rubber during mix
ing and storage. These antidegradants lose their effectiveness at curing temperatures.
(i.e. Phosphites) While phosphite antioxidants are very effective as polymer stabiliz
ers, they are burned up during higher vulcanization temperatures.

dynamic flex – refers to the stress applied to a rubber product during its intended
use. Most antiozonants and certain amines are designed to provide anti-flex cracking
properties to rubber products.

The free radical scavenging ability of certain chemical groups of antidegradants are limited
by elevated temperatures. As an example, most, if not all, hindered phenols are capable of
providing long-term thermal stability with temperatures ranging from 0–575ºF. On the
other hand, phosphites, hydroxylamines and thiosynergists loose their effectiveness during
vulcanization. Thiosynergists are most effective at free-radical scavenging or hydroperoxide
decomposition during polymer processing. They are not effective as long-term thermal
stabilizers. By sacrificing themselves during the curing process, they lessen the workload on
the more thermally stable antidegradants.

peroxide decomposers:
Most peroxide decomposers are derived from di- and tri-valent phosphorus compounds.
They are thermally activated to decompose peroxides and hydroperoxides. In the presence
of dialkyl esters, hydroperoxides are reduced to alcohols, and the sulfide group is oxidized
to an acid which is capable of further catalyzing the decomposition of hydroperoxides to
more stable molecules.

effect of uv light
The degradation of rubber can also be triggered by UV light. Hindered amines (HALS),
commonly thought of as being effective UV light stabiliaers, are also useful for long-term
thermal stability. Their effectiveness is the result of free-radical scavenging. However, HALS
are virtually ineffective at temperatures higher than 300ºF. Therefore, hindered amines should
be used in combination with benzimidazole or certain hindered phenols in order to provide
long-term thermal stability.
ANTIOXIDANTS AND ANTIOZONANTS: c o n t i n u e d 9

effect of metallic ions

Metal ions will react with oxy radicals and “poison” rubber. In particular, metallic ions of
copper, manganese, cobalt and/or iron will catalyze the oxidative process in rubber. They
break down peroxide radicals and accelerate the oxidation process. The ability of metal ions
to catalyze oxidation can be inhibited by metal deactivators. Certain antidegradants have the
ability to chelate metal ions which decreases the ability of the metal ions to produce radicals.
They are referred to as “metal deactivators”. They can be either antioxidants or antiozonants.
Antiozonanat PD-1 and Antioxidant 58 are examples of Akrochem products that are
excellent metal deactivators.

effect of oxidation on polymers

Upon oxidation, polymer systems will either become soft and tacky or hard and brittle. This is
caused by either polymer chain scissioning (softening) or cross-linking (hardening). Natural
and synthetic polyisoprene, Butyl and “G” type Neoprene polymers tend to undergo chain
scissioning and become soft and tacky. Nitrile, SBR and PBR are some of the polymer systems
that tend to harden or undergo cross-linking.
Non-polar polymer systems such as EPR / EPDM, Silicone / Fluorosilicone and FKM have very
little reaction sites available for oxidation or ozonation to occur. Generally, these saturated
polymer systems do not need the addition of antidegradants. In fact, non-polar polymers can be
used as antidegradants themselves. By blending a non-polar polymer with polar polymer system,
the non-polar polymer will provide added protection to the rubber article from oxidation. As an
example, blending 25 to 30 phr EPDM with natural or synthetic polyisoprene will significantly
retard the oxidative process. The effect of oxidation is highlighted for various polymer systems
in TABLE I on the next page.
 ANTIOXIDANTS AND ANTIOZONANTS: c o n t i n u e d 10

(ANTIOXIDANTS AND ANTIOZONANTS: c o n t i n u e d

TABLE I

RELATIVE ORDER OF POLARITY WITH THE EFFECT OF

OXIDATION ON VARIOUS POLYMER SYSTEMS

High ASTM Effect of Resistance Resistance

Polarity Chemical Name Common Name D 1418 Oxidation to Oxygen to Ozone
Nitrile (50% ACN) Nitrile NBR Hardens Fair Poor
Urethane (Polyester/Polyether) Urethane AU / EU Hardens Excellent Excellent
Ethylene Vinyl Acetate Ethylene Vinyl Acetate EVA Hardens Outstanding Outstanding
Nitrile (30% ACN) Nitrile NBR Hardens Fair Poor
Polyacrylate Acrylic ACM Hardens Excellent Excellent
Epichlorohydrin Epichlorohydrin ECO Hardens Very good Very good
Chlorosulfonated Polyethylene Hypalon® CSM Hardens Excellent Excellent
Chloroprene Neoprene (G types) CR Softens Good Excellent
Chloroprene Neoprene (all others) CR Hardens Good Excellent
Nitrile (20% ACN) Nitrile NBR Hardens Good Fair
Chloronated Polyethylene Chlorinated Polyethylene CPE Hardens Excellent Excellent
Highly Saturated Nitrile Nitrile HNBR Hardens Good Good
Styrene Butadiene GRS SBR Hardens Good Poor
Polybutadiene Butadiene BR Hardens Excellent Poor
Natural Polyisoprene Natural Rubber NR Softens Good Poor
Synthetic Polyisoprene Synthetic Rubber IR Softens Good Poor
®
Polysulfide Thiokol PTR Hardens Excellent Excellent
Halogenated Butyl Butyl HIIR Softens Excellent Excellent
Ethylene Propylene (dimer) EPDM EPDM Hardens Good Excellent
Ethylene Propylene (monomer) EPR EPR Hardens Good Excellent
Isobutylene-Isoprene Butyl IIR Softens Excellent Excellent
Fluorinated Hydrocarbon Fluorocarbon FPM Hardens Excellent Outstanding
Polysiloxane Silicone PSi, VSi, PVSi N/A Excellent Excellent
Fluorinated Polysiloxane Fluorosilicone FVS N/A Outstanding Outstanding

Low
Polarity

Akrochem
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carries aa variety
varietyofofantioxidants
antioxidantsand
andantiozonants
antiozonants that
areare commonly
usedused in rubber
compounding.
compounding. Part II of
of this
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these
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