You are on page 1of 44

Antioxidants & Antidegradants

All polymers & products baded on them are subject to degradation on exposure to the degradative
environments such as:
-

Storage aging
Oxygen
Heat
UV Light & Weathering
Catalytic degradation due to the presence of heavy metal Ions (Cu, Mn, Fe etc.)
Dynamic Flex - Fatigue
Ozone (Static / Dynamic / Intermittent exposure)

These factors degrade rubbers / rubber products causing substantial changes in their technical properties
and ultimately lead to their failure during service or shorten the expected service life in the absence of
Antioxidants.
Type of Degradation

Initiating / Accelerating
Factors

Degradation
Causes

Storage Aging

Surrounding conditions

Oxygen, Light,
Loss of elasticity and tensile strength
Heat, Humidity

Aging due to Heat

Heat
Light, UV light, heat,
humidity, surrounding
conditions

Aging due to Light &


Weathering
Soluble Metal ion
(Cu,Mn,Fe) catalyzed
oxidation
Flex-Fatigue cracking
Ozone Cracking

Cu, Mn, Fe, Co & Ni


Ions as their rubber
soluble fatty acid salts
Intermittent mechanical
strains
Continuous / Intermittent
strains

Type of Failure

Oxygen

Loss of elasticity and tensile strength

Oxygen

Formation of crazed surface, loss of


elasticity and tensile strength

Oxygen

Rapid loss in elasticity and tensile


strength.

Oxygen,
Ozone, Flaws
Ozone

Appearance of cracks (cracking


patterns usually complex)
Extensive cracking at right angles to the
force causing strain

Polymer Degradation Chemistry


.

The formation of free radicals (R ) during polymerization, processing or service of the rubber product is the first stage
of polymer degradation and is called as Initiation of degradation process.

Propagation is the second stage when atmospheric oxygen reacts with the free radicals
.
( ROO ) radicals

.
(R ) to form Peroxy

Peroxy radical further reacts with labile Hydrogen atom of the polymer to form unstable hydroperoxides (ROOH).

ROO

RH

.
ROOH + R

Hydro peroxides immediately decompose via hemolytic cleavage to form alkoxy and hydroxyl radicals and
further propagate the degradation mechanism.
ROOH

RO

OH

Propagation stage of degradation process is very rapid compared to the Initiation stage. This autocatalytic
oxidation reaction progresses until termination takes place by formation of stable products.

Free radicals R can undergo following reactions depending on their own relative stability :

Dimerize (cross link),


.
Disproportionate (exchange H becoming alkane & olefin),
.
Abstract H (chain transfer),
Cleave (rupture polymer chain),
Rearrange,
React with oxygen.
Auto-oxidation depends on the relative C H bond dissociation energy.
Strongest Bond

Weakest Bond

Primary

Secondary

Tertiary

Allyic

98.0 kcal.

94.5 kcal

91.0 kcal

85.0 kcal

R CH H

R CH H

R CH

RCH=CH-CRH-H

Dimerization causes polymer hardening while cleavage reduces polymer chain lengths (change in
hardness & elastic properties and causing fatigue crack initiation points.

Cleavage may also release of gases (resulting in separations).

Since all the vulcanization ingredients are still present; degradation can take place by continued
changes in the state of vulcanization during the rubber product service.

This causes Reversion or marching modulus due to changes in the nature of the sulphur cross links.

The Termination Stage reactions progress as follows :

A) Chain Scission
2 R2HCOO

ROO + OH

R2C=O + R2CHOH + O2

ROH

O2

Scission predominates in polymers like NR, IR, IIR (unsaturated polymers which have electron
donating groups such as -CH3 attached to the carbon atom adjacent to the double bond and hence
vulnerable).

Scission results in the decrease of molecular weight leading to softening of the aged / over cured
vulcanizates, reduction in tensile properties etc.

B) Cross linking
2R

2 R3COO

RR
R3COOCR3 + O2

2 RO
R

+ ROO

ROOR

ROOR

Cross linking predominates in case of polymers like BR, SBR, NBR, CR, etc. which have
comparatively less active double bonds or somewhat deactivated double bonds due to the presence
of electron-withdrawing groups such as halogens (e.g. CR, Chloro/Bromo Butyl Rubbers). Cross
linking results in brittleness, gelation and reduction in elongation of the polymer.
Effect of Degradation on Elastomers

Elastomers

Effect Of Degradation

Natural Rubber ( NR )

Scission ( Softens )

Poly Isoprene ( IR )

Scission ( Softens )

Polychloroprene ( CR )

Cross linking & Scission ( Harden )

Styrene Butadiene Rubber ( SBR )

Cross linking & Scission ( Harden )

Acrylo Nitrile Butadiene Rubber ( NBR )

Cross linking ( Harden )

Polybutadiene Rubber ( BR )

Cross linking ( Harden )

Isobutylene Isoprene Rubber ( IIR )

Scission ( Softens )

Ethylene Propylene Rubber ( EPM )

Cross linking & Scission ( Harden )

Ethylene Propylene Ter-polymer ( EPDM )

Cross linking & Scission ( Harden )

Chlorosulfonated Polyethylene ( CSM )

Cross linking ( Harden )

Polyacrylic Rubber ( ACM )

Cross linking ( Harden )

Fluorinated Hydrocarbon Rubbers ( FPM )

Cross linking ( Harden )

Polysulfide Rubbers ( T )

Cross linking ( Harden )

Chloro Isobutylene Isoprene Rubber ( CIIR )

Cross linking ( Harden )

This model does not account several factors. Other factors to be considered are :
o
o
o

Relative oxidation rates of different polymers,


Presence of amorphous and crystalline zones in polymers,
Bulk properties which limit oxygen permeation,
Various mix of polymer structures,Reactive nature and structure of propagating radicals

R & ROO

Differences in polymer crystallinity (some polymers have both amorphous and crystalline phase (e.g.
SBS copolymer).

Free radicals generally migrate to the amorphous phase and the oxidation takes place in this phase.

The presence of metallic ions such as Cu, Mn, Fe, Co cause catalytic peroxide break down that
accelerates the initiation of oxidation.

The permeability of oxygen into a polymer is a key factor that will affect the overall oxidation.

EFFECT OF OXYGEN:

Only 1 2 % of combined oxygen is enough to render the rubber product useless.

Polymer oxidation is a complex process involving many factors -processing conditions (e.g.
temperature, shear rate), presence of catalysts of oxidation, compounding formulation design etc.

Oxidation causes Chain scission and Cross linking resulting in the loss of elastic properties of
vulcanizates. Both occur simultaneously - the one which prevails, determines the final product
properties.
The cure system selection also influences the ageing resistance of the rubber product. The
Conventional Cure Systems are more prone to oxidative degradation than the Semi EV or EV
Cure systems.

EFFECT OF HEAT :

Heat accelerates the process of oxidation and effects of oxidation are observed sooner and are more
severe as the temperature increases.

In case of NR, in the absence of oxygen, more cross links are formed initially, followed by Reversion
as cross links and polymer chains are broken.

The oxidative heat ageing causes loss of Tensile Strength, Elongation at Break and overall Elasticity
of the rubber vulcanizates.
Effect of Heat on NR Vulcanizates:
Temperature, C

Combined Oxygen, %

Loss of Tensile Strength, %

60

1.2

50

110

0.65

50

110

Nil. (e.g.N2 atmosphere)

Negligible

EFFECT OF UV - LIGHT & WEATHERING:

UV-light promotes free radical oxidation of the rubber surface which results in the formation of a film
of oxidized rubber on the surface of the product (called as Frosting) .

Heat & Humidity accelerate this process.

Light colored rubber products are more prone to UV-light attack than the black colored products (as
carbon black itself acts as a UV-light absorber).

UV-light attack is more severe in case of rubber products with a thin cross section.

EFFECT OF HEAVY METAL IONS:

Hydro peroxides (ROOH) are the main source of free radicals for the initiation of autocatalytic
oxidation reactions.

Decomposition of hydro peroxides is accelerated by heat , light and polymer soluble fatty acid salts of
metals like Cu , Mn , Fe , Co & Ni .

The rubber soluble metallic compounds catalyze hydro peroxide decomposition to free radicals
according to following scheme.

Direct reaction of metallic compound with polymer in the early stage of the degradation may also
result in free radicals as follows:

RH + MX2
RH + MX

R + MX + HX
.
R + M + HX

Stearates and Oleates of Cu & Mn are highly active catalysts of oxidative degradation of NR. Less
soluble forms like Oxides of Cu & Mn react with fatty acids to produce highly rubber soluble
compounds.

The first corrective approach is to eliminate all the sources of these harmful metals or their soluble
salts. It is possible to protect polymers by incorporating substances which react with ionic metals to
give stable co-ordination complexes.

EFFECT OF DYNAMIC FATIGUE:

Vulcanized rubber surface often has a few flaws resulting from several factors such as rough mould
surface, grit content in rubber & other compounding ingredients, ozone attack. .

During repeated deformation, the stresses get concentrated at these flaws or cracks which grow
under repeated dynamic conditions causing mechanical rupture.

Flex-Fatigue cracking is also due to rubber being subjected to repeated deformations in air (ozone
may be absent!) resulting in oxidative fatigue break down.

The Antiflexcracking agents, in addition to being Antioxidants and Antiozonants; possess the ability to
reduce the rate of crack growth.

Rate of oxidation of rubber is proportional to the amount of Combined Sulphur Atoms in the cross
linked net work.

The Semi EV & EV cure systems (with fewer number of combined sulphur atoms per cross link) in NR
based compounds exhibit good heat ageing properties but poor dynamic flex-fatigue resistance.

However, SBR based Semi EV & EV cure systems exhibit both good heat ageing & dynamic flexfatigue resistance.

Ozone cracking and Flex cracking may occur at the same time involving complex mechanisms.

Para-phenylenediamine antidegradants (PPDs) offer excellent protection to rubber vulcanizates as


Antioxidants, Antiozonants &. Antiflexcracking agent.

EFFECT OF OZONE:
.

Longer wave length UV light photolyzes Nitrogen Dioxide to yield Oxygen atoms [O ] and Nitrogen
Oxide.

The Oxygen atoms then combine with Oxygen molecules present in the atmosphere to form Ozone.

In unpolluted areas the ozone concentration is 2 to 5 pphm. In more polluted areas it can reach to 40
to 50 pphm.

Ozone is also formed in the stratosphere by the action of short wave length UV-light on oxygen.
Although the flux of short wave length UV light is absorbed in the upper atmosphere, the
concentration of ozone in the troposphere is still appreciable due to the presence of Nitrogen Oxide.

Oxygen atoms liberated by this photolysis of oxygen molecules also combine with oxygen molecules
to form ozone.

Since ozone is formed by photolytic reaction, its concentration in the atmosphere peaks at mid-day
and is negligible at night.

Ozone concentration in the atmosphere is not temperature dependent but it does peak off during the
summer months when the sun light is more directly incident.

The atmospheric ozone concentration varies on daily basis and is dependant on the severity of the
sun light, weather conditions, geographic location, air pollution and the season.

The ozone absorption occurs at a linear rate for a typical elastomer.

The ozone absorption is proportional to the concentration of ozone.

The rubber surface which is not stressed also undergoes reaction with ozone to form oxidized film but
does not show typical ozone cracks.

No crack growth occurs unless the specific stress value is exceeded. This value is known as Critical
Stress Value.

When the rubber is stressed just above the critical stress value, the ozone cracks are few in numbers
but are large in length and depth.

As the stress is increased to a high stress value, the ozone cracks increase in number and are finer in
size.

In addition to large number of double bonds present in the highly unsaturated rubbers, ozone also
reacts with saturated polymers and the polysulphide chains at a comparatively slower rate.

Unsaturated polymers which contain electron donating groups (e.g. methyl groups in NR) are more
vulnerable to ozone attack.

The unsaturated polymers containing electron-withdrawing groups (e.g. Chlorine in CR, Bromine in
BIIR) are less vulnerable to ozone attack due to the deactivating effect imposed on the double bonds
by the halogen atoms.

Ozone reacts with the double bonds in the rubber molecule causing chain scission. The chain
scission results in the formation of surface cracks in the direction perpendicular to the applied strain.

The ozonation reactions proceed as follows :

Under strain these ozonides easily decompose and break the double bonds resulting in the
appearance of surface cracks and as this mechanism repeats, the cracks grow deeper.

Under unstressed conditions, a silver grey film is formed on the rubber surface which is known as
frosting. Frosting is accelerated by hot & humid conditions.

Role of Antidegradants:

Antioxidants & Antiozonants are used to protect the polymers from degradation.

Antioxidants are highly effective ingredients and have a dramatic impact on the service life of the
rubber product although being present at extremely low concentrations (0.5 3.5 phr).

Antioxidants do not completely eliminate oxidative degradation, but they substantially inhibit the rate
of auto oxidation by interfering with the radical propagation reaction.

Depending on the types and combinations of antioxidants used, the polymer can be protected during
the entire phase of the products life cycle.

The Antioxidants are categorized as :

A) Primary Antioxidants (Chain Terminating)


e.g. Amines & Phenolic.
B) Secondary Antioxidants (Peroxide Decomposers)
e.g. Phosphites & Thioesters.

Addition of an Antioxidant ( AH ) in small dosage ( 1.0 - 2.0 phr ) interrupts the degradative reactions
as follows :
R

AH

RH + A .

ROO +

AH

ROOH + A . (Prevents chain breaking.)

RO

AH

ROH + A ........... (Scavenges alkoxy free radicals.)

ROOH +

AH

Inert products (Prevents degradation.)

ROH

AH

Inert products. (Prevents degradation.)

(Scavenges free radicals.)

In order to inhibit the degradation cycle (cascading effect) the antioxidants function as follows :
a) Scavenge the free radicals before they have opportunity to grow in numbers rapidly,
b) Reduce the peroxides & hydro peroxides to alcohols before they produce additional radicals.

Secondary Aryl Amines, Diamines as well as Sterically Hindered Phenolic Antioxidants act by
donating their reactive hydrogen atom (N-H, O-H ) to the free radicals as shown below:
R

ROO

+ AH

RH

+ AH

ROOH + A

+ A

(A is a harmless radical)

Thus the Peroxy Radical is offered a more easily abstractable hydrogen by an externally added
hydrogen donor (antioxidant) and the polymer backbone remains unaffected until the H-donor
(antioxidant) is consumed.

In the above process, the Antioxidants themselves get converted to relatively stable radicals which do
not propagate further.

According to the mode of action the antioxidants may be grouped as :


-

H-donors,
Hydro peroxide decomposers,
Metal deactivators,
UV stabilizers etc.

Amine class of primary antioxidants is highly effective due to their ability to act as chain terminators
and peroxide decomposers. Antioxidants of this class are most widely used in rubber compounds
requiring high degree of protection.

Role of Antiozonants:

The exact mechanism of ozone protection of rubber vulcanizates is still not established!

Following four theoretical models have been proposed :


1. Inert barrier theory.
2. Competitive reaction theory.
3. Reduced critical stress theory.
4. Chain repair theory.

10

The Inert Barrier Theory proposes that the antiozonant migrates from the bulk of the rubber to the
surface to form a film. This film functions as a physical barrier which protects the reactive polymer
double bonds by keeping ozone out of contact.

The Inert Barrier Theory Mechanism is similar to ozone protection offered by waxes and non reactive
polymers such as EPDM, Halogenated butyl rubber, halogenation of the surface of rubber vulcanizate
etc.

The Reduced Critical Stress Theory proposes that the rubber vulcanizate surface is modified by the
migration of the antiozonant on the surface or just below the surface of the rubber.

This modification relieves the internal and surface stresses and the vulcanizate behaves as if it was
unstressed or at lower than critical stress required for ozone crack formation.

The Chain Repair Theory proposes that antiozonant reacts directly with the ozonide or the carbonyl
oxide forming a low molecular weight, inert & self healing film which attaches the antiozonant to the
rubber.

The Competitive Reaction Theory is sub divided into Scavenger Theory & Protective Film Theory.

The Scavenger Theory proposes that as the antiozonant migrates to the surface; it selectively reacts
with ozone and protects the polymer double bonds until the antiozonant is exhausted.

Protective Film Theory proposes that once the antiozonant has been fully exhausted, the reaction
products of the antiozonant form an Inert Protective Film over the surface of the rubber vulcanizate.

The Competitive Reaction theory is substantiated by experiments and is well accepted.

CLASSIFICATION OF ANTIOXIDANTS:
According to
Function

According to
According to
Chemical Types ASTM D4676

Staining / Non Staining

Phenolic

Antioxidants

Phosphates

Antiozonant / Anti flex cracking Agent

Thioesters

Cure / Cross link modifiers

Amines

Multifunctional

Class 1
Class 2

Para Phenylenediamines (PPDs)

Class 3
Class 4

Phenolics

Class 5
Class 6

Aromatic Phosphites

Trimethyl-dihydroquinolines (TMQs)
Alkylated Diphenylamines (DPAs)
Diphenylamine - Ketone Condensates

The antioxidants can also be classified in two types according to the way in which they function :

- Preventive antioxidants which inhibit the formation of free radicals (R ) during the initiation stage.

- Antioxidants which interrupt the propagation cycle by reacting with (R ) and (ROO ) radicals and
thus introducing new termination reactions.

Hindered Phenols and Secondary Aryl Amines act as Primary Antioxidants by donating their reactive
Hydrogen (O-H , N-H ) to the polymer free radicals, particularly Peroxy radicals, formed during the
propagation stage of polymer degradation process.
ROO

+ AH

ROOH + A

11

The antioxidant radical (A ) formed during the above process must be stable to discontinue the
propagation of new radicals.

The radical (A in most cases is stabilized by electron delocalization or resonance.

.)

PARAPHENYLENE DIAMINES ( ASTM : D4676 CLASS-1).

The general structure of PPDs can be represented as follows :

Three types of PPDs are used in the Rubber Industry.


1. PPD Type I : N, N-dialkyl-p-phenylenediamine.
2. PPD Type II : N-alkyl-N-aryl-p-phenylenediamine.
3. PPD Type III : N,N-diaryl-p-phenylenediamine.

Paraphenylene Diamine antidegradants (PPDs) function as primary antioxidants and are recognized
as the most powerful class of chemical antiozonants, Antiflexcracking agents and Antioxidants.

PPDs are extensively used in tyres, beltings and molded & extruded rubber products as antiozonants
& Antiflexcracking agents at 1.0 4.0 phr dosages. However, being highly staining & discoloring type,
PPDs are not used in white or colored products.

PPD antidegradants are also used as polymer stabilizers.

PPDs vary in chemical structure and in performance characteristics depending on the substitutions on
the nitrogen atoms.

R & R1 are secondary alkyl groups (C6 or larger). These PPDs are generally liquids at room
temperature and represent single chemical component > 90%.

12

In case of 77PD both the substituent groups are alkyl groups (branched C7).

In case of 88PD both the substituent groups are alkyl groups (branched C8).

Dialkyl PPDs :
-

Offer excellent static ozone resistance even in the absence of wax.


Are not very effective under dynamic conditions.
Do not leach out in water.
Are more sensitive to oxygen and hence suffer from lack of persistency and poor shelf-life
(3 to 4 months only).
- Are highly basic in nature and hence scorchier.
- Used in combination with alkyl-aryl PPDs to obtain static and dynamic ozone protection.
- Dosage 1.0 to 2.0 phr.

13

R is a secondary alkyl group and R1 is hydrogen or a primary alkyl substituent (usually methyl). These
PPDs are generally consist of a single component or purposeful mixture of two or more major
components. The products can be liquids or solids.

In case of IPPD, R is isopropyl group and R1 is hydrogen.

In case of 6PPD, R is (1,3-dimethylbutyl) group and R1 is hydrogen.

In case of CPPD, R is cyclohexyl group and R1 is hydrogen.

In case of 8PPD, R is octyl group and R1 is hydrogen.

Alkyl Aryl PPDs:


-

Offer best all-round performance as Antidegradants against all degradative forces.

Offer excellent antioxidant, static & dynamic ozone resistance and anti-flex cracking properties.

Exhibit optimum migration rate due to the presence of bulky aromatic ring on one side and a
branched alkyl chain on the other side.

Are less volatile than di-alkyl PPDs. (Lower losses during storage, processing & cure and hence
offer long term protection to rubber vulcanizates).

Are slightly basic in nature and hence influence scorch & cure characteristics.

The water leaching properties depend on molecular weight of the

PPD and the pH of water. (e.g. IPPD is easily leached out in water but 6PPD does not leach out
in water to any appreciable extent.)

Exhibit high solubility in rubber hence do not exhibit blooming tendencies.

Dosages used in rubber compounds are from 1.0 phr to 4.0 phr. Their effectiveness increases as
the dosages are increased.

Are stable & have good shelf-life (12 months).

14

15

R and R1 can be the same or different groups consisting of hydrogen or alkyl groups (usually methyl).
Therefore this type of PPDs can be individual components or mixtures of three or more isomers.

Diaryl PPDs are generally solids at ambient temperatures.

In case of DPPD both R & R1 are hydrogen atoms.

In case of DTPD, R1, R2, R3, R4 may be hydrogen or methyl groups.

Comparatively slower migration rate due to the presence of bulky aromatic rings and hence
persistent, non-extractable by fuels & solvents and is retained in the compound (in which originally
incorporated) to offer long term protection.

Limited solubility in rubber hence exhibit blooming tendencies ( over 0.7 phr in NR & 1.0 phr in SRs )
Less effective at lower dosages ( but exhibit bloom at higher dosages).

Good antioxidant, static & dynamic ozone resistance and anti-flex cracking properties.

16

Comparatively less basic in nature and hence does not influence scorch or cure rate.

Generally used in combination with alkyl-aryl PPDs to obtain static and dynamic ozone protection
(Dosage 0.5 to 1.0 phr). Resume activity when other PPDs get depleted.

More stable & good shelf-life (12 months).

Antiozonant Action: Diaryl PPD


H

O2

O3

N
O

H
-

H2O

N
O
H

O
O2

O3

Catalytic process mechanism of polymer protection: How DPPD Antidegradant works.


NH

NH

DPPD
O

NH

ROO

NH

.
N

N
R

DPQI
ROO

ROO .

POLYMER ATTACHED

O
N

POLYMER ATTACHED

DPQI M O
ROO

POLYMER ATTACHED

DPQI DO

17

PPD antiozonants exhibit following common functions :

- All PPDs migrate to the surface of the rubber product to react with ozone directly and competitively.
- The migratory losses of antiozonants can occur by migration to adjacent stock.
- The effectiveness of PPD antiozonants in rubber vulcanizates can be improved by incorporation of
waxes and synergistic antioxidants. This helps in the reduction of PPD dosages for adequate ozone
protection.
-

The use of higher wax dosages / selection of improper wax grades can be detrimental to the
performance of Antiozonants.

- All PPDs decrease the rate of cut - growth of rubber vulcanizates.


- Di alkyl & Alkyl-Aryl PPDs increase polymers critical stress necessary for ozone crack initiation.
- The use of antioxidants along with PPDs protects the PPDs from direct oxidation.
- The Dialkyl-PPDs are initially the most active antiozonants followed by Alkyl-Aryl-PPDs & then the
Di-Aryl-PPDs. This order of activity reverses as the ageing progresses due to oxidation and exposure
of PPDs.
- For extended protection of rubber vulcanizates blends of PPD antiozonants are often used.
- The solubility of PPD antiozonants depends on the solubility parameter of the rubber itself.
(Example: Diaryl PPDs have low solubility in NR and hence bloom above 1.0 phr dosage.)
- All PPDs exhibit high solubility in NBR based compounds and hence do not migrate easily
to the surface to offer ozone protection.
- Diaryl-PPDs are more effective and persistent compared to other PPDs in polychloroprene
(CR) based compounds. However, PPD antiozonants can cross link CR or other
halogenated polymers causing bin cure.
- PPD antiozonants are easily oxidized by oxidizing agents (e.g. Lead Oxide) or even during
storage by oxygen or ozone.
- PPD antiozonants are not added in the Rubber-Carbon black master batch as oxidation of
this blend destroys the activity of PPD antiozonant.

The catalytic mechanism generally recognized to occur on inclusion of Phenolic and Amine
antioxidants / antidegradants to protect polymeric materials against degradative factors can be
represented as follows:

18

In this mechanism, the original diphenylamine antioxidant is converted to diphenylamine-N-oxide.

The N-oxide can either trap R and then thermally eliminate diphenylhydroxylamine directly.

The diphenylhydroxylamine then behaves as a hydrogen donating antioxidant by neutralizing ROO


and the catalytic cycle is complete.

This process uses polymer as a source of hydrogen to moderate, compete with and control the
propagating step of the free radical oxidation process.

The creation of double bonds in the polymer has minimal effect on the overall physical properties
because polymer chains are not being broken or cross-linked.

This mechanism is often called as Chain breaking hydrogen abstractor / Chain breaking hydrogen
donor mechanism.

COMPARISONS OF ANTIDEGRADANTS IN NR-TRUCK TREAD COMPOUND @ 2.0 phr.


NR Protection
SR Protection
Demattia Flex, kc
Static
Dynamic
Static
Dynamic
Control
27
87
IPPD
75
23
100
100
100
100
430
6PPD
48
26
100
90
85
80
300
77PD
Liquid
19
160
65
130
75
200
DTPD
105
15
150
65
125
70
225
- DTPD is expected to show comparatively much better performance during long term exposure tests due to its
slower migration rate.
- NR & SR ozone protection under static & dynamic conditions as per standard ASTM procedure indexed @
IPPD = 100 .
Antidegradant M.P.,C MS @ 120C, min

COMPARISON OF TMQ AND 6PPD IN TRUCK TREADS


Base Formulation: NR - 75, BR1220 - 25, N339 Black - 50, Aromatic Oil - 8, Zinc Oxide - 5,
Stearic Acid - 2, CBS - 0.6, Sulphur 2.5
Fatigue Life , kc to failure at 100% Extension

TMQ

6PPD

Unaged

Aged

Dynamic Ozone
Resistance @ 20
pphm. 96 hr.
(Crack Rating)

28.5

30.0

15.0

1.0

68.0

50.0

42.0

167

280

2.0

88.0

60.0

58.0

200

387

3.0

94.0

62.0

60.0

207

400

1.0

62.0

132.0

75.0

440

500

2.0

89.0

180.0

110.0

600

733

3.0

100.0

195.0

125.0

650

833

6PPD/ TMQ
Dosages, phr

% T.S. Retention
(85C12 days)

Unaged

Aged
(85C-5 days)

% Improvement over
Control

Ozone Crack Rating : 10 No Cracks , 0 Complete Failure

19

The test results indicate that:

6PPD Antidegradant provides high degree of protection against Oxidative Heat Ageing,
Flex-Fatigue (Unaged & Aged), and Dynamic Ozone Resistance even at 1.0 phr dosage.

The degree of protection increases as the dosage is increased further. The test results confirm
that 6PPD Antidegradant is almost three times more effective than TMQ antioxidant in this
respect.

TMQ antioxidant offers excellent oxidative heat ageing resistance to rubber vulcanizates which is
comparable to 6PPD.

Considering the costs involved; one would prefer use of TMQ antioxidant so that the 6PPD
antioxidant included in the rubber compound is available for protection against other degradative
forces.

EVALUATION OF TMQ AND 6PPD IN NR/BR -TRUCK TREAD COMPOUND.


Base Formulation: NR - 75, BR1220 - 25, N339 Black - 50, Aromatic Oil - 8, Zinc Oxide - 5, Stearic Acid - 2,
CBS - 0.6, Sulphur - 2.5.
6 PPD / TMQ Dosages phr
Fatigue Life , kc to Failure at 100% Extension
% Tensile Strength
Retention
6 PPD
TMQ
Aged
% Retention
Unaged
(Aged, 85C-2days)
phr
phr
( 85C-5 days)
Of Fatigue Life
1.0
60.0
132
135
102
1.0

1.0

72.0

123

137.5

112

1.0

2.0

78.5

118

142

120

1.0

3.0

88.0

113

154

136

2.0

77.5

135

137

101

2.0

1.0

84.5

130

150

115

2.0

2.0

88.5

135

132

98

2.0

3.0

92.0

135

162

120

3.0

88.0

156

158

101

3.0

1.0

92.5

145

150

103

3.0

2.0

96.0

148

161

109

3.0

3.0

96.5

162.5

187.5

115

The test results indicate that:

The inclusion of TMQ antioxidant along with 6PPD improves oxidative heat ageing and the extent of
improvement is proportional to the dosages of 6PPD and TMQ.

The improvements are smaller at higher dosages under the test conditions suggesting acceptable
performance at optimized ratio of 6PPD: TMQ at 2: 1.

At higher dosages of 6PPD & TMQ further improvements are obtained indicating options available for
obtaining still higher performance.

20

IPPD REPLACEMENT BY 6PPD. (REASONS)

6PPD is not a skin sensitizer like IPPD,

6PPD is much less volatile than IPPD (Better retention in rubber compounds),

6PPD is not easily leached out in water like IPPD,

6PPD is not scorchier like IPPD,

If the losses of IPPD due to volatility & water leaching are taken into account, then at equal dosages
6PPD shows better performance than IPPD.

THE ROLE OF WAXES.

Waxes migrate quickly to the surface of rubber vulcanizates to form a physical barrier against ozone
attack.

A critical of wax bloom is required to form a continuous film for optimum static ozone protection.

Solubility and mobility of waxes govern their ability to form a sufficient level of bloom which is also
dependent on polymer & filler type added, loadings, state of cure and time & temperature of storage
after vulcanization.

Paraffin waxes are produced by solvent extraction of lubricating oil fractions and then separated into
desired sub-fractions by step wise crystallization.

Paraffin waxes contain normal paraffins (alkanes) with slightly branched chain paraffins (iso alkanes)
with generic formula (Cn H2n+2) where n = 18 to 50. The Melting Points vary from 52 to 54C (C18 to
C36) to 66 to 68C (C22 to C50).

Low molecular weight fractions (< C24) migrate faster at lower temperatures e.g. 0C but dissolve in
rubber as the temperature rises.

High molecular weight fractions ( > C24 ) migrate slower at low temperatures but faster at high
temperatures e.g. 40 C

A typical Blended Paraffin Wax grade contains a mol. wt range of C19 to C48 with majority fractions of
C25 to C33 range and thus provides a sufficient range of fractions which responds over a wide range of
ambient temperatures.

The Microcrystalline Waxes (MC-Waxes) are amorphous in nature and are extracted from higher
boiling lubricant oil fractions. These are predominantly branched chain saturated structures with C34
to C70 chains with Melting Point range of 57C to 99C and typical carbon chain length of C60 .

Paraffin wax has large and well defined crystals where as MC-Wax has crystals which are small and
of irregular shape.

The branched nature and higher mol-wt of MC-waxes result in slower diffusion rates through rubber
vulcanizates at lower temperatures and are effective when the rubber vulcanizate temperature is
high.

21

Paraffin waxes offer best static ozone protection at low temperatures while MC-Waxes protect best at
high vulcanizate temperatures.

A blend of Paraffin Wax & MC-Wax would provide best protection at ambient exposure temperatures
of rubber products under static conditions. No chemical reactions are involved between wax and
ozone.

Use of waxes in rubber compounds reduces the fatigue life and dynamic ozone resistance of the
rubber vulcanizates.

Waxes alone do not offer ozone protection under dynamic conditions due to lack of adhesion
between wax film & vulcanized rubber surface and the inextensibility of the wax bloom (film).

The PPD antidegradants do provide ozone protection against both static and dynamic conditions due
to Chemical Reactions with ozone besides film formation.

Any change in ozone concentration and atmospheric temperature will influence the rate of chemical
reactions between ozone and PPDs.

Increase in PPD dosages results in slight increase in wax bloom and thus at lower wax dosages the
ozone resistance is improved significantly.

The wax bloom thickness is higher in case of NR / BR blends than 100% NR compounds.

At normal levels of PPD-Wax blends, there is no synergism between PPD and Waxes under static or
dynamic conditions. However, significant synergism is observed under intermittent conditions due to a
combination of effective static ozone protection of wax and dynamic ozone protection of PPDs.

Blended Wax & PPD Antidegradants combinations will provide excellent ozone protection over a wide
range of temperatures under Static, Dynamic as well as Intermittent (alternating static & dynamic)
conditions.

At high dosages of blended wax ( > 3.0 phr ) the flex-fatigue life of rubber vulcanizates reduces due to
ozone attack at the cracks alone resulting in increased crack depth of the exposed ( & unprotected )
rubber surface. This can be prevented by the presence of PPD Antidegradant through its chemical
reactions with ozone.

WAXES AND THEIR TYPICAL PROPERTIES


Properties
Avg. Mol-Weight
% Normal Paraffins
% Iso Paraffins & Napthenes
Typical Carbon Chain length
Melting Point ,C / Bloom
thickness, micron @ 1.5phr
(Melting point and bloom thickness have no
direct co-relationship. Values given in this
table are typical and after 50 days at Room
Temperature).

Paraffin Wax
350 420
High

MC-Wax
490 800
Low

PE Wax

PP Wax

Low

High

C26
51-53 / 0.41
54-56 / 2.4

C60
74-76 / 1.3
79-81 / 0.9

85-87 / 0.48

105 / 0.00

56-58 / 3.5

82-84 / 0.22

99-101 / 0.05

59-61 / 2.64
64-66 / 2.26
67-69 /2.06

84-86 / 0.15
89-91 / 0.08
-

22

23

TRIMETHYL-DIHYDROQUINOLINES (TMQs) ( ASTM : D4676 CLASS-2)

TMQs represent a group of antidegradants based on polymerized Aniline-Acetone condensation


products. The individual products differ by the degree of polymerization and Dimer + Trimer +
Tetramer Contents.

TMQs function as primary antioxidants and are recognized powerful class of chemical antioxidants,
used to protect rubber articles from degradation by atmospheric oxygen at higher temperatures.
It is well known that only the secondary aminic groups (= NH) function as antioxidants by the
formation of nitroxyl radical ( - NO ) and thus the Dimer, Trimer & higher oligomers content in TMQ
only act as effective antioxidants.

24

The Contents of Amine Impurities (which cause several processing problems) also differ considerably
from supplier to supplier.

The primary aminic groups (- NH2) do not function as antioxidants. Hence products which contain
higher proportions of primary aminic groups are weaker antioxidants and are responsible to activate
sulphur cross linking and scorching of Rubber Compounds.

Primary aminic groups destabilize Insoluble Sulphur by decreasing its transition temperature to
soluble Sulphur and thus causing scorching and sulphur bloom problems for Rubber compounds.

The formation of isopropyl-bis-aniline (or bisaniline A) and Monomer-Aniline Adducts during TMQ
manufacture; are responsible for dramatically decreasing the Peptization activity as well as initiating
cross linking reactions causing viscosity increase of NR based compounds at the rubber processing
temperatures.

The monomer content in TMQ antioxidant is also considered as an objectionable impurity since it is
leached out in water and can cause porosity in thicker cross section extrudates.

TMQ oligomers are widely used in the Rubber Industry as general purpose, high activity and
inexpensive amine class antioxidants and offer excellent resistance to thermo-oxidative ageing of
elastomers & their vulcanizates.

TMQs are in tyres, beltings and molded & extruded rubber products as powerful antioxidants at 0.5
2.0 phr dosages. TMQs are moderately staining & discoloring type, TMQs can be used in colored
products at small dosages.

Low volatility of TMQ due to polymeric nature ensures maximum retention in Elastomers .

Low mobility of TMQ ensures high retention and minimizing losses through diffusion or extraction.

TMQ is Highly persistent & Non-blooming antioxidant with minimal effects on the processing and
curing characteristics of Rubber Compounds,

Due to Very high activity; TMQ is effective even at lower dosages,

TMQ is only mildly discoloring and does not cause any contact staining.

25

MECHANISM OF TMQ ANTIOXIDANT REACTIONS

TMQs act as alkyl radical (R ) scavenger which immediately stops auto-oxidation process.

The hindered aromatic amine antioxidants get oxidized due to peroxy radicals to form nitroxyl radicals

which act as scavengers of alkyl radicals (R ).

The process proceeds cyclically forming nitroxyl radicals until the nitroxyl radicals are destroyed by
side reactions.

TMQs Activity in Rubber Compounds:


a) Effect of TMQ Dosages in NR Tread Compound
(Base Compound: NR-100, Peptizer-0.15, ZnO 5, St. Acid 2, N 330 Black 45, Aromatic Oil 5, Wax 0.5,
MBS 0.5, S 2.3.)
Ageing in Oxygen Bomb @ 70C 20 atm pressure.
TMQ, phr

0.5

1.0

1.5

2.0

No. of days for 50 % drop in T.S.

10

15

19

21

Even at 0.5 phr dosage, TMQ is an highly active antioxidant for NR.

Antioxidant activity improves as TMQ dosage is increased to 2.0 phr.

26

b) Comparison of TMQ against other antioxidants in NR Tread Compound :


(Base Compound: NR-100, Peptizer-0.15, ZnO 5, St. Acid 2, N 330 Black 45, Aromatic Oil 5, Wax 0.5,
MBS 0.5, S 2.3, Antioxidant 2.5. )
Tensile Strength Retention After Ageing In Hot Air @ 100 C
No. of Days

Control

ADPA (L)

TMQ

6 PPD

IPPD

25.5

50.2

55.3

55.5

55.5

10.2

25.5

34.0

38.3

40.8

6.8

17.0

21.3

28.1

28.5

6.0

10.2

12.8

15.0

17.0

PHENOLIC ANTIOXIDANTS ( ASTM : D4676 CLASS-3)

Phenolic antioxidants are primary antioxidants and are classified chemically according to the number
of Phenolic groups in the molecule.

In general, the more sterically hindered antioxidants are less discoloring but have lower antioxidant
activity in rubber application.

The Phenolic Antioxidants are Non-Staining type and are used in the Rubber Industry for the
manufacture of white/colored rubber products and as stabilizers of raw Synthetic Rubbers.

Phenolic Antioxidants are of following types:


Mono-functional Phenols (Type 1),
Bi-functional Phenols (Type 2),
Multi-functional Phenols (Type 3).

The Phenol radical (A ) can cause polymer degradation but this is prevented by the hindered physical
structure (e.g. substitution by styrene) at 2,6 position.

27

Sterically Hindered phenols act by scavenging RO And ROO Radicals via Hydrogen atom transfer
from the OH group to form hydroperoxides and phenoxyl radicals. The reaction mechanism is given
below:

The radical (A ) is stabilized by electron delocalization or resonance as shown below:

The discoloration tendency of Phenolic Antioxidants is due to the formation of Stilbenequinone which
is explained as follows :

These products are low cost, weaker, less persistent, exhibit higher volatility & slight discoloration
tendency on long term ageing of the rubber vulcanizates.

28

Styrenated Phenol is much less volatile & provides long term protection and is widely used in white /
coloured latex based goods at the dosage of 1.0 - 2.0 phr.

BHT is more volatile and provides only short term protection. It is mostly used as an in process
stabiliser for synthetic polymers to impart raw polymer storage stability.

These represent the most important class of non staining antioxidants.

These antioxidants have low volatility, good antioxidant activity and exhibit minimal discoloration to
rubber vulcanizates.

Depending upon the position of linkages, bisphenols are subdivided into


bisphenolic antioxidants.

The ortho bridged bisphenolic antioxidants exhibit excellent antioxidant performance but show
discoloration (pinking) tendency to rubber vulcanizates.

The para bridged bis phenolic antioxidants show slightly lower antioxidant performance but do not
exhibit discoloration effect on rubber vulcanizates.

Thiobisphenols exhibit high antioxidant activity compared to similar bisphenols.

Thiobisphenols generate sulphur compounds which react with polymers during antioxidant protection
reaction and compliment antioxidant activities of thiobisphenols.

Thiobisphenols cause comparatively higher discoloration of rubber vulcanizates than bisphenols.

ortho or para bridged

29

PHENOLIC ANTIOXIDANTS ( ASTM : D4676 CLASS-3)


Multi-functional Phenols (Type 3)

Multifunctional phenolic antioxidants are very high performance antioxidants, exhibit extremely low
volatility and do not cause contact / migratory staining or discoloration of the rubber products.

Higher molecular weight of multifunctional phenolic antioxidants also contributes to practically no


leaching and extraction from rubber products by water or solvents and ensuring long term protection
against oxidation.

Chemical structure of multifunctional phenols is given below:

Butylated reaction product of para cresol and dicyclopentadiene (e.g. Wingstay L) is the most popular
multifunctional phenolic antioxidant used both in solid rubber products and latex based products.

The resistance to oxidative degradation of rubber is due to a particularly favorable pattern of


substitution on the phenolic group.

Color stability is due to the Stearic impossibility to form highly conjugated and colored by-products
like quinones

Alkylated Diphenyl Amines (DPAs): ( ASTM : D4676 CLASS-4)

This class of antioxidants represents Substituted Amine Antioxidants which are complex reaction
products of diphenylamine and various alkylating agents.

The substituent is selected to achieve a desired balance of cost and performance characteristics.

Alkylated Diphenyl Amines are moderately staining and discoloring.

These antioxidants are generally used as stabilizers of raw synthetic polymers and as general
purpose antioxidants for rubber vulcanizates.

30

Aromatic Phosphites: ( ASTM : D4676 CLASS-5)

Aromatic phosphites are phosphphorus esters of aromatic phenols.

Diphenylamine Ketone Condensates: ( ASTM : D4676 CLASS-6)

These antioxidants are complex reaction products of diphenylamine and alkyl ketones (primarily
acetone), some of which are further condensed with formaldehyde to produce products of high
molecular weight. These antioxidants are low melting point resins or liquids.

31

There are two different types of ADPA condensates viz. low temperature reaction products and high
temperature reaction products.

The high temperature reaction products are reactive towards oxygen and provide some flex
cracking resistance but are severely staining and discoloring.

They are also volatile and do not provide long term protection against the degradative forces that
constantly act on rubber products.

These products are mostly used in cheap mechanical rubber products, some non critical tyre
applications and as a stabilizer for emulsion SBR.

These antioxidants reduce the building tack of uncured rubber compounds making product (e.g. tyres,
conveyor beltings etc) building process more difficult.

The low temperature condensation products are not very reactive towards oxygen but are less
staining and discoloring.

These are comparatively less volatile and can provide medium term protection to the rubber
vulcanizates.

These types of ADPAs have low solubility in oil and hence suitable for oil resistant compounds based
on NBR.

The recommended dosage of ADPA antioxidants is 1.0 2.0 phr for various rubber products
manufacture.

PROPERTIES OF ANTIOXIDANTS / ANTIDEGRADANTS

For selecting a proper Antioxidant/Antidegradant for specific end-use requirements following factors
are considered to be important for the choice.
a)
b)
c)
d)
e)
f)
g)
h)

Discoloration & Staining,


Volatility,
Solubility,
Chemical Stability,
Physical form,
Antioxidant/Antidegradant concentration,
Cost,
Health & Toxicity concerns.

Discoloration & Staining

Discoloration refers to colour imparted to the rubber compound itself.

Staining takes place in two forms viz. Contact stain and migration stain.

Contact stain is a discoloration or stain imparted to another surface which is in contact with rubber.

Migration staining is a discoloration or stain which results in an article adjacent to or nearby the
rubber compound.

32

All these forms of discoloration are due to oxidation products of the antioxidants themselves in nearly
all the cases.
In general, phenolic antioxidants are non-discolouring and the amines are discolouring.

Volatility

Volatility of antioxidant is related to both the molecular weight and the type of molecule. Generally,
greater the molecular weight, less is the volatility.

The type of molecule however, has a greater effect than the mol. Weight (e.g. .Hindered Phenols) has
high volatility in comparison with amine antioxidants of the approx. same molecular weight.

Loss of antioxidants results due to low volatility during processing, curing and usage of the rubber
article under severe operating conditions.

VOLATALITY OF ANTIOXIDANTS / ANTIOZONANTS AT 100 C


Antioxidants / Antiozonants
ADPA ( Liquid - Low Viscosity )

Loss on Heating at 100 C, % w / w


4 Days
8 Days
12 Days
37.00
48.00
54.00

ADPA ( Liquid - High Viscosity )

28.00

35.00

40.00

ADPA ( Solid - Resin )

0.60

0.50

0.50

77 PD

7.50

13.20

17.00

IPPD

4.25

6.40

9.00

6 PPD

2.50

4.50

6.20

DTPD

2.50

4.00

6.00

PBNA

2.50

4.70

6.30

TMQ

0.15

0.20

0.20

Solubility

Solubility of antioxidants in rubber as well as in solvents (in which the rubber article would come in
contact with) is an important factor to be considered while making the choice of antioxidant for a
particular end-use.

Poor solubility in rubber of a particular antioxidant means only small quantities of the antioxidant can
be added without causing any bloom.

Solubility can also affect the performance, processing, leaching out in water, solvent and even FDA
status.

Phenolic and Phosphite antioxidants generally have high solubility in rubber and blooming does not
occur.

33

Chemical Stability

The stability of an antioxidant towards, heat, light, oxygen etc. is important if it is supposed to have
maximum effectiveness for long periods.

Many amine antioxidants are affected by oxidative reactions and phenolic antioxidants are affected by
heat in the presence of acidic materials.

Among the PPDs, dialkyl PPDs are oxidised very fast and are effective for short duration whereas
alkyl aryl PPDs and diaryl PPDs are more persistent.

Physical Form

Solid, free-flowing and non-dusty material are generally preferred over liquid antioxidants because of
ease of handling & weighing,

Health Safety & Environmental Concerns & change over to automated conveying & weighing
systems.

Antioxidants / Antiozonants Concentration

Determining proper level of Antidegradant to use is a complex question whose answer depends on
cost, polymer type, end-use, application, staining requirements, etc.

Most materials show an optimum level, based on laboratory ageing studies and increased levels are
not required.

One is encouraged to use sufficient material to ensure the presence of an optimum dosage so that
after extended use part of the antioxidant may be destroyed or rendered inactive and still the rubber
product is well protected.

This optimum level is very difficult to predict since it depends on so many other factors e.g. curing
system, nature of polymer, fillers used, etc.

TMQ type antioxidants can be added up to 8.0 phr and the performance is directly proportional to the
dosage used for long term ageing of the rubber product.

The ppd class of antidegradants can be used from 1 to 4.0 phr level.

As far as the non-staining antioxidants are concerned; these are effective at 0.5 - 2.0 phr range and
levels above this are not required.

Cost

Cost of overall Antidegradant system is the most important factor. For specialised products like tyre,
tube, V-belts, hose, etc. this may not be a limiting factor. However; for cheaper rubber products, the
antioxidants are selected after considering the total service life expected from the product itself.

While selecting antioxidant/antidegradants for products coming in contact with food, or are intended
for pharmaceutical use, one must confirm the suitability of the antioxidants chosen for a particular end
product.

34

Health & Toxicity Concerns

Antioxidants / Antidegradants used in rubber compounds intended for food & drugs contact should be
FDA / BGA approved.

Use of Antioxidants / Antidegradants of known health hazards should be avoided.

Information on Health, Safety & Environmental Control is updated continuously. One must consult a
responsible chemical manufacturer for the update before selecting the material for intended use or
refer to the latest edition of the BRMA Book.

The physical form of the antioxidants may vary from supplier to supplier ( e.g. Liquid, Powder,
Flakes, Pastilles, Rods etc.). Ease of handling & transportation, clean & dust-free characteristics are
the factors to be considered.

How to select the antioxidant system?


1. Identify Primary Degradation Factors.
- Oxygen,
- Heat,
- Light, Weathering & Other gases,
- Moisture, Steam,
- Ozone,
- Metal ions,
- Flex-Fatigue and other types of Stresses & Strains.
2. Define Service Environments / Requirements.
- Staining & Discoloration,
- Temperature,
- Static / Dynamic / Intermittent,
- Life cycle desired,
- Toxicological concerns,
- Cost.
3. Select appropriate type of Antioxidant & Antidegradant.
- Staining / Non-staining
- Mono functional / Multifunctional (e.g. PPD Antidegradant)
- Blends of Antioxidants and/or Antidegradants Different functions / Same function but
difference in reactivity / Same functionality and reactivity. )
- Refer to (easily) available Product Range and select the appropriate products. If
necessary, consult the Manufacturer.

35

Summary Table:
Antidegradants & Antioxidants

Chemicals

Structure

ASTM D 4676
Class 1
PPD
Anti degradants

Staining
Protection against
or
Heat &
Ozone
Flex
Non
Fatigue
Staining Oxidation
ST
Excellent Excellent Excellent

Para phenylenediamines (PPDs)


(General Structure)

Type 1
Dialkyl PPD
Antidegradant
77PD

ST

Excellent

Excellent

Fair

Notes
Primary Antioxidants. Donate reactive Hydrogen (N-H) to the polymer peroxy free radicals
(RCOO.) during the propagation stage of polymer degradation. All PPDs migrate to the
surface of the rubber product and react directly and competitively with ozone. Migratory losses
can occur to adjacent compounds. Effectiveness of PPDs can be improved by incorporation of
waxes and synergistic antioxidants. PPDs decrease the rate of cut - growth of rubber
vulcanizates. Use of antioxidants along with PPDs protects the PPDs from direct oxidation. Di
alkyl & Alkyl-Aryl PPDs increase polymers critical stress necessary for ozone crack initiation.
The Dialkyl-PPDs are initially the most active antiozonants followed by Alkyl-Aryl-PPDs & then
the Di-Aryl-PPDs. Order of activity reverses as the ageing progresses due to oxidation and
exposure of PPDs. The solubility of PPDs antiozonants depends on the solubility parameter of
the rubber itself. (Example, Diaryl PPDs have low solubility in NR and bloom above 1.0 phr
dosage.) All PPDs exhibit high solubility in NBR based compounds and hence do not migrate
easily to the surface to offer ozone protection. Diaryl-PPDs are more effective and persistent
compared to other PPDs in polychloroprene (CR) compounds. However, PPD antiozonants
can cross link CR or other halogenated polymers causing bin cure. PPD antiozonants are
easily oxidized by oxidizing agents (e.g. Lead Oxide) or even during storage. PPD
antiozonants are not added in the Rubber-Carbon black master batch as oxidation of this
blend destroys the activity of PPDs.
A liquid at room temperature. Excellent static ozone resistance. Offers long term static ozone
protection. Not very effective under dynamic conditions. Highly basic nature& hence scorchy.
Does not leach out in water. High volatility at elevated temperatures. More sensitive to oxygen
and heat hence poor persistency & shelf-life. A metal ion (Cu, Mn, Fe) deactivator. Causes
severe contact & migration staining. Used with alkyl-aryl PPDs to obtain static and dynamic
ozone protection for NR based tire compounds.
Dosage:1.0 to 2.0 phr.

N,N-Bis (1,4-dimethylpentyl)-pphenylenediamine

Chemicals

Structure

Type 2
Alkyl-Aryl PPD
Antidegradant
6PPD

Staining
Protection against
or
Heat &
Ozone
Flex
Non
Fatigue
Staining Oxidation
ST
Excellent Excellent Excellent

N-(1,3-Dimethylbutyl)-N'-phenyl-pphenylenediamine
Type 2
Alkyl-Aryl PPD
Antidegradant
IPPD

ST

Excellent

Excellent

Excellent

Notes
Offer excellent antioxidant, static & dynamic ozone resistance and anti-flex cracking
properties. Exhibit optimum migration rate. Are less volatile than di-alkyl PPDs. Lower losses
during storage, processing & cure. Offer long term protection to rubber vulcanizates.
IPPD is highly basic in nature and influence scorch & cure. IPPD is easily leached out in water
but 6PPD does not. 6PPD is much less volatile & basic than IPPD. If the losses of IPPD due to
volatility & water leaching are taken into account, then at equal dosages 6PPD shows better
performance than IPPD. 6PPD exhibits high solubility in rubber hence no blooming. IPPD is a
skin irritant hence is substituted by 6PPD in most parts of the world. IPPD & 6PPD are stable
& have good shelf-life. Dosages: 1.0 phr to 4.0 phr.
Effectiveness of these PPDs increases as the dosages are increased.

N-phenyl-N isopropyl-pphenylenediamine
Type 3
Diaryl PPD
Antidegradant
DPPD

ST

Very Good Very Good Excellent

Type 3
Diaryl PPD
Antidegradant
DTPD+DPPD

ST

Very Good Very Good Very Good

ASTM D 4676
Class 2
Polymerized
Trimethyl
Quinoline
Antioxidant
TMQ

Mild
Discolor
ation

N,N-diphenyl- ppd

No
Contact
staining
Polymerized 2,2,4-Trimethyl-1,2dihydroquinoline

Excellent

Modest
(Static)

Modest

Slower migration rate hence persistent, non-extractable by fuels & solvents and retained in the
compound to offer long term protection. Limited solubility in rubber hence bloom over 0.7 phr
in NR & 1.0 phr in SRs. Good antioxidant, static & dynamic ozone resistance and anti-flex
cracking properties. Does not influence scorch or cure rate. Used in combination with alkylaryl PPDs. Resume activity when other PPDs get depleted. Dosage: 0.3 to1.0 phr.

TMQ is widely used in the Rubber Industry as general purpose, high activity amine class
antioxidant. TMQ is highly persistent, non-blooming antioxidant and has minimal effects on
processing and curing characteristics of rubber compounds. TMQ offers excellent resistance
to thermo-oxidative ageing of elastomers. Its low volatility (due to polymeric nature) ensures
maximum retention, low mobility, and minimized losses through diffusion and extraction by
solvents / fuels / oils. Due to Very high activity TMQ is effective even at lower dosages. TMQ
antioxidant along with 6PPD offers improved oxidative heat ageing resistance proportional to
the dosages of 6PPD and TMQ. TMQ is only mildly discoloring and does not cause contact
staining. TMQ also exhibits a weak antiozonant activity. The composition and performance of
TMQ varies from supplier to supplier.
Dosage: 0.7 2.0 phr.

Chemicals

Structure

ASTM D 4676
Class 2
Antidegradant
ETMQ

Staining
Protection against
or
Heat &
Ozone
Flex
Non
Fatigue
Staining Oxidation

Notes

ST
Discolor

Excellent

Excellent

Very
good

A liquid at room temperature.


ETMQ is used in the Rubber Industry as Antiozonant & Antioxidant for general purpose rubber
based compounds (e.g. Tire side walls, cushion gums etc. & Beltings). Particularly effective in
SBR compounds. Non blooming. Causes severe contact staining. Also used as an antioxidant
for animal feeds.
Dosage: 2.0-3.0 or higher (alone) , Or 2:1 ratio with 6PPD/IPPD.

Non
Staining
Pale
Yellow
Or pink
Discolor
ation

Good

Modest
(Static)

Fair

Phenolic antioxidants are primary antioxidants. Classified by the number of phenolic groups in
the molecule. More Sterically hindered antioxidants are less discoloring but have lower
antioxidant activity in rubber application. The Phenolic Antioxidants are Non-Staining type and
are used for the manufacture of white/colored rubber products and as stabilizers of raw
Synthetic Rubbers. The Phenol radical can cause polymer degradation but this is prevented
by the hindered physical structure (e.g. substitution by styrene) at 2, 6 position. Sterically
Hindered phenols act by scavenging RO. And ROO. Radicals via Hydrogen atom transfer from
the OH group to form hydro peroxides and phenoxyl radicals.

Non
Staining
Pale
Yellow
Discolor
ation

Good

Modest
(Static)

Fair

Low cost, comparatively weaker, less persistent antioxidant. Slight discoloration tendency on
long term ageing of the rubber vulcanizates. Styrenated Phenol is much less volatile &
provides long term protection and is widely used in white / coloured latex based goods,
general mechanical goods and footwear products. Dosage:1.0 - 2.0 phr.

Non
Staining
Pale
Yellow
Discolor
ation

Good

BHT is more volatile and provides only short term protection. It is mostly used as in process
stabiliser for synthetic polymers to impart raw polymer storage stability. BHT also finds nonrubber applications (e.g. Food) and is used as polymer stabilizer at 0.5 to 1.5 phr dosage.
Dosage: 1.0 to 2.0 phr for rubber products manufacture.

6-Ethoxy-2,2,4-trimethyl-1,2dihydroquinoline
ASTM D 4676
Class 3
Phenolic
Type 1
Monofunctional

General Structure
Type 1
Monofunctional
Antioxidant SPH

n=1-3
Styrenated Phenol
Type 1
Monofunctional
Antioxidant BHT

Butylated hydroxytoluene

Chemicals

Structure

ASTM D 4676
Class 3
Phenolic
Type 2
Bifunctional

Staining
Protection against
or
Heat &
Ozone
Flex
Non
Fatigue
Staining Oxidation

Notes

Non
Staining
Pale
Pink
Discolor
ation

V. Good

These antioxidants have low volatility, good antioxidant activity and exhibit minimal
discoloration to rubber vulcanizates.
Depending upon the position of linkages, bisphenols are subdivided into ortho or para
bridged bisphenolic antioxidants.

Non
Staining
Pale
Pink
Discolor
ation

V. Good

22M46 is a highly potent and is most effective antioxidant for sulfur cured rubber products.
22M46 is also an effective antioxidant for polychloroprene based products. 22M46 has a very
low volatility and is most suitable for high temperature processing or product performance.
22M46 does not bloom on uncured stocks and gives protection against Copper and
Manganese ion catalyzed oxidative ageing. These properties of 22M46 make it an interesting
antioxidant even for critical carbon black reinforced rubber compounds! 22M46 is used in
colored compounds; however; white colored products may show slight pink coloration on
prolonged exposure to light. 22M46 is an excellent polymer stabilizer and is also used as an
antioxidant for Hot Melt Adhesives based on EAM, EVA etc. Dosage: 0.5-2.0 phr

Non
Staining
Pale
Pink
Discolor
ation

V. Good

Thiobisphenols exhibit high antioxidant activity compared to similar bisphenols.


Thiobisphenols generate sulphur compounds which react with polymers during antioxidant
protection reaction and compliment antioxidant activities of thiobisphenols. Thiobisphenols
cause comparatively higher discoloration of rubber vulcanizates than bisphenols.
Dosage: 0.5-2.0 phr

Non
Staining
Pale
Pink
Discolor
ation

V. Good

Multifunctional phenolic antioxidants are very high performance antioxidants, exhibit extremely
low volatility and do not cause contact / migratory staining or discolorations of the rubber
products.
Higher molecular weight of multifunctional phenolic antioxidants also contributes to practically
no leaching and extraction from rubber products by water or solvents and ensuring long term
protection against oxidation.
The ortho bridged bisphenolic antioxidants exhibit excellent antioxidant performance but
show discoloration (pinking) tendency to rubber vulcanizates.

General Structure
Type 2
Bifunctional
Antioxidant
22M46

2.2-methylenebis (6-t-butyl-4methyl
phenol)
Type 2
Bifunctional
Thiobis phenols
Antioxidant
TBMC

4,4-thiobis-6-(t-butyl metacresol
ASTM D 4676
Class 3
Phenolic
Type 3
Multifunctional
Ortho bridged

General Structure

Chemicals

Structure

Type 3
Multifunctional
Polyphenol
Antioxidant
Wingstay L
(Goodyear)

Staining
Protection against
or
Heat &
Ozone
Flex
Non
Fatigue
Staining Oxidation
Non
Staining

Notes

V. Good

Butylated reaction product of para cresol and dicyclopentadiene ( Wingstay L ) Is the most
popular multifunctional phenolic antioxidant used both in dry rubber and latex based products
where color stability, low volatility and long term protection against heat and oxidative
degradation is desired. The resistance to oxidative degradation is due to a particularly
favorable pattern of substitution on the phenolic group. Color stability is due to the stearic
impossibility to form highly conjugated and colored by-products like quinones.
Dosage: 1-2 phr.

V. Good

The para bridged bis phenolic antioxidants show slightly lower antioxidant performance but
do not exhibit discoloration effect on rubber vulcanizates.

V. Good

Irganox anti-oxidants are phenolic based anti-oxidants that hinder thermally induced oxidation
of polymers where high temperature applications are used. Unlike hindered amines, antioxidants are consumed - and not regenerated - in the stabilization process. Irganox 1010
offers excellent protection against over bake yellowing by terminating free radicals in
conventional solvent-based and powder coating systems. The major usage of Iraganox 1010
is in Thermoplastics rather than rubbers. Dosage: 0.5-1.0 phr

Good

This class of antioxidants represents Substituted Amine Antioxidants which are complex
reaction products of diphenylamine and various alkylating agents.
The substituents are selected to achieve a desired balance of cost and performance
characteristics. Alkylated Diphenyl Amines are moderately staining and discoloring. These
antioxidants are generally used as stabilizers of raw synthetic polymers and as general
purpose antioxidants for rubber vulcanizates.

No
Discolor
ation
Reaction product of Butylated pcresol & dicyclopentadiene.

ASTM D 4676
Class 3
Phenolic
Type 3
Multifunctional
Para bridged

Non
Staining
No
Discolor
ation

General Structure
Type 3
Multifunctional
Para bridged
Antioxidant
Irganox 1010
(Ciba)

Tetrakis [Methylene 3-(3,5 di-t-butyl 4 hydroxyphenyl) propionate]


methane
ASTM D 4676
Class 4
Alkylated DPAs
(Antioxidant)

ST
Discolor

Diphenyl amines
(General Structure)

Chemicals

Structure

Diphenyl Amines
(DPAs)
(Antioxidant )

Staining
Protection against
or
Heat &
Ozone
Flex
Non
Fatigue
Staining Oxidation
NST
Discolor

Good

Styrenated Diphenyl amine a straw colored-amber liquid. Is highly active, low volatility
antioxidant and protects rubbers against degradation due to heat, light and oxygen. It is non
blooming, non hydrolysable, non staining but discoloring type antioxidant and does not
influence the cure rate of the rubber compound. Styrenated Diphenyl amine is widely used as
a polymer stabilizer for the manufacture of staining type synthetic rubbers. It is used in some
non critical tire compounds, automotive & mechanical molded goods. Dosage: 1.0 3.0 phr.

NST
Discolor

Good

Dark tan liquid. Mostly di substituted with some mono & tri substitution. Some ortho
substitution. Highly active non-staining & mildly discoloring antioxidant for NR & Synthetic
Rubbers. Low volatility. Offers very good heat resistance to rubber vulcanizates. Nonblooming. Suitable for CR based compounds. Dosage:1.0-2.0 phr

ST
Discolor

Good

4,4-Bis (,-dimethylbenzyl) diphenylamine (DCDPA) is a grayish white powder with melting


point of 90 deg C. DCDPA is a slightly staining type antioxidant which offers good heat and
flex-cracking resistance to rubber vulcanizates and is used in the rubber products based on
NR, IR, BR, SBR, NBR, CR & ACM. DCDPA is less discoloring than ODPA and is especially
effective against heat for ACM based compounds. Dosage: 1.0 4.0 phr.

ST

Good

Good

Octylated diphenylamine (ODP) is a brownish to purple colored antioxidant (Flakes) with


melting point of 75 deg C. Octylated diphenylamine (ODP) is used as a stabilizer in the
manufacture of synthetic rubbers. Octylated diphenylamine (ODP) is a staining and blooming
type antioxidant which offers good heat and flex-cracking resistance to rubber vulcanizates
and is used in the rubber products based on NR, IR, BR, SBR, NBR, & CR. It is most widely
used antioxidant in CR based rubber compounds since it does not influence the bin storage
properties.
Dosages: 1.0 2.0 phr.

NST

Good

Phosphite antioxidants are hydro peroxide (ROOH) decomposers and are always used in
combination with H-donors e.g. hindered phenols. The phosphites are oxidized to phosphates
and RO. & ROO. Radicals are reduced by the reaction with the formation of trivalent
phosphorus compounds.
The phosphites are hydrolyzed easily in presence of acidic materials. They are also destroyed
during sulphur vulcanization and hence are not effective with sulphur cured products.

Alkylated diphenylamines
(Styrenated, Octylated, Heptylated,
Nonylated)
Antioxidant
SDPA
Wingstay 29
(Goodyear)

Notes

p-oriented Styrenated Diphenyl amine


Antioxidant
DCDPA
Naudard 445
(Chemtura)
4,4, bis (,-domethylbenzyl)
diphenylamine
ODPA
(Antioxidant)

Octylated Diphenyl amine


ASTM D 4676
Class 5
Aromatic
Phosphites

General Structure

Chemicals

Structure

Antioxidant
TNPP

Staining
or
Non
Staining

Heat &
Oxidation

Ozone

Flex
Fatigue

NST

Good

ST

Modest

Protection against
Notes
Phosphite antioxidants are used as in-process stabilizers and as stabilizers during Synthetic Rubber
e.g. SBR manufacture.
Phosphites can be used with non-sulphur cured products.
Phosphites give excellent color retention properties because they act as reducing agents.
Phosphite antioxidants are also widely used in the manufacture of adhesives for tack retention.
The recommended dosages are 1.0 2.0 phr.

Trinonyl phosphate
ASTM D 4676
Class 6
Diphenylamine Ketone
Condensates
(Antioxidant)
Acetone Diphenyl amine condensates
(ADPA)

Modest

Modest

These antioxidants are complex reaction products of diphenylamine and alkyl ketones (primarily
acetone), some of which are further condensed with formaldehyde to produce products of high
molecular weight. These antioxidants are low melting point resins or liquids.
There are two different types of ADPA condensates viz. low temperature reaction products and high
temperature reaction products. The high temperature reaction products are reactive towards oxygen
and provide some flex cracking resistance but are severely staining and discoloring. They are also
volatile and do not provide long term protection against the degradative forces that constantly act
on rubber products. These products are mostly used in mechanical rubber products, some non
critical tyre applications and as a stabilizer for emulsion SBR. These antioxidants reduce the building
tack of uncured rubber compounds making product (e.g. tyres, conveyor beltings etc) building
process more difficult.
The low temperature condensation products are not very reactive towards oxygen but are less
staining and discoloring. These are comparatively less volatile and can provide medium term
protection to the rubber vulcanizates. These types of ADPAs have low solubility in oil and hence
suitable for oil resistant compounds based on NBR. Dosages: 1.0 2.0 phr.

Chemicals

Structure

Other
Antioxidants
Napthyl
Amines
PAN
(Antioxidant)

Staining
Protection against
or
Heat &
Ozone
Flex
Non
Fatigue
Staining Oxidation
ST

Good

ST

Very Good

NST

Very Good

Notes
Highly effective antioxidants, but toxicological risk! (Carcinogenic).
Usage discontinued in the Rubber Industry.

Phenyl -napthyl amine


PBN
(Antioxidant)

Phenyl -napthyl amine


MMBI
& ZMMBI
Antioxidants

and

1,2-Mercapto-4(5)methylbenzimidazole

These are heterocyclic SH-compounds and are different from the usual phenol/amine
antioxidants.
These are used with other antioxidants for synergistic effect on heat resistance properties &
metal as metal deactivators. This effect depends on the vulcanization system. x MMBI is more
effective in vulcanizates produced with Thiuram and Dithiocarbamate accelerators than in
sulfenamide or thiazole accelerators.
The combinations are particularly suitable for compounds which contain low levels of sulfur
and high levels of accelerators.
These products offer no protection from cracking, whether caused by flexing, ozone or the
action of light and oxygen.
MMBI and ZMMBI give little protection from heavy metal poisoning when used individually.
However, the protection is enhanced by using combinations with other antioxidants like
22M46. TMQ & MMBI and ZMMBI combinations ore suitable antioxidants for rubber products
based on peroxide-cured rubber products.
Dosage: 1:1 in combination with phenolic antioxidants/amine antioxidants.

Zinc salt of 1,2-Mercapto-4(5)methylbenzimidazole

Chemicals

Structure

Other
Antioxidants
Thioesters
TDPE type

Staining
Protection against
or
Heat &
Ozone
Flex
Non
Fatigue
Staining Oxidation
NST

Good

NST

Good

NST

Good

NST

Good

DIdodecyl 3.3 thiodipropionate

Notes
The Thioesters are esters of thiodipropionic acid. These are secondary antioxidants and are
used with phenolic or amine antioxidants.
Thioesters are highly effective peroxide decomposers for long term heat resistance when used
in combination with phenolic antioxidants.
Thioesters are destroyed during sulphur vulcanization. Hence, not used for Sulphur vulcanized
rubber products. Thioester antioxidants find applications in Plastics and TPE s. Exhibit
blooming tendency at higher dosages.

DIoctadecyl 3.3 thiodipropionate


Other
Antioxidants
Dithio
Carbamates
ZDBC
Zinc dibutyl dithiocarbamate

Dithiocarbamates are moderate antioxidants but their use is limited due to the activating effect
on sulphur based cure systems.
One of the widely used dithiocarbamate is Nickel Dibutyl dithiocarbamate (NBC). It is used as
an antiozonant for SBR, BR, NBR, ECO and CR based compounds. It is also used as an
antioxidant and heat age resistor for CSM and EPDM.
Nickel Dibutyl dithiocarbamate should not be used with NR since it is a pro-oxidant with NR.
Another dithiocarbamate is Zinc dibutyl dithiocarbamate. This product is used as a stabiliser
for Butyl rubber production and as an antioxidant for rubber based adhesives.

NiDBC
(NBC)

Nickel dibutyl dithiocarbamate


For selecting a proper antioxidants / antidegradants for specific end-use requirements following factors are considered to be important for the choice.
a ) Discoloration & Staining
b ) Volatility
c ) Solubility
d ) Chemical Stability
e ) Physical form
f ) Antioxidant/Antidegradant concentration
g ) Cost
h ) Health & Toxicity concerns

You might also like