Antidegradants and waxes

Dr. Muhammad Farooq

 Retarders and inhibitors of vulcanisation
• Vulcanisation retarders and inhibitors have been used in rubber
compounds for many years as a means of increasing processing safety.
A vulcanisation retarder increases scorch time, thereby improving
processing safety, but also slows down the rate of vulcanisation. This
reduced rate of vulcanisation, however, is often an undesirable effect.
True vulcanisation inhibitors, on the other hand, increase scorch safety
whilst having no adverse effect on the rate of vulcanisation.
• Substances that fall into the first category are acidic in nature, for
example benzoic acid, salicylic acid and phthalic anhydride. They
prolong scorch time in thiazole accelerated compounds but their effect
in sulphenamide accelerated stocks is poor . N chlorosuccinimide,
nitroparaffins, sulphenic acid and sulphonic acid derivatives have been
described as retarders but appear to have little practical significance.
 continued
• N-nitrosodiphenylamine (NDPA) has a positive effect on the processing safety of
compounds accelerated with sulphenamides . It prolongs the induction period
with regard to the onset of cure but does not reduce the rate of vulcanisation. As
such it can be classified as a vulcanisation inhibitor. However, it is no longer in
use because of toxicological concerns.
• The major and most effective representative of the class of vulcanisation
inhibitors is N-(cyclohexylthio)phthalimide (CTP), often termed pre-vulcanisation
inhibitor (PVI). It is effective with a wide range of polymers, accelerators and
other compounding ingredients. It neither affects vulcanisate properties nor
causes staining or porosity. Although most effective in sulphenamide accelerated
stocks, it is also used with both MBT and MBTS. There is a linearity about its
response that allows the dosage necessary to give a certain scorch resistance to
be readily determined. In most applications 0.1–0.3 phr is used. The scorch
resistance increases proportionally with the dosage and an addition of 0.1 phr
causes a considerable improvement . Furthermore the addition of PVI permits
processing at elevated temperatures, thereby increasing productivity.
 Antidegradants
• Elastomer-based products suffer irreversible changes to their
required design properties during service. These changes, brought
about by a number of agents such as oxygen, ozone, heat, light
and mechanical deformation, are collectively referred to as
ageing. In addition to a loss in mechanical properties, changes in
surface aspect can occur that, whilst perhaps not damaging with
regard to performance, impair appearance. In order to combat
these detrimental changes additives, often collectively referred to
as antidegradants, are employed.
• Typical loading levels are of the order of 1–4 phr. Antidegradants
can be conveniently categorised into antioxidants and
antiozonants. However, this is not an unambiguous division since
these materials often impart additional benefits in addition to
their primary function. A multitude of antidegradants are
commercially available and no attempt will be made here to
describe the entire range but only those of major importance. An
 Antioxidants
• Antioxidants are often further referred to as ‘staining’ and ‘non-
staining’, designations associated with the effect of these
materials on the staining characteristics of the compound to
which they are added.
Phenolics
• The most important group of non-staining antioxidants is based
on phenol. Whilst not as powerful as some staining antioxidants,
phenolics are nevertheless an important class of antidegradants
due indeed to their non-staining and non-discolouring nature.
• Appropriately they are applied in white and coloured
vulcanisates. This group includes monophenols, bisphenols,
thiobisphenols, polyphenols and hydroquinone derivatives. 2,6-
di-t-butyl-p-cresol, frequently referred to as BHT , is the most
widely used phenolic antioxidant. It is also representative of the
basic, generic building block of all phenolic antioxidants.
 Phosphites
• Phosphites are the second major class of non-staining antioxidants.
The most commonly used material of this class I
tris(nonylphenyl)phosphite, (TNP; Figure 6.24). However, it suffers
from a tendency to hydrolyse during prolonged contact with moisture
and it is destroyed during vulcanisation. Nevertheless, its exceptional
non-tinting property has made it the industry’s standard non-staining
SBR stabiliser. TNP is ideally suited to the emulsion polymerisation
process because of its liquid physical form.
 Thioesters
• A third category of antioxidants comprises thioesters with
essentially two classes of materials: the bis-
(alkylthiopropionate)diesters (BTPDE) and the
alkylthiodipropionate esters (TDPE). Typical structures are
shown in Figure 6.25. As for phosphite-based antioxidants,
they are destroyed during vulcanisation and thus find little
use in the rubber industry. They are used primarily for the
stabilisation of polyolefins.
 Amines
• Historically, amine-based antioxidants were the first really
effective rubber antioxidants. The materials can be categorised as:
naphthylamines, diphenyl amine derivatives, dihydroquinolines
and paraphenylenediamines. The naphthylamines, phenyl-β-
naphthylamine (PBNA) and its companion phenyl-α
naphthylamine (PANA), whilst extremely effective antioxidants
have now almost disappeared due to toxicological concerns .
• Structures of the four types are shown in Figure 6.26.
 Bound antioxidants
• In 1972, The Malaysian Rubber Producers Research Association reported that
quinonediimines could provide bound antioxidant activity , the antioxidant becoming
attached to the elastomer during vulcanisation. This prevents the antidegradant from
being extracted during service of the rubber article thereby providing long term
protection.
• At the time the materials were not commercialised but recently one such product
has been introduced, N-1,3-dimethyl butyl-N´-phenyl-p-quinone diimine (QDI), Figure
6.27. In addition to providing long term antioxidant protection it can also serve as a
peptiser, a vulcanisation retarder and can enhance polymer-filler interaction
 Antiozonants
• Under deformation vulcanisates that are susceptible to ozone attack have a
critical elongation below which cracks will not form. This varies with the type of
rubber and compounding ingredients, but it is usually in the range of 5–10% for
diene rubbers.
• Above this critical elongation cracks do appear, becoming progressively more
numerous as a function of time. The incorporation of antiozonants in the
compound, however, provides a marked improvement in the resistance to ozone
attack. They function by migrating from the bulk of the vulcanisate to the surface
where they react preferentially with the ozone thereby safeguarding the
integrity of the component.
• The most widely used antiozonants are the substituted para-phenylenediamines.
They not only offer protection against ozone but also function as antioxidants
and as outstanding antiflex agents. Nickel dithiocarbamates are also active as
antiozonants but they are of minor importance in terms of usage
 Para-phenylenediamines
• Para-phenylenediamines, the most widely used class of
antidegradant, provide protection against oxygen, ozone,
metal ions and flex fatigue. One major drawback, however, is
that they are discolouring and staining. They can be
conveniently grouped into three categories based on the
chemical nature of substituents (see Figure 6.29): diaryl-p
phenylenediamines, dialkyl-p-pheylenediamines and alkyl-
aryl-p-phenylenediamines.
 Diaryl-p-phenylenediamines
• The diaryl-p-phenylenediamines are the least
reactive of the p-phenylene diamines towards
ozone but they possess relatively low volatility
and provide long protection. Due to their
basicity they have an activating effect on
sulphur cure systems. The most widely used
diaryl derivative is the diphenyl, Figure 6.30.
 Dialkyl-p-phenylenediamines
• The most common member of this group incorporates branched
C7 substituents (Figure 6.31). The dialkyls provide superior ozone
resistance but do not offer the same degree of protection against
oxygen as other phenylenediamines. They are more volatile than
the diaryls and hence do not provide such long-term protection.
As for other p-phenylenediamines they also provide flex crack
resistance and protect against metal ion catalysed degradation.
 Alkyl-Aryl-p-phenylenediamines
• The alkyl-aryl-p-phenylenediamines offer the best all round
antidegradant protection. They are not as reactive as the dialkyls but
are not as volatile, thus provide longer protection. The most widely
used antiozanant in this group is the product bearing a phenyl and a
branched C6 alkyl group, 6PPD, Figure 6.32. The isopropyl analogue,
IPPD, is also commonly used but is gradually being replaced by 6PPD;
IPPD is more readily leached from vulcanisates during service.
 Triazine derivative
• (N-1,4-dimethylpentyl-p-phenylenediamino)-1,3,5-triazine,
although an active antiozonant is not used extensively in the
rubber industry due to its limited solubility in synthetic
rubbers and its high cost. It functions also as an antioxidant
and is non-staining. The structure is shown in Figure 6.33.
 Waxes
• Waxes provide protection from ozone by blooming to the surface of
the rubber component. However, unlike the p-phenylenediamines
they offer only physical protection. This is a result of the formation
of a thin film of wax at the surface acting as a barrier toward ozone
attack of the elastomer. If, however, the film is ruptured, for
example on flexing of the component, the ozone resistance is lost.
Waxes therefore are effective with regard to static ozone protection
only and do not provide protection under dynamic conditions.
• The migration rate of the wax is important in providing optimum
static ozone protection. Often a blend of paraffin and
microcrystalline waxes are used in order to provide protection over
a wide range of temperature.
 Antireversion agents
• Reversion of sulphur-based crosslinks and the consequent loss in vulcanisate
properties presents a major challenge to the rubber compounder. A number of
additives are available that, in one way or another, provide some protection
against reversion.
Zinc carboxylates
• A blend of aliphatic and aromatic zinc carboxylic acid salts is commercially
available that provides reversion resistance by promoting the formation of
sulphidic crosslinks of lower sulphur rank. The general structure of the material
is shown in Figure 6.34. Its mechanism of action is due to increased solubility in
the rubber matrix compared to the zinc salt of stearic acid . The latter is
normally generated in situ as a result of the reaction between zinc oxide and
stearic acid.
The data shown in Table 6.4 clearly demonstrate the effect of the material on
crosslink network structure
 Thiophosphoryl derivatives
• Thiophosphoryl derivatives such as ZBPD (Figure 6.35)
provide improvement in reversion resistance when added to
a sulphenamide cure system . Again, reversion resistance is a
result of the formation of a crosslink network containing a
higher proportion of monosulphidic crosslinks. Data listed in
Table 6.5 demonstrate the effect for a ZBPD based
compound
 Silane coupling agents
• Silane coupling agents possess multifunctional activity. Their major role is, as the
name implies, as a coupling agent between silica filler and elastomer. This action
provides significant improvements in the physical properties of vulcanisates . The
most widely used material, bis-(3-triethoxysilylpropyl)-tetrasulphide TESPT is
shown in Figure 6.36. It also functions, however, as a sulphur donor, providing an
‘equilibrium cure system’. Its mechanism of action is associated also with the
formation of crosslinks of lower sulphur rank. The effect of TESPT on the network
structure of a NR based compound is shown in Table 6.6
 Sulphenimide accelerator
• A commercially available sulphenimide accelerator, TBSI ,
provides a long scorch delay together with a slow cure rate
. Its effect on network structure is once again to shift the
distribution of crosslink type towards lower sulphur rank
thus enhancing reversion resistance. Its effect on network
structure of a NR based compound is shown in Table 6.7
 Hexamethylene-1,6-bis thiosulphate
disodium dihydrate (Duralink HTS)
• Duralink HTS (Figure 6.37), is a material that
functions during vulcanisation by forming hybrid
crosslinks composed of hexamethylene and
sulphidic moieties.The presence of these hybrid
crosslinks increases the reversion resistance of
the network and is particularly beneficial in
maintaining flex/fatigue resistance.
 1,3-Bis(citraconimidomethyl)benzene (BCI-
MX; Perkalink 900)
• The most recently introduced antirevesion agent, 1,3-
bis(citraconimidomethyl)benzene (Perkalink 900; Figure 6.38),
functions by a crosslink compensation mechanism. It compensates
for the loss of polysulphidic crosslinks during the process of reversion
with crosslinks based essentially on a carbon-carbon structure. The
material reacts at the onset of reversion and can be added to existing
compounds with no further change in formulation. Its effect on the
network structure of a NR based compound is shown in Table 6.8.